CN1125796A - Dry polyurethane synthetic skin with high-solidity, divisible shapes and zero-pollution - Google Patents
Dry polyurethane synthetic skin with high-solidity, divisible shapes and zero-pollution Download PDFInfo
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Abstract
The synthetic polyurethane leather without pollution is made up of polyol, polyisocyanate and chain-growing agent through such steps as prepolymerization by means of slow-reaction ejection shaping method in reverse operation mode to form precursor of polyurethane, spreading the precursor ons eparable paper on conveying belt, baking to form polyurethane but keeping its viscosity, sticking cloth substrate, and baking for solidification.
Description
The present invention relates to the synthetic skin of dry type Polyurethane (PU) that high-solidity, divisible shapes zero pollutes, especially refer to utilize polyalcohol (Polyol) and polyisocyanate (Polyisocyanate), the chain lengthening agent is adopted the contrary operation mode of slowing down the reaction jet forming method along the impact mixing head of reaction ejecting device, slow down the reaction of impacting in the mixing head, after the prepolymerization reaction of carrying out each composition makes into the precursor of Polyurethane, implement coating processing, make precursor fully flow expansion, ejaculation is coated on the release liners on the conveyer belt and through baking oven for heating and is made precursors reaction become polyurethane resin, when it keeps viscosity, the base cloth of fitting thereon, again through baking oven for heating make the polyurethane resin sclerosis high-solidity, divisible shapes and the synthetic skin of zero Polyurethane of polluting.
By the preparation of at present general Polyurethane coating, the preparation that is broadly divided into (A) polyurethane resin reaches (B) the preparation two-stage of coating.Wherein the A stage is that polyalcohol, polyisocyanate, chain elongation agent and solvent are carried out the batch polymerisation in polymerization reaction trough, to synthesize polyurethane resin, in B stage look the needs of purposes or coating operation thereafter, add solvent or plasticizer in the polyurethane resin that generates in the A stage again, add colouring agent or other additives, be mixed into coating through mechanical agitation.When the preparation polyurethane resin in A stage, in the batch bucket groove of being everlasting, react and formed in about 6-8 hours with stirring rod.Prepare coating in the B stage and also often take 1-2 hours.
Existing manufacturing Polyurethane is synthesized skin, in respect of wet type and two kinds of methods of dry type.Wherein damp process is the Polyurethane coating that adopts the above-mentioned B stage to make and coats on the base cloth and drying forms.Yet the preparation of its Polyurethane coating is consuming time, and adopts solvent, needs to reclaim, so and be not suitable for.
Wherein dry process means and be coated with one deck one liquid type PU coating earlier on release liners, through baking oven with solvent (MEK, TOL) volatilization and form about 0.015-0.02 m/m surface layer of a bed thickness, coating one deck two-liquid type PU following layer on the surface layer of drying again, when following layer is still possessed viscosity, the base cloth of fitting thereon, again through the solvent (MEK of baking oven with following layer, TOL) (dried following layer thickness is about 0.02-0.025m/m) for volatile dry, because following layer is a two-liquid type PU resin, the semi-finished product of applying base cloth (together with release liners) must be positioned over the maturation chamber of 50 ℃ of temperature and carry out maturation in 48 hours, make following layer be formed netted bridge formation and can bring into play due rerum natura.
Damp process ties up to and directly is coated with one deck one liquid type PU coating on the base cloth, enter in the water then and solidify, solidify carry out when, solvent (being generally DMF) Hui Heshui in the one liquid type PU coating exchanges, the space that coating layer Central Plains DMF occupies is replaced by water and then solidifies, lest the displacement of DNF and water also not exclusively still has a spot of remnant, the people DMF in washing process gel coating more thoroughly clean, entering baking oven then carries out drying and water evaporates is removed, the occupied space of moisture content promptly forms hole in the coating thus, becomes one and has continuous hole, the wet type semi-finished product of the about 0.25-0.3m/m coating of thickness.In order to make the wet type semi-finished product have the outward appearance of skin sample, people carry out facing with the dry-type processing method again, and are coated with the thick 0.01-0.14m/m that is about at the used solid of this dry process of carrying out.
Hence one can see that, dry process is because total only about 0.035-0.045m/m of coating layer thickness, 0.27-0.34 m/m far away from damp process, as above the wet type coating has continuous hole, so whole feel, the wet type synthetic leather is much better than the synthetic skin of dry type, but damp process is because cost is high, so if people are can be with the generous sense of dry process acquisition as damp process, must on cost, get the mastery, and then break the high price situation of the synthetic skin of wet type for a long time, and dry process to obtain abundant coating, must be dependent on does not have solvent, and high solid shape PU coating just might be realized.
More than commonly use the preparation method of Polyurethane coating, must adopt a large amount of solvents, uneconomical and contaminated environment is arranged, harm sanitarian shortcoming on the cost, therefore noticeable with the preparation of the high-solidity, divisible shapes Polyurethane coating that adopts a small amount of (or not adopting) solvent at present.
In view of this, make the trend of the synthetic skin of Polyurethane at present, change the dry type high-solidity, divisible shapes mode that adopts into.And meet in the method for making of dry type, high-solidity, divisible shapes resin, have with reaction jet forming method (Reaction Injection Molding) manufacturing polyurethane elaster person more suitable at present.
Moulding product with reaction ejection formation manufactured synthetic resin are well-known, are that the Polyurethane based resin molded articles of beginning often is widely used with manufacturing Polyurethane based elastomers especially.The reaction jet forming method is to form the forming method that synthetic resin is attached most importance to via the mobile material composition of binary at least that mixing makes quick response can form synthetic resin in forming model.Flow composition mixes at conflict mixing head (impingement mixer) usually.For further evenly mixing mixture is injected in the forming model via back mixing (after mixing) mechanism.The polyalcohol that uses the higher molecular weight that cooperates arbitrarily and material compositions such as the catalyst that contains the chain lengthening agent, blowing agent and the material composition that contains polyisocyanate compounds be binary at least, and the method for utilizing the reaction ejection formation to make polyurethane elasters such as polyurethane elaster or Polyurethane urea elastomer is known.
For improving the rerum natura of reaction ejection formed piece, for example percentage elongation can be set about from its chemical composition, uses the polyalcohol (as Polyoxyalkylene polyol) of higher molecular weight usually, can improve the percentage elongation of moulding product.Yet along with the increase of this polyalcohol molecular weight, the viscosity in the reaction system can rise, and the mobile of reactant liquor is sharply descended, and on the formed products surface of gained phenomenons such as pin hole, depression can take place, the difficult formed products that obtains excellent surface.
Reaction injection molding method as another often use plasticizer to be added in the reaction system reducing viscosity, and this often makes the heat resistance variation of formed products, and when being used to be coated with, plasticizer often oozes out the problem of the adherence aspect of filming in the back that is shaped from the formed products surface.
Generally be used to make the reaction injection molding method of polyurethane elaster in addition, can add the low boiling halogenated hydrocarbon compound as blowing agent, to reduce the viscosity of reaction system, but because the reaction of system is very fast, the finger property touched of coating is difficult for stable control, phenomenons such as swelling take place in the reaction post-foaming that finishes of being everlasting on coating, have a strong impact on itself and the strong stability of base cloth applying.
Therefore, when adopting reaction injection molding method, the issuing velocity of RIM building mortion, the viscosity of raw material, composition must take into account the balanced and restriction on the prescription.Also must note the equilibrium of processing procedure and character in addition to the material of reaction injection molding product.
An object of the present invention is to provide the synthetic skin of Polyurethane that a kind of high-solidity, divisible shapes zero pollutes, system adopts polyalcohol (Polyol) and polyisocyanate (Polyisocyanate), the chain lengthening agent makes into precursor along the impact mixing head (impingement mixer) of reaction device for injection moulding, and viscosity descends and can flow under case of exothermic reactions, ejaculation is coated on the release liners on the conveyer belt, and make precursors reaction become polyurethane resin through baking oven for heating, at resin precursor when baking oven for heating continues to be reacted into polyurethane resin and keeps viscosity, the base cloth of fitting thereon, drying heating make the polyurethane resin sclerosis high-solidity, divisible shapes and do not produce the synthetic skin of Polyurethane of solvent recovery problem.
The present invention adopts the reaction jet forming method of making polyurethane elaster, only employing slows down the contrary operation mode of reaction, because each composition of general reaction jet forming method also must be with powerful ejaculation pressure hardened forming in the model of the injection moulding device of short time along the impact mixing head immediate response of reaction device for injection moulding.Because the initial reaction stage of HCO/OH is an exothermic reaction, each reaction raw materials is the process elevated temperature very easily of pressurized delivered again, and the utmost point is unfavorable for the control of system, especially the cooling control section of mixing head.So should use instead under no pressure precursor stream is opened up on release liners, and be not to spray with crunch to flow out mixing head, this forming method is not that the present invention expects.Because during the reaction ejection formation, each composition in impacting mixing head can carry out polymerisation and heat release immediately in hybrid reaction.And the inventive method is promptly in impacting mixing head, do not make each composition immediate response, and make under its situation that forms precursor, utilize again exothermic reaction emit heat make this precursor be controlled to do not make its continue reaction and at high temperature viscosity descend under the state that can flow, utilize no pressure current to open up and be sprayed on the release liners.
In detail, the present invention adopts the contrary operation mode of slowing down the reaction jet forming method, slow down the reaction of impacting in the mixing head, after the prepolymerization reaction of carrying out each composition makes into the precursor of Polyurethane, be coated with processing, make performed polymer fully flow expansion, can carry out quick-hardening in the baking oven for heating stage thereafter and be reacted into polyurethane resin.Only can finish in 2-3 minutes before and after this full polymerization reaction time.
That is the present invention mainly utilizes the fast reaction of the reaction injection molding method of general polyurethane elaster, in addition control impact mixing head in-20 ℃-30 ℃ to slow down the polymerisation of each composition, make into the precursor of tool flowability, it is coated on the release liners, make it in 2-3 minutes of course of conveying, finish polymerisation through 70-200 ℃ of baking ovens, this is reflected under the situation without solvent and can be made into the high-solidity, divisible shapes polyurethane resin, and at high temperature still have under the state of thermal viscosity, the applying base cloth thereon, through 80 ℃ of-130 ℃ of baking oven for heating, make the polyurethane resin sclerosis make the synthetic skin of dry type Polyurethane again.
Be applicable to the polyalcohol of making the synthetic skin of PU of the present invention, be advisable with the many alcohol of polyoxy alkylene (Polyoxy alkylene polyol).Generally speaking, more reduce the hydroxyl valency of the many alcohol of polyoxy alkylene, then its degree of unsaturation is higher.Be the lower person of hydroxyl valency, the alkylidene oxide of carbon number more than 3 of the main alkylidene oxide of the many alcohol of polyoxy alkylene, especially the amount of alkylidene oxide is more, so the reacting dose of the alkylidene oxide of carbon number more than 3 when it is made is more, thereby the also side reaction of the identical alkylidene oxide of generation mostly, so form the less event of degree of unsaturation.The degree of unsaturation that is used for the many alcohol of polyoxy alkylene of the present invention needs below 0.05meq/g, especially to be advisable below the 0.03meq/g.Be preferably in below the 0.025meq/g.In addition, the molecular weight of the many alcohol of polyoxy alkylene is required to be 1000-3000, and is better with 1500-2000 especially.The hydroxyl value of per in addition 1 molecule is 1.2-2.0 for good, and is used for the many alcohol of polyoxy alkylene of the present invention and also can be mixtures more than two kinds certainly, this moment average degree of unsaturation, molecular weight is as mentioned above.
The interior adding of the initiator alkylidene oxygen addition polymerization that the many alcohol of above-mentioned polyoxy alkylene tie up to multivalence forms, and alkylidene oxygen system adopts at least a and ethylidene oxygen in propylidene oxygen and the butylene oxide, especially adopts propylidene oxygen and ethylidene oxygen.The hydroxyl cording of this polyether polyol has the hydroxyl of higher level of reactivity, that is need contain 1 grade of hydroxyl of higher rate.Therefore, on the molecule chain end of polyether polyol, need there be the oxidation ethylidene.The many alcohol of this kind polyoxy alkylene get for additional oxidation ethylidene add oxypropylene or oxybutylene addition polymerization in the multivalence initiator after.Oxidation ethylidene system adds to molecule chain end, also can be present in strand inside.The content that is present in the oxidation ethylidene of molecular end part is required to be 5 weight % at least, is preferably 8 weight %.The content of the oxidation ethylidene of the many alcohol of polyoxy alkylene is higher, and then the hydrophily of the synthetic skin of the Polyurethane of gained system is higher.When if hydrophily is higher, synthetic skin suction is excessive, the stability variation, and unsuitable.Contain whole oxidation ethylidene content in the many alcohol of polyoxy alkylene that are present in the interior oxidation ethylidene this moment below 35 weight %, especially to be advisable below the 25 weight %.Most of in addition oxidation ethylidene is good with the end portion that is present in strand.And do not need purposes when low for the hydrophily of the synthetic skin of Polyurethane system, the upper content limit of oxidation ethylidene is not so limited.
Employed multivalence initiator when making the many alcohol of above-mentioned polyoxy alkylene is in respect of polyalcohol, polyhydric phenols, polyamine, alkanolamine etc.Ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, neopentyl glycol, 1 are for example arranged, 4-butanediol, 1,6-hexylene glycol glycerine, three methanol-based propane, isoamyl tetrol, two glycerine, glucose, sucrose, bisphenol-A, ethylenediamine etc.They can be a kind, also can be more than two kinds and share.The multivalence initiator is good with polyalcohol especially.Additional oxypropylene or 1,2 or 2 in this class multivalence initiator, in the alkylidene oxide that carbon numbers such as 3-oxybutylene are 3 at least a kind, the polyoxy alkylene that secondly can add ethylene oxide and be purpose is alcohol how.The many alcohol of polyoxy alkylene system with internal oxidation ethylidene to the multivalence initiator in regular turn or mix and add ethylene oxide and the alkylidene oxide of carbon number 3 or more, in the end the stage adds ethylene oxide and gets.
The used many alcohol of polyoxy alkylene of the present invention also can be the condensate of tool α, β-unsaturated group monomer.Contain the many alcohol of this polymeric polyoxy alkylene and be known as condensate/polyalcohol, for example monomer such as polypropylene nitrile or styrene and getting in the many alcohol of polyoxy alkylene.Condensate is with the microgranular how alcohol of polyoxy alkylene that is scattered in, and system is scattered in the many alcohol of polyoxy alkylene unchangeably usually.Contain the polymerization scale of construction in the polymeric polyalcohol usually below 40 weight %, be advisable with 5-30 weight % especially.This contains the whole hydroxyl valency of the many alcohol of polymeric polyoxy alkylene below 35, is good with 2-25 especially.
High molecular weight polyols beyond the many alcohol of the used aforementioned polyeneization of the present invention or other high molecular active dydrogen compounds composition mode arbitrarily share.But it uses and is nonessential.Yet with the rerum natura that improves the synthetic skin of Polyurethane is purpose, maybe can use for other purposes.For example for reducing the hydrophily of the synthetic skin of Polyurethane, the higher high molecular weight polyols of hydrophobicitys such as polybutadiene that contains hydroxyl with employing is good, this kind high molecular weight polyols is that the mean molecule quantity of each OH base is more than 400, especially being good more than 800, be good at 1.6-4 polyalcohol with the average OH radix of each molecule.The mean molecule quantity of each OH base is being good below 10000.As for this kind high molecular weight polyols, in respect of the hydrocarbon system condensate that contains hydroxyl of the polybutadiene that contains hydroxyl, polyester body, polyoxygenated tetramethylene polyalcohol etc.As for the macromolecule active dydrogen compounds beyond the high molecular weight polyols, also can share high molecular polyamine or contain 1 grade of amido more than or the high-molecular weight compounds of 1 above hydroxyl of 2 grades of amidos with 1 grade or 2 grades amido more than two.The molecular weight that is equivalent to each functional group of this family macromolecule amount active dydrogen compounds is preferably more than 800 more than 400, and the sense radix of each molecule is 2-8.Each functional group's molecular weight is being good below 10000.As for this kind compound, the hydroxyls of the part that makes aforementioned polyoxygenated tetramethylene polyalcohol of serving as reasons-all convert amido to and compound or to the polyisocyanate compounds reaction of aforementioned polyoxygenated tetramethylene polyalcohol and excessive equivalent and must end on have the isocyanates of performed polymer of isocyanate group through adding water decomposition, converting the compound that amido forms to.And for the situation of using the high molecular active dydrogen compounds can share this type of aforementioned polyoxygenated tetramethylene polyalcohol, its use amount for both total amounts relatively below 40 weight %, especially being good below the 20 weight %.
Chain lengthening agent used in the present invention can be polyalcohol tethers elongation agent, and the molecular weight that for example has 2-4 hydroxyls is in the low molecular weight polyols below 4000.This chain lengthening agent includes ethylene glycol or 1, representative chain lengthening agent such as 4-butanediol, and other have many alcohol of polyalcohol, low molecular weight polyoxy alkylene beyond above-mentioned, the polyalcohol of tertiary amine base are arranged, or do not have the polyalcohol of amido.They also can share more than two kinds.As for polyalcohol tethers elongation agent,, but be not to be so limited in respect of following illustrative compound.So that are advisable for a kind in the 4-butanediol at least in spent glycol and 1.
Ethylene glycol, 1,4-butanediol, neopentyl glycol, 1,6-hexylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, triethanolamine, N-alkyl diethanol amine, N-alkyl diethanol amine, bisphenol-A-alkylidene oxide addition product.
Chain lengthening agent composition is employing 5-45 weight % to the overall height molecular weight active dydrogen compounds composition that contains the many alcohol of the polyoxy alkylene ratio with the total amount of chain lengthening agent, is advisable to adopt 10-35 weight %.For improving the heat resistance or the hardness of the synthetic skin of Polyurethane, can adopt the chain lengthening agent of more amount, this moment, the amount of chain lengthening agent was advisable with 15-35 weight %.When making the good synthetic skin of rerum natura such as percentage elongation, be advisable at 10-25 weight % with the amount of chain lengthening agent composition.
Polyisocyanate compounds composition system forms by the compound with at least two isocyanate group is at least a.Be advisable to use aromatic poly-isocyanate.Particularly, methyl diphenylene diisocyanate, the polynary phenyl isocyanate of polymethylene, toluenediisocyanate, and their modifier.Especially be good with the aqueous modifier that uses 4,4 ' methyl diphenylene diisocyanate.As for modifier, for example can use pre-polymerization build modifier or carbodiimides modifier.The isocyanate group content of polyisocyanate compounds is good with at least 12 weight %, is the best with 15-25 weight % especially.The use amount of polyisocyanate compounds composition is 0.8-1.3 times of equivalents to the total equivalent of high molecular active dydrogen compounds composition and chain lengthening agent composition, and to use 0.9-1.2 times of equivalents more suitable.
Making Polyurethane is when synthesizing skin, can use the small amount of foaming agent.As for blowing agent, also can share both in respect of trichlorine fluoroethane, dichloro alkylene, other halogenation hydrocarbon system blowing agents and water.
In the present invention, can make apparatus reduce the dichlorofluoromethane low boiling halogenated hydrocarbon in addition of viscosity effect as blowing agent, can solve especially the viscosity problem of the material composition that causes with the many alcohol of high molecular polyoxy alkylene, also can prevent simultaneously because the defective of using Arcton 11 to follow.Low boiling halogenated hydrocarbon beyond this Arcton 11 is advisable with the halogenated hydrocarbon with fluorine atom that does not become ozone problem control object.Particularly, in respect of 1,1-two chloro-2,2,2-HFC-143a (HCFC-123), 2,2,2-HFC-143a (HCFC-123), 1,1-two chloro-1-fluoroethanes (HCFC-141b), 1-chloro-2,2-Difluoroethane (HCFC-142), 1-chloro-1,2-Difluoroethane (HCFC-142b) and carrene etc.Especially with 1,1-two chloro-2,2, the 2-trichloroethanes is good.They also can share more than two kinds, look other blowing agents such as also can share the low boiling halogenated hydrocarbon in case of necessity.But other blowing agents that become the halogenated hydrocarbon (comprising Arcton 11) of control object are being advisable below 1/2 with weight ratio.
Make the use amount of the synthetic used low boiling halogenated hydrocarbon of skin of PU of the present invention,, below about 15 weight portions, especially be advisable with about 2-10 weight portions with respect to how pure 100 weight portions of polyoxy alkylene.
When making the synthetic skin of Polyurethane, in above-mentioned raw materials, add general essential additive such as catalyst or further use additive arbitrarily.Can be metal series catalysts or tertiary amine series catalysts such as organo-tin compound as for catalyst.As for additive arbitrarily, for example can be filler, colouring agent, ultra-violet absorber, light stabilizer, antioxidant, flame retardant etc.Filler then has organic fiber, calcium carbonate, other ground pigments such as inorfils such as glass fibre or Wallostonite, synthetic fiber, mica, other tabular fillers etc., the loading of this class filler is the more the time, then the viscosity of material composition or operability more are a problem, to full synthetic resin raw material, with below about 30 weight %, especially below 20 weight %, being good.These additives mainly are to cooperate the material composition that contains active dydrogen compounds, and isocyanate group only also can cooperate with nonreactive compound and contain the isocyanate compound material composition.
The present invention also can carry out esterification with polyacid, chain lengthening agent along the contrary operation mode of impact of mixing of reaction ejecting device with polyalcohol earlier, carry out adding the precursor that polyisocyanate makes into Polyurethane at the latter end that impacts head again after the prepolymerization reaction, spraying again, dry through form the synthetic skin of Polyurethane.Wherein used polyacid can be the polyacid commonly used that polyester manufacture is used.
Below, illustrate embodiment and comparative example, but the present invention is not limited by these embodiment for further specifying the present invention.Embodiment and comparative example use following raw material.Polyalcohol Diol-1000: be with dipropylene glycol and expoxy propane addition polymerization and glycol, the goods Diol-1000 of Mitsui Toatsu Chemicals, Ltd of molecular weight about 1000: hydroxyl valency=112.Diol-2000: be with dipropylene glycol and expoxy propane addition polymerization and the glycol of molecular weight 2000, the goods Diol-2000 of Mitsui Toatsu Chemicals, Ltd: hydroxyl valency=56.Aromatic polyamine MDI-LK:4,4 '-the aqueous MDI of carbonyl diimine modification of methyl diphenylene diisocyanate.The MDI-LK that Mitsui Toatsu Chemicals, Ltd makes.NCO％＝28.3。Catalyst: L-1020:1,1: 2 mixture of 4-diazabicylo (2,2,2) octane and dipropylene glycol, the goods of Mitsui Toatsu Chemicals, Ltd.Embodiment 1-2 manufacturing process, condition
Use small-sized reaction emission forming machine, (eastern nation mechanical industry (strain) system NR-226) is with proportioning raw materials shown in the table 1 and the synthetic skin of molding condition shaping PU resin.Isocyanate index is about 1.05.Embodiment 2
Get 1 according to the weight meter, 5.8 parts of 6-hexylene glycols, 80 parts of trimethylolpropanes, 4.2 parts of hexylene glycols, phthalic acid is introduced temperature respectively with 4.2 parts of isophthalic acids for 5.8 parts and is remained on 25-32 ℃ impacting in the head mixing of reaction Jet forming machine, carry out esterification, get the polyester polyol (molecular weight 1800) of degree of unsaturation 0.04meq/g (free OH 0.17 weight %), thereafter in mix to impact head terminal add in addition 30 parts of TDI-80 (SUMITOMO CHEMICAL-Bayer Co., Ltd.) with isocyanate index NCO/OH is 0.95 precursor, it is 1.5kgf/cm that pressure is penetrated in control
2Make this precursor impact the head outflow from mixing, adjusting the ejaculation amount is 3.0kg/min, the stream spread-coating is distributed on the release liners under it, send in the baking oven of infrared ray heating region section that temperature is controlled at 70 ℃, 110 ℃, 150 ℃, 180 ℃, make the precursor of coating on the release liners in 2-3 minutes of course of conveying, finish polymerisation.
Table 1
Reaction test
| The embodiment number | ????1 | ????2 |
| ????Diol-1000 | ????100 | |
| ????Diol-2000 | ????100 | |
| ????MDI-PH | ????32 | |
| ????MDI-LK | ????16 | |
| ????L-1020 | ????0.3 | ????0.3 |
| Material temperature (℃) | ????28—32℃ | ????28—32℃ |
Utilize the reaction device for injection moulding, to penetrate pressure 2.0kgf/cm
2, 10 seconds ejaculation time, adjust ejaculation amount 1-6kg/min, 25-32 ℃ of the liquid temperature of each composition are to react ejection formation.
The described polyisocyanate compounds composition of table 2 is inserted in the raw material tank of reaction device for injection moulding, to make isocyanate index be the ratio of NCO/OH=0.8-1 and give ejaculation to mix both.(isocyanate index means isocyanate compound equivalent 100 times for the ratio of full active dydrogen compounds equivalent).
The article shaped of gained, in 25 ℃, leave standstill 3 in the constant temperature and humidity cabinet of humidity 50% after, measure rerum natura.Assay method is as described below.The intensity rerum natura
Tensile strength, percentage elongation, respectively according to the synthetic skin method of inspection of CNS 10270 polyamine fat, measurement result is as shown in table 2.Fluidity test
Utilize the reaction device for injection moulding, to penetrate pressure 2.0kgf/cm
2, 10 seconds ejaculation time, adjust the ejaculation amount and enable to coat (ejaculation amount: 4.5kg/min), confirm the flowability of reactant liquor on the release liners on the conveyer belt.Its result is as shown in the table.
Table 2
| Embodiment | ||
| The kind of polyalcohol | Polyester polyol | |
| The amount of polyalcohol (weight portion) | ????100 | |
| The kind of chain lengthening agent and consumption (weight portion) | 1,6-hexylene glycol 5.8 | |
| The kind of chain lengthening agent and consumption (weight portion) | 1,4-hexylene glycol 4.2 | |
| Mobile assessment | Well | |
| Open defects such as edema | Do not have | |
| The rerum natura of Polyurethane epithelium | Thickness | ????0.2?mm |
| Tensile strength kgf/cm 2(CNS10269) | Total number 10,270 65-80 class-mark K6771 | |
| Percentage elongation (CNS 10269) | Total number 10,270 150-200 class-mark K6771 | |
| 100% stress kgf/cm 2 | ????80—90 | |
Learn by table 1,2, utilize polyalcohol and polyisocyanate, chain lengthening agent to adopt the contrary operation mode of slowing down the reaction jet forming method along the impact mixing head of reaction ejecting device, slowly impact the Polyurethane precursor of mixing head internal reaction gained, available no pressure and low-pressure (5kgf/cm
2Below) stream exhibition is sprayed on the release liners, and do not contain solvent, do not have open defects such as surface of synthetic leather edema when drying harden, and can in 2-3 minutes short time, harden into the high-solidity, divisible shapes Polyurethane and synthesize skin.The rerum natura of the rerum natura of the synthetic skin of the Polyurethane of gained and the synthetic skin of CNS10270 Polyurethane is suitable.
Claims (5)
1. the dry type Polyurethane of high-solidity, divisible shapes zero pollution is synthesized skin, it is characterized in that being to adopt the contrary operation mode of slowing down the reaction jet forming method along the impact mixing head that temperature remains on-20 ℃-30 ℃ reaction ejecting devices by 10-40 weight % polyalcohols and 15-25 weight % polyisocyanate, 15-35 weight % chain lengthening agent, slow down the esterification of impacting in the mixing head, after the prepolymerization reaction of carrying out each composition made into the precursor of Polyurethane, it was 0-4kgf/cm that pressure is penetrated in control
2Implement coating processing, make precursor fully flow expansion, ejaculation is coated on the release liners on the conveyer belt and is controlled at 70-180 ℃ baking oven for heating through temperature and makes precursors reaction become polyurethane resin, when it keeps viscosity, the base cloth of fitting thereon, again through baking oven for heating make the polyurethane resin sclerosis high-solidity, divisible shapes and the synthetic skin of zero Polyurethane of polluting.
2. the dry type Polyurethane of high-solidity, divisible shapes zero pollution is synthesized skin, it is characterized in that being by 10-40 weight % polyalcohols and 15-25 weight % polyacids, 15-35 weight % chain lengthening agent are adopted the contrary operation mode of slowing down the reaction jet forming method along the impact mixing head that temperature remains on-20 ℃-30 ℃ reaction ejecting devices, slow down the esterification of impacting in the mixing head, carry out the prepolymerization reaction of each composition, thereafter after latter end adding 15-35 weight % polyisocyanate of mixing the impact head made into the precursor (isocyanate index NCO/OH is about 0.9-1.2) of Polyurethane, it was 0-4 kgf/cm that pressure is penetrated in control
2Implement coating processing, make precursor fully flow exhibition, ejaculation is coated on the release liners on the conveyer belt and is controlled at 70-180 ℃ baking oven for heating through temperature and makes precursors reaction become polyurethane resin, when it keeps viscosity, the base cloth of fitting thereon, again through baking oven for heating make the polyurethane resin sclerosis high-solidity, divisible shapes and the synthetic skin of zero Polyurethane of polluting.
3. the synthetic skin of the dry type Polyurethane that high-solidity, divisible shapes as claimed in claim 1 or 2 zero pollutes, wherein polyalcohol is that degree of unsaturation is how pure the polyoxy alkylene of the following molecular weight 1000-3000 of 0.05 meq/g is.
4. the synthetic skin of the dry type Polyurethane that high-solidity, divisible shapes as claimed in claim 1 or 2 zero pollutes, wherein polyisocyanate system be selected from methyl diphenylene diisocyanate, the polynary phenyl isocyanate of polymethylene, toluenediisocyanate with and the modifier group in more than one.
5. the synthetic skin of the dry type Polyurethane that high-solidity, divisible shapes as claimed in claim 1 or 2 zero pollutes, wherein chain lengthening agent system is selected from by ethylene glycol, 1,4-butanediol, neopentyl glycol, 1, more than one in 6-hexylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, triethanolamine, N-alkyl diethanol amine, N-alkyl diethanol amine, the bisphenol-A-alkylidene oxide addition product group.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN94119162A CN1053025C (en) | 1994-12-30 | 1994-12-30 | Dry polyurethane synthetic skin with high-solidity, divisible shapes and zero-pollution |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN94119162A CN1053025C (en) | 1994-12-30 | 1994-12-30 | Dry polyurethane synthetic skin with high-solidity, divisible shapes and zero-pollution |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1125796A true CN1125796A (en) | 1996-07-03 |
| CN1053025C CN1053025C (en) | 2000-05-31 |
Family
ID=5039145
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN94119162A Expired - Lifetime CN1053025C (en) | 1994-12-30 | 1994-12-30 | Dry polyurethane synthetic skin with high-solidity, divisible shapes and zero-pollution |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1053025C (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI498217B (en) * | 2012-11-16 | 2015-09-01 | Ming Chiun Lee | A solvent-free synthetic leather process |
| CN103938460A (en) * | 2013-01-18 | 2014-07-23 | 浙江新富来实业有限公司 | Water dyeing method of semi-polyurethane leather |
| CN108914615A (en) * | 2018-09-26 | 2018-11-30 | 安徽安利材料科技股份有限公司 | A kind of preparation method of high solid bright mirror surface wrinkle coat of paint |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59145129A (en) * | 1983-02-08 | 1984-08-20 | Asahi Glass Co Ltd | Reaction injection molding method |
| EP0328159A3 (en) * | 1987-03-11 | 1989-10-25 | Imperial Chemical Industries Plc | Improved polyurea reaction injection molding compositions |
| JPH02296816A (en) * | 1989-05-12 | 1990-12-07 | Asahi Glass Co Ltd | Reaction injection molding |
-
1994
- 1994-12-30 CN CN94119162A patent/CN1053025C/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| CN1053025C (en) | 2000-05-31 |
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Expiration termination date: 20141230 Granted publication date: 20000531 |