CN100465205C - Method for preparing Soft polyurethane foam with excellent ball elasticity - Google Patents
Method for preparing Soft polyurethane foam with excellent ball elasticity Download PDFInfo
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- CN100465205C CN100465205C CNB2004100615089A CN200410061508A CN100465205C CN 100465205 C CN100465205 C CN 100465205C CN B2004100615089 A CNB2004100615089 A CN B2004100615089A CN 200410061508 A CN200410061508 A CN 200410061508A CN 100465205 C CN100465205 C CN 100465205C
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Abstract
The object of this invention is to improve ball reboundability (a rebound elastic function) without reducing physical properties such as mechanical strengths, compressive strengths and the like of a flexible polyurethane foam. In a method for forming a flexible polyurethane foam using a molding composition comprising an organic diisocyanate, a high molecular polyol, a catalyst, a foam stabilizer, a foaming agent using water or water and an arbitrary foaming agent, a low molecular compound having an adjacent carbon-carbon unsaturated bond and a carbonyl group is added to the composition as a modifier in 1-20wt.% based on the high molecular polyol.
Description
Technical field
The present invention relates to the preparation method of flexible PU foam, relate in more detail by using specific modification agent to improve the preparation method of the elastic flexible PU foam of ball.
Background technology
Recently, in all areas of industrial technology, the plastics material is widely used as important material, and wherein, the polyurethanes resin is reused in various uses owing to good rerum natura, economy, plasticity and wide application etc.
The polyurethanes resin in molecule because urethane bond arranged, polyaddition reaction by vulcabond and the compound that reactive hydrogen is arranged is synthetic, because various character such as wear resistant, weather resistance and even mechanical characteristics, resistance are good, can obtain large-scale molding, so be widely used in synthetic leather, coating or foam, the fibre product etc. from soft to hard.
Purposes as polyurethanes resin foam (material of foam and even goods), be used as cushioning material at vehicles such as furniture, bedding or automobiles in sheet material etc., particularly use in the cushioning material at automobile, the requirement on the industry is very big, and is also very many to various performance demands.
As the flexible foam that in cushioning material, uses, physical strength not only, rerum naturas such as compressive strength, and ball rebound resilience (ballistic properties) is important as function, past, in order to improve the ball rebound resilience, consider from the viewpoint of urethane manufactured materials, adopted and in the molecular chain of macromolecule polyol, imported the ether unit (with reference to patent documentation 1) that comes from oxyethane, perhaps improve the methods such as hydroxyl equivalent of macromolecule polyol, but if these methods of employing, though the ball rebound resilience improves, and causes the tension strength at break that stretches, stretching, physical strength such as elongation and even drawing crack intensity or compressive strength etc. reduce such problem when disrumpent feelings.In addition, as polymeric polyisocyanate, the terminal prepolymer of isocyanate group of use diphenylmethanediisocyanate and poly-(oxyalkylene) polyol reaction has been proposed, improve anti-elastic preparation method (with reference to patent documentation 2), but can not reach bounce-back property and other mechanical property two aspects can both fully meet the demands.
Disclose by phenylene diisocyanate and diphenylmethanediisocyanate and long-chain polyhydric alcohol polyoxyethylene polyoxypropylene polyvalent alcohol and whipping agent between using, the preparation method's (with reference to patent documentation 3) of flexible PU foam who does not need the excellent spring of fragmentation procedure, with oxygen ethylidene random polymerization waited contain oxygen ethylidene compound and polyvalent alcohol share, come the air flow of specific flexible PU foam, the method of the drag value during compression etc. (with reference to patent documentation 4) etc., but when not reducing physical strength and compressive strength etc., do not improve the ball rebound resilience.
Patent documentation 1: special table 2003-514040 communique (summary)
Patent documentation 2: the spy opens 2003-147044 communique (summary)
Patent documentation 3: the spy opens flat 8-245746 communique (claims 1 of claims of summary and patent)
Patent documentation 4: the spy opens 2003-105050 communique (claims 1 of claims of summary and patent)
Summary of the invention
As described in the 5th～6 section, the flexible PU foam that in the cushioning material of automobile etc., obtains reusing, not only rerum natura such as physical strength, compressive strength but also this function of ball rebound resilience (ballistic properties) also are important, the appearance that strong hope has improved the elastic flexible PU foam of ball when not reducing the rerum natura of physical strength and compressive strength etc.In the prior art, because bounce-back property and other mechanical property two aspects can not be all fully satisfied, so realize that fully satisfying of this two aspect is problem to be solved by this invention.
The inventor etc. are in order to address the above problem, studied and do not reduced the rerum natura of physical strength and compressive strength etc. and improve the elastic modification method of ball, given overall consideration to the main raw material organic diisocyanate and the polyvalent alcohol of flexible PU foam, whipping agent and surfactant and other auxiliary agent, polymerizing condition and polymerizing catalyst, also have the regulation of air permeability etc. of flexible PU foam and fragmentation etc., carried out various researchs, repeatedly carried out experiment and many-sided observation.
In these processes, as experimental study and tentative accumulation achievement, in order to solve above-mentioned problem, find not obtain sufficient achievement by the upgrading to polyvalent alcohol or polymeric polyisocyanate etc. of passing through in the background technology of above-mentioned (the 5th～6 section), flexible PU foam is shaped and adds modification agent with composition, to solving problem of the present invention is effective, and then again various modification agents are studied, discovery does not reduce to the rerum natura of the physical strength that makes flexible PU foam and compressive strength etc. by using specific modification agent that to improve the ball rebound resilience be very effective, thereby has finished the present invention.
Be shaped with the modification agent of composition as the flexible PU foam among the present invention, be to use the material of the low molecular compound of such carbon carbon unsaturated link(age) with adjacency of dialkyl maleate and carbonyl, it is effective especially adding 1～20 weight % with respect to macromolecule polyol.
The present invention is the preparation method of flexible PU foam, basic main composition key element be in flexible PU foam is shaped with composition interpolation as the carbon carbon unsaturated link(age) with adjacency of the modification agent of flexible PU foam and the low molecular compound of carbonyl, it is characterized in that by organic diisocyanate (A), macromolecule polyol (B), catalyzer (C), surfactant (D), whipping agent (E), in the method for the shaping that other auxiliary agent constitutes with the preparation of compositions flexible PU foam, with respect to macromolecule polyol add 1～20 weight % as the low molecular compound (α, beta-unsaturated carbonyl compound) of the carbon carbon unsaturated link(age) with adjacency of the modification agent of said composition and carbonyl (F).
And, among the present invention, if specific organic diisocyanate or macromolecule polyol or whipping agent etc., its better effects if.
Among the present invention, in order to improve the ball rebound resilience of flexible PU foam, by with the viewpoint different of the prior art to upgradings such as polyvalent alcohol or polymeric polyisocyanates, interpolation contains the modification agent of the low molecular compound of carbon carbon unsaturated link(age) with adjacency and carbonyl in flexible PU foam is shaped with composition, can find out very significantly that this modification method is and the diverse new tool of the thought of existing method, can obtain not reduce the rerum natura of physical strength and compressive strength etc. and significantly improve the elastic achievement of ball, can be described as the new technology that be gazed at.
It should be noted that employedly among the present invention have the carbon carbon unsaturated link(age) of adjacency and the low molecular compound of carbonyl is common known compound, use from the starting material or their properties-correcting agent of seeing on the one hand as urethane resin.In the manufacturing of flexible PU foam, for example as cell (cell) opener, use the monoesters reaction product (with reference to the special patent claims of opening the 2000-38431 communique) of organic acid anhydride and alkoxylate primary alconol, its reaction product, consistent with upgrading material of the present invention in form, it is low molecular compound with carbon carbon unsaturated link(age) and carbonyl, but its application target, use-pattern, the formation of invention itself is different fully, the spy opens technology and the present invention of being put down in writing in the 2000-38431 communique and has virtually no connection, in addition, even under situation about just using as the starting material or their properties-correcting agent of common urethane resin always from the past, its application target, use-pattern, the formation of invention itself is also different fully, so the above-mentioned known fact of learning that thus can be beyond all doubt is not the prior art that the present invention is had instruction and hint.
More than be that the summary of creation process of the present invention, basic comprising of the present invention is described, in general, the present invention is made of following invention unit group, (1) invention is basic invention, and invention thereafter is to specialize and even embodimentization (need to prove the invention group all is referred to as " the present invention ") inventing substantially.
(1), the preparation method of flexible PU foam, it is characterized in that by organic diisocyanate (A), macromolecule polyol (B), catalyzer (C), surfactant (D), make water or water and arbitrarily in the method for the preparation of compositions flexible PU foam that constitutes of the whipping agent of whipping agent (E), other auxiliary agent, adding with respect to macromolecule polyol as modification agent is the carbon carbon unsaturated link(age) with adjacency of 1～20 weight % and the low molecular compound (F) of carbonyl in said composition.
(2), the preparation method of the flexible PU foam in (1), it is characterized in that organic diisocyanate (A) be selected from diphenylmethanediisocyanate, polymethylene polyphenylene polymeric polyisocyanate, toluene support vulcabond separately or the mixture more than 2 kinds.
(3), the preparation method of the flexible PU foam in (2), it is characterized in that in the isomer constituent ratio of diphenylmethanediisocyanate (MDI), 2,2 '-MDI and 2, the total content of 4 '-MDI isomer are 1～60 weight %.
(4), the preparation method of the flexible PU foam in (1) or (2), it is characterized in that macromolecule polyol (B) is that number-average molecular weight is 1,000～10,000, standard official can polyether glycol and/or the polyester polyol of radix more than 2.
(5), the preparation method of each described flexible PU foam of (1)～(4), it is characterized in that modification agent (F) uses dialkyl maleate.
(6), have the elastic flexible PU foam of high ball, it is characterized in that making by each manufacture method of (1)～(5).
Among the present invention, flexible PU foam can not reduce the rerum natura of physical strength and compressive strength etc. and significantly improve ball rebound resilience (ballistic properties).
And, by manufacturing of the present invention have an elastic flexible PU foam of high ball, can in the industrial use that mainly is the cushioning material used as automobile, obtain utilizing very widely.
Among the present invention,, discussed basic comprising of the present invention above, below of the present invention group above-mentioned invention embodiment has been carried out concrete detailed description as the means of technical solution problem.
Among the present invention, as flexible PU foam being shaped with the modification agent of composition, use the carbon carbon unsaturated link(age) with adjacency of specified quantitative and the low molecular compound of carbonyl, be not reduce the rerum natura of physical strength and compressive strength etc. in fact and significantly improve ball rebound resilience (ballistic properties), obtain the modification agent of corresponding action effect therewith, put down in writing the effect of each starting material, polymerizing condition and polyreaction etc.
(1) organic diisocyanate (A)
Employed organic diisocyanate (A) uses common vulcabond among the present invention, can enumerate 2 as aromatic diisocyanate, 4-toluene support vulcabond (TDI), 2,6-toluene support vulcabond, 4,4 '-diphenylmethanediisocyanate (MDI), 2,4 '-diphenylmethanediisocyanate, 2,2 '-diphenylmethanediisocyanate, polyphenylene polymethylene polymeric polyisocyanate (p-MDI), 1,5-naphthylene vulcabond (NDI), 1,4-naphthylene vulcabond, to phenylene diisocyanate (PPDI), between phenylene diisocyanate, o-Xylol support vulcabond (XDI), m-xylene support vulcabond, 4,4 ' diphenyl ether vulcabond, 2,2 '-diphenyl propane 4,4 '-vulcabond, 3,3 '-dimethoxy phenylbenzene-4,4 '-vulcabond, the nitro diphenyl diisocyanate, diphenyl propane vulcabond etc., as aliphatic diisocyanate, can enumerate tetramethylene diisocyanate, hexamethylene diisocyanate, the 2-methyl isophthalic acid, 5-pentane vulcabond etc.In addition, as alicyclic diisocyanate, can enumerate 1-methylcyclohexane-2,4-vulcabond (hydrogenation TDI), isophorone diisocyanate (IPDI), dicyclohexyl methyl hydride-4,4 '-vulcabond (hydrogenation MDI) etc., and, also can use the various modification bodies such as polymer, urethane modification body, urea modification body, allophanates modification body, biuret body (PVC ユ ウ レ Star ト) modification body of these vulcabond.
Above-mentioned vulcabond can a kind of independent or mixing use more than 2 kinds.When need to prove the mixture of mixture, TDI and the MDI of the mixture, TDI, TDI and the MDI that particularly use above-mentioned MDI, MDI and p-MDI and p-MDI, can obtain the flexible PU foam of better quality.
In diphenylmethanediisocyanate (MDI), have 2,2 '-MDI, 2,4 '-MDI, 4, these 3 kinds of isomer of 4 '-MDI, the isomer constituent ratio of using among the present invention is preferred 2,2 '-MDI and 2, the total content of the isomer of 4 '-MDI are 1～60 weight %, more preferably 2～55 weight %.The content that adds up to is if be lower than lower limit, and the storage stability of vulcabond descends easily, surpasses the upper limit, and the hardness of gained flexible PU foam reduces easily.
(2) macromolecule polyol (B)
Macromolecule polyol (B) is to carry out the polyvalent alcohol that addition polymerization forms urethane with vulcabond, and among the present invention, hope is polyether glycol and/or polyester polyol.And, wish that number-average molecular weight is 1,000～10,000, standard official's energy radix is more than 2.Number-average molecular weight is if be lower than lower limit, and gained foamy flexibility deficiency surpasses the upper limit, and foamy hardness reduces easily.The average functional group (the active hydrogen atom number of per molecule) of standard official's energy radix representation polyvalent alcohol is in fact because so terminal unsaturation has only number seldom.
Can use polypropylene ethene polyvalent alcohol (PPG), polytetramethylene ether glycol (PTG) etc. as polyether glycol.As polyester polyol, can use the adipate glycol polyester polyol of condensation polymer type polyester polyvalent alcohol, the polycaprolactone polyol of lactone polyester polyol etc.
(3) catalyzer (C)
Among the present invention, catalyzer (C) can use various urethane catalyzer well-known in the art.
For example can enumerate triethylamine, tripropyl amine, Tributylamine, N-methylmorpholine, N-ethylmorpholine, dimethyl benzyl amine, N, N, N ', N '-tetramethyl-hexamethylene-diamine, N, N, N ', N ', N ＂-five methyl diethylentriamine, two-(2-dimethyl aminoethyl) ether, triethylenediamine, 1,8-diaza-bicyclo (5,4,0) hendecene [7], 1,2-methylimidazole, dimethylethanolamine, N, N-dimethyl-N-hexanol amine, organometallic compounds such as their organic acid salt, ス Na ス オ Network ト エ-ト, zinc naphthenate in addition.In addition, preferred N, N-dimethylethanolamine, N, N-diethylethanolamine etc. has the amine catalyst of active hydrogen.
The addition of catalyzer (C) is with respect to preferred 0.01～10 weight % of polyvalent alcohol (B).
(4) surfactant (D)
Surfactant can use common tensio-active agent, is fit to use silicone based tensio-active agent.For example can enumerate SRX-274C, the SF-2962 of Japanese ユ ニ カ-L-520, the L-5309 of system, eastern beautiful DOW CORNING system, DC-5169, the F-220 of SHIN-ETSU HANTOTAI's chemical industry system etc. of エ ア-プ ロ ダ Network Star system.
The addition of surfactant (D) is with respect to preferred 0.01～10 weight % of polyvalent alcohol (B).
(5) whipping agent (E)
Whipping agent mainly makes water.Water produces carbon dioxide gas by the reaction with isocyanate group, thus foaming.In addition, also can make water and additional any whipping agent.For example can share lower boiling organic compound such as a spot of pentamethylene or iso-pentane, also can using gas load that (ダ ス ロ-デ Application グ) device is sneaked in stoste, dissolved air, nitrogen or liquefied carbon dioxide foam.
The addition of whipping agent adds according to the setting density of resulting product, is 0.5～15 weight % with respect to polyvalent alcohol (B) usually.Surpass last existence foaming and be difficult to stable situation, the situation that existence can not foam effectively under being lower than.
(6) modification agent
Modification agent is the material that constitutes main composition key element of the present invention, adds the effect of the rerum natura of performance improvement raising foaming product to the shaping of flexible PU foam in composition.
The specific modification agent that uses among the present invention is for rerum naturas such as the physical strength that does not reduce flexible PU foam, compressive strengths and to improve the ball rebound resilience be very effective.The ball rebound resilience is also referred to as bounce-back property performance, is one of rheological properties of foaming product.When foaming product is given mechanical deformation, it is elastic that deflection hour is deformed into, and removes external force deformation and disappear and return to original state, if surpass the certain deformation amount, causes that surrender flows, and can not return to original state, produces tension set.
Ball rebound resilience value is to the index of the energy of this elasticity limit, measures according to JIS-K6400, and unit is not with c.g.s., is " % ".
Modification agent, it is effective especially to add 1～20 weight % with respect to macromolecule polyol.Be lower than the insufficient situation of existence upgrading effect down, surpass the situation that other rerum natura of last existence reduces.
Among the present invention, have the carbon carbon unsaturated link(age) of adjacency and the low molecular compound of carbonyl (α, β-unsaturated carbon based compound) as flexible PU foam being shaped with the modification agent of composition, using.
Having the carbon carbon unsaturated link(age) of adjacency and the low molecular compound of carbonyl is to be the compound of representative with the dialkyl maleate, it is unsaturated carboxylic acid, the ester of unsaturated carboxylic acid or acid anhydrides or acid amides or halogenide, unsaturated aldehyde or beta-unsaturated ketone and their various substitutive derivatives etc.
Enumerating concrete compound is toxilic acid, maleic acid ester, fumaric acid, fumarate, vinylformic acid, acrylate, methacrylic acid, methacrylic ester, methylene-succinic acid, itaconic ester, and can use multiple materials such as propenal, Methylacrylaldehyde, Ba Dousuan, benzoquinones, isophorone.
Wherein, maleic acid ester particularly is from considering preferred with the speed of response of primary amine, viscosity, aspects such as Combination, foul smell, security, price with organic diisocyanate or polyvalent alcohol.
Have the carbon carbon unsaturated link(age) of adjacency and the low molecular compound of carbonyl, it is also indeterminate to improve the very effective reason of ball rebound resilience for rerum natura such as the physical strength that does not reduce flexible PU foam, compressive strength, but infers it is owing to be the following reaction and the effect of example with the maleic acid ester.
The flexible PU foam of following formula is shaped with the basic cpd that exists in the composition (Base), act on the carbon-to-carbon unsaturated bond that in flexible PU foam is shaped with composition, adds as the dialkyl maleate with low molecular compound (α, beta-unsaturated carbonyl compound) of modification agent in abutting connection with carbon carbon unsaturated link(age) and carbonyl.
Then, the Michael reaction that α, beta-unsaturated carbonyl are shown below.
The aminated compounds from shown in change 3 formulas of organic diisocyanate that exists in polyurethane foam is shaped with composition carries out Michael reaction particularly.This aminated compounds is shown below, and the water reaction of organic diisocyanate and whipping agent generates [R-NHCOOH] intermediate, then generates R-NH
2
R—NCO+H
2O→[R—NHCOOH]→R—NH
2+CO
2
Therefore, among the present invention, by make water or water and arbitrarily the whipping agent of whipping agent (E) prepare in the method for flexible PU foam, its notable feature is to make up as the carbon carbon unsaturated link(age) with adjacency of modification agent and the low molecular compound (F) of carbonyl.
Then in the addition reaction product〉the N-H base be shown below and organic diisocyanate in the isocyanic ester radical reaction.
The result generates the replacement urea that is shown below.
Infer owing to generated aforesaid replacement urea, suppressed the generation of common urea, improved bounce-back thus.
(7) other auxiliary agent
Among the present invention, also can use the chain extension agent in the common polyaddition reaction as required.
The common low molecular compound with the active hydrogen base more than 2 is used in chain extension agent in the carboxylamine polyisocyanate polyaddition, can make spent glycol, propylene glycol, 1 particularly, 4-butyleneglycol, 1,5-pentanediol, dimethyltrimethylene glycol, diethanolamine, trolamine etc.
In addition, as various additives, can use fire retardant, softening agent, oxidation inhibitor, UV light absorber, tinting material, weighting agent, internal mold release, other processing aid.
It should be noted that in these auxiliary agents do not have the material with the reactive hydrogen of isocyanate reaction, can be pre-mixed polyurethane foam and be shaped with using in the composition.
(8) flexible PU foam
Among the present invention, the flexible PU foam goods that rerum naturas such as the not reduction physical strength of preparation method's preparation of the flexible PU foam by above-mentioned detailed description, compressive strength have significantly improved ball rebound resilience (bounce-back) are also included within the scope of the present invention, are used as the cushioning material that vehicles such as furniture, bedding or automobile are improved with the function of sheet material etc.
(9) prepare foam by the urethane foamable reaction
Among the present invention,, use generally well-known urethane reaction technology as the method for preparing polyurethane foam.For example make the pure and mild organic diisocyanate reaction of macromolecular multi-component, come polymer to quantize and foamingization the purpose flexible PU foam that obtains foaming by the chain extension agent.
In this reaction, certainly can use an amount of tertiary amine as required as previously mentioned, be known polymerizing catalyst in the urethane reaction of representative with the organic metal salt of tin, lead, titanium etc.
Below, by embodiment, do contrast with comparative example, specify the present invention in more detail, enumerate preferred embodiment, but the invention is not restricted to following embodiment.(" ratio " put down in writing in embodiment and the comparative example and " % " represent weight ratio and weight % respectively.)
(the modulation example of raw material)
(modulation of polyvalent alcohol pre-composition)
According to the modulation of the ratio shown in the table 1 polyvalent alcohol pre-composition OH-1～OH-11.
Table 1
| OH —1 | OH —2 | OH —3 | OH —4 | OH —5 | OH —6 | OH —7 | OH —8 | OH —9 | OH —10 | OH —11 | |
| Polyvalent alcohol 1 polyvalent alcohol 2 polyvalent alcohols 3 polyvalent alcohols 4 catalyzer 1 catalyzer 2 catalyzer 3 catalyzer 4 catalyzer 5 surfactants 1 surfactant 2 surfactants 3 water DOM cell openers | 70 30 0.5 0.05 0.7 3.5 9.2 | 70 30 0.5 0.05 0.7 3.5 0.5 9.2 | 70 30 0.5 0.05 0.7 3.5 5 9.2 | 70 30 0.5 0.05 0.7 3.5 10 9.2 | 70 30 0.5 0.05 0.7 3.5 20 9.2 | 60 40 0.05 0.3 1 3 | 60 40 0.05 0.3 1 3 5 | 100 0.05 1.5 1 4 | 100 0.05 1.5 1 4 5 | 100 0.05 1.5 1 4 | 100 0.05 1.5 1 4 5 |
Polyvalent alcohol 1:FA-703 (Sanyo changes into industry system polyether glycol hydroxyl valency 34 (mgKOH/g))
Polyvalent alcohol 2:FA-728R (Sanyo changes into industry system polyether glycol hydroxyl valency 28 (mgKOH/g))
Polyvalent alcohol 3:N-2200 (Japanese polyurethane industry system polyester polyols alcoholic extract hydroxyl group valency 60.5 (mgKOH/g))
Polyvalent alcohol 4:GP-3000 (Sanyo changes into industry system polyether glycol hydroxyl valency 56 (mgKOH/g))
Catalyzer 1: tertiary amine catalyst (eastern Cao makes amines catalyst)
Catalyzer 2: tertiary amine catalyst (eastern Cao makes amines catalyst)
Catalyzer 3: tertiary amine catalyst (TEDA-L33 east Cao's system)
Catalyzer 4: metal catalyst (DABCO T-9 エ ア-プ ロ ダ Network Star system)
Catalyzer 5: morpholine class catalyzer (KAOLIZER No.22 flower king system)
Surfactant 1: silicon class surfactant B4113LF (go-Le De シ ユ ミ Star ト system)
Surfactant 2: silicon class surfactant B-8719 (go-Le De シ ユ ミ Star ト system)
Surfactant 3: silicon class surfactant SE-232 (Japanese ユ ニ カ-system)
DOM: toxilic acid two-2-(ethyl hexyl) ester
(modulation of isocyanic ester)
According to the modulation of the ratio shown in the table 2 isocyanic ester.
Table 2
| NCO—1 NCO—2 NCO—3 | |
| Isocyanic ester A B C D | 52 30 48 70 100 |
In the table 2,
A: diphenylmethanediisocyanate
B:MR-200 (Japanese polyurethane industry system polymer MDI)
C:MF-24MR (Japanese polyurethane industry system polymer MDI)
D: toluene support vulcabond
Embodiment 1～6 and comparative example 1～5
According to the compounding ratio that table 1 and table 2 are put down in writing, compounding polyvalent alcohol pre-composition and isocyanate prepolymer composition, with after their temperature adjustments to 25 ℃, weighing in the poly-cup (Port リ カ Star プ) of 2000ml stirred for 10 seconds with hand mixer with revolution 3000rpm.After stirring end, the vinylformic acid box that injects inside dimension 250 * 250 * 250mm immediately foams.After leaving standstill 24 hours, be cut into the shape of regulation, the project shown in the his-and-hers watches 3 is measured.The measuring method of rerum natura is according to JIS K 6400.
Table 3
| The polyvalent alcohol pre-composition | Polymeric polyisocyanate | Isocyanate index | Ball rebound resilience % | Apparent density kg/m 3 | 25% compressive strength N/100cm 2 | Tensile strength kPa | Elongation % | Drawing crack N/m | Compression set % | |
| Comparative example 1 | OH-1 [0] | NCO-1 | 90 | 56 | 40.0 | 20.8 | 91 | 111 | 3.5 | 5.2 |
| Comparative example 2 | OH-2 [0.5] | NCO-1 | 90 | 57 | 40.4 | 19.6 | 97 | 112 | 3.4 | 3.6 |
| Embodiment 1 | OH-3 [5] | NCO-1 | 90 | 64 | 40.7 | 19.3 | 92 | 106 | 3.5 | 5.5 |
| Embodiment 2 | OH-4 [10] | NCO-1 | 90 | 66 | 43.5 | 20.8 | 90 | 97 | 3.5 | 5.8 |
| Embodiment 3 | OH-5 [20] | NCO-1 | 90 | 66 | 44.2 | 21.1 | 91 | 96 | 3.4 | 5.9 |
| Comparative example 3 | OH-6 [0] | NCO-2 | 100 | 66 | 44.0 | 19.6 | 84 | 98 | 5.3 | 3.9 |
| Embodiment 4 | OH-7 [5] | NCO-2 | 100 | 72 | 44.3 | 19.2 | 87 | 99 | 5.3 | 4.0 |
| Comparative example 4 | OH-8 [0] | NCO-3 | 100 | 27 | 27.6 | 42.0 | 135 | 193 | 7.7 | 4.0 |
| Embodiment 5 | OH-9 [5] | NCO-3 | 100 | 33 | 27.8 | 41.6 | 137 | 197 | 7.6 | 4.1 |
| Comparative example 5 | OH-10 [0] | NCO-3 | 111 | 42 | 25.3 | 34.8 | 86 | 153 | 5.1 | 1.3 |
| Embodiment 6 | OH-11 [5] | NCO-3 | 111 | 50 | 25.7 | 34.4 | 87 | 150 | 5 | 1.2 |
Isocyanate index in the table 3 be NCO base with formulation in the ratio of the reactive hydrogen atom number that exists.25% compressive strength N/100cm
2Measuring method according to whole the compression of JIS K 6400 working sample sheets 10 * 10cm.
Numeral in [] in the polyvalent alcohol pre-composition is the weight ratio of modification agent DOM.
The result's of embodiment and comparative example investigation
Contrast by the various embodiments described above and each comparative example is verified clearly, in the present invention, by compounding specific modification agent of the present invention (DOM) 1～20 weight %, the rerum naturas such as physical strength, compressive strength that make flexible PU foam do not reduce and significantly improve ball rebound resilience (bounce-back property performance).
The polyvalent alcohol pre-composition uses identical raw material with polymeric polyisocyanate, the comparative example 1 that the amount of modification agent DOM changes, 2 and the group of embodiment 1～3, the group of comparative example 3 and embodiment 4, the group of comparative example 4 and embodiment 5, the group of comparative example 5 and embodiment 6, by contrasting each embodiment and comparative example, compressive strength that shows each embodiment and tensile strength that can be clear and definite, stretch and drawing crack intensity, mechanical all character such as compression set, with the basic identical degree of each comparative example, but significantly improve with respect to each comparative example ball rebound resilience value, significantly improve the bounce-back performance, be appreciated that meaningful property and significant brilliance that the present invention constitutes thus.
Claims (4)
1. the preparation method of flexible PU foam, it is characterized in that by organic diisocyanate (A), macromolecule polyol (B), catalyzer (C), surfactant (D), make water or water and arbitrarily in the method for the preparation of compositions flexible PU foam that constitutes of the whipping agent of whipping agent (E), other auxiliary agent, add as the carbon carbon unsaturated link(age) with adjacency of 1～20 weight % of modification agent and the low molecular compound (F) of carbonyl with respect to macromolecule polyol in said composition, this low molecular compound as modification agent (F) is a dialkyl maleate.
2. the preparation method of flexible PU foam according to claim 1 is characterized in that organic diisocyanate (A) is the independent or mixture more than 2 kinds that is selected from diphenylmethanediisocyanate, polymethylene polyphenylene polymeric polyisocyanate, toluene support vulcabond.
3. the preparation method of flexible PU foam according to claim 1 is characterized in that macromolecule polyol (B) is that number-average molecular weight is 1,000～10,000, and standard official can polyether glycol and/or the polyester polyol of radix more than 2.
4. have the elastic flexible PU foam of high ball, it is characterized in that making according to each described manufacture method of claim 1～3.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004004865A JP4556161B2 (en) | 2004-01-09 | 2004-01-09 | A method for producing a flexible polyurethane foam having excellent ball rebound properties. |
| JP20044865 | 2004-01-09 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1644599A CN1644599A (en) | 2005-07-27 |
| CN100465205C true CN100465205C (en) | 2009-03-04 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2004100615089A Expired - Fee Related CN100465205C (en) | 2004-01-09 | 2004-12-27 | Method for preparing Soft polyurethane foam with excellent ball elasticity |
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| Country | Link |
|---|---|
| JP (1) | JP4556161B2 (en) |
| CN (1) | CN100465205C (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6214129B2 (en) * | 2011-12-13 | 2017-10-18 | 株式会社東洋クオリティワン | Manufacturing method of different hardness mold foam |
| CN104448203A (en) * | 2014-12-23 | 2015-03-25 | 金华派对乳胶工艺品有限公司 | Formula and preparation method of polyurethane soft high-resilience filling product |
| CN105131233B (en) * | 2015-07-21 | 2017-10-10 | 浙江川洋家居股份有限公司 | A kind of polyester modification sponge and preparation method thereof |
| KR101756071B1 (en) * | 2016-05-30 | 2017-07-11 | 코스맥스 주식회사 | Hybrid urethane foam and cosmetic kits using the same |
| CN108530595A (en) * | 2018-04-11 | 2018-09-14 | 东莞市秦粤丰鞋材有限公司 | PU footwear materials and its manufacturing method and application |
| CN112409560B (en) * | 2019-08-21 | 2022-09-20 | 万华化学（北京）有限公司 | High-resilience polyurethane foam and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4025817A1 (en) * | 1990-08-16 | 1992-02-20 | Bayer Ag | METHOD FOR THE PRODUCTION OF OPEN CELL POLYURETHANOUS FUELS AND THEIR USE AS UPHOLSTERED MATERIAL |
| CN1239106A (en) * | 1998-06-17 | 1999-12-22 | 气体产品与化学公司 | Dimensional stabilizing, cell opening additives for polyuretane flexible and rigid foams |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03244620A (en) * | 1990-02-23 | 1991-10-31 | Asahi Glass Co Ltd | Production of polyurethane foam |
| JPH0559144A (en) * | 1991-08-28 | 1993-03-09 | Asahi Glass Co Ltd | Production of flexible polyurethane foam |
-
2004
- 2004-01-09 JP JP2004004865A patent/JP4556161B2/en not_active Expired - Fee Related
- 2004-12-27 CN CNB2004100615089A patent/CN100465205C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4025817A1 (en) * | 1990-08-16 | 1992-02-20 | Bayer Ag | METHOD FOR THE PRODUCTION OF OPEN CELL POLYURETHANOUS FUELS AND THEIR USE AS UPHOLSTERED MATERIAL |
| CN1239106A (en) * | 1998-06-17 | 1999-12-22 | 气体产品与化学公司 | Dimensional stabilizing, cell opening additives for polyuretane flexible and rigid foams |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2005194486A (en) | 2005-07-21 |
| JP4556161B2 (en) | 2010-10-06 |
| CN1644599A (en) | 2005-07-27 |
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