CN100545189C - The production method of flexible polyurethane foam using hydrated metal salt blowing agents - Google Patents
The production method of flexible polyurethane foam using hydrated metal salt blowing agents Download PDFInfo
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- CN100545189C CN100545189C CNB2005100875786A CN200510087578A CN100545189C CN 100545189 C CN100545189 C CN 100545189C CN B2005100875786 A CNB2005100875786 A CN B2005100875786A CN 200510087578 A CN200510087578 A CN 200510087578A CN 100545189 C CN100545189 C CN 100545189C
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Abstract
Urethane raw by will containing polyvalent alcohol, poly-isocyanide ester, whipping agent and catalyzer and proportion are that 1.5 to 4.0 inorganic compound hydrate is mixed and made the flexible polyurethane foam using hydrated metal salt blowing agents that above-mentioned urethane raw foams and curing reaction prepares.Inorganic compound hydrate is preferably ferrous sulfate hydrate, calcium sulfate hydrate or magnesium sulfate hydrate.The preferred decomposition temperature of above-mentioned inorganic compound hydrate is from 100 to 170 ℃.Then, the foaming and the rising of solidifying the exothermic temperature cause are lowered by the evaporation of water that is decomposed to form of above-mentioned inorganic compound hydrate.
Description
Invention field
The present invention relates to produce the method as the flexible polyurethane foam using hydrated metal salt blowing agents of pad material, described material can be made furniture, bedclothes, car seat etc.
Background technology
Up to now, production density is 25kg/m
3Or during lower flexible polyurethane foam using hydrated metal salt blowing agents, under the situation that only makes water as whipping agent, because the water yield to be added increases, foaming and curing exotherm temperature reach 170 ℃ or higher.Therefore, might since the oxidative degradation (coking) of urethane and spontaneous combustion and the flexible polyurethane foam using hydrated metal salt blowing agents that obtains owing to coking and painted.For avoiding these situations, knownly can not change the conventional water yield of adding and add methylene dichloride or Liquid carbon dioxide as frothing aid.
But, methylene dichloride is a kind of material to generation baneful influences such as environment, so its use is managed.On the other hand, need special equipment feed Liquid carbon dioxide under high pressure with the Liquid carbon dioxide foaming, and be steadily foaming, working condition is restricted, and production cost also improves.Therefore, for absorbing heat, known technology has the interpolation polyolefin powder, as polyethylene powders (for example, referring to JP-T-2002-532596 (page 2) and JP-A-6-199973 (the 2nd and 3 page)).
In the prior art of above-mentioned interpolation polyolefin powder, although observe reducing the influence of foaming and solidified exothermic temperature, the amount that polyolefin powder must be provided is with effective reduction calorific value.In this case, the raising of polyolefin powder amount causes the density of the elastic polyurethane that obtains too high, and physical properties such as compressed residual strain (compressive residual strain) are damaged.Because be the destruction that prevents these physical propertiess, polyolefin powder can not mix with capacity, so have the problem that can not effectively reduce foaming and solidified exothermic temperature, result, painted can't the alleviating that coking produces.
Summary of the invention
The present invention arises at the historic moment when considering problems of the prior art.The purpose of this invention is to provide the method for preparing flexible polyurethane foam using hydrated metal salt blowing agents, it can effectively reduce foaming and solidified exothermic temperature and alleviate painted that coking produces.
For realizing this purpose, the method that the present invention produces flexible polyurethane foam using hydrated metal salt blowing agents comprises that the urethane raw that will contain polyvalent alcohol, polymeric polyisocyanate, whipping agent and catalyzer and proportion are that 1.5 to 4.0 inorganic compound hydrate is mixed, above-mentioned urethane raw is foamed and curing reaction, and wherein the raising owing to above-mentioned foaming and curing exotherm temperature alleviates by the evaporation of water that above-mentioned inorganic compound hydrate degraded produces.
The method that the present invention produces flexible polyurethane foam using hydrated metal salt blowing agents is characterised in that the degradation temperature of above-mentioned inorganic compound hydrate is preferably 100 to 170 ℃.
The method that the present invention produces flexible polyurethane foam using hydrated metal salt blowing agents is characterised in that above-mentioned inorganic compound hydrate is preferably ferrous sulfate (iron sulfate) hydrate, calcium sulfate hydrate or magnesium sulfate hydrate.
According to the present invention, can show following advantage.
The present invention produces in the method for flexible polyurethane foam using hydrated metal salt blowing agents, the inorganic compound hydrate blending of urethane raw and proportion 1.5 to 4.0, and the urethane raw that obtains foams and curing reaction.Therefore, when foaming and curing, inorganic compound hydrate produces water by adding thermal destruction, removes vaporization heat (vaporization heat) by evaporation of water again and reduces owing to foaming and solidifying the heat generation that brings.Therefore, foaming and solidified exothermic temperature can effectively reduce, and the aberration of high-temperature part and low temperature part can alleviate as a result, so the painted of the flexible polyurethane foam using hydrated metal salt blowing agents that obtains can alleviate.
In addition, because the proportion of inorganic compound hydrate is 1.5 to 4.0, than great, the volume of the inorganic compound hydrate of blending is little, therefore changes the physical properties of flexible polyurethane foam using hydrated metal salt blowing agents than the polyolefin powder of routine for it, and for example there is very little risk for density.
Produce in the method for flexible polyurethane foam using hydrated metal salt blowing agents in the present invention, the decomposition temperature of above-mentioned inorganic compound hydrate is preferably set to 100 to 170 ℃.Therefore, the degraded of inorganic compound hydrate temperature in foaming and solidification process reaches 100 ℃ or when higher, at this moment forms water and the water that forms evaporates.Therefore, can effectively reduce heat by evaporation of water and produce, thereby strengthen advantage of the present invention.
Produce in the method for flexible polyurethane foam using hydrated metal salt blowing agents in the present invention, above-mentioned inorganic compound hydrate is preferably ferrous sulfate hydrate, calcium sulfate hydrate or magnesium sulfate hydrate.These inorganic compound hydrate improve with foaming and solidified temperature degrades, and wherein forms water and the water that forms evaporates.Therefore, can effectively reduce heat by the latent heat of vaporization of water and produce, therefore can fully show advantage of the present invention.
The accompanying drawing summary
Fig. 1 show exothermic temperature among embodiment 1 and the comparative example 2 (℃) and the consumption time (minute) between relation.
Detailed Description Of The Invention
Hereinafter describe embodiment of the present invention in detail.
(hereinafter referred is bubble to low-density flexible polyurethane foam using hydrated metal salt blowing agents in the embodiment of the present invention The foam material) as follows preparation. That is, by containing polyalcohol, PIC, foaming The urethane raw of agent and catalyst and proportion are that 1.5 to 4.0 inorganic compound hydrate is mixed Close, above-mentioned urethane raw is foamed and curing reaction. Because above-mentioned foaming and solid The heat of change generation falls by the latent heat of the water evaporation of the degraded formation of inorganic compound hydrate Low. When foaming and the temperature rise that solidifies arrive, for example 170 ℃ or when higher, induce the foam material The oxidative degradation of material, i.e. coking and form the painted of flexible polyurethane foam using hydrated metal salt blowing agents. This phenomenon The evaporation of water heat (heat of vaporization) that forms by the degraded of removal inorganic compound hydrate obtains pressing down System. The foamed material of the present embodiment can be by foaming and curing under room temperature and atmospheric pressure Plate (slab stock) elastic foam material that produces, or pass through urethane raw (liquid The phase reaction mixture) notes that are charged to mould and under the clamping mould, its foaming and curing obtained Mould foamed material. Like this, owing to highly be aniseed (bulky block) foam about 1m Heat generally by finalizing the design at the continuous production of elastic plate strand foam material, often takes place in material Accumulation and flavescence, so yellow that the method for the present embodiment effectively causes as anti-coking Measure.
At first, above-mentioned urethane raw is described.
PPG or PEPA are as polyalcohol. Wherein, since PPG with The sound response of PIC, and it can be hydrolyzed unlike PEPA, thereby be excellent Choosing. Can use the compound of the PPG that formed by polymer and its modification as poly-Ethoxylated polyhydric alcohol, described polymer is by polypropylene glycol, polytetramethylene glycol or polyhydroxy-alcohol and epoxy third Alkane or ethyleneoxide addition polymerization form. Glycerine, DPG etc. can be used as polyhydroxy-alcohol.
By the trihydroxylic alcohol of glycerine and expoxy propane and other ethyleneoxide addition polymerization acquisition, logical Cross the dihydroxylic alcohols that DPG and expoxy propane and other ethyleneoxide addition polymerization form, waiting can To be particularly useful as the polyester ether polyalcohol. PEO unit in the PPG is about 10 To 30mol%. When the content of PEO unit is high, compare hydrophily when low with content Improve and improve with the ability of mixing of high polar molecule such as polyisocyanate compounds. As a result, The reactivity of polyalcohol strengthens. In polyalcohol, the degree of functionality of hydroxyl and the number of hydroxyl can Change by control material composition, molecular weight, condensation level etc.
By with polycarboxylic acid such as adipic acid or phthalic acid and polyalcohol such as ethylene glycol, diethyl two The PEPA of the condensation that alcohol, propane diols or glycerine reaction obtain reaches the polyester based on lactone Polyalcohol and can be used as PEPA based on the polyalcohol of Merlon.
With the PIC of above-mentioned polyol reaction be the chemical combination with a plurality of isocyanate groups Thing specifically can use toluene di-isocyanate(TDI) (TDI), 4, the 4-methyl diphenylene diisocyanate (MDI), 1,5-naphthalene diisocyanate (NDI), triphenylmethane triisocyanate, benzene two methylenes Group diisocyanate (XDI), 1, hexamethylene-diisocyanate (HDI), dicyclohexyl methyl hydride two isocyanides The product of acid esters, isophorone vulcabond (IPDI), its modification etc. PIC Isocyanate index is 100 or still less maybe can surpasses 100 but usually about 90 to about 130 Scope in. Isocyanate index represents with percentage, is the NCO of PIC Group and equivalent proportion as the oh group of the polynary alcohol and water of blowing agent.
Blowing agent is used for foaming polyurethane resin and forms flexible polyurethane foam using hydrated metal salt blowing agents. For example, Use pentane outside dewatering, pentamethylene, hexane, cyclohexane, carrene, carbon dioxide etc. Be in the situation of water when blowing agent, combined amount is preferably 7 with respect to the polyalcohol of 100 weight portions To 13 weight portions, to obtain density as 25kg/m3Or lower flexible polyurethane foam using hydrated metal salt blowing agents. When the combined amount of water less than 7 weight portions, the little and flexible polyurethane foam using hydrated metal salt blowing agents of the degree of foaming Density trends towards surpassing 25kg/m3 When the combined amount of water greater than 13 weight portions, foaming and solidifying The time temperature rise easily, and be difficult to temperature is reduced. By as above setting the combined amount of water, Usually can obtain density is 15 to 25kg/m3Flexible polyurethane foam using hydrated metal salt blowing agents.
Catalyst is used for accelerating the reaction of polyalcohol and PIC formation urethanes, Specifically can use tertiary amine such as triethylenediamine, dimethylethanolamine or N, N ', N '-trimethyl ammonia The base ethyl] piperazine, organo-metallic compound such as tin octoate, acetate, alkali metal alcoholate etc. If need, urethane raw and foamed material stabilizing agent, crosslinking agent, filler, stabilizing agent, The fusion such as colouring agent, fire retardant, plasticizer. The foamed material stabilizing agent can use silicone compounds, Anion surfactant, such as neopelex or lauryl sodium sulfate, polyethers silicon Oxygen alkane, phenolic compound etc.
Above-mentioned proportion is that 1.5 to 4.0 inorganic compound hydrate is by generating the material of water after the thermal degradation.As proportion is 1.5 to 4.0 inorganic compound hydrate, can be terra alba (CaSO
4.2H
2O, dihydrate gypsum, proportion: 2.32, decomposition temperature: 128 to 163 ℃), ferrous sulfate-water to five hydrate (FeSO
4.H
2O is to FeSO
4.5H
2O, proportion: 2.97, decomposition temperature: 100 to 130 ℃) or its mixture, aluminum oxide-water is to trihydrate (Al
2O
3.H
2O is to Al
2O
3.3H
2O, proportion: 2.4 to 3.4, decomposition temperature: 150 to 360 ℃), cupric sulfate pentahydrate (CuSO
4.5H
2O, proportion: 2.29) ,-water is to magnesium sulfate heptahydrate (MgSO
4.H
2O is to MgSO
4.7H
2O, proportion: 2.57 to 1.68, decomposition temperature: 150 ℃, median size 50 μ m) etc.The combination water that contains in the inorganic compound hydrate as the solid crystal stable existence under the room temperature is a crystal water.Ferrous sulfate hydrate, calcium sulfate hydrate or magnesium sulfate hydrate are preferred inorganic compound hydrate.This is because these inorganic compound hydrate are 100 ℃ or when higher, along with urethane raw foaming and solidification value rising are decomposed to form water gradually in temperature.
The proportion of inorganic compound hydrate is necessary for 1.5 to 4.0, and preferably from 2.0 to 3.0.When proportion less than 1.5 the time, can only add the inorganic compound hydrate (powder) of predetermined weight, and the hydrate of large volume is when adding in urethane raw such as the polyvalent alcohol to, powder and polyvalent alcohol can not be by thorough mixing and stirrings.In addition, the destruction that the increase of inorganic compound hydrate volume causes the flexible polyurethane foam using hydrated metal salt blowing agents physical properties in the flexible polyurethane foam using hydrated metal salt blowing agents.On the other hand, when proportion surpasses 4.0, raw material at flexible polyurethane foam using hydrated metal salt blowing agents, especially in the long-time storage process of polyvalent alcohol, inorganic compound hydrate trends towards precipitation, and the dispersed variation in liquid reaction mixture, thereby inorganic compound hydrate reduces the function reduction of exothermic temperature.Proportion is preferably from 100 to 170 ℃ of the decomposition temperatures of 1.5 to 4.0 inorganic compound hydrate.When decomposition temperature is lower than 100 ℃, in urethane raw foaming and solidified starting stage,, form water promptly in the stage of low exothermic temperature, therefore might have a negative impact to foaming and curing, the water of formation can be used as whipping agent.By way of parenthesis, under the situation of dihydrate gypsum, when being heated to 100 ℃ or when higher, 1.5mol is just arranged is free water by decomposition and inversion to every 2mol water in the molecule.
Proportion is that the combined amount of 1.5 to 4.0 inorganic compound hydrate is preferably 3 to 150 weight parts with respect to 100 weight part polyvalent alcohols, more preferably from 20 to 100 weight parts.When combined amount less than 3 weight parts, the water yield that is decomposed to form is very little so can not fully reduce foaming and the rising of the exothermic temperature that solidify to produce.On the other hand, when combined amount surpasses 150 weight parts, unnecessary water improves exothermic temperature as whipping agent thereby might quicken foamable reaction.
Inorganic compound hydrate is preferably mixed with the array configuration of multiple hydrate, for example calcium sulfate hydrate and magnesium sulfate hydrate.So then can foam and the solidified exothermic temperature thereby can effectively reduce, also can reduce the combined amount of inorganic compound hydrate in the function of the inorganic compound hydrate of temperature range performance widely.
Urethane raw foams and curing reaction, thereby generates flexible polyurethane foam using hydrated metal salt blowing agents.At this moment the reaction below the complicated and main generation of reaction.Just, other polyreaction (urethanum form reaction) is arranged between polyvalent alcohol and polymeric polyisocyanate, polymeric polyisocyanate and as the foamable reaction between the water of whipping agent, and crosslinked (curings) between reaction product and the polymeric polyisocyanate reacts.
In this case, adopt a step Method Of Accomplishment (one-shot method) of direct reaction between any polyvalent alcohol and the polymeric polyisocyanate, or polyvalent alcohol and polymeric polyisocyanate react in advance and obtain terminal prepolymer with isocyanate groups itself and the prepolymer process of polyol reaction then, formation polyurethane foamed material.
So the flexible polyurethane foam using hydrated metal salt blowing agents density that obtains is 25kg/m
3Or lower, be generally 15 to 25kg/m
3, be 5% or lower by the definite compressed residual strain of JIS K 6400-4:2004 (method A), be 5 or lower in foaming and solidified high-temperature part and low temperature part color distortion, and contain inorganic compound hydrate.Color distortion is the difference of high-temperature part and the yellowness index (Δ YI) of low temperature part when foaming and curing herein.
Therefore, flexible polyurethane foam using hydrated metal salt blowing agents has low density, and promptly density is 25kg/m
3Or it is lower and have good damping performance and light weight.Generally speaking, flexible polyurethane foam using hydrated metal salt blowing agents is that wherein cell (bubble) has the structure of connection and the foam materials of reset capability.For making low-density like this foam materials, must obtain 40 times or higher foaming ratio.In addition, the compression residual strain is little and cushioning ability is kept for a long time.In addition, because color distortion is little, no problem aspect color.And, preferably by the definite hardness of JIS K 6400-4:2004 (method D) from 110 to 150N, the tension force that JIS K 6400-4:2004 determines is from 100 to 150kPa, and the elongation of determining by JIS K 6400-4:2004 from 100 to 200%.If hardness surpasses 150N, then might become too hard and reduce cushioning ability by flexible polyurethane foam using hydrated metal salt blowing agents.In flexible polyurethane foam using hydrated metal salt blowing agents, from the mineral compound of inorganic compound hydrate keep but this inorganic compound hydrate proportion be above-mentioned 1.5 to 4.0 and volume little, so its influence to the physical properties of flexible polyurethane foam using hydrated metal salt blowing agents is little.Flexible polyurethane foam using hydrated metal salt blowing agents with such physical properties is suitable for forming furniture such as chair and sofa, the cushioning material of bedclothes such as bed, mattress, pillow, automotive seat etc.
Producing under the situation of flexible polyurethane foam using hydrated metal salt blowing agents, proportion is 1.5 to 4.0 inorganic compound hydrate and for example contain polyether glycol, polymeric polyisocyanate, mix as the water of whipping agent and the urethane raw of amine catalyst.For example dihydrate gypsum or ferrous sulfate hydrate are as inorganic compound hydrate.The preparation method of flexible polyurethane foam using hydrated metal salt blowing agents foams polyether glycol and polymeric polyisocyanate reaction and further curing reaction with polymeric polyisocyanate and water effect simultaneously.
In preparation process, when foaming and curing, inorganic compound hydrate is heated to 100 ℃ or higher, thereby makes the water evaporation that is converted into free water and formation as the water of combination water by decomposition.By evaporation of water remove vaporization heat and since foaming and the generation of solidified foam materials heat be lowered.Therefore, can reduce foaming and solidified exothermic temperature.Foaming of the present invention and solidified exothermic temperature can be suppressed at 170 ℃ or lower, and foam materials reaches 170 ℃ or higher sometimes in foaming and solidified temperature when not mixing inorganic compound hydrate.Therefore, owing to be exposed to the foam materials coking that 170 ℃ or higher temperature produce and avoid.
The advantage of above-mentioned embodiment hereinafter will be described.
In the process of flexible polyurethane foam using hydrated metal salt blowing agents of preparation embodiment of the present invention, proportion is that 1.5 to 4.0 inorganic compound hydrate is mixed with urethane raw, and polyvalent alcohol and polymeric polyisocyanate react also and foam.Therefore, when foaming and curing, inorganic compound hydrate forms water by thermal degradation, removes vaporization heat by evaporation of water, thereby reduction foaming and solidified heat produce.
Therefore, foaming and solidified exothermic temperature can effectively reduce, and the decrease of temperature speed that once increased can be quickened.As a result, can reduce, thereby can reduce the painted of the flexible polyurethane foam using hydrated metal salt blowing agents that obtains owing to produce the color distortion of high-temperature part and low temperature part inductive foam materials.
In addition, because inorganic compound hydrate proportion is above-mentioned 1.5 to 4.0, the volume of blended inorganic compound hydrate is little, thus change the physical properties of the flexible polyurethane foam using hydrated metal salt blowing agents that obtains, little as the possibility of density.
And, preferably from 100 to 170 ℃ of the decomposition temperatures of inorganic compound hydrate.Therefore, temperature is elevated to 100 ℃ or higher when foaming and curing, and inorganic compound hydrate begins to be decomposed to form water, the water evaporation of formation.Therefore, can effectively reduce heat by the water vaporization heat produces.
In addition, inorganic compound hydrate is preferably ferrous sulfate hydrate, calcium sulfate hydrate or magnesium sulfate hydrate.These inorganic compound hydrate are 100 ℃ or improve with foaming and solidified temperature when higher and be decomposed to form water gradually that in temperature the water of formation evaporates.Therefore, can effectively reduce heat by evaporation of water produces.
Flexible polyurethane foam using hydrated metal salt blowing agents density by above-mentioned acquisition is 15 to 25kg/m
3, the definite compressed residual strain of JIS K6400-4:2004 (method A) is 5% or still less, color distortion is 5 or still less, and to contain proportion be 1.5 to 4.0 inorganic compound hydrate.Therefore, its density is low and have little compressed residual strain, and shows as the good physical properties of flexible polyurethane foam using hydrated metal salt blowing agents.In addition, produce, can reduce the oxidative degradation that is generally high-temperature part, thereby alleviate the color distortion between high-temperature part and the low-temp. portion branch by reducing the unnecessary heat of foaming and solidified.Therefore, even product is partly made from high-temperature internal part and low-temperature surface, also can prevent painted problem.In addition, coming proportion in the comfortable flexible polyurethane foam using hydrated metal salt blowing agents is that the mineral compound of 1.5 to 4.0 inorganic compound hydrate is almost to the not influence of physical properties of flexible polyurethane foam using hydrated metal salt blowing agents.
Hereinafter will be by embodiment and the embodiment above comparative example's more detailed description, but the invention is not restricted to these embodiment.
Embodiment 1 to 9 and comparative example 1 to 3
Show that at first, below the proportion that uses among each embodiment and the comparative example is 1.5 to 4.0 inorganic compound hydrate.
Dihydrate gypsum: dihydrate gypsum proportion is 2.32, and median size is 40 μ m
Ferrous sulfate hydrate: ferrous sulfate one water is to the mixture of five hydrates, and proportion is 2.97, and median size is 40 μ m
Magnesium sulfate hydrate: magnesium sulfate heptahydrate, proportion are 1.68, and median size is 50 μ m
Polyethylene powders: new LDPE (film grade) powder, proportion are 0.93, and median size is 40 μ m, are produced by Mitsui Chemicals Inc
Along band ground, the vaporization heat of water is 2259J/g, and the thawing latent heat of polyethylene powders is 198J/g.The effect of water absorption heat is compared obvious excellence with polyethylene powders so.
With table 1,2,3 urethane raws that contain polyvalent alcohol, poly-isocyanide ester, whipping agent, foam materials stablizer and catalyzer that show respectively and above-mentioned proportion are that 1.5 to 4.0 inorganic compound hydrate is mixed and prepared mixture.Comparative example 1 shows and does not wherein add the embodiment that proportion is 1.5 to 4.0 inorganic compound hydrate, and comparative example 2 and 3 shows the embodiment that only adds polyethylene powders.
These mixtures are rendered to length and width separately, dark size is respectively in the foaming vessel of 500mm, foam under room temperature and normal atmosphere, carry out reacting by heating (curing) by process furnace then, obtain elastic plate strand foam material thus.The resilient sheet-like foam materials cutting that obtains forms the stratiform polyurethane foamed material.According to following measuring method measure polyurethane foamed material density, hardness, tension force, prolongation, compressed residual strain, the highest exothermic temperature, descend 10 ℃ of required times and color distortion from the highest exothermic temperature.It the results are shown in table 1, and 2 and 3.Table 1, the meaning of mark shows below in 2 and 3.
(measuring method)
Density (kg/m
3): measure according to JIS K 7222:2004.
Hardness (N): measure according to JIS K 6400-2:2004 (method D).
Tension force (kPa): measure according to JIS K 6400-5:2004.
Prolongation property (%): measure according to JIS K 6400-5:2004.
Compressed residual strain (%): measure according to JIS K 6400-4:2004.
The highest exothermic temperature (℃): thermopair is inserted into the middle body of foaming vessel, determines the top temperature that shows in foaming and the solidification process.
Descend 10 ℃ of required times from the highest exothermic temperature: after measuring the highest exothermic temperature, determine from the highest exothermic temperature descend 10 ℃ of required times (minute).
Color distortion: by colourimeter [SM color computer SM-4, produce by Suga TestInstruments company limited] high-temperature part (middle body) and the low temperature part (side line part) of foam materials in foaming and the curing reaction are measured yellowing (white content), and measure the color distortion (Δ YI) between them.
(table 1, the mark in 2 and 3)
Polyvalent alcohol GP3000: by the polyether glycol that Sanyo Chemical Industries company limited produces, hydroxy number: 56 (mg-KOH/g).
Amine catalyst LV33: by the catalyzer based on amine of Chukyo Yushi company limited production.
Siliconefoam material settling out agent B8110: produce by Goldschmidt.
Stannous octoate MRH110: produce by Johoku Chemical company limited.
Poly-isocyanide ester T-80: toluene diisocyanate (toluene diisocyanate, 80 weight % 2,4-toluene diisocyanate and 20 weight % 2, the mixture of 6-toluene diisocyanate), produce by NipponPolyurethane Industry company limited.
Table 1
Embodiment 1 embodiment 2 embodiment 3 embodiment 4 embodiment 5 embodiment 6
Water 7.0 7.0 7.0 5.0 7.0 5.0
Amine catalyst LV33 0.4 0.4 0.4 0.4 0.4 0.4
Silicon cave foam materials stablizer
B8110 1.0 1.0 1.0 1.0 1.0 1.0
Stannous octoate MRH110 84.1 84.1 84.1 62.8 84.1 62.8
Poly-isocyanide ester T-80 110 110 110 110 110 110
Isocyanide ester index 30-100 30-50
Ferrous sulfate hydrate-30--100-
Density (kg/m
3) 17.6 17.3 21.0 22.4 20.6 24.8
Hardness (N) 114 111 142 131 141 144
Tension force (1Pa) 130 135 105 145 123 108
Prolong (%) 170 173 105 203 118 105
Compressed residual strain (%) 4.5 4.3 4.8 3.1 4.1 4.7
The highest exothermic temperature (℃) 141 145 105 132 112 102
Descend from the highest exothermic temperature
10 ℃ of required time (minute) 9 10 8797
Color distortion (Δ YI) 3.0 2.8 1.9 2.1 1.8 1.7
Table 2
Embodiment 7 embodiment 8 embodiment 9
Water 7.0 7.0 7.0
Amine catalyst LV33 0.4 0.4 0.4
Silicon cave foam materials stablizer
1.0 1.0 1.0
B8110
Stannous octoate MRH110 0.2 0.2 0.2
Poly-isocyanide ester T-80 84.1 84.1 84.1
Isocyanide ester index 110 110 110
Dihydrate gypsum--10
Density (kg/m
3) 17.1 20.8 17.6
Hardness (N) 114 141 121
Tension force (kPa) 130 103 123
Prolong (%) 170 107 143
Compressed residual strain (%) 4.5 4.8 4.7
The highest exothermic temperature (℃) 137 118 127
Descend from the highest exothermic temperature
9 7 8
10 ℃ of required time (minute)
Color distortion (Δ YI) 3 1.2 2.1
Table 3
Comparative example 1 comparative example 2 comparative examples 3
Water 7.0 7.0 7.0
Amine catalyst LV33 0.4 0.4 0.5
The agent of siliconefoam material settling out
B8110 1.0 1.0 1.0
Stannous octoate MRH110 0.2 0.2 0.2
Poly-isocyanide ester T-80 84.1 84.1 84.1
Isocyanide ester index 110 110 110
Polyethylene powders-30.0 100.0
Density (kg/m
3) 16.9 18.0 can't measure
Hardness (N) 128 122
Tension force (kPa) 97 85
Prolong (%) 87 83
Compressed residual strain (%) 10.8 7.4
The highest exothermic temperature (℃) 187 143
Descend from the highest exothermic temperature
10 ℃ of required time (minute) 22 18
Color distortion (Δ YI) 12.1 5.1
As table 1 and 2 and embodiment 1 to 9 as shown in, foaming and the highest exothermic temperature of solidified can be suppressed to 145 ℃ or lower, can shorten to 10 minutes or still less from the highest exothermic temperature decline 10 ℃ of required times, color distortion can be reduced to 3.0 or still less.Therefore, the flexible polyurethane foam using hydrated metal salt blowing agents that obtains is a low density 17.3 to 24.8kg/m
3, hardness is 111 to 144N, and tension force is 105 to 145kPa, and prolongation property is 105 to 203%, and the compressed residual strain is 3.1 to 4.8%.Concrete, in embodiment 9, by mixing total amount little magnesium sulfate heptahydrate and dihydrate gypsum to 20 weight parts, the highest exothermic temperature can be suppressed to 127 ℃, and color distortion can be reduced to 2.1, and density is low to moderate 17.6kg/m
3Thereby, the performance of acquisition optimum balance.
Generally speaking, at the flexible polyurethane foam using hydrated metal salt blowing agents that is used for furniture such as mattress, the thick standard of color distortion is 5 or still less, at the flexible polyurethane foam using hydrated metal salt blowing agents that is used for automotive seat material and furniture protection pad, the compressed residual strain is 5% or still less, so these standards can be fully satisfied.Exothermic temperature can be suppressed to low temperature, the reason that color distortion can fully reduce and obtain low foaming flexible polyurethane foam using hydrated metal salt blowing agents is a hypothesis based on reducing exothermic temperature owing to remove vaporization heat by evaporation of water, and the water that is decomposed to form of the inorganic compound hydrate by proportion 1.4 to 5.0 is induced by thermogenesis in foaming with when solidifying.
On the contrary, as shown in table 3, under the situation of the inorganic compound hydrate that does not contain proportion 1.4 to 5.0 (comparative example 1), the highest exothermic temperature reaches 187 ℃ high temperature, becomes 22 minutes long-time from the highest exothermic temperature 10 ℃ of required times that descend.Therefore, color distortion is shown as 12.1 high value and compressed residual strain and is shown as 10.8% high value.Under the situation that polyethylene powders adds with 30 weight parts (comparative example 2), because long from the highest exothermic temperature 10 ℃ of required times that descend, promptly 18 minutes, just to maintain the pyritous time long owing to foam materials, and color distortion brings up to 5.1.As mentioned above, the thick standard of color distortion is 5 or still less, therefore can not satisfy this standard.In addition, polyethylene powders with 100 weight part blended situations under (comparative example 3), urethane raw becomes pasty state, thereby can not foam.
According to the foregoing description 1 and comparative example's 2 result, in Fig. 1, illustrate exothermic temperature (℃) and the consumption time (minute) relation.As shown in Figure 1, be appreciated that the degree that descends from the highest exothermic temperature is big among embodiment 1 than in comparative example 2.Required time T1 from 10 ℃ of the highest exothermic temperature (141 ℃) declines in embodiment 1 is 9 minutes, and the required time T2 from 10 ℃ of the highest exothermic temperature (143 ℃) declines is 18 minutes in comparative example 2.The water that decompose to produce by dihydrate gypsum in embodiment 1 is observed from the highest exothermic temperature and is reduced temperature fast, thereby but in comparative example 2 polyethylene powders observe from the highest exothermic temperature as holding temperature and slowly reduce temperature.
Also might change and definite embodiment of the present invention.
Monohydrated sodium carbonate (Na
2CO
3.H
2O, proportion 2.25,100 ℃ of decomposition temperatures), a water monocalcium phosphate (Ca (H
2PO
4)
2.H
2O, proportion 2.22,109 ℃ of decomposition temperatures) etc. also can be 1.5 to 4.0 inorganic compound hydrate as proportion.
Water-swelling and the water that absorbs in when heating evaporation and absorb the water-absorbing material of heat, as contain (methyl) acrylic acid units or (methyl) acrylate unit also can mix by saturation state as the unitary water-insoluble of main formation (methyl) vinylformic acid water-absorbing resin.
The porose inorganic materials that absorbs water, as, hemi-hydrated plaster, kaolin, diatomite, gac etc. also can mix by saturation state.
Flexible polyurethane foam using hydrated metal salt blowing agents can be as the lining material and the ceiling material of automotive interior material such as arrangements for automotive doors, other bat materials etc.
In addition, will describe below can be from the technical conceive of above-mentioned embodiment understanding.
The present invention produces the method for flexible polyurethane foam using hydrated metal salt blowing agents, and wherein above-mentioned ferrous sulfate hydrate is preferably the ferrous sulfate of a water to five water, and calcium sulfate hydrate is preferably terra alba.According to production method, inorganic compound hydrate can be in urethane raw foaming and solidify reaction process at 100 ℃ or be decomposed to form water gradually with the temperature rising when higher.
The present invention produces the method for flexible polyurethane foam using hydrated metal salt blowing agents, and wherein above-mentioned exothermic temperature is preferably set to 170 ℃ or lower.According to production method, can prevent coking and obtain the physical properties of the excellence of flexible polyurethane foam using hydrated metal salt blowing agents product, as color distortion and compressed residual strain.
The present invention produces the method for flexible polyurethane foam using hydrated metal salt blowing agents, the multiple above-mentioned inorganic compound hydrate of wherein preferred mixing.According to production method, the function of inorganic compound hydrate can be in temperature range displaying widely, so can effectively reduce the combined amount of foaming and solidified exothermic temperature and minimizing inorganic compound hydrate.
Obtain flexible polyurethane foam using hydrated metal salt blowing agents by the urethane raw reaction that will contain polyvalent alcohol, poly-isocyanide ester, whipping agent and catalyzer, its density is 15 to 25kg/m
3, the compressed residual strain that JIS K 6400-4:2004 (method A) measures is 5% or still less, foaming and when solidifying the color distortion of high-temperature part and low temperature part be 5 or still less, and to contain proportion be 1.5 to 4.0 inorganic compound hydrate.Under situation about so constituting, foam materials is showed the suitable physical properties of flexible polyurethane foam using hydrated metal salt blowing agents as cushioning material etc.
Although the present invention is described in detail with reference to its specific embodiments, clearly can under the prerequisite that does not change spirit of the present invention and scope, do various changes and modification to it to those skilled in the art.
The application is based on the 2004-331737 of Japanese patent application 2004-220409 that submitted on July 28th, 2004 and submission on November 6th, 2004, and its full content is hereby incorporated by.
Claims (10)
1. produce the method for flexible polyurethane foam using hydrated metal salt blowing agents, comprise and to contain polyvalent alcohol, poly-isocyanide ester, the urethane raw of whipping agent and catalyzer and proportion are that 1.5 to 4.0 inorganic compound hydrate is mixed, and urethane raw is foamed and curing reaction, be 7 to 13 weight parts with respect to the polyvalent alcohol of 100 weight parts wherein as the combined amount of the water of whipping agent, and proportion is that the combined amount of 1.5 to 4.0 inorganic compound hydrate is 3 to 150 weight parts with respect to the polyvalent alcohol of 100 weight parts, and wherein foams and solidify the exothermic temperature that causes and increase the evaporation of water that is decomposed to form by inorganic compound hydrate and be reduced.
2. the method for the production flexible polyurethane foam using hydrated metal salt blowing agents of claim 1, wherein said inorganic compound hydrate decomposition temperature is from 100 to 170 ℃.
3. the method for the production flexible polyurethane foam using hydrated metal salt blowing agents of claim 1, wherein said inorganic compound hydrate is ferrous sulfate hydrate, calcium sulfate hydrate or magnesium sulfate hydrate.
4. the method for the production flexible polyurethane foam using hydrated metal salt blowing agents of claim 2, wherein said inorganic compound hydrate is ferrous sulfate hydrate, calcium sulfate hydrate or magnesium sulfate hydrate.
5. the method for the production flexible polyurethane foam using hydrated metal salt blowing agents of claim 3, wherein said ferrous sulfate hydrate is that a water is to five aqueous ferrous sulfates.
6. the method for the production flexible polyurethane foam using hydrated metal salt blowing agents of claim 3, wherein said calcium sulfate hydrate is a terra alba.
7. the method for the production flexible polyurethane foam using hydrated metal salt blowing agents of claim 4, wherein said ferrous sulfate hydrate is that a water is to five aqueous ferrous sulfates.
8. the method for the production flexible polyurethane foam using hydrated metal salt blowing agents of claim 4, wherein said calcium sulfate hydrate is a terra alba.
9. the method for the production flexible polyurethane foam using hydrated metal salt blowing agents of claim 1, wherein said exothermic temperature is set at 170 ℃ or lower.
10. the method for the production flexible polyurethane foam using hydrated metal salt blowing agents of claim 1 is wherein mixed multiple inorganic compound hydrate.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004220409 | 2004-07-28 | ||
| JP2004220409 | 2004-07-28 | ||
| JP2004331737 | 2004-11-16 |
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| Publication Number | Publication Date |
|---|---|
| CN1727376A CN1727376A (en) | 2006-02-01 |
| CN100545189C true CN100545189C (en) | 2009-09-30 |
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| CN109836556A (en) * | 2019-01-31 | 2019-06-04 | 四川大学 | A kind of low VOC polyurethane foam material and preparation method containing molysite |
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| CN103951980B (en) * | 2013-09-18 | 2017-02-08 | 烟台德邦科技有限公司 | Wet-heat dual curing silicone composition |
| EP3420008A1 (en) * | 2016-02-26 | 2019-01-02 | Solvay SA | Process for the preparation of a polyurethane foam |
| US20170251824A1 (en) * | 2016-03-07 | 2017-09-07 | Purple Innovation, Llc | Cushions including a coated elastomeric cushioning element and related methods |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109836556A (en) * | 2019-01-31 | 2019-06-04 | 四川大学 | A kind of low VOC polyurethane foam material and preparation method containing molysite |
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| CN1727376A (en) | 2006-02-01 |
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