CN1295225A - Electric refrigerator - Google Patents

Electric refrigerator Download PDF

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Publication number
CN1295225A
CN1295225A CN00126940A CN00126940A CN1295225A CN 1295225 A CN1295225 A CN 1295225A CN 00126940 A CN00126940 A CN 00126940A CN 00126940 A CN00126940 A CN 00126940A CN 1295225 A CN1295225 A CN 1295225A
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polyvalent alcohol
refrigerator
addition
parts
propylene oxide
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CN1133676C (en
Inventor
荒木邦成
福田克美
小室淳
横仓久男
伊藤丰
菅野正义
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Hitachi Ltd
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Hitachi Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4833—Polyethers containing oxyethylene units
    • C08G18/4837—Polyethers containing oxyethylene units and other oxyalkylene units
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
    • C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
    • C08J9/125—Water, e.g. hydrated salts
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
    • C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
    • C08J9/141—Hydrocarbons
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25D—REFRIGERATORS; COLD ROOMS; ICE-BOXES; COOLING OR FREEZING APPARATUS NOT OTHERWISE PROVIDED FOR
    • F25D23/00—General constructional features
    • F25D23/08—Parts formed wholly or mainly of plastics materials

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Combustion & Propulsion (AREA)
  • Physics & Mathematics (AREA)
  • Mechanical Engineering (AREA)
  • Thermal Sciences (AREA)
  • General Engineering & Computer Science (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Refrigerator Housings (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)

Abstract

The present invention provided a refrigerator external appearance of which is improved by preventing its surface from being strained and deformed. In a refrigerator provided with a heat insulator packed with rigid foamed polyurethane obtained by using at least polyol, aromatic isocyanate, and a mixed blowing agent composed of cyclopentane and water, the polyol contains three or more kinds of mixtures prepared by adding initiators respectively composed of m-tolylenediamine and o-tolylenediamine to polyol by using ethylene oxide and/or propylene oxide.

Description

Refrigerator
The refrigerator of rigid urethane foam that the present invention relates to filling.
In the body of thermal insulating box of refrigerator, in the space of outer container and interior case, adopt to have the rigid urethane foam of bubble as adiabatic material.This rigid urethane foam is under the condition that whipping agent, catalyzer, surfactant are arranged, and the reaction of polyhydroxy reactant and isocyanate prepolymer composition is obtained.Whipping agent in the past is to adopt the single fluoromethane of low, the hard-decomposed trichlorine of gas thermal conductivity in body of thermal insulating box.
But, be released in the atmosphere after, damage the ozone layer and cause Greenhouse effect, surface temperature is risen.Though also once adopted 1 of product instead, the whipping agent that 1-two chloro-1-list fluoroethane is used as heat insulating member, it also is identified as the restriction object, will ban use of in 2003.
In addition, not adopting freonll-11 and the so-called free-floride that can reduce depletion of the ozone layer is a whipping agent, is that the center begins to adopt the hydrocarbon based compound with Europe, for example the pentamethylene whipping agent is used for the adiabatic material of refrigerator.For example, the refrigerator of following rigid urethane foam or the body of thermal insulating box or the insulated door of refrigerated tank have been proposed to adopt, these rigid urethane foams are low density and the mobile rigid urethane foams improved that adopted the mixed foaming agent of pentamethylene and iso-pentane, or have adopted the low density of mixed foaming agent of pentamethylene and water and the rigid urethane foam of high workability.These prior aries are opened flat 11-201628 communique Japanese kokai publication hei 11-140155 communique, spy, the spy opens in the flat 11-248344 communique and discloses.
But the hydrocarbon blowing agents of pentamethylene or iso-pentane is compared with whipping agent in the past, exists the problem of gas thermal conductivity height, poor insulation property.Especially for the rigid urethane foam of the mixed foaming agent that has adopted pentamethylene and water,, wish to develop and to improve heat insulating ability, energy-conservation urethane material from the position of global warmingization and global environment protection.
The more and more large-scale change of refrigerator and refrigerated tank, be provided with the storage box body of the corresponding differing temps of various food (18 ℃, 0 ℃, 3 ℃, 5 ℃ etc.) also more and more diversifiedly, for example the superiors are that refrigerating chamber, middle level are that vegetable compartment, lower floor are upper strata refrigeration chamber and lower floor's refrigeration chamber etc.
In recent years, maximization and saving spatialization along with refrigerator and refrigerated tank, also cause narrow gapization of spatial and complex-shapedization in the box body wall, because the outer side at interior case has obstacles such as a lot of copper pipes, aluminium strip, paper tape, polystyrene sheet, distribution, so, foam is not easy to flow at the refrigerator pars intramuralis, and is insufficient to the filling of this part.In order to address this problem,, preferably adopt the urethane material of low density, good fluidity in order to form uniform foam in top part, bottom, back side portion, handle portion, hinge portion.From this point, the urethane material of the mixed foaming agent of pentamethylene and water also with replace freonll-11 similarly, be badly in need of developing low density, thermal conductivity is low and guarantees the material of intensity.
For this reason, adopt the low density rigid polyurethane foam of the mixed foaming agent of pentamethylene and water, require the distortion little, that be placed on outer container surface iron plate under the low temperature environment of foamy swell increment little and thermal conductivity is low, compressive strength and dimensional stabilizing.
The formation of the bubble that in urethane resin, foams, be not only foaming dosage, the water yield, catalyzer, surfactant is regulated with the chemical constitution of polyvalent alcohol and isocyanic ester and make that bubble produces, the physical phenomenon of growth, the flowability in the intermiscibility of raw material, reactivity, the foaming process also has a significant impact.From this point,, must make various material optimal doseizations in order to satisfy above-mentioned requirements.
But the rigid urethane foam of employing pentamethylene whipping agent is compared with the whipping agent that replaces freonll-11, because saturated vapo(u)r forces down, the pressure in the crafters is also low, is easy to generate contraction after the filling.Therefore, pack density is crossed when hanging down, and produces surface deformation, causes the finished product rate low, and the intensity of casing and door is also low.
That is, in the low-density rigid urethane foam, be subjected to the expansion of gas in the bubble, the influence of contraction, it is big that the foamy linear expansivity becomes.In the filling of low density rigid urethane foam, even also can keep shape of product and when strengthening fill-up, rate of expansion, the swell increment of casing during filling and door increase in order after filling, to shrink.Mainly be to adopt highdensity urethane material, foamy is mobile poor in the past, though foaming is pressed with increasing, the method for increase urethane fill-up can be guaranteed intensity, but urethane foam leaks easily.
The present inventor is in order to adopt the low density rigid urethane foam and to realize its characteristic, to having done research as whipping agent and water, the reactive catalyzer of control of the polyvalent alcohol of main raw material and isocyanic ester, formation bubble, the surfactant of regulating surface phenomenon.Specifically, various starting material are carried out appropriate combination, developed such rigid urethane foam material: reduce the swell increment of low density rigid polyurethane foam when the urethane foaming demoulding, even even and the filling rate change of mould temperature variation of when foaming and fill-up etc., its swell increment is also little, thermal conductivity is low, compressive strength and dimensional stabilizing are good.
The purpose of this invention is to provide and prevent refrigerator surface deformation, that outward appearance is good.
To achieve these goals, refrigerator of the present invention, in the space between outer container and interior case, the adiabatic material of rigid urethane foam in filling, and this rigid urethane foam has adopted polyvalent alcohol, aromatic isocyanate and at least as the pentamethylene of whipping agent and the mixed foaming agent of water; It is characterized in that, in this rigid urethane foam, contain the mixture of ingredients more than 3 kinds that oxyethane that initiator that useful toluylenediamine and ortho-toluene diamine constitute causes and/or propylene oxide addition obtain as polyhydroxy reactant.
In addition, the polyhydroxy reactant of above-mentioned rigid urethane foam is a polyether glycol, the initiator with toluylenediamine, ortho-toluene diamine, dihydroxyphenyl propane, trolamine formation that wherein contains more than 90% causes the mixture of oxyethane and/or propylene oxide addition, from the distance urethane inlet planar section more than the 500mm at least, the density that thickness is about the adiabatic material of sandwich layer of 20～25mm is 29～33kg/m 3, thermal conductivity is 17.5～18.0mW/mK when 10 ℃ of medial temperatures.
In addition, the aromatic isocyanate composition of above-mentioned rigid urethane foam, employing has added the mixture of performed polymer modification tolylene diisocyanate in the '-diphenylmethane diisocyanate polykaryon, use the mixed foaming agent that has made up 1.2～1.6 weight parts waters and 14～18 weight part pentamethylene in the polyvalent alcohol of 100 weight parts to make its reaction.
The polyhydroxy reactant of above-mentioned rigid urethane foam is the mixture that is made of following composition: on toluylenediamine addition polyvalent alcohol 44～55 weight parts of the OH value 400～500 that obtains of propylene oxide and oxyethane and propylene oxide, on ortho-toluene diamine addition polyvalent alcohol 10～20 weight parts of the OH value 450～500 that obtains of propylene oxide and oxyethane, on trolamine addition polyvalent alcohol 10～20 weight parts of the OH value 350～450 that obtains of propylene oxide, on dihydroxyphenyl propane addition polyvalent alcohol 10～20 weight parts of the OH value 250～300 that obtains of propylene oxide, on diethanolamine addition polyvalent alcohol 3～8 weight parts of the OH value 450～480 that obtains of propylene oxide, the TriMethylolPropane(TMP) OH value 1256 of 2～5 weight parts, the average OH value of this polyvalent alcohol is 400～450.
Fig. 1 is that the skiagraph of polyurethane adiabatic material in filling in the body of thermal insulating box and insulated door of refrigerator and refrigerated tank.
Fig. 2 is the sampling pattern figure that measures sampling from the mode chart and the urethane of 4 some foam filling urethane in body of thermal insulating box.
The present inventor is suitable for the low close of refrigerator and household freezer body of thermal insulating box most in order to develop The degree RPUF, the mixed foaming agent of employing pentamethylene and water subtracts swell increment Little, selected that pyroconductivity is low, the most suitable polyalcohol of compressive strength and good stability of the dimension.
At first, for the swell increment that reduces foam, lower pyroconductivity, guarantee compressive strength and Dimensional stability, attempted many importings some with having the aromatic rings that causes easily steric hindrance The polyalcohol that initator is synthetic.
But the addition polymer of aromatic rings initator is if cooperate many amounts with single component Or mix the intermiscibility utmost point of PPG composition then with xenogenesis composition such as PEPA etc. End reduces. As a result, produce easily muddiness during premix, during preservation, raw material components viscosity also changes, Charging quantity changes easily during foaming.
The most suitable polyalcohol that adopts among the application is according to various epoxides and swell increment Investigation result, the material that discovery is dissolved in the pentamethylene blowing agent easily is effective for foam expansion . From this point, mainly select the addition polymer of expoxy propane, in order to obtain other Rerum natura, also and use oxirane, it is many to become the polyethers that does not contain the xenogenesis compositions such as PEPA Unit's alcohol.
In addition, in the aromatic rings initator, usually use toluylenediamine, in order to obtain other All rerum naturas are with toluylenediamine addition polymer and the adjacent first that can high response obtains to solidify property The PPG of 3 components system of phenylenediamine addition polymer and usefulness is for the control swell increment Effective.
But the ortho-toluene diamine addition product is compared with the toluylenediamine addition product, its raw material components The viscosity height becomes high response easily, so foam filling is in the wall of body of thermal insulating box the time, Produce easily space or crack. Therefore, when mixing the ortho-toluene diamine addition product, former in order to make Material component reduced viscosity and the reactive balance of acquisition are with joining of lacking than the toluylenediamine addition product Resultant is used, and in order to improve intensity and intermiscibility, the toluylenediamine addition product has also been used Propylene oxide adduct and expoxy propane and ethylene oxide adduct.
In addition, except that the initiator with aromatic nucleus, in order to obtain the balance of characteristic, the polymkeric substance that selected the 3rd composition adopts dihydroxyphenyl propane series initiators, the 4th composition to adopt the trolamine series initiators to cause the propylene oxide addition accounts for more than 90% of the suitableeest precursor composition.
In addition, for isocyanate prepolymer composition,, selected the composition that in normally used '-diphenylmethane diisocyanate polykaryon, has mixed performed polymer modification tolylene diisocyanate in order to obtain thermal conductivity attenuating, compressive strength and dimensional stability.Its reason is that during employing '-diphenylmethane diisocyanate polykaryon, though initial reaction is slow, reaction is in a single day got up, and the tendency of tackify is rapidly arranged, and hinders flowability easily, and causes the bubble junction easily.For this reason,, can make distance shortening between tackify behavior gentlenessization, amino-formate bond and urea key high densityization or cross-linking set, form even fine abscess, therefore select the isocyanic ester of mixed stocker by mixing performed polymer modification tolylene diisocyanate.
In addition, optimum mix about pentamethylene and water, catalyzer, surfactant and by to reducing swell increment, low density, thermal conductivity reduces, compressive strength and dimensional stability are considered, the result, the optimum mix of finding pentamethylene and water is, polyvalent alcohol for 100 weight parts, the water of combination 1.2～1.6 weight parts and the pentamethylene of 14～18 weight parts, in Primary Catalysts, also use trimethylammonium amino-ethyl piperidines, 3 poly-catalyzer of five methyl diethylentriamine and three (3-dimethylamino propylidene) six hydrogen-S-triazine etc., selected rapid reaction, high solidified nature, the surfactant of low surface tension has been finished the present invention.
For accomplished the object of the invention urethane material, the use level of the water of pentamethylene whipping agent and auxiliary blowing agent also has a significant impact.Usually, the use level of pentamethylene and water all adopts often, so easy realization low densityization.
But, when the water use level for a long time, the dividing potential drop of the carbon dioxide gas in the abscess increases, and swell increment and thermal conductivity are also increased.When the pentamethylene use level also for a long time, compressive strength and poor dimensional stability.Therefore, the best fit amount of pentamethylene and water is, for the polyvalent alcohol of 100 weight parts, and the water of best combination 1.2～1.6 weight parts and the pentamethylene of 14～18 weight parts.
In addition, according to the investigation result to the foam expansion amount, find the thickness difference according to heat-insulating shield, foam is thick more, and swell increment is big more.This is that the foam inside temperature was also high more when adiabatic material reacted because the thickness of plate is thick more, and expansion and the temperature head of shrinking are also big more, so swell increment increases.In addition, inject urethane in the refrigerator of real machine and the refrigerated tank casing after, be positioned over low temperature following time, in casing, the surperficial iron plate of left and right side is easy to generate distortion.
Used polyvalent alcohol among the present invention, for example polyvalent alcohol has the polyvalent alcohol more than 3 yuan of 3 yuan of alcohol, Glycerol dimer, methyl glucoside, sorbyl alcohol, sucrose etc. of 2 yuan of alcohol, glycerine, TriMethylolPropane(TMP) etc. of propylene glycol, dipropylene glycol etc.The alkylene polyamine of polyamine has quadrol, diethylenetriamine etc.Alkanolamine has monoethanolamine, diethanolamine, trolamine, Yi Bingchunan etc.Aromatic polyamine has 2,4-tolylene diamine, 2,3-tolylene diamine, 2,6-tolylene diamine, 3,4-tolylene diamine etc., diaminodiphenyl-methane, dihydroxyphenyl propane, polymethylene polyphenyl base polyamine etc.
In addition, the average OH value of polyether glycol mixed component is reduced to 400 when following, and compressive strength and poor dimensional stability were crossed 450 o'clock, and foam becomes fragile.Stable average OH value is 400～450 o'clock, aspect the making rigid urethane foam, and the result that can obtain.
As catalysts, for example can adopt the late effect property catalyzer etc. of 3 poly-catalyzer, dipropylene glycol and usefulness of tertiary amine, three (the 3-dimethylamino propylidene) six hydrogen-S-triazine etc. of trimethylammonium amino-ethyl piperidines, five methyl diethylentriamine, tetramethyl-hexamethylene-diamine, triethylenediamine, Tetramethyl Ethylene Diamine etc., as long as reactivity meets all and can adopt.
The use level of catalysts is for per 100 weight part polyhydroxy reactants, to be preferably 2～5 weight parts.In addition, surfactant for example can adopt B-8462, B-8461 etc., X-20-1614, the F-392 etc. of SHIN-ETSU HANTOTAI's chemistry system, the SZ-1127 of Japanese You Nika (ュ ニ カ) system etc. of Ge Lutuoshi Mead (go-Le De シ ュ ミ ッ ト) system, consider from premix intermiscibility stability, preferred Si molecular weight be 1800～3000 and Si content be 25～30 be suitable for the lower material of emulsifying effect.The use level of surfactant is that the polyhydroxy reactant of per 100 weight parts cooperates 1.5～4 weight parts.
Isocyanic ester mainly is polykaryon and the performed polymer modification tolylene diisocyanate that adopts '-diphenylmethane diisocyanate.Tolylene diisocyanate can adopt mixture of isomers, promptly 2,4-body 100%, 2,4-body/2,6-body=80/20,65/35 (weight ratio), but also can adopt commodity to be called Mitsui Si Moretuo (ミ ヰ コ ス モ ネ-ト) the Plutarch heat holder of TRC, military field medicine system (the urethane modification tolylene diisocyanate of performed polymer such as ケ ネ-ト) 4040, allophanate-modified tolylene diisocyanate, biuret modified tolylene diisocyanate, isocyanurate-modified tolylene diisocyanate etc.
In addition, 4,4 '-'-diphenylmethane diisocyanate, except the pure product of principal constituent, contain the above coenocytic commodity of 3 nucleomes Mitsui Si Moretuo by name (コ ス モ ネ-ト) the close Lille heat holder of M-200, military field medicine system (the '-diphenylmethane diisocyanate polykaryon of the MR of ミ リ ォ ネ-ト) etc. but can adopt.In addition, also can adopt the aromatic series polyfunctional isocyanate's, carbodiimide modified diphenylmethane vulcabond etc. of the many phenylesters of polyisocyanic acid methylene radical, Tolylamine isocyanic ester, benzene diformazan vulcabond etc. isocyanic ester.
Rigid urethane foam of the present invention, (プ ロ マ-ト) the PU-30 type foaming machine of society of company system forms for available used usually foaming machine, for example Pu Luomatuo.Though its foaming condition is different because of the kind of foaming machine, should possess following condition, that is, and 18～30 ℃ of liquid temperature, outlet pressure 80～150Kg/cm 2, output 15～30kg/min, 35～45 ℃ of moulding box temperature.Preferably following condition, that is, and 20 ℃ of liquid temperature, outlet pressure 100kg/cm 2, output 25kg/min is near 45 ℃ of the moulding box temperature.
Like this, this rigid urethane foam, have standalone configuration bubble, adopt the mixed foaming agent of pentamethylene and water, the swell increment during filling is little, and density is low, thermal conductivity is low, compressive strength and dimensional stability are good.Such rigid urethane foam as the filling of refrigerator thermal insulation material, can be reduced the heat leak amount, reduce power consumption.And the fill-up of adiabatic material reduces, and can reduce the cost of refrigerator.In addition, even place at low temperatures, the distortion of refrigerator is also little, can provide outward appearance good refrigerator.
Below, specify embodiments of the invention and comparative example.In following embodiment and comparative example, " part " or " % " represents weight part, weight % respectively.(embodiment 1)
Polyhydroxy reactant is, average hydroxyl value be 450, addition the toluylenediamine of propylene oxide and propylene oxide and oxyethane be 50 parts of polyether glycols (being called polyvalent alcohol A); Average hydroxyl value be 480, addition the ortho-toluene diamine of propylene oxide be 13 parts of polyether glycols (being called polyvalent alcohol B); Average hydroxyl value be 400, addition the trolamine of propylene oxide be 15 parts of polyether glycols (being called polyvalent alcohol C); Average hydroxyl value be 460, addition the diethanolamine of propylene oxide be 4 parts of polyether glycols (being called polyvalent alcohol D); Average hydroxyl value be 280, addition the dihydroxyphenyl propane of propylene oxide be 15 parts of polyether glycols (being called polyol E); Average hydroxyl value is 3 parts of 1256 TriMethylolPropane(TMP)s (being called polyvalent alcohol F); In 100 parts of polyhydroxy reactants that above-mentioned various polyvalent alcohols mix, 16 parts of pentamethylene whipping agents, 1.5 parts in water, 0.2 part of 1.7 parts of trimethylammonium aminoethylpiperazine, five methyl diethylentriamine, three (3-dimethylamino propylidene), six hydrogen-0.4 part of S-triazine have been cooperated, as 2 parts of organosilicon F-392 of surfactant as catalysts.
137 parts in the mixture of isocyanate prepolymer composition employing '-diphenylmethane diisocyanate polykaryon and performed polymer modification tolylene diisocyanate makes its foaming.The liquid temperature of polyvalent alcohol at this moment and isocyanic ester is adjusted to 20 ℃.Stir earlier polyvalent alcohol and isocyanic ester, in the aluminum mold of 600 * 400 * 75mm that is adjusted to 45 ℃ of reinjecting, the swell increment that the outer container iron plate that measuring influence refrigerator and freezer box is out of shape.At this moment, the many more swell incremenies of filling are big more, so, after will the rate of tamping being set at 115% and 125%, 5 minute, with the demoulding of moulding product, form rigid urethane foam, adopt the 75mmt heat-insulating shield of this rigid urethane foam, change the rate of tamping and measure swell increment.Its result is as shown in table 1.
Table 1
Figure 0012694000111
The rerum natura of the adiabatic material of this table 1 expression aluminum template and body of thermal insulating box (maximum deformation quantity before and after foam expansion amount, sandwich layer density, thermal conductivity, compressive strength, low temperature size changing rate, high temperature size changing rate, the test after poor, the test of deflection).From this table 1 as can be known, the swell increment of the demoulding after 5 minutes is 2.3mm when the rate of tamping is 115%, is 2.7mm when the rate of tamping is 125%.Than adiabatic material attenuating in the past.
Then, carry out the evaluation of real machine casing, the following describes its result with above-mentioned materials.Reference
Description of drawings.
Fig. 1 is the skiagraph of refrigerator and refrigerated tank casing 1, is provided with refrigerating-chamber door 6, vegetable compartment door 7, upper strata refrigerating chamber door 8, lower floor's refrigerating chamber door 9.After earlier being fixed on the utensil that is used for the urethane foam foaming, the liquid temperature control of polyvalent alcohol and isocyanic ester is made as 20 ℃ to the casing of outer container iron plate and interior case resin wall, the utensil temperature is controlled to be 45 ℃, be filled to hard polyurethane foams in the gap and foam.At this moment, the polyvalent alcohol of urethane foam and isocyanic ester react with were depressed in adding of blow(ing) pressure, and the foaming urethane foam is injected into space in the wall that is filled to casing, has made body of thermal insulating box.At this moment, set urethane material inject volume be about 200 liters casing zero tamp (the minimum injection rate that the real machine filling is necessary) after, the rate of the tamping injection with 110%.
Fig. 2 is that expression is measured the take mode chart of sampling at 4 some foam fillings to mode chart and urethane on the body of thermal insulating box with urethane.From the body of thermal insulating box bottom central part branch of refrigerator and refrigerated tank, take adiabatic material foam sample, carry out various evaluation of physical property.At first, sandwich layer density is estimated like this: after measuring the sample size and weight of 200mm * 200mm * 20mmt, estimate except that the value that weight obtains with volume.Thermal conductivity also adopts the HC-073 type (10 ℃ of heat flowmeter method, medial temperatures) of the great smart machine of English society system to estimate.
Compressive strength is estimated like this: the fltting speed with 4mm/min is out of shape the foam sample of 50mm * 50mm * 20mmt, and the stress when removing 10% distortion with original load area is estimated with the value that obtains.Low temperature size changing rate and high temperature size changing rate are estimated like this: the foam of 150mm * 300mm * 20mmt was placed 24 hours down at-20 ℃, or placed 24 hours down at 70 ℃, estimate thickness change at that time.
These results represent in table 1.As known from Table 1, sandwich layer density is 29.2kg/m 3, density is lower, and thermal conductivity is 17.6mW/mK, and is lower.Compressive strength is up to 0.15MPa, and the low temperature size changing rate is-1.1%, and the high temperature size changing rate is 1.6%, and changing value is smaller.
In addition, outer container top layer iron plate deflection is that the deformation measurement utensil that adopts square bar central part at the surface smoothing of length 300mm that dial card is installed carries out.Assay method is that the mensuration utensil is connected on the iron plate face of outer container top layer, measures distortion maximum value at this moment.The lateral deflection of casing is measured like this: the deflection before the first determination test, after clear and definite its distributes, in-10 ℃ thermostatic chamber, placed 48 hours, take out immediately with before the test in the thermostatic chamber then and similarly measure deflection, the maximum deformation quantity after deflection difference before and after the evaluation test and the test.
Also expression in table 1 of these results.As known from Table 1, the deflection difference before and after the test is 0.1mm, and maximum deformation quantity is 0.3mm, all is smaller value.
In the refrigerator and refrigerated tank that have formed body of thermal insulating box (this body of thermal insulating box has carried out the foam filling of hard polyurethane foams), assembling freeze cycle parts (compressor/condenser/vaporizer) are measured.The result is that the heat leak amount reduces by 4%, and electric power consumption also reaches every month energy-conservation about 1Kwh.
From this point as seen, the rigid urethane foam of present embodiment, the swell increment during filling is little, and density is low, thermal conductivity is low, compressive strength and dimensional stability are good.In addition, as the adiabatic material filling of refrigerator, can reduce the heat leak amount, reduce power consumption to the rigid urethane foam of present embodiment.In addition, the fill-up of adiabatic material can reduce, thereby reduces the cost of refrigerator.Even place at low temperatures, the distortion of refrigerator is also little, and the refrigerator outward appearance is good.(comparative example 1)
With the polyvalent alcohol A60 part shown in the table 1, polyvalent alcohol C20 part, polyvalent alcohol D20 part, 12 parts of pentamethylene whipping agents, 1.7 parts in water, as catalysts 0.3 part of 1.8 parts of tetramethyl-hexamethylene-diamines, five methyl diethylentriamine, three (3-dimethylamino propylidene), six hydrogen-0.5 part of S-triazine, cooperate as 1.8 parts of organosilicon B-8462 of surfactant.In addition, the '-diphenylmethane diisocyanate polykaryon that is used as isocyanic ester makes its foaming for 140 parts.At this moment the liquid temperature of polyvalent alcohol and isocyanic ester is adjusted in 20 ℃.
Stir earlier polyvalent alcohol and isocyanic ester, in the aluminum mold of 600 * 400 * 75mmt that is adjusted to 40 ℃ of reinjecting, the rate of tamping with 115% and 125% makes the foam molded product demoulding after 5 minutes, the swell increment of mensuration hard polyurethane foams.
Its result is as shown in table 1.As known from Table 1,5 minutes after amounts of the demoulding are 4.9mm when the rate 115% of tamping, and are 5.6mm when the rate 125% of tamping, and swell increment is bigger.
Then, similarly to Example 1, outer container iron plate and interior case with refrigerator and refrigerated tank, after being fixed on the utensil that is used for the urethane foam foaming, the liquid temperature control of polyvalent alcohol and isocyanic ester is made as 20 ℃, the utensil temperature is controlled to be 40 ℃, is filled in the gap hard polyurethane foams and foaming.At this moment, be set in inject volume be about 200 liters casing zero tamp after, the rate of the tamping foam filling with 110% is made into the body of thermal insulating box of refrigerator and refrigerated tank.Bottom central part branch from body of thermal insulating box, take adiabatic material foam sample, estimate sandwich layer density, thermal conductivity, compressive strength, low temperature size changing rate, high temperature size changing rate, carry out the low temperature of body of thermal insulating box again and place (10 ℃/48 hours) test, deflection difference before and after the deformation test of evaluation outer container top layer iron plate and the maximum deformation quantity after the test.
Also expression in table 1 of these results.As known from Table 1, sandwich layer density is 34.5kg/m 3, thermal conductivity is up to 18.5mW/mK, and compressive strength is 0.11MPa, and the low temperature size changing rate is-2.1%, and the high temperature size changing rate is 1.8%, changing value is bigger.
In addition, body of thermal insulating box to refrigerator and refrigerated tank carries out the result that low temperature is placed, and the deflection difference before and after the deformation test of exterior door skin iron plate is 0.22mm, and the maximum deformation quantity after the test is 0.66mm, bigger, on the external door iron plate of body of thermal insulating box, produced distortion.(embodiment 2)
With the polyvalent alcohol A40 part shown in the table 1, polyvalent alcohol B30 part, 28 parts of polyol Es, polyvalent alcohol F2 part, 17 parts of pentamethylene whipping agents, 1.3 parts in water, as catalysts 0.2 part of 1.5 parts of tetramethyl-hexamethylene-diamines, five methyl diethylentriamine, three (3-dimethylamino propylidene), six hydrogen-0.6 part of S-triazine, cooperate as 2.2 parts of organosilicon B-8461 of surfactant.In addition, be used as 135 parts of the '-diphenylmethane diisocyanate polykaryon of isocyanic ester and performed polymer modification tolylene diisocyanates, make its foaming.At this moment the liquid temperature of polyvalent alcohol and isocyanic ester is adjusted in 25 ℃.
Stir earlier polyvalent alcohol and isocyanic ester, in the aluminum mold of 600 * 400 * 75mmt that is adjusted to 40 ℃ of reinjecting, the rate of tamping with 115% and 125% makes the foam molded product demoulding after 5 minutes, the swell increment of mensuration hard polyurethane foams.
Its result is as shown in table 1.As known from Table 1,5 minutes after amounts of the demoulding are 2.4mm when the rate 115% of tamping, and are 2.9mm when the rate 125% of tamping, than adiabatic material reduction in the past.
Then, similarly to Example 1, be fixed to the casing of refrigerator and refrigerated tank on the utensil that is used for the urethane foam foaming after, the liquid temperature control of polyvalent alcohol and isocyanic ester is made as 25 ℃, the utensil temperature is controlled to be 40 ℃, is filled in the gap hard polyurethane foams and foaming.At this moment, set to inject volume be about 200 liters casing zero tamp after, the rate of the tamping foam filling with 115% is made into body of thermal insulating box.From the bottom central part branch of body of thermal insulating box, take adiabatic material foam sample, estimate sandwich layer density, thermal conductivity, compressive strength, low temperature size changing rate, high temperature size changing rate.Carry out the low temperature of body of thermal insulating box again and place (10 ℃/48 hours) test, deflection difference before and after the deformation test of evaluation outer container top layer iron plate and the maximum deformation quantity after the test.
Also expression in table 1 of these results.As known from Table 1, sandwich layer density is 31.8kg/m 3, lower, thermal conductivity is 17.8mW/mK, and is lower, and compressive strength is 0.14MPa, and the low temperature size changing rate is-1.3%, and the high temperature size changing rate is 1.5%, and is smaller.
In addition, the deflection difference before and after the deformation test of the outer container top layer iron plate of body of thermal insulating box is 0.09mm, and the maximum deformation quantity after the test is 0.29mm, is smaller value.In addition, in the refrigerator and refrigerated tank that have formed body of thermal insulating box (this thermal insulator has been carried out the foam filling of hard polyurethane foams), assembling freeze cycle parts (compressor/condenser/vaporizer) are measured.The result is that the heat leak amount reduces by 3%, electric power consumption also reaches every month energy-conservation approximately 1KWh.
From this point as seen, the rigid urethane foam of present embodiment, the swell increment during filling is little, and density is low, thermal conductivity is low, compressive strength and dimensional stability are good.In addition, as the adiabatic material filling of refrigerator, can reduce the heat leak amount, reduce power consumption to the rigid urethane foam of present embodiment.In addition, the fill-up of adiabatic material can reduce, thereby reduces the cost of refrigerator.Even place at low temperatures, the distortion of refrigerator is also little, and the refrigerator outward appearance is good.(comparative example 2)
In 10 parts of the polyvalent alcohol B60 parts shown in the table 1, polyvalent alcohol C10 part, polyvalent alcohol D20 part, polyol E, cooperate 11 parts of pentamethylene whipping agents, 1.4 parts in water, 0.5 part of 1.2 parts of tetramethyl-hexamethylene-diamines, five methyl diethylentriamine, three (3-dimethylamino propylidene), six hydrogen-0.6 part of S-triazine as catalysts, as 1.8 parts of organosilicon B-8462 of surfactant.In addition, be used as the '-diphenylmethane diisocyanate polykaryon of isocyanic ester and the mixture of performed polymer modification tolylene diisocyanate and make its foaming for 137 parts.At this moment the liquid temperature of polyvalent alcohol and isocyanic ester is adjusted in 25 ℃.
Stir earlier polyvalent alcohol and isocyanic ester, in the aluminum mold of 600 * 400 * 75mmt that is adjusted to 40 ℃ of reinjecting, the rate of tamping with 115% and 125% makes the foam molded product demoulding after 5 minutes, the swell increment of mensuration hard polyurethane foams.
Its result is as shown in table 1.As known from Table 1,5 minutes after amounts of the demoulding are 4.1mm when the rate 115% of tamping, and are 5.2mm when the rate 125% of tamping, and swell increment is bigger.
Then, similarly to Example 1, with the outer container iron plate and the interior case of refrigerator and refrigerated tank, after putting into the foaming apparatus of urethane foam, the liquid temperature control of polyvalent alcohol and isocyanic ester is made as 25 ℃, the apparatus temperature is controlled to be 40 ℃, be filled in the gap hard polyurethane foams and foaming.At this moment, be about 200 liters casing with the injection volume, set zero tamp after, the rate of the tamping foam filling with 115% is made into the body of thermal insulating box of refrigerator and refrigerated tank.Bottom central part branch from body of thermal insulating box, take adiabatic material foam sample, estimate sandwich layer density, thermal conductivity, compressive strength, low temperature size changing rate, high temperature size changing rate, carry out the low temperature of body of thermal insulating box again and place (10 ℃/48 hours) test, deflection difference before and after the deformation test of evaluation outer container top layer iron plate and the maximum deformation quantity after the test.
Also expression in table 1 of these results.As known from Table 1, sandwich layer density is 35.2kg/m 3, thermal conductivity is up to 18.8mW/mK, and compressive strength is 0.09MPa, and is lower, and the low temperature size changing rate is-2.3%, and the high temperature size changing rate is 2.2%, changing value is bigger.
In addition, body of thermal insulating box to refrigerator and refrigerated tank carries out the result that low temperature is placed test, and the deflection difference before and after the deformation test of exterior door skin iron plate is 0.16mm, and the maximum deformation quantity after the test is 0.56mm, bigger, on the external door iron plate of body of thermal insulating box, produced distortion.(embodiment 3)
In 20 parts of the polyvalent alcohol A30 parts shown in the table 1, polyvalent alcohol B20 part, polyvalent alcohol C20 part, polyvalent alcohol D10 part, polyol E, cooperate 18 parts of pentamethylene whipping agents, 1.2 parts in water, 0.3 part of 1.7 parts of tetramethyl-hexamethylene-diamines, five methyl diethylentriamine, three (3-dimethylamino propylidene), six hydrogen-0.5 part of S-triazine as catalysts, as 2.2 parts of organosilicon B-8461 of surfactant.In addition, be used as 140 parts of the '-diphenylmethane diisocyanate polykaryon of isocyanic ester and performed polymer modification tolylene diisocyanates, make its foaming.At this moment the liquid temperature of polyvalent alcohol and isocyanic ester is adjusted in 20 ℃.
Stir earlier polyvalent alcohol and isocyanic ester, in the aluminum mold of 600 * 400 * 75mmt that is adjusted to 45 ℃ of reinjecting, the rate of tamping with 115% and 125% makes the foam molded product demoulding after 5 minutes, the swell increment of mensuration hard polyurethane foams.
Its result is as shown in table 1.As known from Table 1,5 minutes after amounts of the demoulding are 2.4mm when the rate 115% of tamping, and are 3.1mm when the rate 125% of tamping, than adiabatic material reduction in the past.
Then, similarly to Example 1, the casing of refrigerator and refrigerated tank is put into the foaming apparatus of urethane foam after, the liquid temperature control of polyvalent alcohol and isocyanic ester is made as 20 ℃, the apparatus temperature is controlled to be 45 ℃, is filled in the gap hard polyurethane foams and foaming.At this moment, be about 200 liters casing with the injection volume, after setting zero was tamped, the rate of the tamping foam filling with 115% was made into body of thermal insulating box.From the bottom central part branch of body of thermal insulating box, take adiabatic material foam sample, estimate sandwich layer density, thermal conductivity, compressive strength, low temperature size changing rate, high temperature size changing rate.Carry out the low temperature of body of thermal insulating box again and place (10 ℃/48 hours) test, deflection difference before and after the deformation test of evaluation outer container top layer iron plate and the maximum deformation quantity after the test.
Also expression in table 1 of these results.As known from Table 1, sandwich layer density is 32.5kg/m 3, lower, thermal conductivity is 17.5mW/mK, and is lower, and compressive strength is 0.13MPa, and than higher, the low temperature size changing rate is-1.1%, and the high temperature size changing rate is 1.4%, and is smaller.
In addition, the deflection difference before and after the deformation test of the outer container top layer iron plate of body of thermal insulating box is 0.07mm, and the maximum deformation quantity after the test is 0.27mm, is smaller value.In addition, in the refrigerator and refrigerated tank that have formed body of thermal insulating box (this thermal insulator has been carried out the foam filling of hard polyurethane foams), assembling freeze cycle parts (compressor/condenser/vaporizer) are measured.The result is that the heat leak amount reduces by 3.5%, electric power consumption also reaches every month energy-conservation approximately 1KWh.
From this point as seen, the rigid urethane foam of present embodiment, the swell increment during filling is little, and density is low, thermal conductivity is low, compressive strength and dimensional stability are good.In addition, as the adiabatic material filling of refrigerator, can reduce the heat leak amount, reduce power consumption to the rigid urethane foam of present embodiment.In addition, the fill-up of adiabatic material can reduce, thereby reduces the cost of refrigerator.Even place at low temperatures, the distortion of refrigerator is also little, and the refrigerator outward appearance is good.(embodiment 4)
In the polyvalent alcohol A45 part shown in the table 1, polyvalent alcohol B15 part, polyvalent alcohol C10 part, polyvalent alcohol D7 part, 20 parts of polyol Es, polyvalent alcohol F3 part, cooperate 16 parts of pentamethylene whipping agents, 1.5 parts in water, 0.3 part of 1.5 parts of tetramethyl-hexamethylene-diamines, five methyl diethylentriamine, three (3-dimethylamino propylidene), six hydrogen-0.5 part of S-triazine, cooperate as 2.2 parts of organosilicon B-8461 of surfactant as catalysts.In addition, be used as 132 parts of the '-diphenylmethane diisocyanate polykaryon of isocyanic ester and performed polymer modification tolylene diisocyanates, make its foaming.At this moment the liquid temperature of polyvalent alcohol and isocyanic ester is adjusted in 20 ℃.
Stir earlier polyvalent alcohol and isocyanic ester, in the aluminum mold of 600 * 400 * 75mmt that is adjusted to 40 ℃ of reinjecting, the rate of tamping with 115% and 125% makes the foam molded product demoulding after 5 minutes, the swell increment of mensuration hard polyurethane foams.
Its result is as shown in table 1.As known from Table 1, the swell increment of the demoulding after 5 minutes is 2.6mm when the rate 115% of tamping, and is 3.2mm when the rate 125% of tamping, than adiabatic material reduction in the past.
Then, similarly to Example 1, the casing of refrigerator and refrigerated tank is put into the foaming apparatus of urethane foam after, the liquid temperature control of polyvalent alcohol and isocyanic ester is made as 20 ℃, the apparatus temperature is controlled to be 40 ℃, is filled in the gap hard polyurethane foams and foaming.At this moment, be about 200 liters casing with the injection volume, after setting zero was tamped, the rate of the tamping foam filling with 110% was made into body of thermal insulating box.From the bottom central part branch of body of thermal insulating box, take adiabatic material foam sample, estimate sandwich layer density, thermal conductivity, compressive strength, low temperature size changing rate, high temperature size changing rate.Carry out the low temperature of body of thermal insulating box again and place (10 ℃/48 hours) test, deflection difference before and after the deformation test of evaluation outer container top layer iron plate and the maximum deformation quantity after the test.
Also expression in table 1 of these results.As known from Table 1, sandwich layer density is 30.5kg/m 3, lower, thermal conductivity is 17.9mW/mK, and is lower, and compressive strength is 0.16MPa, and than higher, the low temperature size changing rate is-0.9%, and the high temperature size changing rate is 1.6%, and is smaller.
In addition, the deflection difference before and after the deformation test of the outer container top layer iron plate of body of thermal insulating box is 0.08mm, and the maximum deformation quantity after the test is 0.29mm, is smaller value.In addition, in the refrigerator and refrigerated tank that have formed body of thermal insulating box (this thermal insulator has been carried out the foam filling of hard polyurethane foams), assembling freeze cycle parts (compressor/condenser/vaporizer) are measured.The result is that the heat leak amount reduces by 3%, electric power consumption also reaches every month energy-conservation approximately 1KWh.
From this point as seen, the rigid urethane foam of present embodiment, the swell increment during filling is little, and density is low, thermal conductivity is low, compressive strength and dimensional stability are good.In addition, as the adiabatic material filling of refrigerator, can reduce the heat leak amount, reduce power consumption to the rigid urethane foam of present embodiment.In addition, the fill-up of adiabatic material can reduce, thereby reduces the cost of refrigerator.Even place at low temperatures, the distortion of refrigerator is also little, and the refrigerator outward appearance is good.(comparative example 3)
To the addition shown in the table 1 toluylenediamine of propylene oxide be cooperate 13 parts of pentamethylene whipping agents, 1.1 parts in water, 0.3 part of 1.8 parts of tetramethyl-hexamethylene-diamines, five methyl diethylentriamine, three (3-dimethylamino propylidene), six hydrogen-0.3 part of S-triazine in polyether glycol A20 part, polyvalent alcohol B30 part, polyvalent alcohol C10 part, polyvalent alcohol D10 part, 20 parts of polyol Es, polyvalent alcohol F10 part as catalysts, as 1.8 parts of organosilyl B-8462 of surfactant.In addition, '-diphenylmethane diisocyanate polykaryon and the performed polymer modification tolylene diisocyanate that is used as isocyanic ester makes its foaming for 135 parts.At this moment the liquid temperature of polyvalent alcohol and isocyanic ester is adjusted in 20 ℃.
Stir earlier polyvalent alcohol and isocyanic ester, in the aluminum mold of 600 * 400 * 75mmt that is adjusted to 45 ℃ of reinjecting, the rate of tamping with 115% and 125% makes the foam molded product demoulding after 5 minutes, the swell increment of mensuration hard polyurethane foams.
Its result is as shown in table 1.As known from Table 1, the swell increment of the demoulding after 5 minutes is 4.5mm when the rate 115% of tamping, and is 5.5mm when the rate 125% of tamping, and swell increment is bigger.
Then, similarly to Example 1, with the outer container iron plate and the interior case of refrigerator and refrigerated tank, after putting into the foaming apparatus of urethane foam, the liquid temperature control of polyvalent alcohol and isocyanic ester is made as 20 ℃, the apparatus temperature is controlled to be 45 ℃, be filled in the gap hard polyurethane foams and foaming.At this moment, be about 200 liters casing with the injection volume, set zero tamp after, the rate of the tamping foam filling with 115% is made into the body of thermal insulating box of refrigerator and refrigerated tank.Bottom central part branch from body of thermal insulating box, take adiabatic material foam sample, estimate sandwich layer density, thermal conductivity, compressive strength, low temperature size changing rate, high temperature size changing rate, carry out the low temperature of body of thermal insulating box again and place (10 ℃/48 hours) test, deflection difference before and after the deformation test of evaluation outer container top layer iron plate and the maximum deformation quantity after the test.
Also expression in table 1 of these results.As known from Table 1, sandwich layer density is 35.8kg/m 3, thermal conductivity is up to 18.3mW/mK, and compressive strength is 0.12MPa, and the low temperature size changing rate is-1.9%, and the high temperature size changing rate is 2.1%, changing value is bigger.
In addition, body of thermal insulating box to refrigerator and refrigerated tank carries out the result that low temperature is placed test, and the deflection difference before and after the deformation test of exterior door skin iron plate is 0.15mm, and the maximum deformation quantity after the test is 0.63mm, bigger, on the external door iron plate of body of thermal insulating box, produced distortion.(embodiment 5)
In 20 parts of the polyvalent alcohol A30 parts shown in the table 1, polyvalent alcohol B20 part, polyvalent alcohol C20 part, polyvalent alcohol D10 part, polyol E, cooperate 14 parts of pentamethylene whipping agents, 1.6 parts in water, 0.3 part of 1.5 parts of tetramethyl-hexamethylene-diamines, five methyl diethylentriamine, three (3-dimethylamino propylidene), six hydrogen-0.5 part of S-triazine as catalysts, as 2.2 parts of organosilyl B-8461 of surfactant.In addition, be used as 140 parts of the '-diphenylmethane diisocyanate polykaryon of isocyanic ester and performed polymer modification tolylene diisocyanates, make its foaming.At this moment the liquid temperature of polyvalent alcohol and isocyanic ester is adjusted in 20 ℃.
Stir earlier polyvalent alcohol and isocyanic ester, in the aluminum mold of 600 * 400 * 75mmt that is adjusted to 40 ℃ of reinjecting, the rate of tamping with 115% and 125% makes the foam molded product demoulding after 5 minutes, the swell increment of mensuration hard polyurethane foams.
Its result is as shown in table 1.As known from Table 1, the swell increment of the demoulding after 5 minutes is 2.4mm when the rate 115% of tamping, and is 2.9mm when the rate 125% of tamping, than adiabatic material reduction before.
Then, similarly to Example 1, the casing of refrigerator and refrigerated tank is put into the foaming apparatus of urethane foam after, the liquid temperature control of polyvalent alcohol and isocyanic ester is made as 20 ℃, the apparatus temperature is controlled to be 40 ℃, is filled in the gap hard polyurethane foams and foaming.At this moment, be about 200 liters casing with the injection volume, after setting zero was tamped, the rate of the tamping foam filling with 110% was made into body of thermal insulating box.From the bottom central part branch of body of thermal insulating box, take adiabatic material foam sample, estimate sandwich layer density, thermal conductivity, compressive strength, low temperature size changing rate, high temperature size changing rate.Carry out the low temperature of body of thermal insulating box again and place (10 ℃/48 hours) test, deflection difference before and after the deformation test of evaluation outer container top layer iron plate and the maximum deformation quantity after the test.
Also expression in table 1 of these results.As known from Table 1, sandwich layer density is 32kg/m 3, lower, thermal conductivity is 18mW/mK, and is lower, and compressive strength is 0.12MPa, and than higher, the low temperature size changing rate is-0.8%, and the high temperature size changing rate is 1.5%, and is smaller.
In addition, the deflection difference before and after the deformation test of the outer container top layer iron plate of body of thermal insulating box is 0.09mm, and the maximum deformation quantity after the test is 0.26mm, is smaller value.
In addition, in the refrigerator and refrigerated tank that have formed body of thermal insulating box (this thermal insulator has been carried out the foam filling of hard polyurethane foams), assembling freeze cycle parts (compressor/condenser/vaporizer) are measured.The result is that the heat leak amount reduces by 4%, electric power consumption also reaches every month energy-conservation approximately 1KWh.
From this point as seen, the rigid urethane foam of present embodiment, the swell increment during filling is little, and low density, thermal conductivity are low, compressive strength and dimensional stability are good.In addition, as the adiabatic material filling of refrigerator, can reduce the heat leak amount, reduce power consumption to the rigid urethane foam of present embodiment.In addition, the fill-up of adiabatic material can reduce, thereby reduces the cost of refrigerator.Even place at low temperatures, the distortion of refrigerator is also little, and the refrigerator outward appearance is good.(comparative example 4)
The toluylenediamine that has added propylene oxide shown in the table 1 is polyether glycol A25 part, polyvalent alcohol B35 part, polyvalent alcohol C20 part, polyvalent alcohol D10 part, polyvalent alcohol F5 part, 14 parts of pentamethylene whipping agents, 1.0 parts in water, 0.5 part of 1.2 parts of tetramethyl-hexamethylene-diamines, five methyl diethylentriamine as catalysts, three (3-dimethylamino propylidene), six hydrogen-0.5 part of S-triazine, cooperates as 1.8 parts of organosilyl B-8462 of surfactant.In addition, '-diphenylmethane diisocyanate polykaryon and the performed polymer modification tolylene diisocyanate that is used as isocyanic ester makes its foaming for 140 parts.At this moment the liquid temperature of polyvalent alcohol and isocyanic ester is adjusted in 20 ℃.
Stir earlier polyvalent alcohol and isocyanic ester, in the aluminum mold of 600 * 400 * 75mmt that is adjusted to 40 ℃ of reinjecting, the rate of tamping with 115% and 125% makes the foam molded product demoulding after 5 minutes, the swell increment of mensuration hard polyurethane foams.
Its result is as shown in table 1.As known from Table 1, the swell increment of the demoulding after 5 minutes is 4.8mm when the rate 115% of tamping, and is 5.7mm when the rate 125% of tamping, and swell increment is bigger.
Then, similarly to Example 1, with the outer container iron plate and the interior case of refrigerator and refrigerated tank, after putting into the foaming apparatus of urethane foam, the liquid temperature control of polyvalent alcohol and isocyanic ester is made as 20 ℃, the apparatus temperature is controlled to be 40 ℃, be filled in the gap hard polyurethane foams and foaming.At this moment, be about 200 liters casing with the injection volume, set zero tamp after, the rate of the tamping foam filling with 115% is made into the body of thermal insulating box of refrigerator and refrigerated tank.Bottom central part branch from body of thermal insulating box, take adiabatic material foam sample, estimate sandwich layer density, thermal conductivity, compressive strength, low temperature size changing rate, high temperature size changing rate, carry out the low temperature of body of thermal insulating box again and place (10 ℃/48 hours) test, deflection difference before and after the deformation test of evaluation outer container top layer iron plate and the maximum deformation quantity after the test.
Also expression in table 1 of these results.As known from Table 1, sandwich layer density is 35.5kg/m 3, thermal conductivity is up to 18.4mW/mK, and compressive strength is 0.11MPa, and is lower, and the low temperature size changing rate is-1.8%, and the high temperature size changing rate is 1.9%, changing value is bigger.
In addition, body of thermal insulating box to refrigerator and refrigerated tank carries out the result that low temperature is placed test, and the deflection difference before and after the deformation test of exterior door skin iron plate is 0.19mm, and the maximum deformation quantity after the test is 0.58mm, bigger, on the external door iron plate of body of thermal insulating box, produced distortion.(embodiment 6)
With the polyvalent alcohol A40 part shown in the table 1, polyvalent alcohol B23 part, polyvalent alcohol C15 part, polyvalent alcohol D5 part, 15 parts of polyol Es, polyvalent alcohol F2 part, 15 parts of pentamethylene whipping agents, 1.4 parts in water, as catalysts 0.2 part of 1.5 parts of tetramethyl-hexamethylene-diamines, five methyl diethylentriamine, three (3-dimethylamino propylidene), six hydrogen-0.4 part of S-triazine, cooperate as 2.2 parts of organosilyl B-8461 of surfactant.In addition, be used as 135 parts of the '-diphenylmethane diisocyanate polykaryon of isocyanic ester and performed polymer modification tolylene diisocyanates, make its foaming.At this moment the liquid temperature of polyvalent alcohol and isocyanic ester is adjusted in 20 ℃.
Stir earlier polyvalent alcohol and isocyanic ester, in the aluminum mold of 600 * 400 * 75mmt that is adjusted to 45 ℃ of reinjecting, the rate of tamping with 115% and 125% makes the foam molded product demoulding after 5 minutes, the swell increment of mensuration hard polyurethane foams.
Its result is as shown in table 1.As known from Table 1, the swell increment of the demoulding after 5 minutes is 2.6mm when the rate 115% of tamping, and is 3.1mm when the rate 125% of tamping, than adiabatic material reduction before.
Then, similarly to Example 1, the casing of refrigerator and refrigerated tank is put into the foaming apparatus of urethane foam after, the liquid temperature control of polyvalent alcohol and isocyanic ester is made as 20 ℃, the apparatus temperature is controlled to be 45 ℃, is filled in the gap hard polyurethane foams and foaming.At this moment, be about 200 liters casing with the injection volume, after setting zero was tamped, the rate of the tamping foam filling with 115% was made into body of thermal insulating box.From the bottom central part branch of body of thermal insulating box, take adiabatic material foam sample, estimate sandwich layer density, thermal conductivity, compressive strength, low temperature size changing rate, high temperature size changing rate.Carry out the low temperature of body of thermal insulating box again and place (10 ℃/48 hours) test, deflection difference before and after the deformation test of evaluation outer container top layer iron plate and the maximum deformation quantity after the test.
Also expression in table 1 of these results.As known from Table 1, sandwich layer density is 31.5kg/m 3, lower, thermal conductivity is 17.9mW/mK, and is lower, and compressive strength is 0.15MPa, and than higher, the low temperature size changing rate is-1.2%, and the high temperature size changing rate is 1.3%, and is smaller.
In addition, the deflection difference before and after the deformation test of the outer container top layer iron plate of body of thermal insulating box is 0.08mm, and the maximum deformation quantity after the test is 0.27mm, is smaller value.
In addition, in the refrigerator and refrigerated tank that have formed body of thermal insulating box (this thermal insulator has been carried out the foam filling of hard polyurethane foams), assembling freeze cycle parts (compressor/condenser/vaporizer) are measured.The result is that the heat leak amount reduces by 3%, electric power consumption also reaches every month energy-conservation approximately 1KWh.
From this point as seen, the rigid urethane foam of present embodiment, the swell increment during filling is little, and low density, thermal conductivity are low, compressive strength and dimensional stability are good.In addition, as the adiabatic material filling of refrigerator, can reduce the heat leak amount, reduce power consumption to the rigid urethane foam of present embodiment.In addition, the fill-up of adiabatic material can reduce, thereby reduces the cost of refrigerator.Even place at low temperatures, the distortion of refrigerator is also little, and the refrigerator outward appearance is good.(embodiment 7)
With the polyvalent alcohol A40 part shown in the table 1, polyvalent alcohol B20 part, polyvalent alcohol C20 part, polyvalent alcohol D10 part, 10 parts of polyol Es, 16 parts of pentamethylene whipping agents, 1.5 parts in water, as catalysts 0.3 part of 1.5 parts of tetramethyl-hexamethylene-diamines, five methyl diethylentriamine, three (3-dimethylamino propylidene), six hydrogen-0.5 part of S-triazine, cooperate as 2.2 parts of organosilyl B-8461 of surfactant.In addition, be used as 140 parts of the '-diphenylmethane diisocyanate polykaryon of isocyanic ester and performed polymer modification tolylene diisocyanates, make its foaming.At this moment the liquid temperature of polyvalent alcohol and isocyanic ester is adjusted in 20 ℃.
Stir earlier polyvalent alcohol and isocyanic ester, in the aluminum mold of 600 * 400 * 75mmt that is adjusted to 45 ℃ of reinjecting, the rate of tamping with 115% and 125% makes the foam molded product demoulding after 5 minutes, the swell increment of mensuration hard polyurethane foams.
Its result is as shown in table 1.As known from Table 1, the swell increment of the demoulding after 5 minutes is 2.3mm when the rate 115% of tamping, and is 2.8mm when the rate 125% of tamping, than adiabatic material reduction before.
Then, similarly to Example 1, the casing of refrigerator and refrigerated tank is put into the foaming apparatus of urethane foam after, the liquid temperature control of polyvalent alcohol and isocyanic ester is made as 20 ℃, the apparatus temperature is controlled to be 45 ℃, is filled in the gap hard polyurethane foams and foaming.At this moment, be about 200 liters casing with the injection volume, after setting zero was tamped, the rate of the tamping foam filling with 110% was made into body of thermal insulating box.From the bottom central part branch of body of thermal insulating box, take adiabatic material foam sample, estimate sandwich layer density, thermal conductivity, compressive strength, low temperature size changing rate, high temperature size changing rate.Carry out the low temperature of body of thermal insulating box again and place (10 ℃/48 hours) test, deflection difference before and after the deformation test of evaluation outer container top layer iron plate and the maximum deformation quantity after the test.
Also expression in table 1 of these results.As known from Table 1, sandwich layer density is 32.9kg/m 3, lower, thermal conductivity is 17.8mW/mK, and is lower, and compressive strength is 0.14MPa, and than higher, the low temperature size changing rate is-1.4%, and the high temperature size changing rate is 1.1%, and is smaller.
In addition, the deflection difference before and after the deformation test of the outer container top layer iron plate of body of thermal insulating box is 0.07mm, and the maximum deformation quantity after the test is 0.29mm, is smaller value.
In addition, in the refrigerator and refrigerated tank that have formed body of thermal insulating box (this thermal insulator has been carried out the foam filling of hard polyurethane foams), assembling freeze cycle parts (compressor/condenser/vaporizer) are measured.The result is that the heat leak amount reduces by 3%, electric power consumption also reaches every month energy-conservation approximately 1KWh.
From this point as seen, the rigid urethane foam of present embodiment, the swell increment during filling is little, and low density, thermal conductivity are low, compressive strength and dimensional stability are good.In addition, as the adiabatic material filling of refrigerator, can reduce the heat leak amount, reduce power consumption to the rigid urethane foam of present embodiment.In addition, the fill-up of adiabatic material can reduce, thereby reduces the cost of refrigerator.Even place at low temperatures, the distortion of refrigerator is also little, and the refrigerator outward appearance is good.
According to the present invention, can provide to prevent refrigerator surface deformation, that outward appearance is good.

Claims (4)

1. refrigerator, in the space between outer container and interior case, the adiabatic material of rigid urethane foam in filling, and this rigid urethane foam has adopted polyvalent alcohol, aromatic isocyanate and at least as the pentamethylene of whipping agent and the mixed foaming agent of water; It is characterized in that, in this rigid urethane foam,, contain the mixture of ingredients more than 3 kinds that in the initiator that is made of toluylenediamine and ortho-toluene diamine addition of ethylene oxide and/or propylene oxide obtain as polyhydroxy reactant.
2. refrigerator as claimed in claim 1, it is characterized in that, the polyhydroxy reactant of above-mentioned rigid urethane foam is a polyether glycol, wherein contain the initiator that constitutes with toluylenediamine, ortho-toluene diamine, dihydroxyphenyl propane, trolamine more than 90% and cause the mixture that oxyethane and/or propylene oxide addition obtain, from the distance urethane inlet planar section more than the 500mm at least, the density that thickness is about the adiabatic material of sandwich layer of 20～25mm is 29～33kg/m 3, thermal conductivity is 17.5～18.0mW/mK when 10 ℃ of medial temperatures.
3. refrigerator as claimed in claim 2, it is characterized in that, the aromatic isocyanate composition of above-mentioned rigid urethane foam, employing has the mixture of performed polymer modification tolylene diisocyanate in the '-diphenylmethane diisocyanate polykaryon, use the mixed foaming agent that has made up 1.2～1.6 weight parts waters and 14～18 weight part pentamethylene in 100 weight part polyvalent alcohols to make its reaction.
4. refrigerator as claimed in claim 2, it is characterized in that, the polyhydroxy reactant of above-mentioned rigid urethane foam is the mixture that is made of following composition: on toluylenediamine addition polyvalent alcohol 44～55 weight parts of the OH value 400～500 that obtains of propylene oxide and oxyethane and propylene oxide, on ortho-toluene diamine addition polyvalent alcohol 10～20 weight parts of the OH value 450～500 that obtains of propylene oxide and oxyethane, on trolamine addition polyvalent alcohol 10～20 weight parts of the OH value 350～450 that obtains of propylene oxide, on dihydroxyphenyl propane addition polyvalent alcohol 10～20 weight parts of the OH value 250～300 that obtains of propylene oxide, on diethanolamine addition polyvalent alcohol 3～8 weight parts of the OH value 450～480 that obtains of propylene oxide, the TriMethylolPropane(TMP) OH value 1256 of 2～5 weight parts, the average OH value of this polyvalent alcohol is 400～450.
CNB001269402A 1999-11-05 2000-09-08 Electric refrigerator Expired - Fee Related CN1133676C (en)

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CN104558482A (en) * 2013-10-10 2015-04-29 日立空调·家用电器株式会社 Tank unit, hot water supply system and foaming heat insulation materials
CN104662059A (en) * 2012-09-27 2015-05-27 巴斯夫欧洲公司 Rigid polyurethane and polyisocyanurate foams based on fatty acid-modified polyether polyols
CN105218713A (en) * 2014-05-27 2016-01-06 中国石油化工集团公司 A kind of polyvinyl alcohol and its production and use
CN107177028A (en) * 2017-06-13 2017-09-19 合肥华凌股份有限公司 Combined polyether, polyurethane foam and its preparation method and application
CN109251304A (en) * 2018-08-23 2019-01-22 合肥金菱电器有限公司 A kind of flame-retardant polyurethane foam plastic and preparation method thereof
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CN1325864C (en) * 2002-03-13 2007-07-11 松下冷机株式会社 Refrigerator
CN104662059A (en) * 2012-09-27 2015-05-27 巴斯夫欧洲公司 Rigid polyurethane and polyisocyanurate foams based on fatty acid-modified polyether polyols
CN104662059B (en) * 2012-09-27 2016-12-14 巴斯夫欧洲公司 Hard polyaminoester based on fatty acid modified polyether polyol and polyisocyanurate foam
CN104558482A (en) * 2013-10-10 2015-04-29 日立空调·家用电器株式会社 Tank unit, hot water supply system and foaming heat insulation materials
CN105218713A (en) * 2014-05-27 2016-01-06 中国石油化工集团公司 A kind of polyvinyl alcohol and its production and use
CN111219932A (en) * 2014-06-02 2020-06-02 东芝生活电器株式会社 Refrigerator with a door
CN107177028A (en) * 2017-06-13 2017-09-19 合肥华凌股份有限公司 Combined polyether, polyurethane foam and its preparation method and application
CN109251304A (en) * 2018-08-23 2019-01-22 合肥金菱电器有限公司 A kind of flame-retardant polyurethane foam plastic and preparation method thereof

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KR100354637B1 (en) 2002-09-30

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