CN104558482A - Tank unit, hot water supply system and foaming heat insulation materials - Google Patents

Tank unit, hot water supply system and foaming heat insulation materials Download PDF

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Publication number
CN104558482A
CN104558482A CN201410387474.6A CN201410387474A CN104558482A CN 104558482 A CN104558482 A CN 104558482A CN 201410387474 A CN201410387474 A CN 201410387474A CN 104558482 A CN104558482 A CN 104558482A
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CN
China
Prior art keywords
active hydrogen
contg compound
thermal insulation
foaminess
groove
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201410387474.6A
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Chinese (zh)
Inventor
井关崇
伏木隆之
荒木邦成
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Hitachi Appliances Inc
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Hitachi Appliances Inc
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Filing date
Publication date
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Publication of CN104558482A publication Critical patent/CN104558482A/en
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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
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6633—Compounds of group C08G18/42
    • C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6648—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38
    • C08G18/6651—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3225 or polyamines of C08G18/38
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4205—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups
    • C08G18/4208—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups
    • C08G18/4211—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups derived from aromatic dicarboxylic acids and dialcohols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6633—Compounds of group C08G18/42
    • C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/664—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
    • C08G18/6644—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203 having at least three hydroxy groups
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F24—HEATING; RANGES; VENTILATING
    • F24H—FLUID HEATERS, e.g. WATER OR AIR HEATERS, HAVING HEAT-GENERATING MEANS, e.g. HEAT PUMPS, IN GENERAL
    • F24H4/00—Fluid heaters characterised by the use of heat pumps
    • F24H4/02—Water heaters
    • F24H4/04—Storage heaters
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F24—HEATING; RANGES; VENTILATING
    • F24H—FLUID HEATERS, e.g. WATER OR AIR HEATERS, HAVING HEAT-GENERATING MEANS, e.g. HEAT PUMPS, IN GENERAL
    • F24H9/00—Details
    • F24H9/20—Arrangement or mounting of control or safety devices
    • F24H9/2007—Arrangement or mounting of control or safety devices for water heaters
    • 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
    • C08G2110/00—Foam properties
    • C08G2110/0025—Foam properties rigid

Abstract

The invention provides a tank unit with high heat insulation performance and long-term reliability, a hot water supply system and foaming heat insulation materials. The tank unit is provided with a tank for storing liquid, a box body storing the tank and the foaming heat insulation materials arranged between the tank and the box body. Rigid polyurethane foam is used as the foaming heat insulation materials and comprises first activated hydrogen compound wherein the cardinal number of activated hydrogen is 5-8, second activated hydrogen compound wherein the cardinal number of activated hydrogen is 4, and polyester polyol with ester groups and 2-3 functional groups.

Description

Groove unit, hot-water supply system and foaminess thermal insulation material
Technical field
The present invention relates to a kind of groove unit (tank unit), the hot-water supply system possessing groove unit and foaminess thermal insulation material.
Background technology
Hot-water storage type (storage Soup formula) water heater in the past, such as, as as shown in patent documentation 1 (Japanese Unexamined Patent Publication 2011-106791 publication), possess the hot-water storage groove (storage Soup タ Application Network) of storage hot water, cover the outer cover of the formed heat-insulating material of the periphery of hot water storagetank and the periphery of covering formed heat-insulating material.In addition, there will be a known the hot-water storage pond (storage Soup groove) of the foaminess thermal insulation materials such as the injection polyurathamc shown in patent documentation 2 (Japanese Laid-Open Patent Publication 58-160758 publication) as thermal insulation material.In addition, hot-water storage type water heater (hot-water storage groove) is arranged on exposed field usually.
Prior art document
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 2011-106791 publication
Patent documentation 2: Japanese Laid-Open Patent Publication 58-160758 publication
Summary of the invention
The problem that invention will solve
As Patent Document 1, hot-water storage type water heater is in the past that (thermal conductivity is 0.042W/mK by divided glass cotton; It should be noted that, thermal conductivity is with reference to " ' feature of hard polyurethane foams '; [online]; Japanese polyurethane TIA; [Heisei retrieval on October 3rd, 25], internet<URL:http: //www.urethane-jp.org/qa/koushitsu/k-1.htm> ".For the explanation of following thermal conductivity, be also same.), the formed heat-insulating material of polystyrene system (thermal conductivity is 0.034W/mK) is chimeric uses.But, when chimeric multi-disc formed heat-insulating material is used as the thermal insulation material of hot-water storage groove, produces space (gap) at the fitting portion of formed heat-insulating material, cause heat leak to increase due to this gap, sometimes cannot obtain the heat-insulating property of imagination.
In addition, in order to improve heat-insulating property be combined vacuum heat insulation materials time, the outer wall of the hot-water storage groove be made up of curved surface is pasted the vacuum heat insulation materials of tabular.At this moment, causing vacuum heat insulation materials to peel off from the outer wall of hot-water storage groove to prevent the vacuum heat insulation materials of tabular being arranged on the buckling force that curved surface produces, using double sticky tape, caking agent etc. to be pasted onto on the outer wall of hot-water storage groove by vacuum heat insulation materials.Therefore, the man-hour that the stickup of double sticky tape, the coating of caking agent etc. are more is needed.
In addition, in formation on the inwall by formed heat-insulating material vacuum heat insulation materials being withstood on the outer wall of hot-water storage groove, outer cover, space (gap) is created between the low vacuum heat insulation materials of flexibility and the low formed heat-insulating material of flexibility, cause heat leak to increase due to this gap, sometimes cannot obtain the heat-insulating property of imagination.
In addition, as shown in patent documentation 2, be filled with the hot-water storage type water heater (hot-water storage groove) in the past of the foaminess thermal insulation materials such as urethane (thermal conductivity is 0.29W/mK), owing to being stored in the hot water mitigation in hot-water storage groove, the temperature environment that urethane itself exposes maximum up to 90 DEG C ~ about 100 DEG C.Like this, under urethane is exposed on the temperature environment of high temperature, therefore, be sealed in the whipping agent gasification in urethane and replace with ambient atmos.Thus, in the foamed cell of urethane, pressure changes, and becomes the reason of heat-insulating property variation, foamed cell (urethane itself) strength degradation.Like this, using when being used as the thermal insulation material of hot-water storage type water heater (hot-water storage groove) as the polyurathamc of foaminess thermal insulation material, long-term reliability aspect has problems.
Therefore, problem of the present invention is to provide a kind of heat-insulating property excellence, the groove unit with long-term reliability, hot-water supply system and foaminess thermal insulation material.
The method of dealing with problems
In order to address these problems, the feature of groove unit of the present invention is, possess the groove of storing liquid, receive the casing of described groove and be arranged on the foaminess thermal insulation material between described groove and described casing, use hard polyurethane foams as described foaminess thermal insulation material, described hard polyurethane foams comprise hydroxyl value be 5 ~ 8 the 1st active hydrogen-contg compound, hydroxyl value be 4 the 2nd active hydrogen-contg compound and have ester group, functional group number is the polyester polyol of 2 ~ 3.
In addition, the feature of hot-water supply system of the present invention is, possesses described groove unit.
In addition, the feature of foaminess thermal insulation material of the present invention is, possess hard polyurethane foams and formed, and described hard polyurethane foams comprise hydroxyl value be 5 ~ 8 the 1st active hydrogen-contg compound, hydroxyl value be 4 the 2nd active hydrogen-contg compound and have ester group, functional group number is the polyester polyol of 2 ~ 3.
Invention effect
According to the present invention, a kind of heat-insulating property excellence, the groove unit with long-term reliability, hot-water supply system and foaminess thermal insulation material can be provided.
Accompanying drawing explanation
Fig. 1 is the structure iron of the hot-water supply system S of present embodiment.
Fig. 2 is the figure of the groove unit TU that present embodiment is described, a () is front view, b () is side-view, the X-X line sectional view that (c) is Fig. 1 (b), the Y-Y line sectional view that (d) is Fig. 1 (a).
Fig. 3 is the decomposition diagram of the groove unit TU of present embodiment.
Fig. 4 is the Z-Z line sectional view of Fig. 1 (a) of the groove unit TU of present embodiment.
Fig. 5 is the skeleton view of the body of thermal insulating box that the groove unit TU of present embodiment possesses.
Fig. 6 is the drawing in side sectional elevation of the body of thermal insulating box that the groove unit TU of present embodiment possesses.
Fig. 7 is the mode chart of the configuration representing foaminess thermal insulation material and vacuum heat insulation materials, a () (b) is the 1st configuration, c () (d) is the 2nd configuration, and, a () (c) is the Z-Z line profile schema diagram of Fig. 1 (a), (b) (d) is the Y-Y line profile schema diagram of Fig. 1 (a).
Fig. 8 is the partial magnified sectional view near the inlet of body of thermal insulating box, and (a) represents the state before filling-foam thermal insulation material, and (b) represents the state after filling-foam thermal insulation material.
Fig. 9 (a) is the outside side view of body of thermal insulating box, and (b) is the drawing in side sectional elevation near the inlet of body of thermal insulating box.
Nomenclature
S: hot-water supply system's (heat pump-type hot-water supply device); TU: groove unit (hot-water storage type water heater); HPU: heat pump unit; 1: groove (hot-water storage groove); 2: outside plate; 3: outside plate; 4: outside plate; 5: dividing plate; 6: be connected and installed plate; 7,8: top board accessory plate; 9: top board; 10: base plate; 11: inner support; 12: outer support; 13: mechanical(superphosphate)den; 14: thermal-insulating chamber; 15: body of thermal insulating box; 16: foaminess thermal insulation material (hard polyurethane foams); 17: vacuum heat insulation materials; 18: inlet; 19: thermal insulation material anti-leak seal; 20: venting port; 50: thermal insulation material injection nozzle; 101: reducing valve; 102: hot water supply mixing valve; 103: bathing pool mixing valve; 104: hot water filling magnetic valve; 105: reheat interchanger; 106,107: pump; 108: frost-proof triple valve; 109: safety valve; 110: main control unit; 111: compressor; 112: water refrigerant heat exchanger; 113: expansion valve; 114: air-making cryogen interchanger; 115: fan; 116: pump; 117:HPU control device; 118,119: telemanipulator; 121: water supply piping; 122: hot water supply pipe arrangement; 123,124: bathing pool pipe arrangement; 125: water inlet pipe arrangement; 126: hot water exports pipe arrangement.
Embodiment
Below, with reference to suitable accompanying drawing, while be described in detail to enforcement mode of the present invention (hereinafter referred to as " embodiment ").It should be noted that, in the various figures, common part gives identical symbol, and the repetitive description thereof will be omitted.
Hot-water supply system S
Hot-water supply system (heat pump-type hot-water supply device) S of Fig. 1 to present embodiment is used to be described.Fig. 1 is the structure iron of the hot-water supply system S of present embodiment.
Hot-water supply system S possesses groove unit (hot-water storage type water heater) TU of the groove (hot-water storage groove) 1 with storage hot water, the heat pump unit HPU heating the hot water be stored in groove 1 and telemanipulator 118,119.It should be noted that, groove 1 is covered by thermal insulation material described later (vacuum heat insulation materials 17 shown in the foaminess thermal insulation material 16 shown in Fig. 2 etc., Fig. 7).
Groove unit TU possesses groove 1, reducing valve 101, hot water supply mixing valve 102, bathing pool mixing valve 103, hot water filling magnetic valve (Soup は り Electricity magnetic man's cap used in ancient times) 104, reheats interchanger (chase after い だ I Hot and hand over Change device) 105, pump 106, pump 107, frost-proof triple valve 108, safety valve 109 and main control unit 110.
Heat pump unit HPU possesses compressor 111, water refrigerant heat exchanger 112, expansion valve 113, air-making cryogen interchanger 114, fan 115, pump 116 and HPU control device 117.
Use refrigerant piping by compressor 111, refrigerant side heat exchanger tube, expansion valve 113 as the water refrigerant heat exchanger 112 of condenser, connect for ring-type successively as the air-making cryogen interchanger 114 of vaporizer, form heat pump loop (freezing loop).Fan 115, by sending into air (ambient atmos) in air-making cryogen interchanger 114, facilitates the heat exchange of refrigeration agent and air (ambient atmos) in air-making cryogen interchanger 114.Here, such as CO can be used 2refrigeration agent is as refrigeration agent.
Main control unit 110 is connected with HPU control device 117 and telemanipulator 118,119 in the mode that can communicate.Telemanipulator 118,119 has input part (not shown), when user's (not shown) operation inputting part thus the running setting of input hot-water supply system S time, running setting signal is output to main control unit 110.Main control unit 110 by control hot water supply mixing valve 102, bathing pool mixing valve 103, hot water filling magnetic valve 104, pump 106,107, the running of frost-proof triple valve 108 and control flume unit TU.In addition, main control unit 110 is to HPU control device 117 output order.HPU control device 117, according to the running of the instruction control compressor 111 of main control unit 110, fan 115, pump 116, controls the running of heat pump unit HPU thus.As mentioned above, main control unit 110 based on the running setting inputted by telemanipulator 118,119, can control the overall operation of hot-water supply system S.
One end of water supply piping 121 is connected to groove unit TU, and the other end is connected to water-supply source (not shown).One end of hot water supply pipe arrangement 122 is connected to groove unit TU, and the other end is connected to the fire hose first-class hot water supply terminal (not shown).One end of bathing pool pipe arrangement 123,124 is connected to groove unit TU, and the other end is connected to the bathing pool terminal (not shown) of having installed bathing pool (not shown).Pipe arrangement 125,126 connective slot unit TU and heat pump unit HPU.
Then, for hot-water supply system S carry out various running time the action of hot-water supply system S and the flowing of hot water be described.
< boiling running >
First, boiling running is described.Main control unit 110 sends instruction to HPU control device 117, and come to life running.The HPU control device 117 accepting instruction makes compressor 111 and fan 115 run, thus heat pump loop is run.In addition, HPU control device 117 makes pump 116 run.
By making compressor 111 run, the high-temperature high-pressure refrigerant spued from compressor 111 flow into the first side of water refrigerant heat exchanger 112.In addition, by the operation of pump 116, the water at low temperature being stored in groove 1 bottom flow into the second side of water refrigerant heat exchanger 112 by water inlet pipe arrangement 125.Carry out heat exchange by the high-temperature high-pressure refrigerant flowing into the first side of water refrigerant heat exchanger 112 with the water at low temperature flowing into the second side, the water at low temperature of the second side is heated, and becomes high-temperature water.The high-temperature water heated by water refrigerant heat exchanger 112 is exported pipe arrangement 126 by hot water and flows into and be stored in the top of groove 1.In addition, the high-pressure refrigerant of the first side of heat release has been carried out by expansion valve 113 adiabatic expansion by water refrigerant heat exchanger 112, form low-temperature low-pressure refrigerant, carry out heat exchange by air-making cryogen interchanger 114 and air and absorb heat, again flowing in compressor 111.As mentioned above, the hot water the running be stored in by high-temperature-hot-water (high-temperature water) in groove 1 that are stored in groove 1 are heated in boiling running.In addition, to be heated by heat pump unit HPU (water refrigerant heat exchanger 112) and the temperature (hot water outlet temperature) flowing into the high-temperature-hot-water (high-temperature water) on groove 1 top is the temperature of 90 DEG C ~ about 100 DEG C to the maximum.
In addition, when be connected in the pipeline of groove 1, groove 1 produce abnormal pressure time, hot water volume expand because of heating time, hot water is discharged automatically by safety valve 109, ensure that the security of groove 1 internal pressure.
< antifreeze running >
Then, antifreeze running is described.Main control unit 110 switches frost-proof triple valve 108, thus be formed in water supply piping 125, stream that pump 116, the second side of water refrigerant heat exchanger 112, hot water export circulation between pipe arrangement 126, frost-proof triple valve 108.In addition, main control unit 110 sends instruction to HPU control device 117, and the HPU control device 117 accepting instruction makes compressor 111 and fan 115 run, thus heat pump loop is run.In addition, HPU control device 117 makes pump 116 run.Thus, can make to be exported in pipe arrangement 126 and water inlet pipe arrangement 125 circulation by the high-temperature water heated at hot water by water refrigerant heat exchanger 112, thus freezing of pipe arrangement 125,126 can be prevented.
< hot water supply running >
Then, hot water supply running is described.When opening water tap (not shown) that be connected to hot water supply pipe arrangement 122, due to the pipeline pressure of water-supply source (not shown), normal-temperature water flows into groove unit TU from water supply piping 121.The normal-temperature water flowed into is reduced pressure by reducing valve 101, and a part of normal-temperature water flow into the bottom of groove 1.Flow into normal-temperature water by the bottom from groove 1, the high-temperature water be stored in groove 1 is depressed into top, flow into a side of hot water supply mixing valve 102 from the top of groove 1.In addition, remaining normal-temperature water reduced pressure by reducing valve 101 flow into the opposing party of hot water supply mixing valve 102.The high-temperature water flowed into from the top of groove 1 and adjust ratio of mixture by hot water supply mixing valve 102 from the normal-temperature water that reducing valve 101 flows into, forms the hot water of hot water supply temperature, and is supplied to water tap (not shown) by hot water supply pipe arrangement 122.
< hot water fills running >
Then, fill running to hot water to be described.Hot water filling magnetic valve 104 opened by main control unit 110.When hot water filling magnetic valve 104 is opened, due to the pipeline pressure of water-supply source (not shown), normal-temperature water flows into groove unit TU from water supply piping 121.The normal-temperature water flowed into is reduced pressure by reducing valve 101, and a part of normal-temperature water flow into the bottom of groove 1.Flow into normal-temperature water by the bottom from groove 1, the high-temperature water be stored in groove 1 is depressed into top, flow into a side of bathing pool mixing valve 103 from the top of groove 1.In addition, remaining normal-temperature water reduced pressure by reducing valve 101 flow into the opposing party of bathing pool mixing valve 103.The high-temperature water flowed into from the top of groove 1 and adjust ratio of mixture by bathing pool mixing valve 103 from the normal-temperature water that reducing valve 101 flows into, forms the hot water of shower temperature, and is supplied to bathing pool (not shown) by bathing pool pipe arrangement 123.
< reheats running >
Then, be described reheating running.Main control unit 110 makes pump 106,107 run.By the operation of pump 106, the high-temperature water being stored in groove 1 top flow into the first side reheating interchanger 105.In addition, by the operation of pump 107, the bathing pool water of bathing pool (not shown) flow into the second side reheating interchanger 105 by bathing pool pipe arrangement 123.Carry out heat exchange by the high-temperature water flowing into the first side reheating interchanger 105 with the bathing pool water flowing into the second side, bathing pool water is heated.Turned back in bathing pool (not shown) by bathing pool pipe arrangement 124 by the bathing pool water heated by reheating interchanger 105.In addition, carry out warm water in the first side of heat release by reheating interchanger 105 and turn back to the middle part of groove 1.
Groove unit TU
Then, the structure of Fig. 2 to Fig. 6 to the groove unit TU of present embodiment is used to be described.Fig. 2 is the figure of the groove unit TU that present embodiment is described, a () is front view, b () is side-view, the X-X line sectional view that (c) is Fig. 1 (b), the Y-Y line sectional view that (d) is Fig. 1 (a).Fig. 3 is the decomposition diagram of the groove unit TU of present embodiment.Fig. 4 is the Z-Z line sectional view of Fig. 1 (a) of the groove unit TU of present embodiment.Fig. 5 is the skeleton view of the body of thermal insulating box 15 that the groove unit TU of present embodiment possesses.Fig. 6 is the drawing in side sectional elevation of the body of thermal insulating box 15 that the groove unit TU of present embodiment possesses.It should be noted that, Fig. 3, Fig. 4 and Fig. 6 represent the state before filling-foam thermal insulation material 16.
As shown in Figures 2 to 4, groove unit TU possesses the storage groove (hot-water storage groove) 1 of hot water and the outer cover of accommodating groove 1.As shown in Figure 3, the outer cover of groove unit TU possess outside plate 2,3,4, dividing plate 5, be connected and installed plate 6, top board accessory plate 7,8, top board 9, base plate 10, inner support 11 and outer support 12.
In addition, as shown in Fig. 2 (d) He Fig. 4, the internal space of groove unit TU outer cover is divided into mechanical(superphosphate)den 13 and thermal-insulating chamber 14 by dividing plate 5 and top board accessory plate 7,8.
That is, as shown in Figure 5, constitute using outside plate 2,3, dividing plate 5 as side plate, using top board accessory plate 7,8 as top board, the body of thermal insulating box 15 using base plate 10 as base plate, and as shown in Figure 6, its inside is as thermal-insulating chamber 14.In thermal-insulating chamber 14, be configured with groove 1, and by being arranged on inner support 11 pickup groove 1 of base plate 10 one side upward.As shown in Fig. 2 (c) He Fig. 2 (d), between the outer wall and the inwall of body of thermal insulating box 15 of groove 1, (thermal-insulating chamber 14) is filled with foaminess thermal insulation material 16.It should be noted that, as foaminess thermal insulation material 16, have the thermal insulation material formed by synthetic resins foaies such as polyurethane foam, phenol formaldehyde foam, polyisocyanurate foams.But, except polystyrene foam, polyethylene, foamed glass etc.
In addition, as shown in Fig. 2 (d), Fig. 3 and Fig. 4, dividing plate 5 is installed and is connected and installed plate 6 and outside plate 4, top board 9 is installed above.Thus, using outside plate 4, dividing plate 5, top board accessory plate 7 as side plate, to be connected and installed plate 6 as base plate, using top board 9 as top board, using its internal space as mechanical(superphosphate)den 13.In addition, outer support 12 is arranged on the one side down of base plate 10.
In mechanical(superphosphate)den 13, be configured with groove unit TU as the functional component needed for hot-water storage type water heater performance function.Herein, functional component is the reducing valve 101 shown in Fig. 1, hot water supply mixing valve 102, bathing pool mixing valve 103, hot water filling magnetic valve 104, reheats interchanger 105, pump 106, pump 107, frost-proof triple valve 108, safety valve 109, main control unit 110, the pipe arrangement class connecting them, not shown electronics (residual current circuit breaker, electric wire, connection terminal etc.), various sensor (temperature sensor, flow sensor etc.) etc.These functional components are the parts needing to safeguard, be configured in from the thermal-insulating chamber 14 being filled with foaminess thermal insulation material 16 be different internal space mechanical(superphosphate)den 13 in.Thus, functional component can not be buried in foaminess thermal insulation material 16, defines the structure easily can carrying out the maintenance of functional component by taking off outside plate 4.
In addition, by functional component being concentrated in mechanical(superphosphate)den 13, be configured with in thermal-insulating chamber 14 groove 1, for pickup groove 1 inner support 11, be directly connected in groove 1 direct-connected pipe arrangement, for the thermistor (not shown) being arranged on groove 1 side that measures the hot water amount be stored in groove 1 and the thermistor (not shown) be arranged on direct-connected pipe arrangement.By being defined as above the structure be configured in thermal-insulating chamber 14, in thermal-insulating chamber 14 during filling-foam thermal insulation material 16, decrease the structure hindering flowing, thus foaminess thermal insulation material 16 can be made easily to flow in thermal-insulating chamber 14.Thus, in thermal-insulating chamber 14, be suitably filled with foaminess thermal insulation material 16, groove unit (hot-water storage type water heater) TU with high thermal insulation can be formed.
It should be noted that, in groove unit in the past, the connection section of groove and direct-connected pipe arrangement defines the sealed structure using the sealing elements such as O shape ring, seal strip.And the groove unit TU of present embodiment, because groove 1 and the connection section of direct-connected pipe arrangement are buried in foaminess thermal insulation material 16, therefore wish to form the welded construction direct-connected pipe arrangement being welded in groove 1.Thus, the sealed structure that needs are safeguarded can be got rid of, the dismounting needed for maintenance can be exempted, change operation.
In addition, as shown in Figure 5, in thermal-insulating chamber 14 during filling-foam thermal insulation material 16, fill under the state of body of thermal insulating box 15.In body of thermal insulating box 15 (thermal-insulating chamber 14) during filling-foam thermal insulation material 16, in order to prevent the dilatational strain of the body of thermal insulating box 15 caused because of blow(ing) pressure, pressing mold is used to push down body of thermal insulating box 15.As shown in Figure 5, by simplifying the shape of body of thermal insulating box 15, the shape of pressing mold, structure can also be simplified, thus contribute to cutting down cost of equipment.
As shown in Figure 6, body of thermal insulating box 15 defines the shape of the whole periphery surrounding groove 1.Herein, foaminess thermal insulation material 16 (see Fig. 2 (c) (d)) wishes that to be configured to thickness even as much as possible.Because foaminess thermal insulation material 16 is filled between the outer wall of groove 1 and the inwall of body of thermal insulating box 15, therefore by the shape of body of thermal insulating box 15 being set to the shape close to groove 1 shape, the thickness of foaminess thermal insulation material 16 can be made even as much as possible, in addition, in thermal-insulating chamber 14 during filling-foam thermal insulation material 16, foaminess thermal insulation material 16 can be made easily to flow in thermal-insulating chamber 14, the homogenizing etc. of foaminess thermal insulation material 16 density balance can be expected.
It should be noted that, in figure 6, the cross section shape of groove 1 is circular, and by making the cross section shape of body of thermal insulating box 15 for roughly octagon, makes the shape of body of thermal insulating box 15 be shape close to groove 1.
In addition, as shown in Figure 6, the groove 1 be configured in thermal-insulating chamber 14 is fixed by the inner support 11 being arranged on base plate 10 one side upward.By filling-foam thermal insulation material 16 in thermal-insulating chamber 14, define groove 1 by the structure be buried in foaminess thermal insulation material 16.Therefore, the holding capacity that groove 1 pair of earthquake etc. is rocked improves, and bending, the groove 1 that are difficult to produce inner support 11 peel off with the welding of weld part of inner support 11, and shock resistance improves.In addition, due to foaminess thermal insulation material 16 after expanding with the outside plate 2 contacted, 3, dividing plate 5 etc. forms closed state and integrated, therefore the intensity of groove unit TU improves.
< vacuum heat insulation materials 17>
Then, Fig. 7 is used on the basis of foaminess thermal insulation material 16, to use the situation of vacuum heat insulation materials 17 to be described for the heat-insulating property in order to improve body of thermal insulating box 15 further.Fig. 7 is the mode chart of the configuration representing foaminess thermal insulation material 16 and vacuum heat insulation materials 17, a () (b) is the 1st configuration, c () (d) is the 2nd configuration, and, a () (c) is the Z-Z line profile schema diagram of Fig. 1 (a), (b) (d) is the Y-Y line profile schema diagram of Fig. 1 (a).
The 1st configuration shown in Fig. 7 (a) He Fig. 7 (b) has installed the example of vacuum heat insulation materials 17.Vacuum heat insulation materials 17 due to the blow(ing) pressure of foaminess thermal insulation material 16 by the closely sealed outer wall being fixed on groove 1.Therefore, inhibit and produce space (gap) between the outer wall and vacuum heat insulation materials 17 of groove 1, inhibit simultaneously and produce space (gap) between vacuum heat insulation materials 17 and foaminess thermal insulation material 16, the decline of heat-insulating property can be suppressed.
In addition, the 2nd configuration shown in Fig. 7 (c) He Fig. 7 (d) has installed the example of vacuum heat insulation materials 17.Similarly, vacuum heat insulation materials 17 due to the blow(ing) pressure of foaminess thermal insulation material 16 by the closely sealed inwall being fixed on body of thermal insulating box 15.Therefore, inhibit and produce space (gap) between the inwall and vacuum heat insulation materials 17 of body of thermal insulating box 15, inhibit simultaneously and produce space (gap) between vacuum heat insulation materials 17 and foaminess thermal insulation material 16, the decline of heat-insulating property can be suppressed.
In addition, because the blow(ing) pressure by foaminess thermal insulation material 16 can push down vacuum heat insulation materials 17, therefore can prevent the vacuum heat insulation materials 17 of tabular from peeling off from curved surface (outer wall of groove 1 or the inwall of body of thermal insulating box 15).It should be noted that, in the figure 7, the situation for the whole periphery configuration vacuum heat insulation materials 17 at the outer wall of groove 1 or the inwall of body of thermal insulating box 15 is illustrated, but is not limited thereto, and also can be configured in its part.
The injection > of < foaminess thermal insulation material 16
Then, the filling of Fig. 8 and Fig. 9 to foaminess thermal insulation material 16 is used to be described.Fig. 8 is the partial magnified sectional view near the inlet 18 of body of thermal insulating box 15, and (a) represents the state before filling-foam thermal insulation material 16, and (b) represents the state after filling-foam thermal insulation material 16.Fig. 9 (a) is the outside side view of body of thermal insulating box 15, and Fig. 9 (b) is the drawing in side sectional elevation near the inlet 18 of body of thermal insulating box 15.It should be noted that, Fig. 9 (b) represents the state before filling-foam thermal insulation material 16.
Insert thermal insulation material injection nozzle 50 from the inlet 18 as the hole be arranged on a part for body of thermal insulating box 15, in the thermal-insulating chamber 14 of the internal space as body of thermal insulating box 15, inject foaminess thermal insulation material 16.Inject foaminess thermal insulation material 16 thermal-insulating chamber 14 foam, the air in thermal-insulating chamber 14 is discharged from the venting port 20 as the hole be arranged on a part for body of thermal insulating box 15, thus in thermal-insulating chamber 14 filling-foam thermal insulation material 16.It should be noted that, the size of venting port 20 is less than the inlet 18 inserting thermal insulation material injection nozzle 50.
Foaminess thermal insulation material 16 has in the characteristic containing heat-insulating property during moisture and strength degradation.Therefore, foaminess thermal insulation material 16 and contact with moisture is not made.Herein, because groove unit (hot-water storage type water heater) TU is usually disposed in the outdoor, if therefore outside plate 2,3, the outside surface that directly contacts of top board 9 etc. and ambient atmos arranges inlet 18, venting port 20, then moisture may enter into foaminess thermal insulation material 16, thus need waterproof construction, therefore not preferred.
Therefore, as shown in Fig. 8 and Fig. 9 (a), the inlet 18 be arranged on the body of thermal insulating box 15 of groove unit (hot-water storage type water heater) TU of present embodiment is arranged on dividing plate 5.In addition, as shown in Fig. 9 (b), venting port 20 is arranged on dividing plate 5 too.
As shown in Fig. 9 (a), when filling-foam thermal insulation material 16, expose the dividing plate 5 being provided with inlet 18 and venting port 20.On the other hand, as shown in Figures 2 and 3, by time disposed in the outdoor for groove unit TU, the position arranging inlet 18 and venting port 20 in dividing plate 5 is covered by outside plate 4, thus does not directly contact with ambient atmos.Thus, prevent water to invade the inside of body of thermal insulating box 15 from inlet 18, can make foaminess thermal insulation material 16 not with contact with moisture.
As shown in Fig. 8 (a), in thermal-insulating chamber 14 side of inlet 18, paste the thermal insulation material anti-leak seal 19 bonding with dividing plate 5.In addition, the diameter of venting port 20 (see Fig. 9 (b)) is less than inlet 18, does not need thermal insulation material anti-leak seal 19.
As shown in Fig. 8 (a), when thermal insulation material injection nozzle 50 is inserted inlet 18, thermal insulation material anti-leak seal 19 produces recoverable deformation, and thermal insulation material injection nozzle 50 is inserted in thermal-insulating chamber 14.Then, to thermal-insulating chamber 14, the foaminess thermal insulation material 16 of specified amount is injected from the thermal insulation material injection nozzle 50 inserted.When being extracted from inlet 18 by thermal insulation material injection nozzle 50, thermal insulation material anti-leak seal 19 is generally horizontal because of restorer, has clogged inlet 18.Then, as shown in Fig. 8 (b), when carrying out the foaming of foaminess thermal insulation material 16, thermal insulation material anti-leak seal 19 is pressed on the inwall of dividing plate 5 by foaminess thermal insulation material 16, prevents the leakage of foaminess thermal insulation material 16.
Foaminess thermal insulation material 16
Herein, the explanation carried out as used Fig. 1, for groove unit (hot-water storage type water heater) TU, the hot water (high-temperature water) of high temperature is stored in the top of groove 1.Therefore, wish that the heat-insulating property on groove 1 top is high as much as possible.
In addition, flow to the bottom of thermal-insulating chamber 14 from the injection liquid of the foaminess thermal insulation material 16 of thermal insulation material injection nozzle 50 injection, and start foaming from here.Therefore, have more close to the bottom of thermal-insulating chamber 14, the density of foaminess thermal insulation material 16 be higher, tendency that heat-insulating property is higher.In addition, generally speaking, because the region injecting the injection liquid of foaminess thermal insulation material 16 is urethane flowing just term area, therefore the state of polyurethane foam is also good, has the tendency that heat-insulating property improves.
Therefore, as shown in Fig. 9 (a), with dividing plate 5 be the mode of one side upward by body of thermal insulating box 15 traverse, and the inlet 18 be arranged on from dividing plate 5 close to top board accessory plate 7,8 side injects the injection liquid of foaminess thermal insulation material 16.In addition, if the mobility of foaminess thermal insulation material 16 is high, then can fill with good polyurethane foam state, there is the tendency that heat-insulating property improves.
In addition, the explanation carried out as used Fig. 1, the temperature (hot water outlet temperature) of high-temperature-hot-water (high-temperature water) that heated by heat pump unit HPU (water refrigerant heat exchanger 112), that flow into groove 1 top is the temperature of 90 DEG C ~ about 100 DEG C to the maximum.Therefore, under being exposed to the temperature environment of high temperature for a long time as the foaminess thermal insulation material 16 of thermal insulation material of the groove 1 of this high-temperature-hot-water of storage.Generally speaking, if under being exposed to the temperature environment of high temperature, then the heat-insulating property of foaminess thermal insulation material is deteriorated, the strength degradation of foaminess thermal insulation material.
Thus, as the requirement project of the foaminess thermal insulation material 16 of the thermal insulation material for the groove 1 as groove unit TU, require the deterioration of the heat-insulating property under the mobility of raising foaminess thermal insulation material 16, suppression high temperature, suppress the strength degradation after for a long time.
As foaminess thermal insulation material 16, the thermal insulation material formed by synthetic resins foaies such as hard polyurethane foams, phenol formaldehyde foam, polyisocyanurate foams can be enumerated, in the present embodiment hard polyurethane foams is described.
< hard polyurethane foams (foaminess thermal insulation material 16) >
The premix polyhydric alcohol composition of present embodiment comprises active hydrogen-contg compound, suds-stabilizing agent, catalyzer, water and the pentamethylene with active hydrogen base (hydroxyl).Further, the hard polyurethane foams (foaminess thermal insulation material 16) of present embodiment can obtain by using the polyisocyanates with isocyanate group to make premix polyhydric alcohol composition foam.
The active hydrogen-contg compound of present embodiment comprises the 1st active hydrogen-contg compound (A), the 2nd active hydrogen-contg compound (B) and the 3rd active hydrogen-contg compound (C).
1st active hydrogen-contg compound (A) makes oxyalkylene carry out as the polyvalent alcohol (multivalence alcohol) that the hydroxyl value (active hydrogen radix) of active hydrogen base is 5 ~ 8 active hydrogen-contg compound that addition obtains with containing hydroxyl.
As the polyvalent alcohol (multivalence alcohol) that hydroxyl value (active hydrogen radix) is 5, there are glucose (Glucose), seminose, fructose (Fructose), 2,2,6,6-tetra-(hydroxymethyl) hexalin etc.As the polyvalent alcohol (multivalence alcohol) that hydroxyl value (active hydrogen radix) is 6, there are Dipentaerythritol, Sorbitol Powder, N.F,USP MANNITOL, galactitol etc.As the polyvalent alcohol (multivalence alcohol) that hydroxyl value (active hydrogen radix) is 8, there are sucrose (Sucrose), lactose etc.
In addition, the polyvalent alcohol (multivalence alcohol) of the 1st active hydrogen-contg compound (A), as long as the material that cross-linking reaction point is many, its structure is also defined in chain, aliphatics unlike the situation of aftermentioned 2nd active hydrogen-contg compound (B), and it also can have aromatic nucleus.That is, the 1st active hydrogen-contg compound (A) also can be oxyalkylene and hydroxyl value (active hydrogen radix) be 5 ~ 8 phenols carry out the active hydrogen-contg compound etc. that addition obtains.
Wherein, as the polyvalent alcohol (multivalence alcohol) of the 1st active hydrogen-contg compound (A), sucrose (Sucrose) is particularly preferably used.The cross-linking reaction point of sucrose (Sucrose) is many especially, can improve intensity and the dimensional stability of hard polyurethane foams (foaminess thermal insulation material 16).
As the oxyalkylene of the 1st active hydrogen-contg compound (A), can suitably use ethylene oxide, propylene oxide, oxybutylene etc.Wherein, a kind of oxyalkylene can be used, the oxyalkylene that also two or more kinds may be used.In addition, and with two or more oxyalkylene time, them can be made to react successively, also can by their mix after react.
2nd active hydrogen-contg compound (B) makes oxyalkylene carry out as the polyvalent alcohol (multivalence alcohol) that the hydroxyl value (active hydrogen radix) of active hydrogen base is 4 active hydrogen-contg compound that addition obtains with containing hydroxyl.
In addition, the structure of the polyvalent alcohol (multivalence alcohol) of the 2nd active hydrogen-contg compound (B) is limited to chain, aliphatics, does not comprise the material with aromatic nucleus.
As the polyvalent alcohol (multivalence alcohol) that hydroxyl value (active hydrogen group number) is 4, there are Glycerol dimer, tetramethylolmethane, methyl glucoside etc.In addition forming as by carrying out addition polymerization with alcohol the polyamine (diamines) that hydroxyl value (active hydrogen radix) is the polyvalent alcohol (multivalence alcohol) of 4, having quadrol, tolylene diamine, diphenylmethanediamiand, tetra methylol hexanaphthene etc.
Wherein, as the polyvalent alcohol (multivalence alcohol) of the 2nd active hydrogen-contg compound (B), particularly preferably tolylene diamine is used.
As the oxyalkylene of the 2nd active hydrogen-contg compound (B), same with the oxyalkylene of the 1st active hydrogen-contg compound (A), can suitably use ethylene oxide, propylene oxide, oxybutylene etc.Wherein, a kind of oxyalkylene can be used, the oxyalkylene that also two or more kinds may be used.In addition, and with two or more oxyalkylene time, them can be made to react successively, also can by their mix after react.
3rd active hydrogen-contg compound (C) be there is ester group, functional group number is the polyester polyol of 2 ~ 3.The polyester polyol of the 3rd active hydrogen-contg compound (C) can be reacted by the polycarboxylic acid with carboxyl with the polycondensation (polymeric condensation, condensation polymerization) of the polyvalent alcohol (multivalence alcohol) with hydroxyl and obtain.
Herein, the functional group number of the 3rd active hydrogen-contg compound (C) refers to the hydroxyl value of the polyvalent alcohol (multivalence alcohol) before polycondensation.
As the polycarboxylic acid used in the polycondensation of the 3rd active hydrogen-contg compound (C), there are Tetra hydro Phthalic anhydride, terephthalic acid, m-phthalic acid, succsinic acid, hexanodioic acid, toxilic acid, fumaric acid, sebacic acid, oxysuccinic acid etc.
As the polyvalent alcohol (multivalence alcohol) that the hydroxyl value used in the polycondensation of the 3rd active hydrogen-contg compound (C) is 2 ~ 3 (functional group number is 2 ~ 3), there are ethylene glycol, Diethylene Glycol, triethylene glycol, BDO, glycerol, TriMethylolPropane(TMP) etc.
As the 3rd active hydrogen-contg compound (C), particularly preferably use hexanodioic acid binaryglycol ester, ethylene glycol adipate(EGA), hexanodioic acid-BDO ester, 6-caprolactone, hexanodioic acid-1,6-hexylene glycol ester etc.
It should be noted that, as long as premix polyhydric alcohol composition, containing each at least a kind of the 1st active hydrogen-contg compound (A), the 2nd active hydrogen-contg compound (B) and the 3rd active hydrogen-contg compound (C), also can contain two or more.
Like this, premix polyhydric alcohol composition containing the 1st active hydrogen-contg compound (A) as on the basis of active hydrogen-contg compound, also containing lower the 2nd active hydrogen-contg compound (B) of viscosity and prolonging of the delayed-action activator (Rather-late drug as urethane reaction) the 3rd active hydrogen-contg compound (C) that plays a role.
Because the 1st active hydrogen-contg compound (A) cross-linking reaction point is many, define three-dimensional crosslinking structure, therefore molecular structure becomes firm.In addition, premix polyhydric alcohol composition by also containing the 2nd active hydrogen-contg compound (B) on the basis of the 1st active hydrogen-contg compound (A), maintain low viscosity, mobility improves, maintain the elasticity of hard polyurethane foams (foaminess thermal insulation material 16), and except the effect of the 1st active hydrogen-contg compound (A), further suppress the deterioration of the thermal conductivity of hard polyurethane foams (foaminess thermal insulation material 16) under high temperature, intensity and the dimensional stability of hard polyurethane foams (foaminess thermal insulation material 16) can be improved.
As previously mentioned, 3rd active hydrogen-contg compound (C) be there is ester group, functional group number is the polyester polyol of 2 ~ 3, and is by the polycarboxylic acid such as Tetra hydro Phthalic anhydride, terephthalic acid and the polycondensation of polyvalent alcohol (multivalence alcohol) and the one of the polyester polyol obtained.Because phthalic acid (polycarboxylic acid) self can be used as the inhibitor of urethane reaction, therefore urethane reaction is delayed by, and mobility improves.
In the active hydrogen-contg compound contained by premix polyhydric alcohol composition, the 1st active hydrogen-contg compound (A) preferably contains more than 50 quality % and below 80 quality %.If the 1st active hydrogen-contg compound (A) is less than 50 quality %, then the active hydrogen-contg compound composition that cross-linking reaction point is many reduces, the strength degradation of hard polyurethane foams (foaminess thermal insulation material 16).In addition, if the 1st active hydrogen-contg compound (A) is more than 80 quality %, polarity then due to the 1st active hydrogen-contg compound (A) is high, pentamethylene and the compatibility poor of active hydrogen-contg compound comprising the 1st active hydrogen-contg compound (A), the bubble of hard polyurethane foams (foaminess thermal insulation material 16) becomes large.Consequently, thermal conductivity increases.In addition, the deterioration year in year out of thermal conductivity also becomes large.
In addition, in the active hydrogen-contg compound contained by premix polyhydric alcohol composition, the 2nd active hydrogen-contg compound (B) preferably contains more than 15 quality % and below 30 quality %.If the 2nd active hydrogen-contg compound (B) is less than 15 quality %, then the viscosity reduction of premix polyhydric alcohol composition and the strength-enhancing effect of hard polyurethane foams (foaminess thermal insulation material 16) become insufficient.In addition, if the 2nd active hydrogen-contg compound (B) is more than 30 quality %, then the viscosity of premix polyhydric alcohol composition becomes too small, in the reaction process of hard polyurethane foams (foaminess thermal insulation material 16), it spills from the gap of body of thermal insulating box 15 (see Fig. 5), consequently, heat leak amount may become large.
For the premix polyhydric alcohol composition of present embodiment, 1st active hydrogen-contg compound (A), 2nd active hydrogen-contg compound (B) and the 3rd active hydrogen-contg compound (C) all contain, and for the amount contained in premix polyhydric alcohol composition, " as long as the amount of the amount > the 3rd active hydrogen-contg compound (C) of the amount > the 2nd active hydrogen-contg compound (B) of the 1st active hydrogen-contg compound (A) ", and the amount of the 1st active hydrogen-contg compound (A) is more than 2 times of the amount of the 2nd active hydrogen-contg compound (B).It should be noted that, detailed content uses Fig. 9 and table 1 to describe hereinafter.
The suds-stabilizing agent contained in premix polyhydric alcohol composition is not particularly limited, known material can be used.Such as, B8462, B8544, B8545, B8546, B8547 etc. of Evonik company can be used.They are oxyalkylene modified dimethyl polysiloxanes, are the organo-siloxane based compounds that end group has hydroxyl or alkoxyl group etc.Relative to active hydrogen-contg compound 100 mass parts contained in premix polyhydric alcohol composition, the amount of suds-stabilizing agent is preferably 1.0 ~ 4.0 mass parts.
Catalyzer (kicker, resinifying catalyzer, urea acid esterification catalyst etc.) contained by premix polyhydric alcohol composition is not particularly limited, known material can be used.
Such as, as kicker, specifically, pentamethyl-diethylenetriamine, two (dimethyl aminoethyl) ether etc. are applicable.
In addition, as resinifying catalyzer, specifically, N, N, N '-trimethylaminoethyl group thanomin, N, N-dimethyl amino ethoxy ethanol, diethyl cyclohexylamine, Triethylene Diamine, N, N, N '; N "-4-methyl hexamethylene diamine, N, N, N '; N "-4-methyl-diaminopropane, N, N, N ', N "-Tetramethyl Ethylene Diamine etc. is applicable.
In addition, as urea acid esterification catalyst, specifically, N, N ', N "-three (3-dimethylaminopropyl) perhydro-s-triazine, N, N ', N "-three (3-diethyl amino propyl) perhydro-s-triazine etc. is applicable.
These catalyzer may be used alone, can also be 2 or more kinds in combination.Relative to active hydrogen-contg compound 100 mass parts contained in premix polyhydric alcohol composition, catalytic amount is preferably 1.5 ~ 5.0 mass parts.
Water contained by premix polyhydric alcohol composition and the optimum mix of pentamethylene are that relative to active hydrogen-contg compound 100 mass parts contained in premix polyhydric alcohol composition, water is 2.0 ~ 2.5 mass parts, and pentamethylene is 14.0 ~ 18.0 mass parts.As long as the proportioning of water and pentamethylene is just not particularly limited in above-mentioned scope.
The median size of the pentamethylene (liquid) in premix polyhydric alcohol composition is preferably less than 5.5 μm.If more than 5.5 μm, then hard polyurethane foams (foaminess thermal insulation material 16) dimensional stability at high temperature declines, and the quantity in the space formed between body of thermal insulating box 15 (see Fig. 5) and hard polyurethane foams (foaminess thermal insulation material 16) increases.It should be noted that, as long as the median size of pentamethylene is less than 5.5 μm, also can be completely compatible and pentamethylene particle cannot be observed.
As premix polyhydric alcohol composition, except above-mentioned construct, the additives such as weighting agent, fire retardant, reinforcing fiber, tinting material can also be contained as required.They can use known material, are not particularly limited.
Polyisocyanates is not particularly limited, known material can be used.Such as, diphenylmethanediisocyanate (MDI) and derivative thereof or tolylene diisocyanate (TDI) and derivative thereof are applicable.They can be used alone, also can be used in combination.In addition, as MDI and derivative thereof, such as, can enumerate the mixture of MDI and its polymer poly phenyl polymethylene diisocyanate, there is the diphenylmethanediisocyanate derivative etc. of terminal isocyanate group.In addition, as TDI and derivative thereof, such as, the terminal isocyanate prepolymer derivatives etc. of the mixture of 2,4-TDI and 2,6-TDI, TDI can be enumerated.
The hard polyurethane foams of present embodiment is formed by general high pressure foaming machine, such as, can use the PU-30 type foaming machine of PROMART Inc..Foaming condition is such as fluid temperature 18 ~ 30 DEG C, spue pressure 80 ~ 150kg/cm 2, discharge-amount 15 ~ 30kg/min, moulding box temperature be set to about 45 DEG C.
The hard polyurethane foams (foaminess thermal insulation material 16) of present embodiment, by using the premix polyhydric alcohol composition good with the consistency of whipping agent, can be provided in the foaminess thermal insulation material 1 that the space, top layer that formed between body of thermal insulating box 15 and hard polyurethane foams (foaminess thermal insulation material 16) is few.In other words, groove unit (hot-water storage type water heater) TU that appearance deformation can be provided few and hot-water supply system's (heat pump-type hot-water supply device) S.
In addition, the premix polyhydric alcohol composition of present embodiment maintains intensity, the dimensional stability of hard polyurethane foams (foaminess thermal insulation material 16), simultaneously, the mobility of hard polyurethane foams raw material can be improved, reduce the space in complicated shape portion, density variation, improve aesthetic appearance and improve heat-insulating property.Consequently, the energy-conservation of groove unit (hot-water storage type water heater) TU and hot-water supply system's (heat pump-type hot-water supply device) S can be realized.
In addition, the feature being filled with the body of thermal insulating box 15 of the hard polyurethane foams (foaminess thermal insulation material 16) of present embodiment is that deterioration is little, and the hard polyurethane foams taked from the filling polyurethane part of distance inlet 18 at least more than 200mm is less than 3% with the difference (deterioration rate caused because flow distance increases) of the thermal conductivity of the hard polyurethane foams taked from the filling polyurethane part of more than distance 1000mm.In addition, it is characterized in that by heat (high temperature) impact that produces little, thermal conductivity deterioration rate when hard polyurethane foams be placed 60 days in 90 DEG C of atmosphere is less than 20%.In addition, be further characterized in that by heat (high temperature) the physical property deterioration that causes little, compressive strength deterioration rate when hard polyurethane foams be placed 60 days in 90 DEG C of atmosphere is less than 5%.
Embodiment
Below, more specific description is carried out by the hard polyurethane foams (foaminess thermal insulation material 16) of embodiment to present embodiment.It should be noted that, the present invention is not limited to these embodiments.Fig. 9 is the outside side view of body of thermal insulating box 15, is the figure of the position that the hard polyurethane foams (foaminess thermal insulation material 16) cut out is described.Table 1 is the table representing the proportioning of active hydrogen-contg compound and the relation of thermal conductivity and compressive strength.
< embodiment 1 ~ 6>
(1) modulation of premix polyhydric alcohol composition and the making of hard polyurethane foams
As the 1st active hydrogen-contg compound (A), use the addition sucrose of oxyalkylene, as the 2nd active hydrogen-contg compound (B), use the addition tolylene diamine of oxyalkylene, as the 3rd active hydrogen-contg compound (C), use Tetra hydro Phthalic anhydride polycondensation polyester polyol, modulate active hydrogen-contg compound according to the proportioning (polyvalent alcohol proportioning) of the active hydrogen-contg compound shown in table 1.
It should be noted that, the polyvalent alcohol proportioning of the embodiment 1 shown in table 1 represents the 1st active hydrogen-contg compound (A), the 2nd active hydrogen-contg compound (B) of 20 quality %, the 3rd active hydrogen-contg compound (C) of 20 quality % containing 70 quality %.Embodiment 2 ~ 6 and comparative example described later 1 ~ 4 as shown in table 1 too.
It should be noted that, in embodiment 1 ~ 6, active hydrogen-contg compound proportioning (polyvalent alcohol proportioning) is " amount of the amount > the 3rd active hydrogen-contg compound (C) of the amount > the 2nd active hydrogen-contg compound (B) of the 1st active hydrogen-contg compound (A) ", and " amount of the 1st active hydrogen-contg compound (A) is more than 2 times of the amount of the 2nd active hydrogen-contg compound (B) ".
Relative to active hydrogen-contg compound 100 mass parts, be used as 2.5 mass parts organo-siloxanes of suds-stabilizing agent, the 3.0 mass parts tertiary amine catalysts as catalysts, the 2.1 mass parts water as whipping agent and 15.0 mass parts pentamethylene (Nippon Zeon Co., Ltd.'s system), polymethylene polyphenyl group diisocyanate as isocyanate prepolymer composition, carry out filling-foam, make hard polyurethane foams.
It should be noted that, about foaming, use high pressure foaming machine (PROMART Inc., model: PU-30), fluid temperature 18 ~ 30 DEG C, spue pressure 80 ~ 150kg/cm 2, discharge-amount 15 ~ 30kg/min, moulding box temperature be set to the condition of about 40 DEG C under foam.
(2) making of body of thermal insulating box
Then, use the hard polyurethane Recipe of above-mentioned making, be produced on the body of thermal insulating box 15 of internal configuration hot-water storage groove 1.Fig. 9 represents and is being filled in the hard polyurethane foams in body of thermal insulating box 15, position 21 taked by the sample being the position of 200mm in distance inlet 18 (top board accessory plate 8), and takes position 22 at the sample that distance inlet 18 is 1000mm place.Hard polyurethane foams is cut out for measuring from these sample positions 21,22.
(3) measure, evaluate
Then, following test and evaluation are carried out for the premix polyhydric alcohol composition of above-mentioned making and body of thermal insulating box 15.
I () thermal conductivity measures (performance evaluation)
The thermal insulation material part being filled with hard polyurethane foams being at least more than 200mm (position 21) and more than 1000mm (position 22) from the inlet 18 apart from above-mentioned body of thermal insulating box 15 takes the hard polyurethane foams of 200 × 200 × 20 ~ 50mm, uses Ying Hongjing machine Inc. thermal conductivity determinator HC-074 to measure.Result is remembered in the lump in the table of table 1.
Herein, deterioration rate (%) is defined by " thermal conductivity of (thermal conductivity of the thermal conductivity-position 21 of position 22)/position 21 ".
In addition, the thermal insulation material part being filled with hard polyurethane foams being at least more than 200mm from distance inlet 18 takes the hard polyurethane foams of 200 × 200 × 20 ~ 50mm, uses Ying Hongjing machine Inc. thermal conductivity determinator HC-074 to measure for the hard polyurethane foams after placed 60 days in the temperature thermostatic bath of high of 90 DEG C.Result is remembered in the lump in the table of table 1.
Herein, deterioration rate (%) is defined by " (thermal conductivity after 60 days-initial stage thermal conductivity)/initial stage thermal conductivity ".
(ii) compressive strength measures
Measure the compressive strength of the above-mentioned hard polyurethane foams taked from body of thermal insulating box 15 in the following order.
Body of thermal insulating box 15: sent speed 4mm/min to be at least the hard polyurethane foams applying load being filled with 50 × 50 × 20 ~ 50mm of the thermal insulation material part of hard polyurethane foams of more than 200mm and more than 1000mm to from distance urethane raw (premix polyhydric alcohol composition) inlet 18 in the past, the value that loading when generation 10% being out of shape obtains divided by original load area is as compressive strength.Result is remembered in the lump in the table of table 1.
Herein, deterioration rate (%) is defined by " (compressive strength of initial stage compressive strength after-60 days)/initial stage compressive strength ".
< comparative example 1 ~ 4>
Similarly, active hydrogen-contg compound is modulated according to the proportioning (polyvalent alcohol proportioning) of the active hydrogen-contg compound shown in table 1.
It should be noted that, comparative example 1 is the formation of not adding the 3rd active hydrogen-contg compound (C).Comparative example 2 is that the condition of " amount of the amount > the 3rd active hydrogen-contg compound (C) of the amount > the 2nd active hydrogen-contg compound (B) of the 1st active hydrogen-contg compound (A) " is set up, but the invalid formation of condition of " amount of the 1st active hydrogen-contg compound (A) is more than 2 times of the amount of the 2nd active hydrogen-contg compound (B) ".Comparative example 3 is that the condition of " amount of the 1st active hydrogen-contg compound (A) is more than 2 times of the amount of the 2nd active hydrogen-contg compound (B) " is set up, but the invalid formation of condition of " amount of the amount > the 3rd active hydrogen-contg compound (C) of the amount > the 2nd active hydrogen-contg compound (B) of the 1st active hydrogen-contg compound (A) ".Comparative example 4 is that the condition of " amount of the amount > the 3rd active hydrogen-contg compound (C) of the amount > the 2nd active hydrogen-contg compound (B) of the 1st active hydrogen-contg compound (A) " is false, the condition also invalid formation of " amount of the 1st active hydrogen-contg compound (A) is more than 2 times of the amount of the 2nd active hydrogen-contg compound (B) ".
As shown in table 1, use the hard polyurethane foams of the premix polyhydric alcohol composition of embodiment 1 ~ 6 all to demonstrate good physical property.
Such as, for mobility, the degradation that distance to inlet increases the thermal conductivity caused is evaluated as index, the deterioration rate of comparative example 1 ~ 4 is more than 3%, particularly comparative example 4, for deterioration rate reaches the deterioration of 6%, and embodiment 1 ~ 6 may be controlled to the deterioration of deterioration rate within 3%.
In addition, for special problematic for the thermotolerance of high-temperature area as water heater, using the degradation caused because of the rheological parameters' change with time of thermal conductivity and the rheological parameters' change with time of compressive strength as index.For thermal conductivity, comparative example 1 ~ 4 is the significantly deterioration that deterioration rate is more than 25%, and in embodiment 1 ~ 6, may be controlled to the deterioration that deterioration rate is less than 20%, by being set to polyurethane formulations of the present invention, can use with better heat-insulating property state within the longer time.
In addition, for the degradation that foamy body (compressive strength) is caused because of rheological parameters' change with time, comparative example 1 ~ 4 to be deterioration rates be more than 10% compressive strength decline, and embodiment 1 ~ 6 may be controlled to the decline that deterioration rate is less than 5%.
As shown in table 1, compared with embodiment 1 ~ 6, in comparative example 1 ~ 4, the use level of the 1st active hydrogen-contg compound (A), the 3rd active hydrogen-contg compound (C) is different from preferable range of the present invention, therefore, the viscosity of polyhydroxy reactant uprises, and mobility is deteriorated, in generation space, complicated shape portion, the deterioration year in year out of density distribution, heat-insulating property increases.
In addition can think, in comparative example 2,4, in the molecular structure of urethane resin, oxyalkylene and hydroxyl value be 4 ~ 8 the polyvalent alcohol use level of carrying out the compound (the 1st active hydrogen-contg compound (A)) that addition obtains to reduce thus three-dimensional crosslinking structure reduces, therefore various degradation.
In addition demonstrate, in order to improve the thermotolerance at high-temperature area, the such polyester polyol of input the 3rd active hydrogen-contg compound (C) can be passed through, and carry out coordinating in preferable range of the present invention from the balance aspect of viscosity, thermal conductivity, mechanical properties and provide.
Variation
It should be noted that, groove unit (hot-water storage type water heater) TU, hot-water supply system (heat pump-type hot-water supply device) S of present embodiment and foaminess thermal insulation material 16 are not limited to the formation of above-mentioned embodiment, within a range not departing from the gist of the invention, various change can be carried out.
As shown in Figure 1, the hot-water supply system S of present embodiment is illustrated as the heat pump-type hot-water supply device S of divergence type, but is not limited thereto.Such as, one-piece type heat pump-type hot-water supply device is also gone for.In addition, be illustrated as the mode of storing high-temperature water (hot water) in the groove 1 of hot-water supply system S, but be not limited thereto.Such as, salt solution (brine) etc. can also be stored by heating liquid.
The foaminess thermal insulation material 16 of the present embodiment mode as the thermal insulation material being used as hot-water supply system S is illustrated, but is not limited thereto.The foaminess thermal insulation material 16 of present embodiment can also be used in the inner lining of furnace of industrial furnace thermal insulation material, high temperature pipeline coverture, circuit, the combustion chamber material of greenhouse boiler, the thermal insulation material of insulation can, the thermal insulation material of heating plant, the thermal insulation material of electric heating device, the lagging material of pipes/tubes line.
[table 1]

Claims (14)

1. a groove unit, is characterized in that, possesses the groove of storing liquid, receives the casing of described groove and is arranged on the foaminess thermal insulation material between described groove and described casing,
Use hard polyurethane foams as described foaminess thermal insulation material,
Described hard polyurethane foams comprise active hydrogen radix be 5 ~ 8 the 1st active hydrogen-contg compound, active hydrogen radix be 4 the 2nd active hydrogen-contg compound and have ester group, functional group number is the polyester polyol of 2 ~ 3.
2. groove unit according to claim 1, it is characterized in that, the use level of described 1st active hydrogen-contg compound is set to A, the use level of described 2nd active hydrogen-contg compound is set to B, the use level of described polyester polyol is set to C, then the relation of A>B>C is set up.
3. groove unit according to claim 2, is characterized in that, the relation of A>2B is set up.
4. the groove unit according to any one of claims 1 to 3, it is characterized in that, described polyester polyol by make at least one hydroxyl value at least one polycarboxylic acid in Tetra hydro Phthalic anhydride, terephthalic acid, m-phthalic acid, succsinic acid, hexanodioic acid, toxilic acid, fumaric acid, sebacic acid, oxysuccinic acid and ethylene glycol, Diethylene Glycol, triethylene glycol, BDO, glycerol, TriMethylolPropane(TMP) be 2 ~ 3 polyvalent alcohol carry out polycondensation and obtain.
5. groove unit according to claim 4, is characterized in that,
Described 1st active hydrogen-contg compound makes oxyalkylene and glucose, seminose, fructose, 2,2,6, at least one polyvalent alcohol in 6-tetra-(hydroxymethyl) hexalin, Dipentaerythritol, Sorbitol Powder, N.F,USP MANNITOL, galactitol, sucrose, lactose carries out the active hydrogen-contg compound that addition obtains
Described 2nd active hydrogen-contg compound is the active hydrogen-contg compound making at least one polyvalent alcohol in oxyalkylene and Glycerol dimer, tetramethylolmethane, methyl glucoside, quadrol, tolylene diamine, diphenylmethanediamiand, tetra methylol hexanaphthene carry out addition to obtain.
6. the groove unit according to any one of claims 1 to 3, is characterized in that,
Described 1st active hydrogen-contg compound is sucrose,
Described 2nd active hydrogen-contg compound is tolylene diamine,
Described polyester polyol be in hexanodioic acid binaryglycol ester, ethylene glycol adipate(EGA), hexanodioic acid-BDO ester, 6-caprolactone, hexanodioic acid-1,6-hexylene glycol ester at least any one.
7. groove unit according to claim 1, is characterized in that, described groove stores the high-temp liquid heated.
8. a hot-water supply system, is characterized in that, possesses the groove unit according to any one of claim 1 ~ 7.
9. a foaminess thermal insulation material, it is characterized in that, possess hard polyurethane foams and formed, and described hard polyurethane foams comprise active hydrogen radix be 5 ~ 8 the 1st active hydrogen-contg compound, active hydrogen radix be 4 the 2nd active hydrogen-contg compound and have ester group, functional group number is the polyester polyol of 2 ~ 3.
10. foaminess thermal insulation material according to claim 9, it is characterized in that, the use level of described 1st active hydrogen-contg compound is set to A, the use level of described 2nd active hydrogen-contg compound is set to B, the use level of described polyester polyol is set to C, then the relation of A>B>C is set up.
11. foaminess thermal insulation materials according to claim 10, is characterized in that, the relation of A>2B is set up.
12. foaminess thermal insulation materials according to any one of claim 9 ~ 11, it is characterized in that, described polyester polyol by make at least one hydroxyl value at least one polycarboxylic acid in Tetra hydro Phthalic anhydride, terephthalic acid, m-phthalic acid, succsinic acid, hexanodioic acid, toxilic acid, fumaric acid, sebacic acid, oxysuccinic acid and ethylene glycol, Diethylene Glycol, triethylene glycol, BDO, glycerol, TriMethylolPropane(TMP) be 2 ~ 3 polyvalent alcohol carry out polycondensation and obtain.
13. foaminess thermal insulation materials according to claim 12, is characterized in that,
Described 1st active hydrogen-contg compound makes oxyalkylene and glucose, seminose, fructose, 2,2,6, at least one polyvalent alcohol in 6-tetra-(hydroxymethyl) hexalin, Dipentaerythritol, Sorbitol Powder, N.F,USP MANNITOL, galactitol, sucrose, lactose carries out the active hydrogen-contg compound that addition obtains
Described 2nd active hydrogen-contg compound is the active hydrogen-contg compound making at least one polyvalent alcohol in oxyalkylene and Glycerol dimer, tetramethylolmethane, methyl glucoside, quadrol, tolylene diamine, diphenylmethanediamiand, tetra methylol hexanaphthene carry out addition to obtain.
14. foaminess thermal insulation materials according to any one of claim 9 ~ 11, is characterized in that,
Described 1st active hydrogen-contg compound is sucrose,
Described 2nd active hydrogen-contg compound is tolylene diamine,
Described polyester polyol be in hexanodioic acid binaryglycol ester, ethylene glycol adipate(EGA), hexanodioic acid-BDO ester, 6-caprolactone, hexanodioic acid-1,6-hexylene glycol ester at least any one.
CN201410387474.6A 2013-10-10 2014-08-08 Tank unit, hot water supply system and foaming heat insulation materials Pending CN104558482A (en)

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