CN103249536A - Device and method for manufacturing expanded polyurethane foam, and heat insulation structure - Google Patents
Device and method for manufacturing expanded polyurethane foam, and heat insulation structure Download PDFInfo
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- 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
- C08J9/122—Hydrogen, oxygen, CO2, nitrogen or noble gases
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C44/00—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles
- B29C44/34—Auxiliary operations
- B29C44/36—Feeding the material to be shaped
- B29C44/46—Feeding the material to be shaped into an open space or onto moving surfaces, i.e. to make articles of indefinite length
- B29C44/461—Feeding the material to be shaped into an open space or onto moving surfaces, i.e. to make articles of indefinite length dispensing apparatus, e.g. dispensing foaming resin over the whole width of the moving surface
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- 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
- C08J9/127—Mixtures of organic and inorganic blowing agents
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B7/00—Mixing; Kneading
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2075/00—Use of PU, i.e. polyureas or polyurethanes or derivatives thereof, as moulding material
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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
- C08G2101/00—Manufacture of cellular products
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- 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
- C08J2201/00—Foams characterised by the foaming process
- C08J2201/02—Foams characterised by the foaming process characterised by mechanical pre- or post-treatments
- C08J2201/022—Foams characterised by the foaming process characterised by mechanical pre- or post-treatments premixing or pre-blending a part of the components of a foamable composition, e.g. premixing the polyol with the blowing agent, surfactant and catalyst and only adding the isocyanate at the time of foaming
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- 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
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/06—CO2, N2 or noble gases
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- 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
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
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- 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
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/18—Binary blends of expanding agents
- C08J2203/182—Binary blends of expanding agents of physical blowing agents, e.g. acetone and butane
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- 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
- C08J2205/00—Foams characterised by their properties
- C08J2205/04—Foams characterised by their properties characterised by the foam pores
- C08J2205/052—Closed cells, i.e. more than 50% of the pores are closed
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- 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
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
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- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
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Abstract
An expanded polyurethane foam is manufactured by mixing a first composition having a polyisocyanate as the main component with an expandable second composition. The expandable second composition is prepared by mixing a main expanding agent and an auxiliary expanding agent into a second composition having a polyol as the main component, and then stored in a storage container. The boiling point of the auxiliary expanding agent is lower than that of the main expanding agent, and the auxiliary expanding agent is gaseous at normal temperature. An agent for increasing the storage pressure is filled into the storage container in a pressurized state, or the liquid layer in the storage container (expandable second composition) is sealed by an air layer. The agent for increasing the storage pressure is a gas that has lower solubility and a smaller diffusion coefficient in the second composition than the auxiliary expanding agent.
Description
Technical field
The present invention relates to have the polyurathamc foam of micro air bubble independently manufacturing installation, this polyurathamc manufacture method and have the insulated structure of this polyurathamc foam, particularly relate to inner be manufacturing installation and the manufacture method of the polyurathamc foam of filling and the insulated structure with this polyurathamc foam in the plate body of hollow or the box-shaped body.
Background technology
The polyurathamc foam is that PIC and polyalcohol are mixed with catalyst and blowing agent (other additives as required) etc., roughly carry out the condensation reaction of PIC and polyalcohol and foaming simultaneously and make the formed body that obtains, in integral body, roughly have independently micro air bubble (below, be called separated foam) equably.When using the low gas of thermal conductivity to make the polyurathamc foam as blowing agent, owing to this gas is enclosed in the separated foam, so can realize excellent heat resisting.
As above-mentioned blowing agent, used so-called " ferrone gas " (halogen that cfc etc. contain two or more halogens is hydro carbons) in the past, but owing to be the material that causes depletion of the ozone layer and greenhouse effects, so limit its production and consumption now.Therefore, in the manufacturing of polyurathamc foam, also to use other materials little to carrying capacity of environment as blowing agent.
As representational blowing agent, can enumerate water, carrene, low boiling fluorine is hydrocarbon, lower hydrocarbon, carbon dioxide (carbonic acid gas) etc., but these materials are compared with ferrone gas, operability equal difference, therefore, in order in formed body, to form uniform separated foam, in the manufacture method and manufacturing installation of polyurathamc foam, carrying out various technological improvements.
For example, the technology of using carbon dioxide manufacturing polyurathamc foam as blowing agent is disclosed in the patent documentation 1.The carbon dioxide that uses in this technology is also used carbon dioxide that the reaction by water and PIC composition generates and these two kinds of the carbon dioxide of supercriticality, subcritical state or liquid condition.
Specifically, in this technology, constituting PIC composition and polyol component is stored in the groove, they mix by mixing head and discharge, but as the carbon dioxide of the liquid condition of blowing agent, with respect to the polyol component in the stream of mixing head, carrying, cooperate with water with the scope of regulation, and in stream, above-mentioned carbon dioxide remains on supercriticality or subcritical state.
Carbon dioxide by using such state is as blowing agent, can improve the Combination of PIC composition and polyol component, and can reduce the use amount as the water of blowing agent, suppress the generation of the urea key of surplus, therefore can access the hard polyurethane foams of low-density and anti-flammability height, excellent in dimensional stability.
In addition, disclose in the patent documentation 2 in the manufacturing installation of making foamed synthetic resins such as polyurathamc foam, use the gas different with blowing agent, improve the Combination of PIC and polyalcohol, and realize improving the diffusive technology when discharging from mixing head.
Specifically, in the above-mentioned manufacturing installation, be provided with the unit of first gas that the mixing that import to promote PIC and polyalcohol stirs at mixing head, be provided with in discharge nozzle portion and import the unit that promotes second gas that scatters.Thus, can promote the mixing of PIC and polyalcohol to stir by first gas, by the uniform distribution of second gas promotion from discharge nozzle portion, therefore can prevent undermixing and can make the separated foam miniaturization, and can prevent the generation in the space in the foamed synthetic resin.
In addition, in this technology, disclose as the pentane class of blowing agent use as one of lower hydrocarbon, also water.Pentane (and water) and catalyst, other additive are mixed together in the polyalcohol, are kept in the groove as polyol component.In addition, first gas that promote to mix stirs, promote second gas of uniformly dispersing, as long as all be to be the gas of gas at normal temperature and pressure, specifically, can illustration rare gas, for fluon (replacement Off ロ Application) class, nitrogen etc.Wherein, viewpoint from the heat-insulating property of the foam that obtains, economy, security, carrying capacity of environment etc., preferred air, nitrogen, carbon dioxide, particularly purity is the carbon dioxide more than 95%, because it is close with the thermal characteristics of the pentane of blowing agent, so can reduce the thermal conductivity of resulting foamed synthetic resin, therefore more preferred.
The prior art document
Patent documentation
Patent documentation 1: No. 4154654 communique of Japan's special permission
Patent documentation 2: TOHKEMY 2009-079173 communique
Summary of the invention
Invent problem to be solved
But polyurethane resin is thermosetting resin, therefore, can not heat recycling as thermoplastic resin, unless utilize certain special technique, it is broken and waste treatment such as bury all to need to carry out burning disposal or compression.Therefore, in the polyurathamc foam, not only just improve heat-insulating property, it is also very important to reduce its density.
Specifically, reduce the density of polyurathamc foam, refer to reduce the amount of the polyurethane resin in the prescribed volume.Therefore, even the polyurathamc volume of foam is big, as long as density is little, then when burning or compressing fragmentation etc. and handle, just tail off as the amount of discarded object, as a result of just can reduce the amount of rubbish.And as long as reduce the density of polyurathamc foam, the polyurethane resin of equivalent just can be made bigger article shaped, therefore sees comparatively desirable from the manufacturing cost aspect.
The polyurathamc foam has the separated foam of blowing agent to constitute by resin part and inclosure, therefore, and in order to reduce the density of polyurathamc foam, as long as increase separated foam.
But, increase separated foam and just mean the use amount that increases blowing agent.For example, using under the situation of lower hydrocarbon as blowing agent such as pentane, because such lower hydrocarbon also is the compound that uses as organic solvent, so if increase its use amount then might increase to the load that environment applies.On the other hand, very little to the load of environment although compare with lower hydrocarbon using under the situation of carbon dioxide as blowing agent, poor as the operability of blowing agent, be difficult to fully increase separated foam.
For example, disclosed technology in patent documentation 1 need be maintained carbon dioxide aqueous when mixing, in mixed stream, be maintained supercriticality or subcritical state, therefore, particularly need to arrange in addition the equipment of suitably keeping supercriticality or subcritical state.In addition, in the patent documentation 1, having enumerated carbon dioxide with liquid directly drops into the example in the polyol component and uses static(al) blender (Static mixer) etc. to carry out the example of mechanical mixture, but directly the example that drops into is difficult to increase the combined amount of carbon dioxide, is difficult to regulate the pressure when discharging under the situation of mechanical mixture.Originally the meltage of carbon dioxide is just limited, therefore, only uses under the situation of carbon dioxide its increment very difficult as blowing agent.
In addition, disclosed technology in the patent documentation 2 is used pentane as blowing agent, and uses first gas to promote to mix and stir, and uses second gas to promote uniformly dispersing, but do not have aspect the increment of realizing blowing agent any open.In addition, the amount as the pentane of blowing agent is increased, as previously mentioned, may increase the load of environment.
At this, disclose as first gas and the preferred highly purified carbon dioxide of second gas, therefore the separated foam by the foamed synthetic resin of this technology manufacturing may contain carbon dioxide.But, first and second gases not only use as blowing agent, but also are used for promoting to mix stirring and uniformly dispersing, even therefore use a large amount of carbon dioxide as these gases, can fully not dissolve in the mixture before solidifying yet, can not cause the increase of separated foam.
The present invention finishes in order to solve such problem, its purpose is that the load that proposes can suppress environment increases, increase the combined amount of blowing agent by simple formation, the polyurathamc foam of less dense can be made, and the technology that is manufactured on the polyurathamc foam that insulated structure possesses can be applicable to.
Be used for solving the method for problem
The manufacturing installation of polyurathamc foam of the present invention, in order to address the above problem, it constitutes: be first composition of main component for be used for mixing with the PIC, foaminess second composition that obtains with mixed blowing agent in second composition that with the polyalcohol is main component, make the manufacturing installation of polyurathamc foam, possess: mix described first composition and described foaminess second composition and with the mixing portion of its discharge, with second storage part with above-mentioned foaminess second composition of the airtight storage of mode that can supply with this mixing portion, as above-mentioned blowing agent, use main foaming agent and have than the low boiling point of this main foaming agent and at the secondary blowing agent of normal temperature as gas, be mixed with above-mentioned main foaming agent and above-mentioned secondary blowing agent in above-mentioned foaminess second composition, in addition, above-mentioned manufacturing installation also possesses the free suppressing portion of free secondary blowing agent that suppresses above-mentioned foaminess second composition that above-mentioned secondary blowing agent stores in above-mentioned second storage part.
In the above-mentioned manufacturing installation, the free suppressing portion of above-mentioned secondary blowing agent can be for being filled in storing pressurized agent filling part in above-mentioned second storage part with the storing pressurized agent with pressurized state, wherein, this storing pressurized agent is that solubility in above-mentioned second composition and diffusion coefficient are than the littler gas of above-mentioned secondary blowing agent.
In addition, in the above-mentioned manufacturing installation, in above-mentioned second storage part, above-mentioned foaminess second composition forms liquid layer, and by filling the inactive gas of this foaminess second composition is formed gas-bearing formation, the free suppressing portion of above-mentioned secondary blowing agent can be for sealing the liquid layer seal member of above-mentioned liquid layer with respect to above-mentioned gas-bearing formation.
In addition, the manufacture method of polyurathamc foam of the present invention, in order to solve above-mentioned problem, it constitutes: it is first composition of main component for mixing with the PIC, foaminess second composition that obtains with mixed foaming agent in second composition that with the polyalcohol is main component, make the method for polyurathamc foam, as above-mentioned blowing agent, use main foaming agent and have than the low boiling point of this main foaming agent and at the secondary blowing agent of normal temperature as gas, this method comprises: the main foaming agent blend step, in second composition that with the polyalcohol is composition, mix main foaming agent, modulate half foaminess, second composition; Secondary blowing agent blend step mixes secondary blowing agent in above-mentioned half foaminess, second composition, modulation foaminess second composition; Mix to discharge step, mixed foaming second composition and first composition and with its discharge; With the free step that suppresses of secondary blowing agent, before step is discharged in above-mentioned mixing, suppress above-mentioned secondary blowing agent dissociating from above-mentioned foaminess second composition.
In the above-mentioned manufacture method, above-mentioned secondary blowing agent is free suppress step can for by the storing pressurized agent with the storage container of internal pressurization in the pressurized storage step of above-mentioned foaminess second composition of storage, wherein, this storing pressurized agent is that solubility in above-mentioned half foaminess, second composition and diffusion coefficient are than the littler gas of above-mentioned secondary blowing agent.
In addition, in the above-mentioned manufacture method, the free step that suppresses of above-mentioned secondary blowing agent can with respect to by the gas-bearing formation that the inactive gas of above-mentioned foaminess second composition is formed, seal the liquid layer sealing step of the liquid layer that is formed by above-mentioned foaminess second composition in storage container.
Above-mentioned purpose of the present invention, other purposes, feature and advantage with reference to accompanying drawing, can be known from the detailed description of following preferred embodiment.
The effect of invention
More than, according to the present invention, can bring into play following effect: can suppress the increase to the load of environment, by simply constituting the combined amount that increases blowing agent, can make the polyurathamc foam of less dense, also can be applicable to and make the polyurathamc foam that insulated structure possesses.
Description of drawings
Figure 1A is the schematic diagram of an example of the structure of the manufacturing installation of the polyurathamc foam of expression embodiments of the present invention 1, and Figure 1B is the schematic diagram of an example of the manufacturing installation of the existing representational polyurathamc foam of expression.
Fig. 2 is the signal piping diagram of an example of the structure of second storage part in the manufacturing installation of the polyurathamc foam represented of expression Figure 1A, storing pressurized agent filling part and secondary blowing agent mixing portion.
Fig. 3 is the summary process chart of an example of the manufacture method of the polyurathamc foam of expression embodiments of the present invention 1.
Fig. 4 A and Fig. 4 B are the schematic diagram of an example of the manufacturing installation of the polyurathamc foam of representing embodiments of the present invention 2 respectively.
Fig. 5 is the schematic diagram of an example of the structure of the manufacturing installation of the polyurathamc foam of expression embodiments of the present invention 3.
Fig. 6 is the signal piping diagram of an example of the structure of second storage part in the manufacturing installation of expression polyurathamc foam shown in Figure 5 and secondary blowing agent mixing portion.
Fig. 7 A～Fig. 7 C is the schematic diagram of an example of the concrete structure of the set liquid layer seal member of expression second storage part shown in Figure 6.
Fig. 8 is the summary process chart of an example of the manufacture method of the polyurathamc foam of expression embodiments of the present invention 3.
Fig. 9 is in the manufacturing installation and manufacture method of expression as the polyurathamc foam of embodiments of the present invention 4, the schematic isometric of the part-structure of the freezer of an example of the insulated structure of the object of filling-foam polyurethane foam.
Figure 10 is in the manufacturing installation and manufacture method of expression as the polyurathamc foam of embodiments of the present invention 4, the integrally-built schematic diagram of the heat pump hot-water supply that possesses hot water tank of an example of the insulated structure of the object of filling-foam polyurethane foam.
The specific embodiment
The manufacturing installation of polyurathamc foam of the present invention, be first composition of main component for be used for mixing with the PIC, foaminess second composition that obtains with mixed blowing agent in second composition that with the polyalcohol is main component, make the manufacturing installation of polyurathamc foam, it possesses: mix above-mentioned first composition and above-mentioned foaminess second composition and with the mixing portion of its discharge, with second storage part with above-mentioned foaminess second composition of the airtight storage of mode that can supply with this mixing portion, as above-mentioned blowing agent, use main foaming agent and have than the low boiling point of this main foaming agent and at the secondary blowing agent of normal temperature as gas, be mixed with above-mentioned main foaming agent and above-mentioned secondary blowing agent in above-mentioned foaminess second composition, and this manufacturing installation possesses also suppress the free free suppressing portion of secondary blowing agent above-mentioned foaminess second composition that above-mentioned secondary blowing agent stores in above-mentioned second storage part.
According to above-mentioned formation, the manufacturing installation of polyurathamc foam possesses the free suppressing portion of secondary blowing agent, therefore can suppress the increase to carrying capacity of environment, by simply constituting the combined amount that increases blowing agent, makes the polyurathamc foam of less dense.Its result also can be applicable to the manufacturing of the polyurathamc foam that insulated structure possesses.
In the above-mentioned manufacturing installation, can constitute: the free suppressing portion of above-mentioned secondary blowing agent will be for being filled in the storing pressurized agent filling part in above-mentioned second storage part as the storing pressurized agent of the solubility in above-mentioned second composition and the diffusion coefficient gas littler than above-mentioned secondary blowing agent with pressurized state.
According to above-mentioned formation, fill the storing pressurized agent by storing pressurized agent filling part in the inside of second storage part, so the space beyond foaminess second composition is filled the storing pressurized agent.Thus, can suppress secondary blowing agent dissociating in second storage part in fact.Therefore, even main foaming agent is mixed into the limit in foaminess second composition, also can stablizes and mix the fully secondary blowing agent of amount, and, need not adopt complicated structure in order to prevent secondary blowing agent from leaking.Therefore, can make the polyurathamc foam of less dense by the simple combined amount that constitutes the increase blowing agent.
In addition, above-mentioned manufacturing installation can constitute: will only mix material that above-mentioned main foaming agent obtains as half foaminess, second composition in above-mentioned second composition time, above-mentioned storing pressurized agent is that solubility and the diffusion coefficient in above-mentioned half foaminess, second composition equates with above-mentioned secondary blowing agent or the gas littler than above-mentioned secondary blowing agent.
According to above-mentioned formation, the gas of storing pressurized agent for being difficult to more than double foaminess of secondary blowing agent, second composition dissolve and spread.Therefore, the storing pressurized agent is difficult to dissolve in foaminess second composition (mixing the composition that secondary blowing agent obtains in half foaminess, second composition), therefore, can further suppress the free of secondary blowing agent.
In addition, can to constitute above-mentioned storing pressurized agent be nitrogen or air to above-mentioned manufacturing installation.
According to above-mentioned formation, nitrogen or air are the also gas of excellence of cheapness, operability, can be suitable as the storing pressurized agent.
In addition, above-mentioned manufacturing installation can constitute: in above-mentioned second storage part, above-mentioned foaminess second composition forms liquid layer, and form gas-bearing formation by filling with respect to the inactive gas of this foaminess second composition, the free suppressing portion of above-mentioned secondary blowing agent is for sealing the liquid layer seal member of above-mentioned liquid layer with respect to above-mentioned gas-bearing formation.
According to above-mentioned formation, though secondary blowing agent will dissociate, sealed liquid layer by the liquid layer seal member from foaminess second composition, therefore, suppressed secondary blowing agent dissociating to gas-bearing formation.Therefore, can suppress the increase to the load of environment, by simply constituting the combined amount that increases blowing agent, make the polyurathamc foam of less dense.
In addition, above-mentioned manufacturing installation can constitute: above-mentioned liquid layer seal member is in above-mentioned second storage part, the movable member that is accompanied by the liquid level position change of above-mentioned liquid layer and can moves is perhaps for being fixed on the partition fixed part in this second storage part under the state that cuts off in above-mentioned second storage part.
According to above-mentioned formation, if the liquid layer seal member is movable member, foaminess second composition (liquid layer) in second storage part though the liquid level change, also can follow and seal, can suppress the free of secondary blowing agent.In addition, if the liquid layer seal member owing to can cut off foaminess second composition (liquid layer) and gas-bearing formation, so can seal liquid level, can suppress the free of secondary blowing agent for cutting off fixed part.
In addition, above-mentioned manufacturing installation can constitute: carry out when utilizing above-mentioned liquid layer seal member to above-mentioned foaminess second composition more than the filling 90 volume % in above-mentioned second storage part of being sealed in of above-mentioned liquid layer.
According to above-mentioned formation, owing to fill above foaminess second composition of 90 volume % in second storage part, so can suppress the reduction of the dissolving ratio of secondary blowing agent.Therefore, can suppress the free of secondary blowing agent.
Above-mentioned manufacturing installation can constitute: the material that only mixes above-mentioned main foaming agent in above-mentioned second composition is during as half foaminess, second composition, also possess with respect to above-mentioned half foaminess, second composition and mix above-mentioned secondary blowing agent, modulate the secondary blowing agent mixing portion of above-mentioned foaminess second composition.
According to above-mentioned formation, also possess secondary blowing agent mixing portion, therefore can effectively stably mix secondary blowing agent.
In addition, can to constitute above-mentioned secondary blowing agent be carbon dioxide to above-mentioned manufacturing installation.
According to above-mentioned formation, carbon dioxide is under the freezing point 79 ℃ at atmospheric boiling point roughly, is very high, chemically stable, the environment resistant also excellent material of foaming power.Therefore, can be suitable as inhibition to the secondary blowing agent use of the load of environment.
In addition, in the above-mentioned manufacturing installation, can constitute above-mentioned main foaming agent and be in lower hydrocarbon and the hydrofluorocarbons at least one.
According to above-mentioned formation, the thermal conductivity of lower hydrocarbon or hydrofluorocarbons is lower, and also little to the load of environment, therefore is suitable as main foaming agent and uses.
In addition, constituting of the manufacture method of polyurathamc foam of the present invention, it is first composition of main component for mixing with the PIC, foaminess second composition that obtains with mixed foaming agent in second composition that with the polyalcohol is main component, make the method for polyurathamc foam, as above-mentioned blowing agent, use main foaming agent and have than the low boiling point of this main foaming agent and at the secondary blowing agent of normal temperature as gas, this manufacture method comprises: mix main foaming agent in second composition that with the polyalcohol is composition, modulate the main foaming agent blend step of half foaminess, second composition; In above-mentioned half foaminess, second composition, mix secondary blowing agent, the secondary blowing agent blend step of modulation foaminess second composition; Mixed foaming second composition and first composition are also discharged step with the mixing of its discharge; Before discharging step in above-mentioned mixing, suppress the free step that suppresses of secondary blowing agent that above-mentioned secondary blowing agent dissociates from above-mentioned foaminess second composition.
According to above-mentioned formation, the manufacture method of polyurathamc foam comprises the free step that suppresses of secondary blowing agent, therefore, can suppress the increase to the load of environment, with the combined amount of simple formation increase blowing agent, makes the polyurathamc foam of less dense.Its result also is fit to use in the manufacturing of the polyurathamc foam that insulated structure possesses.
Above-mentioned manufacture method can constitute: above-mentioned secondary blowing agent is free suppress step for by the storing pressurized agent with the storage container of internal pressurization in the pressurized storage step of above-mentioned foaminess second composition of storage, this storing pressurized agent is that solubility in above-mentioned half foaminess, second composition and diffusion coefficient are than the littler gas of above-mentioned secondary blowing agent.
According to above-mentioned formation, by the pressurized storage step, the space beyond foaminess second composition in the storage container is full of the storing pressurized agent.Thus, can suppress secondary blowing agent dissociating in storage container in fact.Therefore, even main foaming agent is mixed into the limit in foaminess second composition, also can stablizes and mix the fully secondary blowing agent of amount, and there is no need to adopt for the leakage that prevents secondary blowing agent the formation of complexity.Therefore, can increase the combined amount of blowing agent with simple formation, make the polyurathamc foam of less dense.
In addition, above-mentioned manufacture method can constitute: the free step that suppresses of above-mentioned secondary blowing agent is in storage container, with respect to by the gas-bearing formation that the inactive gas of above-mentioned foaminess second composition is formed, seal the liquid layer sealing step of the liquid layer that is formed by above-mentioned foaminess second composition.
According to above-mentioned formation, though secondary blowing agent will dissociate, owing to seal the step sealed liquid layer by liquid layer, suppressed secondary blowing agent dissociating to gas-bearing formation from foaminess second composition.Therefore, can suppress the increase to the load of environment, with the combined amount of simple formation increase blowing agent, make the polyurathamc foam of less dense.
Constituting of insulated structure of the present invention: constituted by internal material and exterior material at least, form the packing space of filling above-mentioned polyurathamc foam between said external material and the above-mentioned internal material, in above-mentioned packing space, be filled with the above-mentioned polyurathamc foam that utilizes above-mentioned manufacturing installation or above-mentioned manufacture method manufacturing.
According to above-mentioned formation, can suppress the increase to the load of environment, increase the combined amount of blowing agent with simple formation.
Above-mentioned insulated structure can constitute: have the inlet that arranges, be used for injecting at above-mentioned packing space the mixture of above-mentioned first composition and above-mentioned foaminess second composition at least one of above-mentioned internal material and said external material, and above-mentioned packing space comprises at least and is communicated with above-mentioned inlet and expands to flat first packing space and be communicated with this first packing space and expand to flat second packing space with respect to this first packing space crisscross.
Above-mentioned such packing space, said mixture flows in the mode around the packing space integral body that has the three-dimensional position relation.But the viscosity of carrying out that the said mixture limit is accompanied by the resinification reaction slowly rises, and foams in the limit, and therefore foaming is easy to generate deviation.When foaming produces deviation in packing space, from guaranteeing the viewpoint of heat-insulating property, need be the density that benchmark is set the polyurathamc foam with the minimum position of frothing percentage just.The low density height that refers to owing to the polyurathamc foam of frothing percentage is so the amount of the polyurathamc foam that the result uses increases.
Relative therewith, according to above-mentioned formation, can in said mixture, promptly expand as the carbon dioxide of secondary blowing agent, even and the viscosity of said mixture rise, also can accept to be expanded with stronger power by the heating of resinification reaction etc.Therefore, even be along with viscosity rises with the mode process of flowing around packing space, also can be in said mixture rapid and good foaming.Its result with existing comparison, can be implemented in more uniform foaming on the whole in the three-dimensional packing space, can further improve the thermal insulation of insulated structure.
In addition, if can realize foaming uniformly on the whole, even be the density that benchmark is set the polyurathamc foam with the minimum position of frothing percentage, the increment of polyurathamc foam seldom gets final product.Therefore, the reduction of manufacturing cost can be realized, and the minimizing of the rubbish when discarded can be realized.
In addition, can constitute: the above-mentioned adiabatic body of making is to be selected from freezer, freezer, heat-insulating shield and the hot water tank at least one.
According to above-mentioned formation, even in freezer, freezer, heat-insulating shield and hot water tank, also can be implemented in foaming uniformly on the whole in the three-dimensional packing space, can further improve the thermal insulation of insulated structure.
Below, with reference to description of drawings preferred embodiment of the present invention.In addition, below in all figure to the identical reference symbol of element annotation identical or that be equal to, omit its repeat specification.
(embodiment 1)
[formation of the manufacturing installation of polyurathamc]
At first, with reference to Figure 1A and Fig. 2, the formation of the manufacturing installation of the polyurathamc foam of embodiments of the present invention 1 is specifically described.Figure 1A is the schematic diagram of an example of the formation of the manufacturing installation 10A of the polyurathamc foam of expression embodiments of the present invention 1, and Figure 1B is the schematic diagram of an example of the manufacturing installation 100 of the existing polyurathamc foam of expression.Fig. 2 represents the pattern piping diagram of an example of the formation of second storage part of the manufacturing installation 10A that represents among Figure 1A and storing pressurized agent filling part.
Shown in Figure 1A, the manufacturing installation 10A of the polyurathamc foam of present embodiment possesses first storage part 11, second storage part 12, mixing portion 13 and storing pressurized agent filling part (secondary blowing agent dissociate suppressing portion) 14.
It is first composition of main component and mixed foaming agent obtains in second composition that is main component foaminess second composition with the polyalcohol that the manufacturing installation 10A of present embodiment mixes with the PIC, makes the polyurathamc foam.First storage part 11 is storing above-mentioned first composition to the mode that mixing portion 13 supplies with, and second storage part 12 is storing foaminess second composition to the mode that mixing portion 13 supplies with.The concrete structure of first storage part 11 and second storage part 12 is not particularly limited, and all can be fit to use known storage container (for example, holding tank etc.) in the manufacturing field of polyurathamc foam.Just, as described later, second storage part 12 is not only storage container but has its specific structure.
Wherein, second storage part 12 and first storage part 11 are similarly known storage container and get final product, but also can constitute: within it under the state of airtight storage foaminess second composition of portion, by storing pressurized agent filling part 14, with the storing pressurized agent of pressurized state blanketing gas.
One example of the concrete formation of second storage part 12 and storing pressurized agent filling part 14 describes with reference to Fig. 2.As shown in Figure 2, present embodiment, second storage part 12 is provided with mixing part 23, pressure regulator 22, gas-bearing formation temperature sensor 24, liquid layer temperature sensor 25 etc. with respect to the holding tank 21 as main body, and second storage part 12 also is connected with storing pressurized agent filling part 14.
The bottom of holding tank 21 connects an end of second supply pipeline 32 and an end of secondary blowing agent mixing line 34.The other end of second supply pipeline 32 shown in Figure 1A, is connected with mixing portion 13, and the other end of secondary blowing agent mixing line 34 is connected with not shown polyalcohol supply source.In addition, be provided with supply pump 35 at second supply pipeline 32, be provided with secondary blowing agent mixing portion 15 and be located thereon the supply pump 33 of trip side in secondary blowing agent mixing line 34, in addition, be provided with the junction of two streams Ps of secondary blowing agent supply unit 50 between these secondary blowing agent mixing portions 15 and the mixing pump 33.
In addition, the concrete formation of pressure regulator 22, mixing part 23, gas-bearing formation temperature sensor 24, liquid layer temperature sensor 25 is not particularly limited, and can utilize the instrument class, agitating unit in storage, circulation various resin raw materials or fields such as other aqueous chemical raw material, synthetic etc.
In the present embodiment, storing pressurized agent filling part 14 is made of storing pressurized agent storage part 41, pressure regulator 42 and storing pressurized agent supply pipeline 43 etc.Storing pressurized agent storage part 41 with the storing pressurized agent with can be in the second storage part 12(holding tank 21) mode supplied with stores because the storing pressurized agent of present embodiment is nitrogen (N
2), so storing pressurized agent storage part 41 is made of nitrogen cylinder.Supply pressure when pressure regulator 42 adjustings supply to 12 fillings of second storage part with the storing pressurized agent.Storing pressurized agent supply pipeline 43 is for connecting the pipe arrangement of holding tank 21 and storing pressurized agent storage part 41 in the mode that can supply with the storing pressurized agent.
In the present embodiment, secondary blowing agent supply unit 50 is made of secondary blowing agent storage part 51, pressure regulator 52, secondary blowing agent supply pipeline 53 and flow control valve 54 etc.Secondary blowing agent storage part 51 is stored secondary blowing agent in the mode that can supply with to the junction of two streams Ps of secondary blowing agent mixing line 34, the secondary blowing agent in the present embodiment is carbon dioxide (carbonic acid gas, CO
2), constituted by dioxide bottle.Supply pressure when pressure regulator 52 adjustings are supplied with from secondary blowing agent to junction of two streams Ps.Secondary blowing agent supply pipeline 53 is with the mode auxiliary connection blowing agent storage part 51 that can supply with and the pipe arrangement of junction of two streams Ps.Flow control valve 54 is the valve of adjusting to the quantity delivered of the secondary blowing agent of junction of two streams Ps.
Secondary blowing agent mixing portion 51 be for will being mixed into the part in the feedstock composition that flows the secondary blowing agent mixing line 34 from the secondary blowing agent that junction of two streams Ps supplies with, and in the present embodiment, secondary blowing agent mixing portion 51 is made of the static(al) blender.Wherein, the other end supply from secondary blowing agent mixing line 34 has only mixed half foaminess, second composition that main foaming agent obtains second composition that with the polyalcohol is main component.Therefore, secondary blowing agent mixing portion 15 mixes secondary blowing agent and modulates foaminess second composition with respect to half foaminess, second composition.
In addition, the concrete formation of supply pump 33,35, storing pressurized agent storage part 41, pressure regulator 42, storing pressurized agent supply pipeline 43, secondary blowing agent storage part 51, pressure regulator 52, secondary blowing agent supply pipeline 53, flow control valve 54 and secondary blowing agent mixing portion 15 is not particularly limited, the pump that can be fit to use storage, circulation to comprise the field of known industrial gas such as nitrogen, carbon dioxide, memory cell, instrument class, valve cell, mixed cell etc.In addition, junction of two streams Ps both can be the formation of connecting pipings simply, also can be for the formation of valve cell is set in addition.
In addition, the concrete formation of the polyalcohol supply source that is connected with secondary blowing agent mixing line 34 is not particularly limited, can be that second modulation portion of main component and second composition that does not comprise main foaming agent and the main foaming agent mixing portion of mixing main foaming agent in this second composition constitute with the polyalcohol by modulation, above-mentioned second modulation portion constitutes half foaminess, second composition that modulation begins to comprise main foaming agent most, can also can be other known structure for not comprising the structure of main foaming agent mixing portion.
Then, in formation shown in Figure 2, the mixing of secondary blowing agent and storing pressurized agent are specifically described to the filling of second storage part 12.As mentioned above, the other end of secondary blowing agent mixing line 34 is connected with not shown polyalcohol supply source, and the raw material of supplying with from this supply source is half foaminess, second composition.And shown in the arrow F0 of Fig. 2, half foaminess, second composition is supplied with to secondary blowing agent mixing line 34 from the polyalcohol supply source by supply pump 33.
Flow direction (direction of arrow F0) with first composition and second composition is benchmark, and secondary blowing agent mixing line 34 connects not shown polyalcohol supply source, supply pump 33, junction of two streams Ps, secondary blowing agent mixing portion 15 and holding tank 21(second storage part 12 successively).In addition, second supply pipeline 32 that is connected with holding tank 21 is benchmark with above-mentioned flow direction (direction of arrow F0) also, connects the 13(of mixing portion not shown among holding tank 21, supply pump 35 and Fig. 2 successively with reference to Figure 1A).
Therefore, (upstream side in secondary blowing agent mixing portion 15 is half foaminess, second composition to flow through the feedstock composition of secondary blowing agent mixing line 34, being foaminess second composition in the downstream) action by supply pump 33 21 flows from the polyalcohol supply source to holding tank, thus, the action of the feedstock composition (foaminess second composition) that flows through second supply pipeline 32 by supply pump 35 13 flowed from holding tank 21 to mixing portion.
[formation of feedstock composition, blowing agent and storing pressurized agent]
Then, more specific description is carried out in feedstock composition, blowing agent and the storing pressurized agent that the present invention is used.
The feedstock composition that uses among the present invention is as first composition of main component with second composition of polyalcohol as main component with PIC.Wherein, the PIC that comprises as first composition, can be corresponding enumerate known compound as the desired rerum natura of polyurathamc foam of purpose etc., typically, can enumerate the PIC of fragrant family, cycloaliphatic ring family or fatty family of the NCO that has more than 2 or modified polyisocyanate that their modifications are obtained etc.
More particularly, for example can enumerate isocyanates based compounds such as benzal vulcabond, methyl diphenylene diisocyanate, polymethylene polyphenyl isocyanate, xyxylene vulcabond, hexamethylene diisocyanate, dimethyl phenylene vulcabond, dibenzyl vulcabond, anthracene vulcabond, dimethyl diphenyl vulcabond, their prepolymer type modification body, urate modification body, urea-modified body etc.
Substituent position is not particularly limited in these compounds.These compounds and modification body can use separately also and can appropriate combination use more than 2 kinds in addition.In addition, in the present embodiment, in order to distinguish as the PIC of individual compound with as the PIC of composition integral body, the former abbreviates " PIC " as, and the latter is called " PIC composition ".Wherein, the preferred PIC composition that uses is not particularly limited in the present embodiment, can be corresponding to the suitable compounds of selection such as purposes of resulting polyurathamc foam.
In addition, as the polyalcohol that comprises in second composition, the corresponding desired rerum natura of polyurathamc foam as purpose etc. can be enumerated known compound, the typical case, can enumerate polyethers is that polyalcohol, polyester are the diene polymer of polyalcohol, polyalcohol, hydroxyl etc.
More particularly, for example, be polyalcohol as polyethers, can be set forth in polyalcohol, carbohydrate, alkanolamine, polyamine, polyphenol and other the initator and to add compound that cyclic ether or oxyalkylene obtain etc.Can make spent glycol, propane diols, diglycol, dipropylene glycol, glycerine, trimethylolpropane, pentaerythrite etc. as above-mentioned polyalcohol, as above-mentioned carbohydrate, can use sucrose, glucose, D-sorbite etc., as above-mentioned alkanolamine, can use diethanol amine, triethanolamine etc., as above-mentioned polyamine, can use ethylenediamine, toluenediamine, diaminodiphenyl-methane, polymethylene polyphenyl base amine etc., as above-mentioned polyphenol, can use bisphenol-A, bisphenol S, phenolic resins is initial stage condensation product etc.In addition, be polyalcohol as polyester, can enumerate the polyalcohol-polyalcohol of polyvalent carboxylic acid condensate system, the polyalcohol of cyclic ester ring-opening polymerisation system, fragrant family PEPA etc.
These compounds can use separately, also can appropriate combination use more than 2 kinds.In addition, in the present embodiment, in order distinguishing as the polyalcohol of individual compound with as the polyalcohol of composition integral body, to abbreviate the former as " polyalcohol ", the latter to be called " polyol component ".Wherein, the preferred polyol component that uses is not particularly limited in the present embodiment, can be corresponding to the purposes of the polyurathamc foam that obtains etc., select suitable compound.
Above-mentioned first composition and second composition also can comprise the composition beyond above-mentioned PIC or the polyalcohol, for example catalyst and various additive.Can enumerate blowing agent, surfactant, filler, stabilizing agent, colouring agent, fire retardant etc. at this so-called additive.In addition, among the present invention, have only blowing agent conduct and the independently composition operation of other additives in these additives.
Above-mentioned catalyst as long as be the composition that promotes the resinification reaction (polycondensation reaction) of PIC and polyalcohol, just can suitably use known compound.Specifically, can enumerate dimethylethanolamine, triethylenediamine, dimethyl cyclohexyl amine, 1, amine catalysts such as 2-methylimidazole, five methyl diethylentriamine, two (2-dimethyl aminoethyl) ether, metallic compound such as lead octoate, dibutyl tin laurate series catalysts, isocyanuric acid esterification catalyst such as three (dimethylaminopropyl), six hydrogen-S-triamine, potassium acetate, potassium octanoate etc.These catalyst can only be used singly, or in combination of two or more kinds.
In addition, be under the situation of the preferred compound that uses in the field of freezer at PIC composition and polyol component, in the above-mentioned catalyst as the alveolation catalyst, can preferably use N, N, N ' N ", N "-five methyl diethylentriamine, can preferably use triethylenediamine as the resinification catalyst.
Above-mentioned catalyst can be included in second composition in advance in the present embodiment.That is, second composition preferably cooperates catalyst at least and modulates in above-mentioned polyol component.In addition, before utilizing blowing agent to produce foaming, can cooperate surfactant to produce bubble to prevent second composition.As surfactant, can be fit to use known poly-organosilicon system: compositions, be not particularly limited.In addition, the additive (filler, stabilizing agent, colouring agent, fire retardant) beyond the surfactant etc. got final product corresponding to suitable cooperations such as the desired rerum naturas of making of polyurathamc foam, and the object of cooperation can also can be first composition for second composition.
Each composition that comprises in first composition and second composition, particularly as the PIC composition of main component and polyol component, as the catalyst of important component in the resinification reaction, its use level, concentration etc. are not particularly limited.These compositions, according to first composition and the quantity delivered of second composition, the various conditions such as mixed characteristic of mixing portion 13 among the desired rerum natura of making of polyurathamc foam, the manufacturing installation 10A, regulate use level or concentration etc. its mixing ratio that becomes proper range is got final product.
Among the present invention, except above-mentioned catalyst, above-mentioned blowing agent also is important composition.This blowing agent as previously mentioned, can be enumerated 2 kinds of main foaming agent and secondary blowing agents.The reaction heat that produces for the chemical reaction by PIC composition and polyol component of the main foaming agent material that can gasify wherein specifically, can be enumerated the lower hydrocarbon of carbon number below 6, hydrofluorocarbons (HFC) etc.Wherein, especially preferably use pentane, isopentane (2-methybutane), c-pentane pentane classes such as (pentamethylene).These pentane classes, boiling point are below 50 ℃, and thermal conductivity is 12.4～14.5mW/mK(25 ℃), have better thermal conductivity, ozone layer destroying coefficient (ODP) is 0, greenhouse effects coefficient (GWP) is 0.0004 low-down value.Therefore, with HFC etc. relatively, little to the load of environment, therefore preferred.
In addition, especially preferably use pentamethylene in the above-mentioned pentane class.The pentamethylene boiling point is about 49 ℃, even therefore mix also and can not gasify with the polyol component (perhaps PIC composition) of (for example about 25 ℃) storage below normal temperature, so can not foam.But, when after mixing portion 13 discharges, polyol component and the reaction of PIC composition, because its reaction heat, temperature can rise to boiling point easily, so pentamethylene can easily foam.
As main foaming agent, corresponding and its service condition, can use HFC or other for fluon.As the example of preferred HFC, can enumerate HFC-134a, HFC-245fa, HFC-365mfc etc.These compounds also have good boiling point and the thermal conductivity of using as main foaming agent, are 0 though GWP is 0.082～0.25 ODP, and are therefore less to the duty ratio of environment.
Above-mentioned secondary blowing agent so long as have the boiling point lower than above-mentioned main foaming agent, at normal temperatures for the material of gas gets final product, can enumerate carbon dioxide (carbonic acid gas, CO as a particularly preferred example
2).In the manufacturing field of polyurathamc foam, known have in polyol component, add water in advance, make the reaction of this water and PIC composition, produce " water foaming " technology of carbon dioxide, but among the present invention, as Figure 1A and shown in Figure 2, with different by the carbon dioxide of " water foaming " generation, with the carbon dioxide additional mixing of gas in second composition.
As previously mentioned, at present, known liquid CO 2 is blended in the polyol component, but is difficult to increase its combined amount.At this, the present invention, with airtight being stored in second storage part 12 of foaminess second composition that is mixed with as the carbon dioxide of secondary blowing agent, the storing pressurized agent is filled in pressurization under this state.Thus, even main foaming agent is mixed into the limit in foaminess second composition, also can stablizes and mix the fully secondary blowing agent of amount, and, complicated structure need do not adopted for the leakage that prevents secondary blowing agent.Therefore, can increase the combined amount of blowing agent with simple formation.
In addition, secondary blowing agent is not limited to carbon dioxide, as long as have than the low boiling point of main foaming agent and be the condition of gas at normal temperature, also can be other gas.The carbon dioxide cheapness, and as previously mentioned, have the real achievement that uses as blowing agent in " water foaming ", so especially preferably use among the present invention, but can use other gas certainly as secondary blowing agent.In addition, also can be in second composition hydrous water, thus mix from mixing portion 13 discharge after, the parallel foaming of being undertaken by secondary blowing agent and the foaming of being undertaken by other " water foaming ".In this case, the water that cooperates in second composition can be called as " the blowing agent propellant " of generation " as the carbon dioxide of main foaming agent ".
Above-mentioned storing pressurized agent in the present embodiment, is used nitrogen so long as get final product than solubility and the little gas of diffusion coefficient of secondary blowing agent to second composition.The inside of the holding tank 21 of storage foaminess second composition is filled with storing pressurized agent (being nitrogen specifically).The storing pressurized agent than secondary blowing agent to second composition indissoluble more, therefore, if make secondary blowing agent be mixed into the limit at the leading portion of holding tank 21 by secondary blowing agent mixing portion 15 in advance, will be suppressed at the free gas that becomes of the secondary blowing agent (carbon dioxide) that dissolves in foaminess second composition.Therefore (dissolving in) more than ever before secondary blowing agent (carbon dioxide) can be mixed, and molten in stable conditionization of depositing can be made.
In addition, as the storing pressurized agent, except nitrogen, can also use air.In this case, storing pressurized agent filling part 14 is not the storing pressurized agent storage part 41 of nitrogen cylinder etc., gets final product and possess the pressurization filling parts that air pressurized is filled in the holding tank 21.In addition, this pressurization filling part gets final product by formations such as known pumps.Nitrogen or air cheapness and operability are also excellent, so preferably use as the storing pressurized agent among the present invention, but also can use other gas as the storing pressurized agent certainly.
In addition, the concrete formation of secondary blowing agent and storing pressurized agent is not limited to above-mentioned carbon dioxide and nitrogen etc.Secondary blowing agent as previously mentioned, has the boiling point lower than main foaming agent, is that gas gets final product at normal temperature, and the storing pressurized agent is so long as get final product with respect to solubility and the diffusion coefficient gas littler than secondary blowing agent of second composition.Namely, among the present invention, storing pressurized agent so long as have can be kept the gas of rerum natura that the material selected as secondary blowing agent (be gas at normal temperature) fully dissolves in the state of foaminess second composition and get final product, and secondary blowing agent is not limited to carbon dioxide, and the storing pressurized agent is not limited to nitrogen etc.The main foaming agent that the secondary blowing agent that can select among the present invention and storing pressurized agent can be used, suitably the material of above-mentioned condition is satisfied in selection.
In addition, as the storing pressurized agent more preferably with respect to identical with secondary blowing agent with diffusion coefficient or littler than the secondary blowing agent gas of solubility of half foaminess, second composition.Under the situation of the solution of foaminess second composition being regarded as polyol component, remove catalyst and main foaming agent, just become major part and be the polyol component of solvent, the storing pressurized agent is so long as get final product with respect to the gas that polyol component more is difficult to dissolve and spread than secondary blowing agent.But, present embodiment particularly, use at normal temperature and can be the pentane class of liquid, therefore main foaming agent also can be considered as solvent, therefore finish half foaminess, second composition that main foaming agent mixes, can be considered as dissolving in the mixed solvent of polyol component and main foaming agent other compositions such as catalyst.Therefore, the storing pressurized agent more preferably more is difficult to the gas that dissolves and spread than secondary blowing agent with respect to " mixed solvent of polyol component and main foaming agent " (i.e. half foaminess, second composition).
[manufacture method of polyurathamc foam]
Then, with reference to Figure 1B and Fig. 3, to the manufacture method of the polyurathamc foam that uses the manufacturing installation 10A shown in Figure 1A, the limit contrasts the limit with existing formation and is specifically described.Figure 1B is the schematic diagram of an example of the manufacturing installation of the existing representational polyurathamc foam of expression, and Fig. 3 is the summary process chart of an example of the manufacture method of the polyurathamc foam of expression present embodiment 1.
In the manufacturing of the polyurathamc foam of present embodiment, mix first composition and in second composition, sneak into foaminess second composition that blowing agent obtains, make the polyurathamc foam, from this point with existing identical.Therefore, no matter in the manufacturing installation 10A of the present embodiment shown in Figure 1A, still at the existing manufacturing installation 100(shown in Figure 1B with reference to patent documentation 1) in, all modulating equally with the PIC is that step and the modulation of first composition of main component is the step of second composition of main component with the polyalcohol.In the process chart of Fig. 3, represent the first composition modulation step S10 and the second composition modulation step S21 enforcement that can walk abreast mutually.
In the above-mentioned example, the first composition modulation step S10 uses the PIC more than a kind or 2 kinds, cooperates known additive as required, modulates first composition and gets final product.In addition, among the second composition modulation step S21, in the polyalcohol more than a kind or 2 kinds, cooperate additives such as catalyst and surfactant, modulate second composition and get final product.
In addition, in the process chart shown in Figure 3, carry out in second composition that the second composition modulation step S21 modulates, mixing the main foaming agent blend step S22 of main foaming agent.Wherein, as main foaming agent, in above-mentioned example, be fit to use the pentane class, in addition also can with existing " water foaming " the same water that cooperates as the blowing agent propellant, in the second composition modulation step S21, also can add blowing agent propellants such as main foaming agents such as pentane class and water.Therefore, step S22 is not necessary operation, can omit with the form that is included among the step S21 yet.
If as being to cooperate main foaming agent (with the blowing agent propellant) in second composition of solution (polyhydric alcohol solutions) of solvent with the polyalcohol, then resulting polyhydric alcohol solutions is half foaminess, second composition as shown in the step S22 bracket.In this half foaminess, second composition, mix secondary blowing agent again, then obtain foaminess second composition.
At this, in the existing manufacturing installation 100 as shown in Figure 1B, at second storage part, 102 storages, half foaminess, second composition as common holding tank, therefore 13 supplies, half foaminess, second composition from second supply pipeline 32 to mixing portion.One end of second supply pipeline, the 32 auxiliary connection blowing agent supply pipelines 134 of manufacturing installation 100, and be provided with secondary blowing agent mixing portion 105 in the downstream of its tie point.The other end auxiliary connection blowing agent storage part 104 of secondary blowing agent supply pipeline 134.
Therefore, in the existing manufacturing installation 100, mechanical mixture is supplied with mixing portion 13 as the carbon dioxide (perhaps directly mix at the interflow) of secondary blowing agent in half foaminess, second composition.In the mixing portion 13, supply with first composition of storage first storage part 11 from first supply pipeline 31, so by their being mixed and discharging, make the polyurathamc foam.But the secondary blowing agent of a mechanical mixture in the way of second supply pipeline 32 (perhaps directly collaborating) can not mix the fully secondary blowing agent of amount in half foaminess, second composition.
Relative therewith, present embodiment, as shown in Figure 2, in half foaminess, second composition, by secondary blowing agent supply unit 50 and secondary blowing agent mixing portion 15, mix the carbon dioxide as secondary blowing agent, modulation foaminess second composition is stored in second storage part 12 with it.And therefore the nitrogen of filling as the storing pressurized agent from storing pressurized agent filling part 14 in the inside of second storage part 12 in second storage part 12, suppress secondary blowing agent and dissociate and the formation gas-bearing formation from foaminess second composition.
That is, process chart as shown in Figure 3 carries out secondary blowing agent blend step S23 by secondary blowing agent supply unit 50 and secondary blowing agent mixing portion 15, thereafter, carries out pressurized storage step (the free step that suppresses of secondary blowing agent) S24.Foaminess second composition that has mixed the secondary blowing agent of abundant amount among the step S23, stable storage in step 24, therefore after mixing discharge step S31 in, mix secondary blowing agent at any time by foaminess second composition of increment and first composition and make its discharge.Its result in foamed solidification step S32, carries out resinification reaction and foamed phenomenon by main foaming agent and 2 kinds of blowing agents of secondary blowing agent are parallel, and frothing percentage is improved than existing, can reduce the density of resulting polyurathamc foam.
In addition, above-mentioned resinification reaction refers to the polycondensation reaction of PIC composition and polyol component, specifically, comprises the amino (NH of polyol component
2) and the NCO of PIC composition (NCO) form the urea key (urea bond ,-reaction NH-CO-NH-) and the hydroxyl of polyol component (OH) and the NCO of PIC composition form ammonia ester bond (reaction NH-CO-O-).In addition, above-mentioned foamed phenomenon refers to also comprise the water (H as the blowing agent propellant of " water foaming " as the pentane class of the main foaming agent phenomenon from the liquid gasification
2O) generate the phenomenon that amino and generation carbon dioxide further produce reaction heat with the isocyanates radical reaction of PIC composition.
In addition, present embodiment can expect to improve the quality of polyurathamc foam by using secondary blowing agent.That is, the use of secondary blowing agent not only only increases the absolute magnitude of blowing agent, reduces the density of polyurathamc foam, and therefore the formed separated foam of polyurathamc foam can improve the rerum natura as heat-insulating material than easier being formed uniformly in the past.
Specifically, the mixture of first composition and foaminess second composition is discharged from mixing portion 13, for example is filled into the packing space of regulation.At this moment, carry out the resinification reaction of PIC composition and polyol component, therefore, said mixture is with in the mode process of flowing of above-mentioned packing space expansion, and its viscosity slowly rises.
At this, secondary blowing agent such as carbon dioxide is gas at normal temperature originally, though therefore on a small quantity also can be in said mixture rapid expansion, and when the resinification reaction taking place and produce adstante febre by " water foaming ", further expansion easily.Therefore, secondary blowing agent can carry out expansion to a certain degree before the viscosity of said mixture rises, even and the rising of the viscosity of said mixture, also can be subjected to above-mentioned heating and can expand with brute force.
In this case, infer before the viscosity of said mixture rises that having produced can be as the atomic little bubble by " nuclear " of the separated foam of secondary blowing agent.Can think thereafter, rise even be accompanied by the viscosity of carrying out said mixture of resinification reaction, be that starting point expands easily with above-mentioned " nuclear " also as the pentane class of main foaming agent and the carbon dioxide that is produced by " water foaming ".Its result can be formed uniformly the separated foam of good size.Therefore, can improve the thermal insulation of resulting polyurathamc foam.
As mentioned above, in the present embodiment, the storing pressurized agent is filled by storing pressurized agent filling part 14 in the inside of second storage part 12, and therefore, the space beyond foaminess second composition is filled the storing pressurized agent.At this, the storing pressurized agent is littler than secondary blowing agent with respect to solubility and the diffusion coefficient of second composition, therefore, dissolve in foaminess second composition.On the other hand, mixed secondary blowing agent in foaminess second composition, therefore, this pair blowing agent will dissociate from foaminess second composition, but owing to filled the storing pressurized agent in second storage part 12, so suppress the free of secondary blowing agent in fact.
Therefore, the dividing potential drop of the secondary blowing agent in foaminess second composition is adjusted to roughly certain, and by mixing portion 13 mixed foamings, second composition and first composition, in the moment of discharging, these mixtures just contain the secondary blowing agent of abundant amount.Its result can use the blowing agent of Duoing than amount in the past to make the polyurathamc foam, therefore can further increase separated foam, obtains the polyurathamc foam of less dense.
Therefore, according to the present invention, even mix main foaming agent in foaminess second composition to the limit, also can stablize and mix the fully secondary blowing agent of amount, and need not adopt complicated formation for the leakage that prevents secondary blowing agent.Therefore, can suppress the load of environment is increased, with the combined amount of simple formation increase blowing agent, make the polyurathamc foam of less dense.
(embodiment 2)
The manufacturing installation of polyurathamc foam of the present invention and manufacture method, be not limited to manufacturing installation 10A and the manufacture method of above-mentioned embodiment 1, so long as blowing agent, use above-mentioned main foaming agent and secondary blowing agent, constitute and these blowing agents are mixed in the storage container of foaminess second composition that obtains in storage, above-mentioned storing pressurized agent is filled in pressurization, just can adopt various formations.At this, in other embodiments of the present invention, specifically describe with reference to Fig. 4 A and Fig. 4 B.Fig. 4 A and Fig. 4 B are respectively the schematic diagrames of an example of manufacturing installation of the polyurathamc foam of expression embodiments of the present invention 2.
Shown in Fig. 4 A, the manufacturing installation 10B of the polyurathamc foam of present embodiment can constitute first storage part 11 among the manufacturing installation 10A that does not possess above-mentioned embodiment 1.In this case, PIC composition (first composition) is supplied with by external device (ED) and is got final product.
That is, manufacturing installation 10B of the present invention possesses second storage part 12, storing pressurized agent filling part 14 and mixing portion 13 at least and gets final product.In addition, the manufacture method corresponding to this manufacturing installation 10B can be the modulation of step S10(first composition shown in the process chart that does not comprise Fig. 3) formation.In the formation shown in Figure 2, secondary blowing agent mixing portion 15 and secondary blowing agent supply unit 50 also can be not included among the present invention.In this case, formation and first storage part 11 of modulating half foaminess, second composition get final product as the external device (ED) formation equally, get final product so long as for second storage part 12 half foaminess, second composition is carried out the outside supply.
In addition, shown in Fig. 4 B, on the basis of secondary blowing agent mixing portion 15 shown in Figure 2 and secondary blowing agent supply unit 50, other manufacturing installations 10C of present embodiment also comprises main foaming agent mixing portion 16 and main foaming agent supply unit 60.Half foaminess, second composition is modulated as long as mix main foaming agent in second composition by main foaming agent mixing portion 16, and its concrete formation is not particularly limited.As above-mentioned embodiment 1 is illustrated, if in second composition from beginning to cooperate the formation of main foaming agent at first, the formation of then modulating second composition is corresponding with main foaming agent mixing portion 16 and main foaming agent supply unit 60.
In addition, according to the purposes of the manufacturing installation 10A～10C of present embodiment, can constitute: second composition is stored in the other storage container, mixes main foaming agent and secondary blowing agent as required.Namely, in the polyurethane manufacturing equipment, the equipment of making the polyurathamc foam is set jointly and not under the situation of the equipment of mixed foaming agent manufacturing polyurethane moulded material, preferred storage does not mix second composition of main foaming agent in advance, therefore, manufacturing installation 10C shown in preferred use Fig. 4 B, thus each blowing agent can be mixed at any time.
At this, the main foaming agent supply unit 60 shown in Fig. 4 B illustrates as the square frame of only putting down in writing pentane, still, also can constitute the water of supplying with as the blowing agent propellant of " water foaming ".
In addition, in the above-mentioned embodiment 1, in Fig. 3, put down in writing as operation independently foaminess second composition has been stored in by the storing pressurized agent the step in the storage container of internal pressurization (pressurized storage step S23), but, among the present invention, the store status that is equivalent to pressurized storage step S23 got final product before mixing discharge step S31.Therefore, pressurized storage step S23 also can not think as manufacturing process independent step.
(embodiment 3)
In above-mentioned embodiment 1 and 2 the manufacturing installation and manufacture method, in order to prevent the leakage of secondary blowing agent from foaminess second composition, as the free suppressing portion of secondary blowing agent or the free step that suppresses of secondary blowing agent, the formation of storing pressurized agent is filled in employing with pressurized state in second storage part 12, but present embodiment 3, as the free suppressing portion of secondary blowing agent or the free step that suppresses of secondary blowing agent, adopt the formation that in second storage part 12, possesses the parts that seal foaminess second composition that forms liquid layer.
[structure of the manufacturing installation of polyurathamc foam]
At first, the structure with reference to the manufacturing installation of the polyurathamc foam of Fig. 5, Fig. 6 and Fig. 7 A～present embodiment of Fig. 7 C is specifically described.Fig. 5 is the schematic diagram of an example of the structure of the manufacturing installation of the polyurathamc foam of expression present embodiment, and Fig. 6 is the signal piping diagram of an example of the structure of second storage part in the manufacturing installation of the polyurathamc foam of expression present embodiment and secondary blowing agent mixing portion.In addition, the schematic diagram of an example of the structure of the liquid layer seal member that arranges in second storage part for expression of Fig. 7 A～Fig. 7 C.
As shown in Figure 5, the manufacturing installation 1D of the polyurathamc foam of present embodiment possesses first storage part 11, second storage part 12, mixing portion 13, first supply pipeline 31 and second supply pipeline 32.The structure of first storage part 11, mixing portion 13, first supply pipeline 31 and second supply pipeline 32 is identical with above-mentioned embodiment 1, omits its explanation.
Wherein, second storage part 12, as shown in Figure 6, same with second storage part 12 of explanation in above-mentioned embodiment 1, it constitutes with respect to the holding tank 21 as main body, be provided with pressure regulator 22, mixing part 23, gas-bearing formation temperature sensor 24 and liquid layer temperature sensor 25 etc., but also be provided with liquid layer seal member described later (secondary blowing agent dissociate suppressing portion) 26 in the inside of holding tank 21.
In addition, same with above-mentioned embodiment 1, be connected with second supply pipeline 32 and secondary blowing agent mixing line 34 at holding tank 21.Second supply pipeline 32 and above-mentioned embodiment 1 are same, connect mixing portion 13 and also are provided with supply pump 35 etc.In addition, secondary blowing agent mixing line 34 is also same with above-mentioned embodiment 1, connects not shown polyalcohol supply source and is provided with the junction of two streams Ps of secondary blowing agent mixing portion 15, secondary blowing agent supply unit 50 and supply pump 33 etc.Secondary blowing agent supply unit 50 and above-mentioned embodiment 1 are same, are made of secondary blowing agent storage part 51, pressure regulator 52, secondary blowing agent supply pipeline 53 and flow control valve 54 etc.
In addition, remove the concrete structure of liquid layer seal member 26 second storage part 12 in addition (namely, holding tank 21, pressure regulator 22, mixing part 23, the structure of gas-bearing formation temperature sensor 24 and liquid layer temperature sensor 25 etc.), the concrete structure of pair blowing agent mixing portion 15, supply pump 33,35 concrete structure, the concrete structure of secondary blowing agent mixing line 34, concrete structure (the secondary blowing agent storage part 51 of secondary blowing agent supply unit 50, pressure regulator 52, the structure of secondary blowing agent supply pipeline 53 and flow control valve 54 grades) also identical with above-mentioned embodiment 1, omit its explanation.In addition, also identical with above-mentioned embodiment 1 for the mixing of secondary blowing agent, omit its explanation.In addition, the formation of feedstock composition (first composition and second composition), secondary blowing agent etc. is identical with above-mentioned embodiment 1, omits its explanation.
Liquid layer seal member 26 is at the parts as the liquid layer of this foaminess of state lower seal second composition F M2 of the airtight storage foaminess second composition F M2 in inside of the holding tank 21 of the main body of second storage part 12.Its concrete formation is not particularly limited, so long as the foaminess second composition F M2 that constitutes liquid layer in holding tank 21 can be got final product with the parts that are filled in the gas-bearing formation isolating seal in the holding tank 21, can adopt known formation.
Specifically, for example, can enumerate resinous cover material or sheet material etc.The kind of these cover materials or the employed resin of sheet material is not particularly limited, so long as form the resin of the foaminess second composition F M2 of liquid layer with respect to the foaminess inactive resin of the second composition F M2 and sealing that can be good, just can suitably use known resin.
In addition, liquid layer seal member 26 also can not be the such solid material of cover material or sheet material, but is made of the little free-flowing material of proportion than the foaminess second composition F M2.Under the situation that is such free-flowing material, form the liquid layer of sealing usefulness with state floating on the liquid layer of the foaminess second composition F M2.Such free-flowing material is not particularly limited, so long as with respect to the foaminess inactive resin of the second composition F M2 and than the material of the proportion little (gently) of the foaminess second composition F M2, just can suitably use known free-flowing material.
If liquid layer seal member 26 is the liquid layer of cover material, sheet material or sealing usefulness, then shown in Fig. 7 A, in holding tank 21, can be accompanied by liquid layer (the foaminess second composition F M2) liquid level shift in position and in this holding tank 21 mobile (for example position of dotted line among the figure).If liquid layer seal member 26 is such " movable member ", even then owing to flowing in the holding tank 21 or flowing out the foaminess second composition F M2 and the liquid level position change of liquid layer, also can follow this change sealed liquid layer.Therefore, can suppress secondary blowing agent dissociating from the foaminess second composition F M2.
In addition, shown in Fig. 7 B, liquid layer seal member 26 can be the partition walls portion 27 of the inside that cuts off holding tank 21.In other words, liquid layer seal member 26 can be depicted as " movable member " that can move as Fig. 7 A in holding tank 21, also can be depicted as Fig. 7 B to be fixed in holding tank 21 and to cut off " partition fixed part " in this holding tank 21.It is last chamber and following chamber that partition walls portion 27 shown in Fig. 7 B cuts off holding tank 21, and can possess peristomes such as not shown hole or slit.Thus, the foaminess second composition F M2 can circulate between last chamber and following chamber via peristome.
When in the holding tank 21 with such partition walls portion 27, flowing into the foaminess second composition F M2, the liquid level of the foaminess second composition F M2 that flows into is near the position of partition walls portion 27, perhaps with the position of partition walls portion 27 roughly under the consistent situation (namely, the foaminess second composition F M2 only is stored in down under the situation of chamber), can near the liquid level of liquid layer (the foaminess second composition F M2) or its, cut off this liquid layer and gas-bearing formation.Thus, be stored in down the foaminess second composition F M2(liquid layer of chamber) can separate with gas-bearing formation in fact, compare with situation about not cutting off, can suppress the total amount that secondary blowing agent dissociates from the foaminess second composition F M2.
In addition, even have gas-bearing formation between the liquid level of liquid layer and the partition walls portion 27, because being cut off wall portion 27, this its gas-bearing formation cuts off, so can reduce the volume of the gas-bearing formation that connects liquid layer in fact.Therefore, even the liquid level of liquid layer is roughly not consistent with partition walls portion 27, also can suppress the total amount that secondary blowing agent dissociates from the foaminess second composition F M2.
In addition, the liquid level of the foaminess second composition F M2 of inflow is positioned under the situation above the position of partition walls portion 27 (that is, the foaminess second composition F M2 not only is stored in down the chamber and also is stored under the situation of chamber), and liquid layer is cut off wall portion 27 and cuts apart.In this case, gas-bearing formation only is present in the chamber, can suppress secondary blowing agent from being arranged in the free total amount of liquid layer of descending the chamber at least.
In addition, for the liquid layer that is stored in the chamber, also can suppress from the total amount of the free secondary blowing agent of this liquid layer.Specifically, secondary blowing agent is with respect to the solubility of the foaminess second composition F M2, and is basically according to Henry's law, proportional with pressure.Therefore, if the volume of the liquid layer of contact gas-bearing formation is few, under this state, the dissolving of secondary blowing agent is just near poised state.Therefore, see in last chamber that the volume of gas-bearing formation is big, the volume of liquid layer is few, and therefore the solubility of secondary blowing agent rises.Its result in the last chamber, also can suppress the total amount that secondary blowing agent dissociates from liquid layer.
So, even under the situation in the liquid of partition walls portion 27 partition liquid layers, as liquid layer integral body (the foaminess second composition F M2), the also total amount of the secondary blowing agent that can suppress to dissociate.
At this, as long as liquid layer seal member 26 sealed liquid layer in holding tank 21, it arranges state and just is not particularly limited, preferably shown in Fig. 7 C, the foaminess second composition F M2 fills under the state more than the 90 volume % in holding tank 21, this foaminess second composition F M2(liquid layer) by 26 sealings of liquid layer seal member.In addition, the position of the partition walls portion 27 in the holding tank 21 is not particularly limited, as long as can will be divided into chamber and these two parts of following chamber in the holding tank 21, and just can be at an arbitrary position.
If liquid layer seal member 26 is " movable members " such as above-mentioned cover material or sheet material owing in holding tank 21, can move, so in holding tank 21 sealed liquid layer (isolating gas-bearing formation and liquid layer fully) fully.Therefore, even by liquid layer seal member 26 sealed liquid layers, through also producing for a long time the free of secondary blowing agent.Relative therewith, if fill the foaminess second composition F M2 more than the 90 volume % in holding tank 21, therefore gas-bearing formation less than 10 volume % this holding tank 21 in then compare considerably lessly with liquid layer, and secondary blowing agent just reaches poised state with dissociating of trace.Therefore, the dissolving ratio that can suppress secondary blowing agent reduces.Even this point liquid layer seal member 26 be partition walls portion 27 such " partition fixed part " too.
In addition, the gas-bearing formation in the holding tank 21 is namely filled the gas (being called " blanketing gas " for convenience of description) in (inclosure) holding tank 21, in the present embodiment, can be carbon dioxide (CO
2).In addition, the kind of the blanketing gas in the holding tank 21 is not limited to carbon dioxide, can be the mist of carbon dioxide and nitrogen, as long as for respect to the inactive gas of the foaminess second composition F M2, also can be carbon dioxide (or nitrogen) gas in addition.The pressure of this blanketing gas is regulated by pressure regulator 22, but does not need as above-mentioned embodiment 1 pressurized.
As 1 explanation of above-mentioned embodiment like that, at present, known in polyol component the mixing material carbon dioxide, but be difficult to its combined amount of increase.At this, the present invention's airtight storage in second storage part 12 is mixed with foaminess second composition as the carbon dioxide of secondary blowing agent, seals the gas-bearing formation that makes in itself and second storage part 12 by liquid layer seal member 26 and isolates.Thus, even in foaminess second composition, main foaming agent is mixed into the limit, also can prevent the leakage of secondary blowing agent, and can stablize and mix the fully secondary blowing agent of amount.Therefore, can increase the combined amount of blowing agent with simple structure.
[manufacture method of polyurathamc foam]
Then, specify the manufacture method of the polyurathamc foam that uses Fig. 5 and manufacturing installation 10A shown in Figure 6 with reference to Fig. 8.Fig. 8 is the summary process chart of an example of the manufacture method of the polyurathamc foam of expression present embodiment 3.
As shown in Figure 8, same with above-mentioned embodiment 1 in the manufacturing of the polyurathamc foam of present embodiment, implement the first composition modulation step S10, the second composition modulation step S21, main foaming agent blend step S22 and secondary blowing agent blend step S23.Wherein, the enforcements that can walk abreast mutually such as the first composition modulation step S10, the second composition modulation step S21, main foaming agent blend step S22 and secondary blowing agent blend step S23.
The first composition modulation step S10 and above-mentioned embodiment 1 are same, use the PIC more than a kind or 2 kinds, cooperate known additive to modulate first composition as required.In addition, same with above-mentioned embodiment 1 among the second composition modulation step S21, in the polyalcohol more than a kind or 2 kinds, cooperate additives such as catalyst and surfactant, modulate second composition.
Then, same with above-mentioned embodiment 1 in main foaming agent blend step S22, in second composition that modulates, mix main foaming agent (blowing agent propellant such as main foaming agent such as pentane class and water), modulate half foaminess, second composition.Wherein, same with above-mentioned embodiment 1, step S22 is not must operation, can omit with the form that is included among the step S21.
Then, among the secondary blowing agent blend step S23, by in half foaminess, second composition that modulates, mixing sufficient carbon dioxide as secondary blowing agent, modulation foaminess second composition.Then, foaminess second composition is stored in second storage part 12, at this moment, as mentioned above, by liquid layer seal member 26 seal foaming second composition in the holding tank 21 of second storage part 12.Therefore, in the present embodiment, this storing step is called as " liquid layer sealing step S25 " as shown in Figure 8.This liquid layer sealing step S25, same with the pressurized storage step S24 of above-mentioned embodiment 1, performance is as the free effect that suppresses step of secondary blowing agent.
Foaminess second composition of stable storage in liquid layer sealing step 25 is discharged among the step S31 in mixing thereafter, mixes at any time with first composition of modulation in the step 10 and discharges.In foamed solidification step S32 thereafter, by main foaming agent and parallel resinification reaction and the foamed phenomenon of carrying out of these 2 kinds of blowing agents of secondary blowing agent, therefore make frothing percentage than rose in the past, can reduce the density of resulting polyurathamc foam.
As mentioned above, in the present embodiment, the inside of second storage part 12 is provided with and will forms foaminess second composition of liquid layer and the liquid layer seal member 26 that liquid layer is isolated and sealed.Thus, even secondary blowing agent will dissociate to gas-bearing formation, also can suppress the free of secondary blowing agent by the sealing of liquid layer seal member 26 from foaminess second composition.
Therefore, in the moment of mixing and discharging foaminess second composition and first composition by mixing portion 13, these mixtures contain the secondary blowing agent of abundant amount.Its result can use than in the past and measure more blowing agent manufacturing polyurathamc foam, therefore can further increase separated foam, obtained the polyurathamc foam of less dense.
Therefore, according to the present invention, even in foaminess second composition main foaming agent is mixed into the limit, also can stablizes and mix the fully secondary blowing agent of amount.And there is no need to adopt complicated structure in order to prevent secondary blowing agent leakage.Therefore, can suppress to the load of environment increase, increase the combined amount of blowing agent with simple structure, make the polyurathamc foam of less dense.
The manufacturing installation of present embodiment or manufacture method can be used in combination with the manufacturing installation of above-mentioned embodiment 1 or 2 or the formation of manufacture method.For example, the manufacturing installation 10A of above-mentioned embodiment 1 possesses storing pressurized filling part 14 as the free suppressing portion of secondary blowing agent, but can also be in second storage part 12 (in the holding tank 21) be provided as the liquid layer seal member 26 of " movable member ", the liquid layer seal member 26 that can also be provided as " partition fixed part " is partition walls portion 27 etc.For the manufacturing installation 10B of above-mentioned embodiment 2 or 10C too.
In the manufacturing installation or manufacture method of present embodiment, illustrated as liquid layer seal member 26 and used as any one the example in the partition walls portion 27 of " movable member " (for example cover material etc.) or " partition fixed part ", but the invention is not restricted to this, as liquid layer seal member 26, also can and use " movable member " and " partition fixed part ".
(embodiment 4)
As the purposes that manufacturing installation and the manufacture method of the polyurathamc foam of above-mentioned embodiment 1 to 3 especially preferably is suitable for, can be set forth in the purposes of packing space filling-foam polyurethane foam of the inside of insulated structure.At this so-called insulated structure, constituted by internal material and exterior material at least, externally form above-mentioned packing space between material and the internal material and get final product.
Specifically, for example, as shown in Figure 9, can enumerate the body of thermal insulating box 200 of freezer.In example shown in Figure 9, body of thermal insulating box 200 constitutes top part and the both sides of freezers, the parts that constitute the outer container 210 that makes exterior material and form as interior case 220 engagings of internal material.Be formed with the packing space of filling-foam polyurethane foam between outer container 210 and the interior case 220, though Fig. 9 is not shown, by in this packing space, filling the polyurathamc foam as heat-insulating material, constitute body of thermal insulating box 200.In addition, be provided with 2 inlets 203 that are used for to packing space filling-foam polyurethane foam in the outer container 210.
In example shown in Figure 9, above-mentioned packing space constitutes 1 packing space by 1 first packing space 201 and 2 second packing spaces 202.First packing space 201 is the flat space corresponding to the top part of freezer, and in addition, in the example shown in Figure 9,2 second packing spaces 202 are corresponding to the flat space of the both sides that connect top part, are communicated with first packing space 201.Therefore, 2 second packing spaces 202 are opposed mutually, are communicated with 1 first packing space 201 in the mode that connects the one end.
In addition, in example shown in Figure 9,2 inlets 203 are positioned at the central portion of the dual-side of top part, and therefore, these inlets 203 arrange in the mode that is communicated with first packing space 201.In addition, the position that these inlets 203 are set also is towards each second packing space 202 position on opposites respectively.In addition, in the example shown in Figure 9, dispose vacuum heat insulation materials 230 respectively in 1 first packing space 201 and 2 second packing spaces 202.Vacuum heat insulation materials 230 is attached to the inner surface of outer container 210, has realized the further raising of the thermal insulation of body of thermal insulating box 200.
In the body of thermal insulating box 200 of such structure, be made as the manufacturing installation 10A filling-foam polyurethane foam of for example using above-mentioned embodiment 1.In this case, mixing portion 13 is installed on the inlet 203 of body of thermal insulating box 200, in mixing portion 13, mix from first composition of first storage part, 11 supplies and foaminess second composition of supplying with from second storage part 12, this mixture is discharged in the inlet 203.Each inlet 203 is communicated with first packing space 201, and therefore, said mixture mode with expansion in first packing space 201 flows.In addition, each inlet 203 is relative with second packing space 202, and therefore, said mixture also flows in the mode of expanding in second packing space 202.
At this, packing space integral body in the body of thermal insulating box 200, the two ends that are communicated with first packing space 201 of inlet 203 are communicated with second packing space 202 respectively, therefore, the mutually orthogonal connection in a plurality of flat spaces forms the packing space that three-dimensional position concerns.And, said mixture from inlet 203 injects flows in the mode around the packing space integral body with three-dimensional position relation, but because this mixture limit is accompanied by the carrying out of resinification reaction and slowly rising edge foaming of viscosity, therefore, foaming is easy to generate deviation.If foaming produces deviation in packing space, from guaranteeing the viewpoint of heat-insulating property, need be the density that benchmark is set the polyurathamc foam with the minimum position of frothing percentage just.The low density height that refers to the polyurathamc foam of frothing percentage, the result, the amount of the polyurathamc foam of use increases.
Relative therewith, among the present invention, as above-mentioned embodiment 1 is illustrated, expand rapidly in said mixture as the carbon dioxide of secondary blowing agent, even and the viscosity of said mixture rises, also can be subjected to the heating that is brought by resinification reaction etc. and can expand with stronger power.Therefore, even along with the viscosity rising and around the packing space process of flowing, in said mixture, also can foam rapidly and well.Its result compared with prior art, can realize more uniform foaming on the whole in the packing space of solid, can further improve the heat-insulating property of insulated structure.As long as realized on the whole foaming uniformly, even be the density that benchmark arranges the polyurathamc foam with the minimum position of frothing percentage, the increment of polyurathamc foam seldom gets final product.Therefore, can realize the reduction of manufacturing cost, and realize the minimizing of the rubbish when discarded.
In addition, body of thermal insulating box 200 shown in Figure 9, packing space constitutes the end that first packing space 201 is positioned at a pair of second packing space 202 with the position relation that is parallel to each other, therefore, flat space has the position relation of quadrature respectively each other, but the structure of the insulated structure that uses among the present invention is not limited thereto, and insulated structure has a plurality of flat spaces at least and intersects mutually and be communicated with the packing space form and get final product.
In addition, the polyurathamc foam of filling in the packing space is not only brought into play the effect as the heat-insulating material of insulated structure, and the effect of the adhering part of structure is kept in performance as the internal material of bonding formation insulated structure and exterior material.In above-mentioned example, constitute outer container 210 and the interior case 220 of body of thermal insulating box 200, under the state that does not have the filling-foam polyurethane foam, just casing is made up mutually, and under the state of inner filling-foam polyurethane foam, so since outer container 210 and interior case 220 by the bonding structure of keeping as insulated structure.
In addition, for example, in the example of the freezer that body of thermal insulating box 200 is such, the thickness of interior case 220 is about 1mm, and the thickness of outer container 210 is for example 0.4mm of not enough 1mm(), the about 40mm of the thickness of polyurathamc foam.Therefore, the polyurathamc foam accounts for the major part of the thickness of body of thermal insulating box 200, and is roughly even as the polyurathamc foam integral body of adhering part as long as the present invention, just can well keep the intensity of body of thermal insulating box 200.That is, as long as the formation inequality of separated foam is seldom, roughly foaming equably on the whole, then under the situation as the layer of polyurathamc foam, the inequality of intensity is few, therefore, can realize that body of thermal insulating box 200 integral intensity improve.
At this, can be as manufacturing installation of the present invention and the suitable insulated structure that uses of manufacture method, beyond the housing that the freezer of above-mentioned body of thermal insulating box 200 grades is used, can also enumerate the structure that requires higher levels of heat-insulating property of household freezer, hot water tank, heat-insulating shield etc.Heat-insulating shield and freezer and hot water tank etc. are compared, and the shape of packing space is also uncomplicated, even such insulated structure so long as require high-caliber heat-insulating property, also can be suitable for the present invention.
For example, as above-mentioned hot water tank, can enumerate the hot water tank that possesses the heat pump hot-water supply.Specifically, as shown in figure 10, heat pump hot-water supply 300 possesses exterior body 310, hot water tank 320, heating part 330, water supply piping 341, entry pipe arrangement 342, goes into water pump 343, goes out hot water pipe arrangement 344, mixes heat supply water pipe arrangement 345, mixes water supply piping 346, heat supply water pipe arrangement 347, heat supply water terminal 348 etc.
Hot water tank 320 is arranged in the exterior body 310, has rectangular-shaped shape.The bottom surface of hot water tank 320 connects the other end of water supply piping 341 and an end of entry pipe arrangement 342, and end face connects the other end of heat accumulation water pipe arrangement 344 and mixes an end of heat supply water pipe arrangement 345.One end of water supply piping 341 is connected with not shown watering.In addition, branch out mixing water supply piping 346 from water supply piping 341.That is the end connection water supply piping 341 that, mixes water supply piping 346.The one end interflow of mixing the other end with the other end that mixes heat supply water pipe arrangement 345 and the heat supply water pipe arrangement 347 of water supply piping 346.In addition, the other end of heat supply water pipe arrangement 347 is provided with heat supply water terminal 348.
Entry pipe arrangement 342 is provided with into water pump 343, and the other end connects heating part 330.Heating part 330 connects an end of hot water pipe arrangement 344, and the other end that goes out hot water pipe arrangement 344 is connected with the end face of above-mentioned hot water tank 320.By going into water pump 343 actions, the water of the below of hot water tank 320 is imported into entry pipe arrangement 342, and 330 are heated in the heating part, from going out the top that hot water pipe arrangement 344 supplies to hot water tank 320.
The mixing heat supply water pipe arrangement 345 that the top of hot water tank 320 connects and from the mixing water supply piping 346 of water supply piping 341 branches, as mentioned above, at heat supply water pipe arrangement 347 interflow, therefore, by in interflow portion valve gear etc. being set, can suitably mix hot water tank 320 the top hot water and from the water that water supply piping 341 branches import, supply to heat supply water pipe arrangement 347.Therefore, just can supply with hot water in the set point of temperature scopes from heat supply water terminal 348.
In the heat pump hot-water supply 300 of said structure, in order to suppress the thermal discharge to atmosphere, be coated with heat-insulating material at hot water tank 320, can use the polyurathamc foam as this heat-insulating material.Therefore, as hot water tank 320, can use to have and the above-mentioned body of thermal insulating box 200 same insulated structures that constitute.
From above-mentioned explanation, those skilled in the art should be able to understand multiple improvement of the present invention and other embodiment.Therefore, above-mentioned explanation should only be interpreted as example, is those skilled in the art are taught as the mode of the enforcement optimum of the present invention that purpose provides.Only otherwise break away from spirit of the present invention, just can carry out material alteration to the detailed content of its structure and/or function.
Industrial utilizability
The present invention can be adapted at the manufacturing field extensive use of polyurathamc foam, can be applicable to that especially inside such as freezer, freezer, cold insulated cabinet, heat-insulating shield, hot water tank have the manufacturing field of insulated structure of the packing space of polyurathamc foam.
Symbol description
The manufacturing installation of 10A～10C polyurathamc foam
11 first storage parts
12 second storage parts
13 mixing portions
14 storing pressurized agent filling parts (secondary blowing agent dissociate suppressing portion)
15 secondary blowing agent mixing portions
16 main foaming agent mixing portions
21 holding tanks (storage container)
26 liquid layer seal members (secondary blowing agent dissociate suppressing portion, movable member)
27 partition walls portions (liquid layer seal member, the free suppressing portion of secondary blowing agent, partition fixed part)
50 secondary blowing agent supply units
60 main foaming agent supply units
200 body of thermal insulating box (insulated structure)
210 outer containers (exterior material)
Case (internal material) in 220
201 first packing spaces (packing space)
202 second packing spaces (packing space)
FM2 foaminess second composition
Claims (16)
1. the manufacturing installation of a polyurathamc foam is characterized in that:
It is first composition of main component and foaminess second composition that obtains at the mixed blowing agent of second composition that is main component with the polyalcohol for being used for mixing with the PIC, makes the manufacturing installation of polyurathamc foam, and it possesses:
Mixing portion, mix described first composition and described foaminess second composition and with its discharge and
Second storage part, with described foaminess second composition of the airtight storage of mode that can supply with this mixing portion,
As described blowing agent, use main foaming agent and have than the low boiling point of this main foaming agent and at the secondary blowing agent of normal temperature as gas, in described foaminess second composition, be mixed with described main foaming agent and described secondary blowing agent,
This manufacturing installation also possesses: the secondary blowing agent suppressing portion of dissociating, suppress free described foaminess second composition that described secondary blowing agent stores in described second storage part.
2. the manufacturing installation of polyurathamc foam as claimed in claim 1 is characterized in that:
The free suppressing portion of described secondary blowing agent is for being filled in storing pressurized agent filling part in described second storage part with the storing pressurized agent with pressurized state, wherein, this storing pressurized agent is that solubility in described second composition and diffusion coefficient are than the littler gas of described secondary blowing agent.
3. the manufacturing installation of polyurathamc foam as claimed in claim 2 is characterized in that:
When in described second composition, only mixing material that described main foaming agent obtains as half foaminess, second composition,
Described storing pressurized agent is that solubility and the diffusion coefficient in described half foaminess, second composition equates with described secondary blowing agent or the gas littler than described secondary blowing agent.
4. the manufacturing installation of polyurathamc foam as claimed in claim 2 is characterized in that:
Described storing pressurized agent is nitrogen or air.
5. the manufacturing installation of polyurathamc foam as claimed in claim 1 is characterized in that:
In described second storage part, described foaminess second composition forms liquid layer, and, form gas-bearing formation by filling with respect to the inactive gas of this foaminess second composition,
The free suppressing portion of described secondary blowing agent is for sealing the liquid layer seal member of described liquid layer with respect to described gas-bearing formation.
6. the manufacturing installation of polyurathamc foam as claimed in claim 5 is characterized in that:
Described liquid layer seal member is in described second storage part, the movable member that is accompanied by the liquid level position change of described liquid layer and can moves is perhaps for being fixed on the partition fixed part in this second storage part under the state that cuts off in described second storage part.
7. the manufacturing installation of polyurathamc foam as claimed in claim 5 is characterized in that:
By the sealing of described liquid layer seal member to described liquid layer, carry out when in described second storage part, filling described foaminess second composition more than the 90 volume %.
8. the manufacturing installation of polyurathamc foam as claimed in claim 1 is characterized in that:
When in described second composition, only mixing material that described main foaming agent obtains as half foaminess, second composition,
Also possess with respect to described half foaminess, second composition and mix described secondary blowing agent, modulate the secondary blowing agent mixing portion of described foaminess second composition.
9. the manufacturing installation of polyurathamc foam as claimed in claim 1 is characterized in that:
Described secondary blowing agent is carbon dioxide.
10. the manufacturing installation of polyurathamc foam as claimed in claim 1, it is characterized in that: described main foaming agent is at least one in lower hydrocarbon and the hydrofluorocarbons.
11. the manufacture method of a polyurathamc foam is characterized in that:
It is first composition of main component and mixed foaming agent obtains in second composition that is main component foaminess second composition with the polyalcohol for mixing with the PIC, makes the method for polyurathamc foam,
As described blowing agent, use main foaming agent and have than the low boiling point of this main foaming agent and at the secondary blowing agent of normal temperature as gas,
This method comprises:
The main foaming agent blend step mixes main foaming agent in second composition that with the polyalcohol is composition, modulate half foaminess, second composition;
Secondary blowing agent blend step mixes secondary blowing agent in described half foaminess, second composition, modulation foaminess second composition;
Mix to discharge step, mixed foaming second composition and first composition and with its discharge; With
The free step that suppresses of secondary blowing agent before step is discharged in described mixing, suppresses described secondary blowing agent dissociating from described foaminess second composition.
12. the manufacture method of polyurathamc foam as claimed in claim 11, it is characterized in that: described secondary blowing agent is free suppress step for by the storing pressurized agent with the storage container of internal pressurization in the pressurized storage step of described foaminess second composition of storage, wherein, this storing pressurized agent is that solubility in described half foaminess, second composition and diffusion coefficient are than the littler gas of described secondary blowing agent.
13. the manufacture method of polyurathamc foam as claimed in claim 11, it is characterized in that: the free step that suppresses of described secondary blowing agent, for in storage container, with respect to by the gas-bearing formation that the inactive gas of described foaminess second composition is formed, seal the liquid layer sealing step of the liquid layer that is formed by described foaminess second composition.
14. an insulated structure is characterized in that,
At least constituted by internal material and exterior material,
Form the packing space of filling described polyurathamc foam between described exterior material and the described internal material,
Be filled with the described polyurathamc foam that utilizes the described manufacturing installation of claim 1 or the described manufacture method manufacturing of claim 11 to obtain in the described packing space.
15. insulated structure as claimed in claim 14 is characterized in that,
Have the inlet that at least one of described internal material and described exterior material, arranges, be used for injecting at described packing space the mixture of described first composition and described foaminess second composition, and
Described packing space comprises at least and is communicated with described inlet and expands to flat first packing space and be communicated with this first packing space and expand to flat second packing space with respect to this first packing space crisscross.
16. insulated structure as claimed in claim 14 is characterized in that:
It is to be selected from freezer, freezer, heat-insulating shield and the hot water tank at least one.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2011-183425 | 2011-08-25 | ||
| JP2011183425 | 2011-08-25 | ||
| JP2011-288425 | 2011-12-28 | ||
| JP2011288425 | 2011-12-28 | ||
| PCT/JP2012/005328 WO2013027416A1 (en) | 2011-08-25 | 2012-08-24 | Device and method for manufacturing expanded polyurethane foam, and heat insulation structure |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103249536A true CN103249536A (en) | 2013-08-14 |
Family
ID=47746175
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201280003910.4A Pending CN103249536A (en) | 2011-08-25 | 2012-08-24 | Device and method for manufacturing expanded polyurethane foam, and heat insulation structure |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JPWO2013027416A1 (en) |
| CN (1) | CN103249536A (en) |
| WO (1) | WO2013027416A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103822089A (en) * | 2014-03-07 | 2014-05-28 | 苏州拓维工程装备有限公司 | Vacuum valve bank box for LNG (Liquefied Natural Gas) liquid-adding machine |
| KR102019167B1 (en) * | 2017-09-12 | 2019-09-10 | (주)대한 | Sponge manufacturing system for vehicle seat |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0791404B2 (en) * | 1990-11-29 | 1995-10-04 | 東京シート株式会社 | Method for manufacturing urethane foam molded product with high-density surface layer |
| JP3030106B2 (en) * | 1991-02-22 | 2000-04-10 | 三洋電機株式会社 | Mixing device for low boiling point blowing agent |
| JP3481563B2 (en) * | 1999-09-30 | 2003-12-22 | 保土谷化学工業株式会社 | Method for producing polyurethane foam |
| JP2008291060A (en) * | 2007-05-22 | 2008-12-04 | Asahi Glass Co Ltd | Method for manufacturing foamed synthetic resin and foamed synthetic resin |
-
2012
- 2012-08-24 WO PCT/JP2012/005328 patent/WO2013027416A1/en active Application Filing
- 2012-08-24 CN CN201280003910.4A patent/CN103249536A/en active Pending
- 2012-08-24 JP JP2013506365A patent/JPWO2013027416A1/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| JPWO2013027416A1 (en) | 2015-03-05 |
| WO2013027416A1 (en) | 2013-02-28 |
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Application publication date: 20130814 |