CN1112134A - Heat isolating material and heat isolating box - Google Patents

Abstract

To protect global environment by using a nonspecific fluorocarbon as a foaming agent and improved in heat insulating properties. A urethane stock solution obtained by mixing the first component consisting of an isocyanate with the second component obtained by adding a foaming agent to a polyol is injected into an outer shell body consisting of an outer box 2 made of steel plate and an inner box 3 made of a high-nitrile styrol-based resin, and the urethane stock solution is expanded and cured to constitute a heat-insulating box body 1 packing a heat-insulating material 4 in the interior. A non-specific fluorocarbon such as HCFC-141b is used as the foaming agent. An additive capable of forming a foaming nucleus, such as fine-particular white carbon, HFC-143 or water is added in a proper amount to the urethane stock solution and viscosity of the urethane stock solution is increased so as to have high viscosity at ordinary temperature by using a polyol having 15000cps to 50000cps viscosity.

Description

Heat isolating material and heat isolating box

The present invention relates to be used for thermal insulation material and body of thermal insulating box on refrigerator etc.

Refrigerators etc. are gone up as the urethane foam of thermal insulation material and are made like this, the 2nd composition mixing that is about to the 1st composition that is made of isocyanic ester and adds whipping agent or surfactant, catalyzer etc. in polyvalent alcohol is stirred, make urethane stoste, again this stoste is injected by the steel plate outer container, and the housing that constitutes such as case in polystyrene, ABS etc. plastic in, above-mentioned urethane stoste carries out making its foaming in the reaction such as polymerization in this housing.In this case, be to use the so-called specific freonll-11 of CFC-11 etc. as whipping agent in the past.

Yet; put into the censure that atmosphere can damage the ozonosphere of atmospheric layer owing to be subjected to Freon gas in recent years; from the viewpoint of the environment of preserving our planet, wish to be transformed into the whipping agent that replaces being used as above-mentioned urethane foam with other material by present specific freonll-11.

In recent years, attempt to use as the surrogate in fluorine Lyons and make whipping agent such as HCFC-123 or HCFC-141b etc.These materials are low to depletion of the ozone layer, and its boiling point approaches CFC-11.

But, because above-mentioned HCFC-123 or the HCFC-141b thermal conductivity when being gaseous state is than above-mentioned CFC-11 height, the thermal conductivity of the urethane foam of the formation 3-10% that descended.Therefore, when being used for as the body of thermal insulating box on the refrigerator, so the casing wall thickness that this box body wall is made than the specific fluorine of present use Lyons is this material and improper.

In view of the above problems, the objective of the invention is to provide a kind of thermal insulation material and body of thermal insulating box, is whipping agent for the environment of preserving our planet has used unspecific fluorine Lyons, and heat-insulating property is better.

Thermal insulation material of the present invention is a main component with isocyanic ester and polyvalent alcohol, (hyelrochloro fluiorocarbon)-fluorine is hydrocarbon, the whipping agent of at least a formation of hydro carbons to be added into cfc, make urethane stoste, and make this stoste foam, harden, when it is characterized in that interpolation becomes the additive of nuclei of bubbles in above-mentioned urethane stoste, make this stoste have high viscosity at normal temperatures.

If make the viscosity of polyvalent alcohol be 15000cps～50000cps at normal temperatures, just can improve the viscosity (claim 2) of urethane stoste.Also can be the tackifier that add carboxymethyl cellulose etc. in urethane stoste, addition be (weight percent) (claim 3) below 5% of polyvalent alcohol.

At this moment, as the additive of above-mentioned nuclei of bubbles, can use fine stopping composition, this moment, its addition can be below 5% (claim 4) of relative urethane stoste weight percent.And, as the additive of nuclei of bubbles, can use the boiling point secondary whipping agent lower than whipping agent, at that time, institute's addition is 0.5～20%(claim 5 of the weight percent of above-mentioned whipping agent).Also have, as the additive of nuclei of bubbles, can employing and isocyanato and hydroxyl reaction can produce the material of gas, at this moment, the gas volume that is produced can be that the mol ratio with respect to whipping agent is 1～30%(claim 6).

Body of thermal insulating box of the present invention is that the above-mentioned thermal insulation material of filling forms (claim 7) between outer container and interior case.In this case, if interior case is made of at the high polynitriles phenylethylene resin series that the polyreaction in the presence of elastomeric forms the mixture of vinyl cyanide compound and distyryl compound, effect better (claim 8) then.

If be discharged in the atmosphere by the whipping agent that constitutes as cfc (HCFC), fluorine hydrocarbon (HFC), hydro carbons (hereinafter referred to as nonspecific fluorine Lyons) such as (HC), because the damaging material of ozonosphere just had been decomposed out at the arrival ozonosphere in the past, therefore, can not damage ozonosphere, and the boiling point of these materials and specific fluorine Lyons are approaching.Therefore, from the viewpoint of the environment of preserving our planet, they are applicable to that substituting specific fluorine Lyons makes whipping agent.Yet, because there be thermal conductivity high defective with this in the gas conduction rate of the whipping agent that is made of these nonspecific fluorine Lyons as thermal insulation material than the height in specific fluorine Lyons.

The inventor be finish so of the present invention, make the related problem that how to reduce thermal conductivity of thermal insulation material of whipping agent for the nonspecific fluorine Lyons of using cfc etc., through various experiments and big quantity research, the scheme that proposes is: add the additive that becomes nuclei of bubbles in urethane stoste, simultaneously, make this urethane stoste have high viscosity (claim 1) at normal temperatures, the thermal conductivity of the thermal insulation material of formation is reduced to and uses specific fluorine Lyons to make the essentially identical degree of thermal conductivity of the existing thermal insulation material of whipping agent.

That is to say, thermal insulation material for the formation after the foaming sclerosis of urethane stoste, if can promote diminishing of the interior bubble that generates of foam, increase number of bubbles, just can reduce thermal conductivity, but because the gaseous tension in the more little micro-bubble of bubble diameter is then high more, so it is quite difficult reducing bubble.Yet,,, just can increase the number of bubbles of generation, thereby can reduce the thermal conductivity of urethane foam by in urethane stoste, adding the additive that becomes nuclei of bubbles according to the inventor's research.

When making urethane stoste have high viscosity at normal temperatures, then, can make the viscosity of polyhydroxy reactant improve (claim 2), at this moment by adopting as macromolecule polyol, if make the viscosity of polyvalent alcohol keep the scope of 15000cps-50000cps at normal temperatures, then can obtain better effect.

In addition, by in urethane stoste, adding tackifier, then can make urethane stoste have high viscosity (claim 3) at normal temperatures as carboxymethyl cellulose etc., at this moment, because tackifier do not participate in reaction, but a kind of extender, addition is the highest to be no more than the weight of 5% polyvalent alcohol.

At this moment, when the number of bubbles that produces increases, if the intensity of walls is low, adjacent bubble can merge each other and become the major diameter bubble, viscosity during by raising urethane stoste normal temperature, just can improve the apparent intensity of the walls of bubble generation during the initial stage, thereby can suppress the fusion between bubble.

Can adopt flour filler, such as carbon black powder or the colloided silica fine powder additive (claim 4) of making become nuclei of bubbles of particle diameter below 10 μ m, at this moment, the addition of filler, suitable scope is to be equivalent to 5% of urethane stoste weight, and its lower limit amount is the population (because be fine powder, weight can approach 0) identical with the number of bubbles of necessity.

Can adopt the additive (claim 5) of making to become nuclei of bubbles as the low-boiling secondary whipping agent of the ratio whipping agent of HFC-143 etc., this moment, suitable addition was 0.5～20% of a whipping agent weight.The boiling point that is preferably secondary whipping agent is lower more than 10 ℃ than the boiling point of whipping agent.

Also can adopt such material to make to become the additive of nuclei of bubbles, be that this material and isocyanato and hydroxyl reaction produce gas (claim 6), the addition of the additive of this moment is to make that the gas volume that produces is more suitable when its mol ratio is 1-30% for whipping agent.In addition, if select for use water, then produce carbon dioxide with the reaction of urethane stoste as additive.

According to thermal insulation material of the present invention,, can not use specific fluorine Lyons to reduce thermal conductivity, thereby the thickness of diathermic wall is increased owing to the above-mentioned thermal insulation material of filling (claim 7) between outer container and interior case.

At this moment, because in the presence of elastomeric through polymerization, the molecular structure densification of the high polynitriles phenylethylene resin series that reaction forms, ventilation property is minimum, so, if, can prevent that effectively gas releases in the thermal insulation material, and can prevent in advance that heat insulating ability from descending with its body of thermal insulating box (claim 8) of making interior case.Equipment during as manufacturing thermal insulation material of the present invention (body of thermal insulating box) can intactly use existing installation.

Embodiment

Below, illustrate the present invention is applied to embodiment on the refrigerator body of thermal insulating box.Fig. 1 shows the body of thermal insulating box 1 of present embodiment; This body of thermal insulating box 1 is that urethane foam thermal insulation material 4 is filled in by in the housing that constitutes as steel outer container 2 with as case in the plastics system and constitute.Case 3 is made of the high polynitriles phenylethylene resin series that the mixture of vinyl cyanide compound and distyryl compound generates through polyreaction in the presence of elastomeric in above-mentioned.

Above-mentioned thermal insulation material 4 is a main component with isocyanic ester and polyvalent alcohol, the an amount of whipping agent that adds by cfc (HCFC-141b) formation in nonspecific fluorine Lyons, make urethane stoste, make stoste foaming sclerosis form this material 4 then, in above-mentioned urethane stoste, be added to the material of nuclei of bubbles, simultaneously, make this urethane stoste under insulation, keep high viscosity.

Manufacturing to this thermal insulation material 4 describes below.That is, above-mentioned urethane stoste is the 1st composition by isocyanic ester specifically and adds the 2nd composition formation that remaining composition also mixes mutually in polyvalent alcohol, then the 1st composition and the 2nd composition is contained in respectively in the other container.Add above-mentioned whipping agent (HCFC-141b) in the full-bodied at normal temperatures polyvalent alcohol respectively quantitatively, be called the surfactant of silicone oil, the catalyzer of Ammonia etc. and as the additive of nuclei of bubbles and constitute above-mentioned the 2nd composition.In addition, be preferably the 2nd composition and in container, keep whipped state always.

From above-mentioned 2 containers, extract the 1st composition and the 2nd composition with injection device and their are mixed stir, inject quantitative urethane stoste then in the housing between above-mentioned outer container 2 and interior case 3 with certain ratio.Thus, in this housing, produce mainly with isocyanato and hydroxyl, simultaneously, form bubble, the urethane foam that a plurality of bubbles are arranged is filled to forms body of thermal insulating box in the housing again because of heating makes the whipping agent gasification in conjunction with the reaction (polyreaction etc.) that generates urethane.Make this thermal insulation material 4(body of thermal insulating box 1) time equipment, can intactly use present equipment.

11 concrete embodiment of the table 1-table 4 that discloses later expression thermal insulation material 4, and represented the characteristic (foam density, thermal conductivity, low temperature dimensional stability) of the thermal insulation material that the one-tenth of urethane stoste of the thermal insulation material of embodiment 1-11 is grouped into and forms.In the table, the one-tenth that shows the urethane stoste of the comparative example 1-7 relative with embodiment in the lump is grouped into and the characteristic of thermal insulation material.These comparative examples 1-7 makes by above-mentioned manufacture method.

In these tables, polyvalent alcohol A is the polyvalent alcohol that uses at present, and under the normal temperature (25 ℃), viscosity is about 5000cps.Polyvalent alcohol B and polyvalent alcohol C are macromolecule polyols, and the viscosity under the normal temperature (25 ℃) is respectively 15000cps and 25000cps.In the table, become to be grouped into that to be the numeral of hurdle unit in () with respect to urethane content contained in the urethane stoste be to be called [pbw(Parts by weight)] below 100 the weight percent %().The thermal conductivity of the thermal insulation material that the refrigerator body of thermal insulating box uses should be at 0.0155(Kcal/mh ℃) below, be more preferably 0.0150(Kcal/mh ℃) below.And should to make its low temperature dimensional stability be below 3%.

At first, table 1 illustrates the thermal insulation material of embodiment 1-3, these examples all use full-bodied urethane C, in urethane stoste (the 2nd composition), add the additive of flour filler simultaneously as nuclei of bubbles, addition is below 5% of urethane stoste weight, specifically, flour filler is the carbon black powder of particle diameter below 10 μ m.Comparative example 1 is that the addition of filler is too much, and comparative example 2,3 is to use the polyvalent alcohol with at present equal viscosity, but does not add filler.

As can be known from Table 1, make polyvalent alcohol and urethane stoste have high viscosity, simultaneously, in urethane stoste, add the additive that becomes nuclei of bubbles in right amount, promptly in the thermal insulation material of the embodiment 1-3 of filler, can reduce thermal conductivity, and size stability is fine.This is based on such reason, by in urethane stoste, adding the additive that becomes nuclei of bubbles, it is filler, can promote to generate in the foam little bubble, thereby the increase number of bubbles, and, by improving urethane stoste viscosity at normal temperatures, just can improve the intensity of the walls of bubble generation during the initial stage, avoid bubble fusion to each other.

The addition of the filler of comparative example 1 is 5.4%, and thermal conductivity worsens.Hence one can see that, and the addition of filler should be lower than 5% of urethane stoste weight.Comparative example 2 and 3 uses the lower polyvalent alcohol A of viscosity, does not add the additive that becomes nuclei of bubbles, makes whipping agent because of using cfc, and causes thermal conductivity to worsen.In addition, also can use fine carbon powder etc. as filler.

Table 2 shows embodiment 4-6 and comparative example 4.In these embodiment 4-6, use the polyvalent alcohol C of very high viscosity, add quantitative boiling point and also will hang down secondary whipping agent more than 10 ℃ than whipping agent (HCFC-141b), promptly fluorine hydrocarbon (HFC-143) is as the additive of nuclei of bubbles.Comparative example 4 is to have added many secondary whipping agents.In addition, for ease of relatively, in last table, put down in writing above-mentioned comparative example 2,3 again.

As known from Table 2, make polyvalent alcohol have high viscosity with urethane stoste, simultaneously, add the additive that becomes nuclei of bubbles in right amount in urethane stoste, promptly the thermal insulation material of the embodiment 4-6 of filler can reduce thermal conductivity, and dimensional stability is good.Wherein the relative whipping agent of the addition of secondary whipping agent is 0.5～20%.

Table 3 expression embodiment 7 and 8, these embodiment use the polyvalent alcohol C of very high viscosity, add quantitatively the material as the additive of nuclei of bubbles, (being called gas generation additive) this material reacts with urethane stoste (isocyanato) can produce gas (carbonic acid gas), and this material is a water herein.Comparative example 5 is to have added too much gas generation additive (water), and comparative example 6-7 adopts the lower polyvalent alcohol A of viscosity but do not add the additive of nuclei of bubbles.

As known from Table 3, make polyhydroxy reactant and urethane stoste have high viscosity, simultaneously, adding in right amount the additive as nuclei of bubbles, i.e. enforcement 6 of water and 7 thermal insulation material can reduce thermal conductivity, and dimensional stability is good.The amount of gas generation additive to represent with respect to the mol ratio of the whipping agent that produces gas, then is 1～30% amount.

Last table 4 shows embodiment 9-11, and these embodiment use full-bodied polyvalent alcohol B(example 9,10) or polyvalent alcohol C(example 11), identical with above-mentioned example 7, added the additive of the gas generation additive (water) of 0.5pbw as nuclei of bubbles.This table has been put down in writing embodiment 7 again, simultaneously, for ease of relatively, has put down in writing comparative example 6-7 again.

As known from Table 4, when utilizing the viscosity of polyvalent alcohol to adjust the normal temperature viscosity of urethane stoste, be more than the 15000cps by the viscosity that makes urethane, just can reduce thermal conductivity.Though not shown in the table, in actual the use, wish that the normal temperature viscosity of polyvalent alcohol is lower than below the 50000cps.

According to the thermal insulation material of embodiment 1-11,, use nonspecific fluorine Lyons to make whipping agent in order to realize protection to global environment; add the additive that becomes nuclei of bubbles in urethane stoste, simultaneously, making this urethane stoste is high viscosity at normal temperature; just can realize fining air bubbles, reduce thermal conductivity.The result is, for as the body of thermal insulating box that uses on the refrigerator, heat insulating ability is good, needn't thicken the thickness of diathermic wall.

For the foregoing description 1-11, though use the high polyvalent alcohol of molecular weight, can improve the viscosity of polyvalent alcohol, but add the tackifier of carboxymethyl cellulose etc. in also can urethane stoste, as long as can improve the viscosity of the urethane stoste of initial reaction stage by the viscosity that improves isocyanic ester, then can obtain desired effect and effect.As whipping agent or become the additive of nuclei of bubbles, do not limit above-mentioned kind, but can use other various.For catalyzer or surfactant, also be the same.

Yet, present body of thermal insulating box, material of case can be used plastics or ABS resin etc. in it.Yet, because there is very weak air permeability in these plastics, long-time after, the gas in the bubble of thermal insulation material releases by interior case, the air displacement higher with thermal conductivity, and heat insulating ability is descended.

Yet, in the body of thermal insulating box 1 of present embodiment, if the material of interior case 3 adopts the high polynitriles phenylethylene resin series that is generated by the mixture of polyvinyl compound and distyryl compound polyreaction in the presence of elastomeric.Because the molecular structure densification of this high polynitriles phenylethylene resin series, ventilation property is minimum, just can prevent the gas leakage in the thermal insulation material 4 effectively, can prevent that in advance heat insulating ability from descending.

Can know from the above description,, can obtain following good result according to the present invention.

Promptly; thermal insulation material according to claim 1; make whipping agent owing to use nonspecific fluorine Lyons; can realize the environment of preserving our planet, in urethane stoste, add the additive that becomes nuclei of bubbles; simultaneously; make this urethane stoste have high viscosity at normal temperatures, can realize fining air bubbles, can the be improved good result of heat insulating ability of result.

For making urethane stoste have high viscosity at normal temperatures, if by adopting as macromolecule polyol, the viscosity that improves polyhydroxy reactant also can (claim 2), if the viscosity normal temperature of polyvalent alcohol can obtain fabulous effect down in the scope of 15000cps-50000cps.By in urethane stoste, adding as the tackifier of carboxymethyl cellulose etc., can make urethane stoste have high viscosity (claim 3) at normal temperatures,,,, be limited to 5% of polyvalent alcohol weight in the interpolation herein only as extender because tackifier do not participate in reacting.

As the additive of air bubble agent, at first, can adopt flour filler, for example, particle diameter is following carbon black powder or colloided silica fine powders (claim 4) of 10 μ m, what the addition of filler was suitable is 5% of urethane stoste weight.As the additive of nuclei of bubbles, can use the boiling point secondary whipping agent lower than whipping agent, HFC-143 etc. (claim 5) for example, addition herein is 0.5～20% of a whipping agent weight.In addition, as the additive of nuclei of bubbles, also can employing and isocyanato or hydroxyl reaction produce the material (claim 6) of gas, at this moment, the addition of additive should make the gas volume that produces with respect to whipping agent, is the amount of 1-30% with the mol ratio.

The body of thermal insulating box of claim 7 according to the present invention, because the above-mentioned thermal insulation material of filling between outer container and interior case, therefore can reduce thermal conductivity in the situation of not using specific fluorine Lyons,, can not thicken the thickness of diathermic wall with respect to the existing casing that uses specific fluorine Lyons.

Because have elastomeric in the presence of by the molecular structure densification of the resin of the high polynitriles polystyrene of polyreaction, ventilation property is minimum, if interior case uses the body of thermal insulating box (claim 8) of this resin, can prevent that effectively gas releases in the thermal insulation material, can prevent in advance that heat insulating ability from descending.

Claims (8)

1, a kind of thermal insulation material, this material is a main component with isocyanic ester and polyvalent alcohol, add in main component that cfc, fluorine are hydrocarbon, hydro carbons at least a more than composition, make urethane stoste, make the foaming of urethane stoste then, sclerosis forms,

It is characterized in that in above-mentioned urethane stoste, add the additive that becomes nuclei of bubbles, simultaneously, make this urethane stoste have high viscosity at normal temperatures.

2, thermal insulation material according to claim 1, it is characterized in that making the viscosity under the polyvalent alcohol normal temperature is 15000cps-50000cps.

3, thermal insulation material according to claim 2 is characterized in that in urethane stoste, adds tackifier such as carboxymethyl cellulose, and addition is below 5% of polyhydroxy reactant weight.

4, thermal insulation material according to claim 1, the additive that it is characterized in that becoming nuclei of bubbles is to be made of flour filler, the amount of interpolation is below 5% of urethane stoste weight.

5, thermal insulation material according to claim 2 is characterized in that the additive that becomes nuclei of bubbles is made of the boiling point secondary whipping agent lower than whipping agent, and addition is 0.5～20% of an above-mentioned whipping agent weight.

6, thermal insulation material according to claim 2, the additive that it is characterized in that becoming nuclei of bubbles is made of the material that produces gas with isocyanato or hydroxyl reaction, and the above-mentioned gas amount that the amount of interpolation should make generation is 1-30% with respect to the mol ratio of whipping agent.

7,, it is characterized in that any described thermal insulation material of filling claim 1 to 6 between outer container and interior case according to a kind of body of thermal insulating box.

8, body of thermal insulating box according to claim 7, case is that mixture by vinyl cyanide compound and distyryl compound constitutes through the high polynitriles phenylethylene resin series of polyreaction generation in the presence of synthetic rubber in it is characterized in that.

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