CN109900058A - Refrigerator, premix glycol composition and hard polyurethane foams - Google Patents
Refrigerator, premix glycol composition and hard polyurethane foams Download PDFInfo
- Publication number
- CN109900058A CN109900058A CN201811032561.4A CN201811032561A CN109900058A CN 109900058 A CN109900058 A CN 109900058A CN 201811032561 A CN201811032561 A CN 201811032561A CN 109900058 A CN109900058 A CN 109900058A
- Authority
- CN
- China
- Prior art keywords
- active hydrogen
- compound
- premix
- glycol composition
- contg
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Polyurethanes Or Polyureas (AREA)
Abstract
本发明提供冰箱、预混多元醇组合物以及硬质聚氨酯泡沫。所述冰箱即使在使冰箱薄壁化的情况下，也抑制绝热性能和外观品质的降低。所述冰箱具备外箱、内箱、配置于前述外箱与前述内箱之间的真空绝热材料、以及填充于前述外箱与前述内箱之间的硬质聚氨酯泡沫，其中，在前述硬质聚氨酯泡沫的厚度为10mm以下的区域，前述硬质聚氨酯泡沫的小室的形状在发泡流动方向上较长。
The present invention provides refrigerators, pre-blended polyol compositions, and rigid polyurethane foams. In the refrigerator, even when the wall of the refrigerator is made thinner, the deterioration of the thermal insulation performance and the appearance quality is suppressed. The refrigerator includes an outer case, an inner case, a vacuum heat insulating material disposed between the outer case and the inner case, and a rigid polyurethane foam filled between the outer case and the inner case, wherein the rigid The thickness of the urethane foam is a region of 10 mm or less, and the shape of the cells of the aforementioned rigid urethane foam is long in the foaming flow direction.
Description
Technical field
The present invention relates to refrigerators and hard polyurethane foams premix polyalcohol.
Background technique
In recent years, in order to meet the consumer demand of high capacity, refrigerator shell is thinning continuous propulsion.With regard to shell
For being thinning, since insulation thickness reduces, there are trade-off relationships with heat-insulating property.Therefore, it has studied cold by adding
But functional component, increase the designs such as thickness of vacuum heat insulation materials to realize and be thinning but reduce energy consumption.In addition, being thinning shell
There is also the worry for leading to strength reduction is thinning, therefore, other than structure design, it is desirable to improve simple hard polyaminoester
The intensity of foam.For example, being described in patent document 1 by keeping the hard polyurethane foams of thinner wall section in refrigerator shell highly dense
Spend (60kg/m3More than) Lai Tigao cabinet intensity.
Existing technical literature
Patent document
Patent document 1: No. 6140279 bulletins of Japanese Patent No.
Summary of the invention
Problems to be solved by the invention
But in patent document 1, the space of hard polyurethane foams material flow is narrow, is lower than 10mm, therefore do not fill out
Filling hard polyurethane foams with filling portion is very difficult.Hard polyurethane foams are not filled by partially due to making refrigerator entirety
Heat-insulating property reduces, therefore the heat leak amount of refrigerator increases.In addition, in the case where shell produces and is not filled by portion, occur to
The strain deformation of portion direction recess, bad order, and and density not sufficiently filled in hard polyurethane foams is not filled by generate
In the case where deviation, also become the factor of shrinkage of part hard polyurethane foams, bad order.
Therefore, it is an object of the present invention to inhibit heat-insulating property and appearance in the case where being thinning refrigerator
The reduction of quality.
The method used for solving the problem
The present invention is a kind of refrigerator, which is characterized in that have outer container, interior case, be configured at aforementioned outer container and aforementioned interior case it
Between vacuum heat insulation materials and the foam filled hard polyurethane foams between aforementioned outer container and aforementioned interior case, aforementioned
Hard polyurethane foams with a thickness of the region below 10mm, the shape of aforementioned hard polyurethane foams cell is in foaming flowing side
It is longer upwards.
The effect of invention
According to the present invention, the tremendous raising of the mobility of hard polyurethane foams raw material, even if being thinning refrigerator
In the case of, also it is able to suppress the reduction of heat-insulating property and exterior quality.
Detailed description of the invention
Fig. 1 is the front view of the refrigerator with door.
Fig. 2 is the front view for removing refrigerator behind the door.
Fig. 3 is the sectional view of refrigerator.
Fig. 4 is to scheme obtained by amplifying the refrigerator side rail portion of Fig. 3.
Fig. 5 is the enlarged drawing of the foamed heat insulation body allocation position (rail portion) of Fig. 1.
Fig. 6 is the hard polyurethane foams of the present embodiment sectional view parallel with foaming direction.
Fig. 7 is the hard polyurethane foams of the present embodiment sectional view vertical with foaming direction.
Symbol description
1: refrigerator；2: body of thermal insulating box；3: revolving door；4: the door of drawer type；5: demarcation plate；6: storeroom；7: foaming
Heat guard；8: Machine Room；9: basic room；10: track reinforcing member；11: screw；12: track；13: interior case；14: outer container；15:
Box (case)；16: track component；17: track support members；18: hinge (hinge)；19: polyurethane adiabatic material；20: vacuum
Heat-insulating material；21,23: the small locular wall of hard polyurethane foams；22: indicating the arrow of foaming flow direction.
Specific embodiment
The refrigerator 1 of present embodiment has interior case 13, outer container 14 and the vacuum being configured between interior case 13 and outer container 14
Heat-insulating material 20.In present embodiment, vacuum heat insulation materials 20 are provided to outer via bonding agents such as double faced adhesive tape, hot-melt adhesives
14 side of case, polyurethane adiabatic material 19 inject the gap of vacuum heat insulation materials 20 and interior case 13 and foaming, it is Nian Jie with interior case 13 or
Person fixes.Wherein, vacuum heat insulation materials 20 can be configured at the centre of interior 13 side of case or interior case 13 and outer container 14, such feelings
Under condition, polyurethane adiabatic material 19 be filled in vacuum heat insulation materials 20 and outer container 14 gap or vacuum heat insulation materials 20 with
The gap of interior case 13 and the gap of vacuum heat insulation materials 20 and outer container 14.The heat-insulating property of body of thermal insulating box 2 is by polyurethane adiabatic material
Material 19 and vacuum heat insulation materials 20 undertake, and especially from the viewpoint of heat-insulating property, preferably improving has about 10 times of polyurethane
The filling ratio of the vacuum heat insulation materials 20 of heat-insulating material heat-insulating property.
However, vacuum heat insulation materials is at high cost, in the case where obtaining necessary performance, vacuum can also be reduced
The filling ratio of heat-insulating material.Here, the filling ratio of vacuum heat insulation materials refers to vacuum heat insulation materials 20 by interior 13 He of case
The ratio in space that outer container 14 is formed passes through formula (volumes of vacuum heat insulation materials)/(volume of vacuum heat insulation materials+poly-
The volume of urethane heat-insulating material) it calculates.About the filling ratio of vacuum heat insulation materials in the refrigerator 1 of present embodiment, wrapping
In the adiabatic space for including the demarcation plate 5 of the top surface of refrigerator 1, the back side, two sides, this 5 faces of bottom surface and storeroom 6, it is set as 30%
Above 80% or less.
As shown in Figure 1, 2, refrigerator 1 is mainly made of body of thermal insulating box 2 and each door, and body of thermal insulating box 2 is with 1 or more preceding
The storeroom 6 of face opening.In the case where having 2 or more storerooms 6, each storeroom 6 is divided with demarcation plate 5, and storeroom 6 is equipped with
There is the door 4 of revolving door 3 or the drawer type for having box 15.
The sectional view of refrigerator 1 is shown in Fig. 3.The door 4 of the box 15 and drawer type that are accommodated in storeroom 6 pulls out together.
It should be noted that in the present embodiment, although being formed in imagination the vegetable compartment in 8 front of Machine Room, lowest part
Storeroom 6 is illustrated, but may be the storeroom of imaginary freezing chamber, upper part.In addition, the side wall of storeroom 6 is equipped with
The door 4 of track 12 as shown in Figure 4, drawer type pulls out while via the track 12 in front-rear direction sliding.
Fig. 5 is the sectional view that display is equipped with the structure of side wall in the part of track 12.As shown in figure 5, track 12 is by following
Part is formed: the track component 16 that is installed on 15 side of box, support in the door 4 and box 15 of 16 drawer type of track component via eating
The track support members 17 of the load of product and the track for improving intensity when track support members 17 to be installed on to interior case 13 increase
Strong component 10.Interior case 13, track support members 17 and track reinforcing member 10 are mainly fixed by screw 11.Wherein, track increases
Strong component 10 uses metal or thermosetting plastics with a thickness of 1mm more than or lower than 10mm etc..
Here, in the inside of interior case 13, recess portion is formed in a manner of storing track support members 17, on the other hand,
The outside of interior case 13, is formed with the protrusion towards 20 side of vacuum heat insulation materials.Therefore, part locating for interior 13 middle orbit 12 of case with
Interior case 12 is closer than other parts with the distance of vacuum heat insulation materials 20.In addition, in the part further there is rail in the outside of case 13
Road reinforcing member 10, thus the track reinforcing member 10 and the gap of vacuum heat insulation materials 20 are narrow.Especially, for exist from
Interior case 13 is to the position of the fixation members such as the screw 11 outstanding of vacuum heat insulation materials 20, more with the gaps of vacuum heat insulation materials 20
It is narrow.Wherein, the fixation member as interior case 13, track support members 17 and track reinforcing member 10, other than screw 11,
It further include set on track support members 17, hook that track reinforcing member 10 is supported with hook fixed structure etc..
In this way, about there are the parts of track 12 in the side wall formed in interior case 13, outer container 14, it is necessary to useful
In the structure that track 12 is fixed on to interior case 13, therefore, works and vacuum insulation set on 13 outside of interior case 13 or interior case
The gap-ratio other parts of material 20 are narrow, and local gap is less than 10mm.Moreover, there is thickness in itself, sticking up in vacuum heat insulation materials 20
Bent and concave-convex surface deviation, when vacuum heat insulation materials 20 are pasted onto outer container 14, there are manufacture deviations.As a result, being set to
The works in 13 outside of interior case 13 or interior case is contacted with vacuum heat insulation materials 20, and the housing material of vacuum heat insulation materials generates
A possibility that cracking, rupture, productivity reduce, and appearance reduces heat-insulating property due to slowly leaking.
Therefore, in the present embodiment, in the region for being less than 10mm with the gap of vacuum heat insulation materials 20, specifically, such as Fig. 5
Shown, in the part locating for inner track support member 17 outside of interior case 13, injects following such polynary with premixing
The polyurethane material of alcohol and foaming, obtain hard polyurethane foams.
The premix polyalcohol of present embodiment contains active hydrogen-contg compound, surfactant, catalyst, water and pentamethylene,
In, active hydrogen-contg compound contains the first active hydrogen-contg compound (A), the second active hydrogen-contg compound (B), third containing reactive hydrogen
At least each one kind of compound (C).Here, it is 200 below containing reactive hydrogen that the first active hydrogen-contg compound (A), which is weight average molecular weight,
Chain fatty compounds of group is addition alkylene oxide in 200 compounds of group of chain fatty containing reactive hydrogen below in weight average molecular weight
Obtained by compound.In addition, the second active hydrogen-contg compound (B) is the addition epoxy in the compound with 4~8 reactive hydrogens
Active hydrogen-contg compound obtained by alkane.In turn, third active hydrogen-contg compound (C) is the addition in monocarboxylic acid or polybasic carboxylic acid
Active hydrogen-contg compound obtained by polyalcohol.Also, as catalyst component, contain cyclic amine compound, cyclic amine compound
Salt, any one of carboxylate.
It is foamed by mixing the premix polyalcohol and polyisocyanate of such composition, is able to maintain that low viscosity,
And it can be set as the reaction than common foamable reaction delayization simultaneously, compared with the past, the tremendous raising of mobility, therefore
It is capable of providing hard polyurethane foams high-intensitive and with high thermal insulation.
As the first active hydrogen-contg compound (A) of present embodiment, specially containing ethylene glycol, diethylene glycol, the third two
Alcohol, dipropylene glycol, tripropylene glycol, 1,3- propylene glycol, 1,4- butanediol, 1,5- pentanediol, hydrazine, ethylenediamine, hexamethylene diamine,
It is more than at least one of diethanol amine, amino ethyl ethanolamine, glycerol, triethanolamine, pentaerythrite and triisopropanolamine
Substance, hereinafter referred to as polyalcohol (A).In addition, the premix glycol composition of present embodiment can be containing at least one above-mentioned
Polyalcohol (A) can also contain two or more.
Here, the polyalcohol (A) of the chain fatty race of low molecular weight with weight average molecular weight greater than 200 polyalcohol compared with,
Strand is short, therefore in having the molecular structure after making to react with polymethylene diisocyanate, more shortens and comes autohemagglutination Asia
The effect of the distance of the aromatic molecule interchain of methyl diisocyanate.In addition, the polyalcohol of the chain fatty race of low molecular weight
(A) reacted with polymethylene diisocyanate urethane bond obtained by being formed be easy with from hydrone (by water with
The reaction of polymethylene diisocyanate, which is formed, to be obtained) urethane bond and/or urea bond form hydrogen bond.Pass through these hydrogen bonds
Formation, promote the aromatic molecule interchain from polymethylene diisocyanate agglutination, bring intensity improve effect.
Moreover, the premix glycol composition of present embodiment other than above-mentioned polyalcohol (A), also contains in hydroxyl value
In 4~8 polyalcohol active hydrogen-contg compound obtained by addition alkylene oxide as the second active hydrogen-contg compound (B) (hereinafter referred to as
For polyalcohol (B)).
Here, the polyalcohol for being 4~8 as hydroxyl value can it is preferable to use sweet specifically, if it is tetrahydroxylic alcohol
Oil, pentaerythrite, methyl glucosamine, toluenediamine etc.；It, can it is preferable to use glucose, mannose, fruits if it is pentabasis alcohol
The monosaccharides such as sugar；It, can it is preferable to use pentaerythrite, D-sorbites etc. if it is hexahydroxylic alcohols；It, can if it is 7~8 yuan of alcohol
With it is preferable to use the glucide and its ramifications such as sucrose, lactose, phenols etc..Wherein, sucrose is particularly preferably used.Sucrose crosslinking points
It is especially more, it can be improved the intensity and dimensional stability of hard polyurethane foams.
As the alkylene oxide of polyalcohol (B), it is preferable to use ethylene oxide, propylene oxide, epoxy butanes etc..Wherein,
Any oxide can be used, two or more oxides also can be used together.And with two or more oxides in the case where,
Them can be made successively to react, or they can also be mixed and be reacted.
In addition, the premix glycol composition of present embodiment can be containing at least one above-mentioned polyalcohol (B), it can also be with
Containing two or more.
Cross-linking reaction point with the polyalcohol (B) compared with low viscosity is more, forms three-dimensional crosslinking structure, and molecular structure becomes jail
Gu therefore, can realize the high intensity of hard polyurethane foams while maintaining low viscosity.Thereby, it is possible to it is above-mentioned more
The effect of first alcohol (A) cooperates with and improves the intensity of hard polyurethane foams.
In turn, in the present embodiment, as third active hydrogen-contg compound (C) (hereinafter referred to as polyester polyol (C)),
Contain active hydrogen-contg compound obtained by the addition polyalcohol in monocarboxylic acid or polybasic carboxylic acid.Polyester polyol (C) and conduct
The compatibility of the pentamethylene of foaming agent is suitably low, therefore effectively vaporization in foamable reaction, and to reducing, thermal coefficient is effective.
As polyester polyol used in present embodiment (C), in particular, it is preferred that being phthalic anhydride ester system polyester polyols
Alcohol, terephthalic acid (TPA) system polyester polyol, benzoic acid derivative polyester polyol etc. have aromatic polyester polyol, they
Aromatic ring with rigidity, thus it is also effective to the high intensity of hard polyurethane foams.
Moreover, the premix glycol composition of present embodiment contains cyclic amine compound, the salt of cyclic amine compound, carboxylic
Any one of hydrochlorate is used as catalyst component.By using these catalyst, the delay of initial foamable reaction can be realized
Gel state brought by the extensionization of brought liquid condition time and the gel time delayization intermediate as reaction
The extension of time can make the tremendous raising of mobility.In the reaction of hard polyurethane foams, premix glycol composition and
The liquid that polyisocyanate mixes becomes cream-colored in initial reaction stage, and foamable reaction starts.Then, if the crosslinking of resin
(gelation) reaction starts, then viscosity rises, and mobility reduces, final to solidify.It is multiple in order to be filled in hard polyurethane foams
Miscellaneous, narrow space, it is effective that extending, which has the time of mobility,.Cyclic amine compound, the salt of cyclic amine compound, carboxylic acid
Salt has the small feature of catalytic activity in initial foamable reaction, therefore is able to extend the time of the state of low viscosity, has
The time of mobility.Initial reaction of the cyclic amine compound in the premix glycol composition and polyisocyanate of present embodiment
In, it is small for the catalytic activity of the reaction of water and polyisocyanate, for the catalytic activity of crosslinking (gelation) reaction of resin
Greatly.Therefore, the time of gelation can be controlled as random length by adjusting additive amount.
Salt, the carboxylate of cyclic amine compound similarly have delayization effect.These catalyst pass through reaction system
Temperature rises, the dissociation of salt occurs and shows catalytic activity.Crosslinking (gelation) reaction both sides' activation of initial reaction and resin,
Thus while being able to extend the time until initial reaction, still, cyclic amine is compared in the control of crosslinking (gelation) reaction of resin
Compound is difficult.
It is preferred that containing polyalcohol (A) to premix 5~10 mass % of glycol composition.Wherein, " 5~10 mass % " is set
For 5 mass % or more, 10 mass % or less.If polyalcohol (A) premixes more lower than 5 mass % of premix glycol composition
The reduction of first alcohol composition viscosity and the improvement effect of intensity are insufficient, in addition, if then there is viscosity change more than 10 mass %
Obtain the worry that liquid becomes larger in refrigerator internal leakage, heat leak amount in too small and hard polyurethane foams reaction process.
It is preferred that containing polyalcohol (B) to premix 70~90 mass % of glycol composition.If polyalcohol (B) is lower than pre-
70 mass % of mixed glycol composition, then the polyol component more than cross-linking reaction point tails off, and premixes the strong of glycol composition
Degree reduces.In addition, if more than 90 mass %, then since the polarity of polyalcohol (B) is high, pentamethylene and premix glycol composition
Compatibility sharply deteriorate, the volatilization quantitative change of pentamethylene is more, can not effectively make to contain pentamethylene in cell.As a result, leading
Hot coefficient increases, and heat leak amount becomes larger.Wherein, polyalcohol (B) as long as substance more than cross-linking reaction point, structure is as more
First alcohol (A) like that, is not limited to chain, aliphatic.Also it can have aromatic rings.
It is preferred that containing polyester polyol (C) to premix 5~10 mass % of glycol composition.The lower polyester of viscosity is more
First alcohol (C) is suitably low with the compatibility of the pentamethylene as foaming agent, effectively gasifies in foamable reaction and is contained in cell
It is interior, thus thermal coefficient reduction and mobility are improved effective.In the case that additive amount is lower than 5 mass %, it can not obtain above-mentioned
Effect.Polyester polyol (C) be synthesized by carboxylic acid with the polycondensation of polyalcohol (such as diethylene glycol), therefore have with it is different
The high primary hydroxyl of polyisocyanate reactant.Therefore, if additive amount is more than 10 mass %, reactivity is high, initial foamable reaction and
The gel time intermediate as reaction becomes faster, and mobility reduces.
It is characterized in that, is succinic acid, adipic acid, decanedioic acid, the substitution carboxylic of aromatic series one as monocarboxylic acid or polybasic carboxylic acid
Acid derivative, two substituted carboxylic acid derivative of aromatic series more than one.Particularly with taking into account, intensity is improved and thermal coefficient reduces
For, preferably phthalic acid ester system polyester polyol, terephthalic acid (TPA) system polyester polyol, benzoic acid system polyester polyol etc.
With aromatic polyester polyol.
In the premix glycol composition of present embodiment, contained with premixing 0.5~1.5 mass % of glycol composition
Any one of cyclic amine compound, the salt of cyclic amine compound, carboxylate.By making such premix polyalcohol and poly- isocyanide
Acid esters reaction can be realized the extension of liquid condition time brought by the delayization of initial foamable reaction and as in reaction
Between gel time delayization brought by the gel state time extension, hard polyurethane foams can be not filled by
It fills to portion to insulation purposes shell with complex shape.In addition, from the aspect of the intensity for ensuring wall surface, preferably in thin-walled
Change refrigerator shell in by the bending strength of hard polyurethane foams be 0.25MPa or more.
It can be containing more other than above-mentioned polyalcohol (A), (B) and polyester polyol (C) in premix glycol composition
First alcohol (hereinafter referred to as polyalcohol (D)).Premix polyol component (polyalcohol (A)+polyalcohol contained in glycol composition
(B)+polyester polyol (C)+polyalcohol (D)) weight average molecular weight be preferably 600~1300, more preferably 800~1000.Weight
In the case that average molecular weight is less than 600, the viscosity for premixing glycol composition is reduced, and mobility improves, but strength reduction.It is another
Aspect, in the case that weight average molecular weight is greater than 1300, viscosity rises, and mobility significantly deteriorates.
Polyol component contained in premix glycol composition (polyalcohol (A)+polyalcohol (B)+polyester polyol (C)+
Polyalcohol (D)) viscosity at 25 DEG C is preferably 2000~6000mPas, more preferably 3000~5000mPas.It uses
In the case where polyol component of the viscosity lower than 2000mPas, the viscosity of hard polyurethane foams raw material is reduced, and mobility mentions
Height, but liquid leakage, hard occurs in insulation purposes housing mould with complex shape when hard polyurethane foams reaction
Polyurethane foam can not be filled in the final filling part of insulation purposes shell with complex shape.On the other hand, viscosity is greater than
In the case where 5000mPas, the mobility of hard polyurethane foams raw material is unable to fully improve, with complex shape exhausted
The complicated shape portion of hot purposes shell generates the deviation in cavity, density.
Surfactant contained in premix glycol composition as present embodiment, is not particularly limited, and can be used
Well known material.The surfactant is alkylene oxide modified dimethyl polysiloxane and has OH or alkoxy etc. on end group
Silicon-type compound.The B8462, B8544 for winning wound corporation can be used for example, B8545, B8546, B8547, step figure public affairs
Take charge of the L6966, L6900, Y16300, SF2937F, SF2938F, SF2936F of Dow Corning Corporation etc. of system.Relative to 100 matter
It measures part and premixes glycol composition, the amount of these surfactants is preferably 1.0~4.0 mass parts.
In addition, catalyst contained in premix glycol composition as present embodiment, is not limited to above-mentioned cyclic amine
Compound, the salt of cyclic amine compound, carboxylate can be catalyst in addition to this.As the type of catalyst, for hair
Bubble catalyst, resinification catalyst, catalyst for trimerization etc. are not particularly limited, and well known material can be used.For example, as hair
Catalyst is steeped, specifically, can be using five methyl diethylentriamine, bis- (dimethylaminoethyl) ethers etc..As resinification
Catalyst, in particular, it is preferred that being N, N, N '-trimethylamine ehtylethanolamine, N, N- dimethylaminoethoxyethanol, diethyl basic ring
Hexylamine, triethylenediamine, N, N, N ', N " -4-methyl hexamethylene diamine, N, N, N ', N " -4-methyl-diaminopropane, N, N, N ' and, N "-four
Methyl ethylenediamine etc..In addition, as catalyst for trimerization, specifically, N, N ', N "-three (3- dimethylamino-propyl) hexahydro-s- three
Piperazine, N, N ', N "-three (3- lignocaine propyl) hexahydro-s- triazine etc. is suitable.They can be used alone, and can also mix
It closes two or more and uses.Glycol composition is premixed relative to 100 mass parts, the additive amount of above-mentioned each catalyst is preferably
0.5~3.0 mass parts.It is anti-and mixing the premix polyalcohol in this way added with catalyst with polyisocyanate
It answers, can be realized the extensionization of liquid condition time brought by the delayization of initial foamable reaction and as solidifying among reaction
The extension of gel state time brought by glue time delay.If cream time (the Cream started with foamable reaction
Time, C.T.) and the gel time (G.T.) that starts of cross-linking reaction be reactive index, then above-mentioned foamable reaction is C.T.=
6~12 seconds, G.T.=35~55 second.
The optimum mix of water and pentamethylene contained in premix glycol composition, it is pre- relative to 100 mass parts
Mixed glycol composition, water are 1.5~2.0 mass parts, and pentamethylene is 14.0~18.0 mass parts.The match ratio of water and pentamethylene
It is just not particularly limited just in the above range.
The hard polyurethane foams of present embodiment can make above-mentioned premix polyhydric alcohol conjugate by using polyisocyanate
Object foams and obtains.Polyisocyanate used in present embodiment can be known, be not particularly limited.For example,
Methyl diphenylene diisocyanate (MDI) or toluene di-isocyanate(TDI) (TDI) and its derivative are suitable.They can be independent
It uses, can also be used in mixed way.As MDI and its derivative, such as MDI can be enumerated and the polyphenylene as its polymer is poly-
The mixture of methylene diisocyanate, methyl diphenylene diisocyanate derivative with terminal isocyanate group etc..This
Outside, as TDI and its derivative, such as 2,4-TDI and 2 can be enumerated, mixture, the terminal isocyanate of TDI of 6-TDI is pre-
Polymers derivative etc..
The rigid polyurethane foam of present embodiment obtained by glycol composition and polyisocyanate mixed foaming will be premixed
Foam foams flow direction comprising cross sectional shape as longitudinal direction, meets the cell of w l ratio (the ratio of width to height)=1.5~3.0.Here,
Hard polyurethane foams are formed by independent air bubble cell.In general, in order to make foaming agent pentamethylene effectively enter small interior,
Promote spherical fragile cells by fast foaming, curing reaction, realizes low thermal conductivity.But fast foaming, solidification are anti-
Ying Zhong, the time with mobility shorten.The delay that the hard polyurethane foams of present embodiment pass through initial foamable reaction
When gel state brought by the extensionization of brought liquid condition time and the gel time delayization intermediate as reaction
Between extension, have high fluidity.The extensionization of gel state time brought by gel time delayization has following spies
Sign: making the shape of cell is longitudinally long ellipse 21 (Fig. 6) on foaming direction.Even if being oval on foaming direction 22
Shape, when using direction of foaming as Y-axis, X-direction section is also the cell (Fig. 7) of circle 23, therefore, the gaseous exchange of X-direction
Substantially unchanged compared with spherical cell, thermal coefficient is also same.As a result, by control raw material (present embodiment it is pre-
Mixed glycol composition+polyisocyanate) to decanting point and the foaming direction of insulation purposes shell, even if in elliptical shape cell
In thermal insulation can be also maintained with it is previous same.For example, if the ellipse of lengthwise is made to be located at the flat of refrigerator shell wall surface
Face direction is then able to suppress the reduction of heat-insulating property.In addition, the hard polyurethane foams of present embodiment are applied to refrigerator
In the case where shell, thermal coefficient is preferably 18.5mW/mK or less.In addition, oval cell accounts for half in all small number of chambers
Number is above, preferably accounts for 80% or more, and a part is comprising even spherical cell.
Hereinafter, using embodiment and comparative example, premix glycol composition to present embodiment and by itself and poly- isocyanide
The effect of hard polyurethane foams obtained by acid esters mixed foaming is illustrated.
Embodiment
(embodiment 1~13)
< premixes glycol composition and isocyanates additive amount >
Use polyol component shown in table 1, modulation premix glycol composition.As polyalcohol (A) ingredient, A: three are used
Propylene glycol, B: triethanolamine, C: at least one of diethylene glycol system polyethers.In addition, as polyalcohol (B) ingredient, using adding
At D: D-sorbite, the E: sucrose, F: toluenediamine, G: at least one of triethanolamine of alkylene oxide.As polyester polyols
Alcohol (C) ingredient, uses H: phthalic acid system, I: at least one of benzoic acid system.
In the polyol component shown in 100 mass parts tables 1,2.5 mass parts of addition (it is public to win wound as the B8462 of surfactant
Department's system).About catalysts, relative to 100 mass parts polyol components, kicker is added and catalyst for trimerization is total
Cyclic annular amine catalyst (cyclic amine compound) A:Dabco33LV, the carboxylic acid of any additive amount is added according to table 1 in 2.0 mass parts
Salt series catalysts B:DabcoTMR2.The catalyst used is to win wound corporation.In 100 mass parts polyol components, addition
As foaming agent 2.0 mass parts water and 16.0 mass parts pentamethylene (ball is apt to corporation), 150 parts as isocyanate prepolymer composition
Polymethylene polyphenyl group diisocyanate, that is, Millionate MR200 (Tosoh corporation).
The small chamber shape w l ratio rate > of <
Hard polyurethane foams containing polyol component shown in embodiment 1~13 are configured at the area below thickness 10mm
In part locating for domain, such as inner track support member in the case where the region in the outside of interior case, with its side of flowing that foams
Hard polyurethane foams are obtained on orthogonal direction, measure the w l ratio relative to foaming flow direction.
It is coated with Carbon Spray FC-153 (fine chemistry industry Japanese firm system) in hard polyurethane foams section, is used
Stereoscope (Keyemce corporation digit microscope VHX-1000/1100ver.1.2) is observed, according to the observation as a result,
Calculate the vertical/horizontal ratio of cell.The average value of 20 cells is shown in table 2.
< thermal coefficient >
About thermal coefficient, 200mm × 200mm × 30tmm foam is cut out from above-mentioned polyurethane foam board, uses hot-fluid
Method Measured Results of Thermal Conductivity device (Ying Hongjing machine corporation, model: HC-73), is evaluated with 10 DEG C of mean temperature.
< bending strength >
Bending strength is measured using Autograph (Shimadzu Seisakusho Ltd.'s corporation, AG-100kNX).From above-mentioned polyurethane foam
Foam plate cuts out 80mm × 250mm × 30tmm hard polyurethane foams, applies load with the feed speed of 10mm/min, will use
Value obtained by width and thickness square of the load divided by hard polyurethane foams when hard polyurethane foams breakage is as bending
Intensity.
In embodiment 1~13, the foaming cell vertical with bending direction becomes more, therefore, bending strength value and comparative example,
Previous example is big compared to more.Even if can also be loaded in the front-back direction to shell as a result, in thinner wall section and show high intensity, with shell
Body intensity improves associated.
[comparative example]
(comparative example 1~3)
< premixes glycol composition and isocyanates additive amount >
Use polyol component shown in table 1, modulation premix glycol composition.As polyalcohol (A) ingredient, A: three are used
Propylene glycol, B: triethanolamine, C: at least one of diethylene glycol system polyethers.In addition, as polyalcohol (B) ingredient, using adding
At D: D-sorbite, the E: sucrose, F: toluenediamine, G: at least one of triethanolamine of alkylene oxide.As polyester polyols
Alcohol (C) ingredient, uses H: phthalic acid system, I: benzoic acid system, J: at least one of adipic acid system.
In the polyol component shown in 100 mass parts tables 1,2.5 mass parts of addition (it is public to win wound as the B8462 of surfactant
Department's system).About catalysts, relative to 100 mass parts polyol components, kicker is added and catalyst for trimerization is total
Cyclic annular amine catalyst A:Dabco33LV, the monoamine catalyst C of any additive amount are added according to table 1 for 2.0 mass parts:
Polycat8.The catalyst used is to win wound corporation.In 100 mass parts polyol components, add as foaming agent
2.0 mass parts water and 16.0 mass parts pentamethylene (ball is apt to corporation), 150 parts of polymethylene polyphenyls as isocyanate prepolymer composition
Group diisocyanate, that is, Millionate MR200 (Tosoh corporation).Fluidity evaluating and hard polyurethane foams evaluation of physical property
It is carried out by method same as embodiment.
It is proved by Examples 1 to 8 and comparative example 1, in premix glycol composition shown in table 1, by containing 5~10 matter
The polyester polyol (C) of the polyalcohol (A) of %, the polyalcohol (B) of 70~90 mass %, 5~10 mass % is measured, to meet this
Viscosity, flowing velocity relative scale and the small chamber shape w l ratio (the ratio of width to height) of the display high fluidity of embodiment.Comparative example
In 1, it is added to big weight polyalcohol (A) ingredient or polyester polyol (C) ingredient, therefore viscosity reduces, bending strength reduces.This
Outside, in comparative example 1, due to the effect of the primary hydroxyl of the polyester polyol largely made an addition in polyester polyol (C) ingredient, reaction
Property is got higher.Since reactivity is got higher, polyurethane foam can not equably rise in housing side portion, and foam seam nearby produces
Life is not filled by cavity.
It is proved by embodiment 9~13 and comparative example 2~4, in premix glycol composition shown in table 1, by using ring-type
Amine catalyst and carboxylate series catalysts, so that the viscosity, the flowing velocity that meet the display high fluidity of present embodiment are opposite
Ratio and small chamber shape w l ratio.Comparative example 2 is since the additive amount of cyclic annular amine catalyst A is few, initial reaction and resinification reaction
Slower than required speed, accordingly, there exist the worries that liquid is leaked from mold.Additive amount of the comparative example 3 due to cyclic annular amine catalyst A
It is more, therefore reactivity is high, loses high fluidity.Monoamine catalyst C of the comparative example 4 due to using not display delay property,
Therefore C.T. and G.T. reacts rapidly.Therefore, in comparative example 3 and 4, due to reactive high, polyurethane foam can not be in shell
Side surface part equably rises, and foam seam nearby generates and is not filled by cavity.
[previous example]
< premixes glycol composition and isocyanates additive amount >
Use polyol component shown in table 1, modulation premix glycol composition.As polyalcohol (A) ingredient, C: two are used
Ethylene glycol system polyethers.In addition, using E as polyalcohol (B) ingredient: sucrose, F: toluenediamine, G: triethanolamine.It is not used poly-
Ester polyol (C) ingredient.
B8462 (Ying Chuan company of 2.5 mass parts as surfactant is added in the polyol component shown in 100 mass parts tables 1
System).Catalysts are, relative to 100 mass parts polyol components, the monoamine catalyst of any additive amount to be added according to table 1
C:Polycat8.The catalyst used is to win wound corporation.In 100 mass parts polyol components, addition is used as foaming agent
2.0 mass parts water and 16.0 mass parts pentamethylene (ball is apt to corporation), 150 parts of polymethylene as isocyanate prepolymer composition it is poly-
Phenyl diisocyanate, that is, Millionate MR200 (Tosoh corporation).Fluidity evaluating and hard polyurethane foams physical property are commented
Valence is carried out by method same as embodiment.
[table 1]
[table 2]
Claims (16)
1. a kind of refrigerator, which is characterized in that
Have outer container, interior case, vacuum heat insulation materials being configured between the outer container and the interior case and foam filled in institute
State the hard polyurethane foams between outer container and the interior case, wherein
In the hard polyurethane foams with a thickness of the region below 10mm, the shape of the cell of the hard polyurethane foams
It is longer on foaming flow direction.
2. a kind of refrigerator, which is characterized in that
Have outer container, interior case, vacuum heat insulation materials being configured between the outer container and the interior case and foam filled in institute
State the hard polyurethane foams between outer container and the interior case, wherein
The hard polyurethane foams have containing active hydrogen-contg compound with a thickness of the region below 10mm, surfactant, urge
The premix glycol composition of agent, water and pentamethylene,
The active hydrogen-contg compound contains the first active hydrogen-contg compound A, the second active hydrogen-contg compound B and third containing activity
Hydrogen compound C,
The first active hydrogen-contg compound A is that weight average molecular weight is 200 compounds of group of chain fatty containing reactive hydrogen below, institute
Stating the second active hydrogen-contg compound B is the active hydrogen-contg compound with 4~8 reactive hydrogens, the third chemical combination containing reactive hydrogen
Object C is the active hydrogen-contg compound obtained by addition polyalcohol in carboxylic acid, as the catalyst, containing cyclic amine compound,
Any one of the salt of cyclic amine compound, carboxylate.
3. a kind of refrigerator, which is characterized in that
With storeroom, the door pulled out together with the container for being accommodated in the storeroom and set on the storeroom side wall,
The track support members of the door are supported,
Have outer container, interior case, the vacuum heat insulation materials being configured between the outer container and the interior case and it is foam filled in
In the refrigerator of hard polyurethane foams between the outer container and the interior case,
The outside of the interior case of the side wall in the part locating for the track support members of inside, the hard polyaminoester
The shape of the cell of foam is longer on foaming flow direction.
4. a kind of refrigerator, which is characterized in that
With storeroom, the door pulled out together with the container for being accommodated in the storeroom and set on the storeroom side wall,
The track support members of the door are supported,
Have outer container, interior case, the vacuum heat insulation materials being configured between the outer container and the interior case and it is foam filled in
In the refrigerator of hard polyurethane foams between the outer container and the interior case,
The outside of the interior case of the side wall in the part locating for the track support members of inside has containing containing activity
Hydrogen compound, surfactant, catalyst, water and pentamethylene premix glycol composition,
The active hydrogen-contg compound contains the first active hydrogen-contg compound A, the second active hydrogen-contg compound B and third containing activity
Hydrogen compound C,
The first active hydrogen-contg compound A is that weight average molecular weight is 200 compounds of group of chain fatty containing reactive hydrogen below, institute
Stating the second active hydrogen-contg compound B is the active hydrogen-contg compound with 4~8 reactive hydrogens, the third chemical combination containing reactive hydrogen
Object C is the active hydrogen-contg compound obtained by addition polyalcohol in carboxylic acid, as the catalyst, containing cyclic amine compound,
Any one of the salt of cyclic amine compound, carboxylate.
5. refrigerator according to claim 1 or 3, which is characterized in that exist with flow direction of foaming to be longitudinal, w l ratio
Meet 1.5~3.0 cell.
6. refrigerator according to claim 2 or 4, which is characterized in that
Contain the first active hydrogen-contg compound A to premix 5~10 mass % of glycol composition,
Contain the second active hydrogen-contg compound B to premix 70~90 mass % of glycol composition,
Contain the third active hydrogen-contg compound C to premix 5~10 mass % of glycol composition,
As the catalyst, contain cyclic amine compound, cyclic amine to premix 0.5~1.5 mass % of glycol composition
Any one of the salt of compound, carboxylate.
7. a kind of premix glycol composition, which is characterized in that
Contain active hydrogen-contg compound, surfactant, catalyst, water and pentamethylene, wherein the active hydrogen-contg compound contains
One active hydrogen-contg compound A, the second active hydrogen-contg compound B and third active hydrogen-contg compound C, described first contains active hydrogenation
It is 200 compounds of group of chain fatty containing reactive hydrogen below, the second active hydrogen-contg compound B that conjunction object A, which is weight average molecular weight,
For the active hydrogen-contg compound with 4~8 reactive hydrogens, the third active hydrogen-contg compound C is that addition is polynary in carboxylic acid
Active hydrogen-contg compound obtained by alcohol contains cyclic amine compound, the salt of cyclic amine compound, carboxylic acid as the catalyst
Any one of salt.
8. premix glycol composition according to claim 7, which is characterized in that with premix glycol composition 5~
10 mass % contain the first active hydrogen-contg compound A.
9. premix glycol composition according to claim 7, which is characterized in that with premix glycol composition 70~
90 mass % contain the second active hydrogen-contg compound B.
10. premix glycol composition according to claim 7, which is characterized in that with premix glycol composition 5~
10 mass % contain the third active hydrogen-contg compound C.
11. premix glycol composition according to any one of claims 7 to 10, which is characterized in that described first contains
Active dydrogen compounds A is ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,3- propylene glycol, 1,4- fourth two
Alcohol, 1,5- pentanediol, hydrazine, ethylenediamine, hexamethylene diamine, diethanol amine, amino ethyl ethanolamine, glycerol, triethanolamine, season
Penta 4 pure and mild triisopropanolamines more than one.
12. premix glycol composition according to any one of claims 7 to 11, which is characterized in that described second contains
The compound with 4~8 reactive hydrogens in active dydrogen compounds B is the addition ring in D-sorbite, sucrose and toluenediamine
One or more of compound obtained by oxygen alkane.
13. premix glycol composition according to any one of claims 7 to 12, which is characterized in that the third contains
Carboxylic acid in active dydrogen compounds C is succinic acid, adipic acid, decanedioic acid, one substituted carboxylic acid derivative of aromatic series, aromatic series two take
For more than one of carboxylic acid derivates.
14. the premix glycol composition according to any one of claim 7 to 13, which is characterized in that polynary to premix
0.5~1.5 mass % of alcohol composition contains any one of cyclic amine compound, the salt of cyclic amine compound, carboxylate.
15. the premix glycol composition according to any one of claim 7 to 14, which is characterized in that the premix is more
Viscosity of first alcohol composition at 25 DEG C is 2000~6000mPas.
16. a kind of hard polyurethane foams, which is characterized in that
In it will premix hard polyurethane foams obtained by glycol composition and polyisocyanate mixed foaming, there are sections
Small chamber shape, for longitudinal direction, meets the cell of w l ratio=1.5~3.0 with direction of foaming.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2017236596A JP6996957B2 (en) | 2017-12-11 | 2017-12-11 | Premix polyol composition |
| JP2017-236596 | 2017-12-11 | ||
| JP2018014311A JP6909738B2 (en) | 2018-01-31 | 2018-01-31 | refrigerator |
| JP2018-014311 | 2018-01-31 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109900058A true CN109900058A (en) | 2019-06-18 |
| CN109900058B CN109900058B (en) | 2021-11-12 |
Family
ID=66943282
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811032561.4A Active CN109900058B (en) | 2017-12-11 | 2018-09-05 | Refrigerator, premix polyol composition and rigid polyurethane foam |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109900058B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116057098A (en) * | 2020-08-31 | 2023-05-02 | 陶氏环球技术有限责任公司 | Rigid polyurethane foam and multilayer insulation components containing the same |
Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4280007A (en) * | 1979-05-21 | 1981-07-21 | Bayer Aktiengesellschaft | Process for the production of cellular polyurethane elastomers |
| US4927861A (en) * | 1987-03-11 | 1990-05-22 | Brastemp S/A | Rigid polyurethane preparation process |
| EP0495134A1 (en) * | 1988-07-27 | 1992-07-22 | Hitachi, Ltd. | Rigid polyurethane foam and heat insulator obtained therefrom |
| WO2000024813A1 (en) * | 1998-10-26 | 2000-05-04 | Bayer Aktiengesellschaft | Method of preparing rigid polyurethane foam |
| CN1347428A (en) * | 1999-04-14 | 2002-05-01 | 拜尔公司 | Polyol mixture for preparation of rigid polyurethane foams |
| CN101144674A (en) * | 2006-09-11 | 2008-03-19 | 日立空调·家用电器株式会社 | Insulators for cooling units |
| CN103374112A (en) * | 2012-04-23 | 2013-10-30 | 日立空调·家用电器株式会社 | Insulation door and insulation box structure |
| CN103374113A (en) * | 2012-04-23 | 2013-10-30 | 日立空调·家用电器株式会社 | Hard polyurethane foam and premixed dolichol for manufacturing the same |
| CN103804711A (en) * | 2014-02-20 | 2014-05-21 | 海信容声(广东)冰箱有限公司 | Low-thermal-conductivity rigid polyurethane foam taking cyclopentane as main body and manufacturing method and applications thereof |
| CN104119490A (en) * | 2014-07-10 | 2014-10-29 | 合肥美的电冰箱有限公司 | A composition, a foam material prepared from the composition, a preparing method of the foam material and applications of the foam material |
| CN105393073A (en) * | 2013-06-07 | 2016-03-09 | 三菱电机株式会社 | Insulated cabinets and refrigerators |
| US20170136711A1 (en) * | 2014-06-11 | 2017-05-18 | Basf Se | Polyurethane compound for producing an integrated insulation component |
| CN206546057U (en) * | 2015-08-05 | 2017-10-10 | 三菱电机株式会社 | refrigerator |
-
2018
- 2018-09-05 CN CN201811032561.4A patent/CN109900058B/en active Active
Patent Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4280007A (en) * | 1979-05-21 | 1981-07-21 | Bayer Aktiengesellschaft | Process for the production of cellular polyurethane elastomers |
| US4927861A (en) * | 1987-03-11 | 1990-05-22 | Brastemp S/A | Rigid polyurethane preparation process |
| EP0495134A1 (en) * | 1988-07-27 | 1992-07-22 | Hitachi, Ltd. | Rigid polyurethane foam and heat insulator obtained therefrom |
| WO2000024813A1 (en) * | 1998-10-26 | 2000-05-04 | Bayer Aktiengesellschaft | Method of preparing rigid polyurethane foam |
| CN1347428A (en) * | 1999-04-14 | 2002-05-01 | 拜尔公司 | Polyol mixture for preparation of rigid polyurethane foams |
| CN101144674A (en) * | 2006-09-11 | 2008-03-19 | 日立空调·家用电器株式会社 | Insulators for cooling units |
| CN103374112A (en) * | 2012-04-23 | 2013-10-30 | 日立空调·家用电器株式会社 | Insulation door and insulation box structure |
| CN103374113A (en) * | 2012-04-23 | 2013-10-30 | 日立空调·家用电器株式会社 | Hard polyurethane foam and premixed dolichol for manufacturing the same |
| CN105393073A (en) * | 2013-06-07 | 2016-03-09 | 三菱电机株式会社 | Insulated cabinets and refrigerators |
| CN103804711A (en) * | 2014-02-20 | 2014-05-21 | 海信容声(广东)冰箱有限公司 | Low-thermal-conductivity rigid polyurethane foam taking cyclopentane as main body and manufacturing method and applications thereof |
| US20170136711A1 (en) * | 2014-06-11 | 2017-05-18 | Basf Se | Polyurethane compound for producing an integrated insulation component |
| CN104119490A (en) * | 2014-07-10 | 2014-10-29 | 合肥美的电冰箱有限公司 | A composition, a foam material prepared from the composition, a preparing method of the foam material and applications of the foam material |
| CN206546057U (en) * | 2015-08-05 | 2017-10-10 | 三菱电机株式会社 | refrigerator |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116057098A (en) * | 2020-08-31 | 2023-05-02 | 陶氏环球技术有限责任公司 | Rigid polyurethane foam and multilayer insulation components containing the same |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109900058B (en) | 2021-11-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US11505670B2 (en) | Polyurethane foams co-blown with a mixture of a hydrocarbon and a halogenated olefin | |
| KR100247099B1 (en) | Method for production of open cell rigid polyurethane foam | |
| ES2672975T3 (en) | Polymers initiated with amine and rigid polyurethane foam obtained from them | |
| ES2375337T3 (en) | THERMALLY ISOLATED INSULATING BASED FOAMS. | |
| CA3125572A1 (en) | Production of rigid polyurethane foam | |
| EP2411436A1 (en) | Production of rigid polyurethane foams and the use thereof | |
| US20200299453A1 (en) | Rigid polyurethane foam | |
| JP5504877B2 (en) | Method for producing open cell rigid foam synthetic resin | |
| KR100323504B1 (en) | Refrigerator | |
| US20090062415A1 (en) | Methods of producing rigid polyurethane foams | |
| CN101284901B (en) | Polyisocyanate combination and method for preparing rigid isocyanurate foam using the same | |
| KR100354637B1 (en) | A Refrigerator | |
| CN101323659A (en) | Tetraalkylammonium carboxylate salts as trimerization catalysts for spray foam applications | |
| CN109900058A (en) | Refrigerator, premix glycol composition and hard polyurethane foams | |
| CN103374112B (en) | Insulated door and heat insulating box | |
| KR100935517B1 (en) | Undiluted solution composition for preparing polyurethane foam with improved adhesion and deformability, polyurethane foam prepared therefrom, and method for manufacturing same | |
| JP2014141595A (en) | Method of manufacturing rigid foam synthetic resin | |
| JP2018119034A (en) | Rigid polyurethane foam composition and method for producing rigid polyurethane foam | |
| US20210380752A1 (en) | Method for preparing a rigid polyurethane foam | |
| JP6996957B2 (en) | Premix polyol composition | |
| JP2001048947A (en) | Manufacturing method of polyurethane foam insulation | |
| JP2600735B2 (en) | Method for producing fine cell rigid polyurethane foam | |
| JPH0689102B2 (en) | Method for manufacturing rigid polyurethane foam | |
| JP2010270324A (en) | Foamable additive for polyurethane foam and method for producing rigid polyurethane foam using the same | |
| CN101144674A (en) | Insulators for cooling units |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB02 | Change of applicant information |
Address after: Tokyo, Japan, Japan Applicant after: Hitachi Global Living Program Co., Ltd. Address before: Tokyo, Japan, Japan Applicant before: Hitachi Household Electric Appliance Co. |
|
| CB02 | Change of applicant information | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |