TW559626B - Case body of a refrigerator - Google Patents

Abstract

A refrigerator having a heat insulating case body or heat insulating door(s), into a space defined between an outer case and a inner case of which, or into an inner space defined between an outer door surface iron plate and an inner door wall of which is injected with hard urethane foam by using a foaming agent mixing the cyclopenthane and water, wherein such heat insulating material is used that skin layers of the hard urethane foam as a whole at a distance of at least 500 mm or greater than that from an injection port of said hard polyurethane foam be from 34 to 37 Kg/m<3> in density, be equal or greater than 0.1 Mpa in pressure strength, and be equal or greater than 0.1 Mpa in bending strength thereof, and that the heat insulating materiel is injected into the space by an amount of a ratio from 30 to 35 g/L to an interior volume thereof.

Description

559626 Α7 Β7 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (1) The present invention relates to a heat-insulating box with a rigid polyurethane foam filled with a mixed blowing agent of cyclopentane and water. refrigerator. In the past, the heat insulation box system of a refrigerator was used in the space between the outer box and the inner box, which was filled with a rigid polyurethane foam with independent air bubbles. The rigid polyurethane foam can be obtained by reacting a polyol component and an isocyanate component in the presence of a foaming agent, a catalyst, and a foam stabilizer. Conventional foaming agents, such as trichloro-fluoromethane, which is a hardly decomposable chlorofluorocarbon (c FC) with low gas thermal conductivity (known examples include Japanese Patent Application Laid-Open No. 5 9 — 8 4 9 13) It is located in the heat insulation part of the refrigerator, but being released into the atmosphere will destroy the ozone layer or produce a greenhouse effect to increase the surface temperature. Therefore, it is necessary to find a substitute. Instead of using a blowing agent such as chlorofluorocarbon (HCFC), 1, 1-dichloro-1-fluoroethane (known examples include Japanese Patent Application Laid-Open No. 3-2 5 8 8 2 3, Japanese Patent Application Laid-Open No. 7-2 5 9 7 8) is used as a heat insulator for refrigerators. However, the ozone depletion coefficient of these alternative foaming agents is not zero, and it is expected that all of them will be abolished in 2003. However, fluorine-free blowing agents with a zero ozone depletion coefficient have prevailed in Europe to replace hydrocarbon-based compounds (known examples include Japanese Patent Application Laid-Open No. 3-15 2 1 60), followed by foaming in cyclopentane in Japan. Agents are also used in the field of refrigerator insulation. However, cyclopentane has higher thermal conductivity of the gas and poorer heat insulation properties than the foaming agents so far. In recent years, cyclopentane-prescribed rigid polyurethane foamed carcass materials have increased energy requirements, ensured energy supply and demand balance, and global warming. When considering the standpoint of saving energy, improving heat insulation effects, and protecting the global environment, amine reduction The importance of the amount of carbamate used has increased, so this point of view needs to be fully expanded to the insulation box and requirements of refrigerators using cyclopentane blowing agents (please read the precautions on the back and fill out this page)

% f This paper size is in accordance with Chinese National Standard (CNS) Λ4 specification (210 X 297 mm) -4- 559626 Α7 Β7 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (2) High performance. Regarding the rigid polyurethane foam material, the main raw material polyol and isocyanate are used to control the chemical structure, and the foaming agent and water to form bubbles. The foaming agent to adjust the interface phenomenon is to control the physical structure, and the catalyst is to control the reactivity. Polyols start to react when they are mixed with isocyanates. Polyurethane foams, which are formed by foaming agents in polyurethane resins and are dispersed by independent cells, require thermal insulation and strength. These physical properties are determined by the chemical structure and density of the polyurethane resin, and the physical structure of the polyurethane foam by the cell pore size and size of the resin skeleton surrounding the bubbles. The chemical structure of the polyurethane resin varies depending on the raw material's polyol, the chemical structure of the isocyanate, and the amount of foaming agent, water, and reactivity controlled by the catalyst. The physical structure of the polyurethane foam is also affected by the chemical structure and reactivity of the raw materials, and the physical phenomena such as bubble generation and growth are controlled by the foam stabilizer, especially the compatibility, reactivity, and foaming process of the raw materials. The fluidity of the reaction solution will be affected. Therefore, in order to form a high-performance polyurethane foam, it is necessary to prepare the most appropriate chemical structure and composition of each raw material. However, the thermal insulation material for the insulation box of the refrigerator with cyclopentane prescription is worse than the conventional CFC and HCFC foaming agents, and it has a high density and poor fluidity. Therefore, if a large amount of polyurethane is not used, In the case of an acid ester, heat insulation performance and strength cannot be ensured. In addition, due to the space saving requirements of the refrigerator, the space in the wall of the cabinet is narrow, and with the increase of the complicated shape of the cabinet or the drive wiring, the polyurethane foam inside the cabinet wall is not easy to flow. Therefore, the foam body is not easy to extend uniformly. The overall density of the surface layer of the top, bottom, back, handle, and hinge of the refrigerator is very different from the density of the core layer, and it is not easy to form a uniform foam (please read the precautions on the back first)

Buding * This paper size applies to Chinese National Standard (CNS) A4 specification (210X 297 mm) -5- 559626 A7 B7 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economy Resinization of air bubbles is likely to occur near the area, and voids are generated. Therefore, high performance of cyclopentane prescription is required. In order to solve this problem, it is necessary to develop a novel polyurethane material capable of combining low density, high fluidity, and high strength characteristics even in the cyclopentane prescription. In other words, a low-density, high-strength cyclopentane-prescribed polyurethane material is filled in a refrigerator. As a result, the amount of heat insulation material can be reduced, the cost can be reduced, or the weight can be reduced. By reducing the amount of heat leakage to save energy, and from the standpoint of global warming and global environmental protection, products such as high-quality refrigerators using cyclopentane blowing agents can be achieved. However, the polyurethane foam using a cyclopentane foaming agent has a lower saturated vapor pressure than conventional foaming agents, so the pressure in the air bubbles is also reduced, which causes problems such as shrinkage and strength reduction. In other words, the density of the foam is generally proportional to the compressive strength, and the higher the density, the higher the compressive strength. This is because the higher the foam density, the higher the proportion of polyurethane resin, and the compressive strength of the foam body increases. For example, if you want to adjust the compressive strength to above 0 · IMP a, the overall density of the surface layer must usually be above 3 8 kg / m3. The current polyurethane materials formulated with cyclopentane cannot have both low shot strength and high strength. . Therefore, the rigid polyurethane foams formulated by the cyclone courtyard are mainly used to ensure the strength. Therefore, a higher urethane with a density of 3 8 kg / m 3 or more is used to fill a large amount of space in the wall of the cabinet. Materials, making insulation materials. From this point of view, the high-performance cyclopentane prescription urethane system will have low density, high fluidity and compressive strength, and excellent dimensional stability will be foamed and filled, which can greatly reduce the amine methyl ester. The amount of acid insulation material used. The object of the present invention is to provide a refrigerator having the following heat-insulating box, (Please read the precautions on the back first

Bu Ding-

This paper size is applicable to Chinese National Standard (CNS) A4 specification (210X 297 public broadcasting) -6-559626 A7 B7 V. Description of the invention (4) The insulation box used for refrigerators and freezers is rigid with foam and filling In polyurethane foams, urethane insulation materials formulated with cyclopentane, which has both low density and high strength, are used to achieve low cost, reduced weight, compressive strength, and dimensional stability. Excellent, high fluidity to reduce the amount of heat leakage, save energy, stable and efficient high-performance thermal insulation box \ Another object of the present invention is to provide an energy-saving, high-efficiency box that can be manufactured in the same way as described above. Refrigerator with insulated door. In order to develop a rigid polyurethane foam body most suitable for use in refrigerators and freezers, the present inventors have carefully considered the ability to have both the low density and high fluidity required by the cyclopentane prescription and improve the urethane resin skeleton. (Cells) Specific countermeasures for strength, such as choosing rigid, low-solubility polyols, reducing the solvent plasticizing effect of the cells of the cyclopentane blowing agent that can completely seal the blowing agent into the cells, or using it in large quantities The method of increasing the partial pressure of carbon dioxide in the gas in the cells with the amount of water used with the cyclopentane foaming agent to increase the pressure in the cells. As a result, the following findings were obtained to complete the present invention. In other words, the object of the present invention is achieved by the following items (1) to (8). (1) In the space formed between the outer box and the inner box of the refrigerator, the heat insulation box of the refrigerator formed by filling a rigid polyurethane foam with a mixed blowing agent of cyclopentane and water is used. The overall density of the surface layer of the rigid polyurethane foam body, which is more than 500 mm from the injection port of the rigid polyurethane foam, is 3 4 to 37 kg / m 3, and the compressive strength is more than 0 · IMpa, and the bending strength is more than 0.4Mpa. Material, and for the inner volume, the paper filled with 30 ~ 3 5 g / L of this paper size is applicable to the Chinese National Standard (CNS) A4 specification (21 × 297 mm) (Please read the notes on the back first -

Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 559626 Α7 Β7 V. Description of the invention (5) Insulation materials in the above space. (2) The component having low cyclopentane solubility of the polyol component containing the rigid polyurethane foam is 60 parts by weight or more, and at least 50 mm from the plane portion of the polyurethane injection port has a thickness of about 20 The thermal conductivity of the core insulation material of ~ 2 5mm is an average temperature of 10 ° C, 18.0 ~ 18.5〇11 ^ / 111. Feet, the core density is 32 ~ 3 4 kg / m3 and 70 ° C in air and At a temperature of -20 ° C, it is composed of a heat-insulating material with a dimensional change rate of 2% or less after standing for 24 hours, and a resin with an elongation of 2 · 6 mm / g or more. A polyol component with low cyclopentane solubility refers to a polyol mixture with an opaque state when 10% by weight of cyclopentane is mixed with a polyol, and is defined as a polyol component with low cyclopentane solubility. (3) A rigid polyurethane foam containing a mixture of toluene diamine, glycerol, sucrose, bisphenol A, ethylene oxide, and / or propylene oxide containing 60 parts by weight or more of cyclopentane having low solubility and added to triethanolamine. When the polyol component of the carcass and the isocyanate component are 100 parts by weight of the catalyst, foam stabilizer, and polyol mixture, the combination of 2 · 0 ~ 2 · 5 parts by weight of water and 10 employees of the Central Standards Bureau of the Ministry of Economic Affairs Consumed by a consumer cooperative. ~ 14 parts by weight of cyclopentane mixed foaming agent. (4) The use of a polyhydric alcohol of 3 0 8 to 4 8 0 obtained by adding ethylene oxide and / or propylene oxide to toluene diamine is used. 4 0 to 5 0 wt% of ethylene oxide and / Or 10 to 20% by weight of a 300-400 polyol obtained by adding propylene oxide to triethanolamine, and a 4-5 0 to 5 0 0 polyol obtained by adding propylene oxide to glycerol-8-this The paper size applies the Chinese National Standard (CNS) A4 specification (210 × 297 mm) 559626 A7 B7 V. Description of the invention (6) 15 ~ 25% by weight, propylene oxide added to sucrose 〇Η 値 4 0 0 ～ 5 to 10% by weight of a polyhydric alcohol of 4 to 50%, a rigid polyurethane composed of a mixture of 5 to 15% by weight of a polyhydric alcohol obtained by adding ethylene oxide to bisphenol A The polyhydric alcohol component of the foam body is composed of a heat insulating material of a rigid polymonthly foam body having an average Η 値 of the polyhydric alcohol of 350 to 450. When the average polyol composition of the mixed polyol is less than 350, the compressive strength or dimensional stability will decrease, and when it is greater than 4,500, the foam body becomes brittle. The average alcohol is 3 5 0 to 4 5 0 can produce stable rigid polyurethane foam. 〇 Η 値 means the number of mg of potassium hydroxide (mgK〇Η / g) required to neutralize 1 g of acetic acid combined with acetic acid obtained from the sample. (5) A refrigerator equipped with a heat insulation door made of a rigid polyurethane foam body using a mixed foaming agent of cyclopentane and water in a space outside the refrigerator and the freezer door iron plate and the inner door wall. The most popular is the use of polyurethane at least 50 mm away from the outer side of the door. The overall density of the rigid polyurethane foam body is 3 5 ~ 3 8 kg / m3 and the compressive strength is more than 0 · IMpa. For urethane materials with a strength of 0. 4Mpa or more, for the internal volume, the heat-insulating material that is actually injected into the space inside the door wall is a heat-insulating door of 36 to 4 2 g / L. (6) — A heat-insulating door with a heat-insulating material, and the polyol component of the rigid polyurethane foam body is a polymer containing 60 parts by weight or more of cyclopentane with low solubility and at least 50 mm from the outer side of the door The urethane filling part has the heat of the core insulation material with a thickness of about 20 to 25 mm (please read the note on the back i4 first! Fill out this page) ¾ This paper scale applies Chinese National Standard (CNS) A4 specification (210X297mm) -9- 559626 A7 i. Description of the invention (,; Conductivity is average temperature lot, 18 · 〇 ^ Cardiac mobility is 32 · 5 ~ 34 · 5k g 1 9 m W / m · / m 3 and 70 ° C and printed at 20 ° C by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs, the degradation rate is 2 and the dimensional change rate is 2 The meaning of the following is that the resin has a flowability of 2. 6 mm / g or more. A heat-insulating material with a fluidity of more than 2.5 mm / g. A polyhydric alcohol component with low cyclopentane solubility means that when 10% by weight of cyclopentane is mixed with a polyol, it forms An opaque polyol blend is defined as a polyol component with low cyclopentane solubility. (7) — A heat-insulating door with a heat-insulating material, which contains toluene diamine, glycerol, sucrose 'bisphenol A, and ethylene oxide, which contain 60 parts by weight or less of cyclopentane with low solubility. And / or propylene oxide is added to the polyol component of the rigid polyurethane foam of triethanolamine mixture, and the isocyanate component is used in combination with 100 parts by weight of the catalyst, foam stabilizer, and polyol mixture, 2. 0 ~ 2 · 5 parts by weight of water and 10 ~ 14 parts by weight of a cyclopentane mixed foaming agent, which is a heat insulating material obtained by a reaction. (8) A kind of heat insulating door provided with a heat insulating material, the heat insulation The material is a polyhydric alcohol of 0 附加 3 8 0 to 4 8 0 obtained by adding ethylene oxide and / or propylene oxide to toluene diamine. 40% to 50% by weight of 'ethylene oxide and / or Polyhydric alcohols obtained by adding propylene oxide to triethanolamine 0.30 to 4 0 0 Polyols 0 to 20% by weight '0.45 to 50 0 to 5 0% obtained by adding propylene oxide to glycerol 15 to 25% by weight of the alcohol, 0.4 to 0 to 4 to 50% of the polyhydric alcohol obtained by adding propylene oxide to sucrose, 5 to 10% by weight. (Added to Shuangcai) 〇H 値 2 0 0 ~ 3 0 0 polyol 5 ~ 15% by weight mixture of China National Standard (CNS) A4 specifications (210X297 / &gt; «) .1. (Please First read the notes on the back ^^^ Fill this page) Order-] 559626 A7 B7 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs V. Invention Note (8) The polyol composition of the rigid polyurethane foam carcass, and The average Η 値 of the polyol is a heat insulating material of a rigid polyurethane foam body of 350 to 450. [Brief description of the drawing] [Fig. 1] It is a model diagram of filling a rigid polyurethane foam body with 4 points of injection. [Fig. 2] A graph showing the relationship between the distance from the injection port of the heat insulating material and the heat insulating density. [Fig. 3] A model diagram of filling a rigid polyurethane foam body with a heat-insulating door body. [Explanation of symbols] 1 ......... Insulation box 2 ......... Urethane injection head 3 ... Urethane Flow 4 ......... Urethane injection port 5 ......... Sample taking position 6 ......... Measurement sample 7 ... ....... Sample taking position (plan view above 50 mm from the injection port) 8 ......... Insulated door body 9 Urethane sample 1 〇 ..... .... Sample distance A (50 mm above the outer cover surface) (Please read the precautions on the back first

Order% This paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm) -11-559626 Printed by A7 B7, Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (9) [Implementation form of the invention] The invented rigid polyurethane foam system is obtained by reacting a basic raw material of a polyol component with an isocyanate in the presence of cyclopentane and <water), a foam stabilizer, and a reaction catalyst. The main reasons for the low density, high fluidity, and strength of cyclopentane formulations are still unknown. Therefore, the solubility, compressive strength, and dimensional stability of cyclopentane blowing agents for various polyols must be investigated. Relationship. As a result, it was found that when the polyol having a lower solubility in the cyclopentane of the foaming agent is compared with the one having a higher solubility, the compound having a lower solubility has superior polyurethane foam compressive strength or dimensional stability. . Polyols also have different solubility in cyclopentane due to the added alkylene oxide. When compared with added propylene oxide, the added propylene oxide has higher solubility. From the viewpoint of the pre-mixing stability of the polyol, those with higher solubility in cyclopentane are better. Conversely, those with lower solubility are more desirable from the viewpoint of improving the cell skeleton strength. In other words, in order to achieve a balance between the compatibility of the cyclopentane blowing agent and the strength of the foam, the selection of the polyol mixed composition is an important factor. The rigid polyurethane foam system of the present invention uses more than 60 parts by weight of a polyol having a low solubility in cyclopentane to improve the strength of the resin skeleton of the air bubbles, and further, in order to improve the stability of premixing, the most appropriate is selected. Of foam stabilizer to reach equilibrium. In this case, when the polyhydric alcohol is mixed, when the blending amount of the polyhydric alcohol having a low solubility is 60 parts by weight or less, the compressive strength and dimensional stability tend to decrease. This is because the rigid straight polyol with lower solubility is stronger than cyclopentane, and its urethane resin wall is stronger. The foaming agent is applicable to Chinese National Standard (CNS) 8-4 specification (210X297mm ~ 12-(Please read the notes on the back first

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559626 Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention (10) It is completely enclosed in the air bubble, which reduces the impact on the solvent plasticization of cyclopentane. In order to reduce the amount of heat leakage from refrigerators and freezers, thermal insulation materials that can reduce the thermal conductivity of the foam body and the surface state of the foam body and the surface layer of the core layer with less difference are superior. The reason is that low-density and high-fluidity urethane materials are less likely to be resinized at the surface and core layers, and the shape of the wall of the refrigerator box is complex and curved, so it has the properties of low density and high fluidity. The urethane material forms a homogeneous foamed body with a density difference between the surface layer and the core layer, and a small difference in the pore size distribution of the air bubbles. In order to achieve a low density, high fluidity and high strength urethane material for the purpose of the present invention, the amount of cyclopentane of the blowing agent and the amount of water used to supplement the blowing agent will have a great effect. If cyclopentane and water are used in large amounts, it is known that the density of the foamed carcass is liable to decrease. In the past, due to the high strength of the skeleton in the air bubble pores, by using a large amount of foaming agent instead of the foaming agent such as fluon, a small amount of water that has an adverse effect on the thermal conductivity can be easily obtained with low Characteristics of density, high fluidity and high strength. However, the cyclopentane prescription for the milder global environment is different from previous foaming agents. When the density of the foam body decreases, the saturated vapor pressure is also lower, so the strength of the skeleton in the air bubble cell is weak, and the foam shrinks and compresses. The problem of poor strength and dimensional stability. In order to increase the saturated vapor pressure of cyclopentane prescriptions, for example, review the countermeasures against conventional foaming agents, reduce the blending amount of cyclopentane foaming agents, increase the amount of water that adversely affects thermal conductivity, and make carbon dioxide in the cells. The increased partial pressure increases the pressure in the air bubble pores, and has both low density and high strength. At this time, when the amount of water mixed with cyclopentane is close to the solubility limit, layer separation occurs during pre-mixing, which becomes the main cause of the deterioration of thermal conductivity. However, the paper size of cyclopentane paper applies the Chinese National Standard (CNS) Λ4 specification (210X297 mm) 13-(Please read the notes on the back first and fill in this page), -5 * 口 559559 Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economy A7 B7 V. Description of the Invention (11) When comparing the alkane formulation with the conventional foaming agents, it is known that the cyclopentane formulation has less effect on the thermal conductivity of water. The most appropriate mixing ratio of water and cyclopentane is 7 parts by weight or less of cyclopentane when 1 part by weight of water is blended. In other words, for 100 parts by weight of the polyol component, 2.0 to 2 to 6 parts by weight of water and 10 to 14 parts by weight of cyclopentane are more desirable. When the polyol component is 100 parts by weight, the compressive strength or dimensional stability is deteriorated when the amount of water is insufficient, and the thermal conductivity tends to be significantly deteriorated when the amount of water is exceeded. When the blending amount of the cyclopentane foaming agent exceeds, the compressive strength or dimensional stability will be deteriorated. Other polyols used in the present invention are, for example, polyester polyols. For example, a polyhydric alcohol and a polyvalent carboxylic acid condensation system and a cyclic ester ring-opening polymerization system may be used. Examples of the polyhydric alcohol include ethylene glycol, glycerol, and trimethylolpropane; examples of the saccharides include sucrose and sorbitol; examples of the alkanolamine include diethanolamine and triethanolamine; examples of the polyamine include ethylenediamine and toluenediamine; and examples of phenol include There are bisphenol A and the like; polycarboxylic acids include adipic acid, phthalic acid, polycarboxylic acids and the like. The polyester polyol is preferably a mixture of 5 to 20 parts by weight. Examples of the reaction catalyst include tertiary amines such as tetramethylhexamethylenediamine, trimethylamine ethylpiperazine, pentamethyldiethylenetriamine, triethylenediamine, and trimethylamine ethylpiperazine. Delayed-acting catalysts such as acid salts, dipropylene glycol, and the like may be used as long as they are conventionally known as long as they are reactive. The ideal amount of the reaction catalyst for 100 parts by weight of the polyol component is 3 to 5 parts by weight. Foam stabilizers such as X — 2 0 — 1 5 4 8, X ~ 2 0 — 1 6 1 4, X — 2 0 — 1 6 3 4 made by Shin-Etsu Chemical, etc., if premixing is considered (please read the notes on the back first) (Fill in this page)

559626 A7 B7 V. Description of the invention (12) When the compatibility is stable, the molecular weight of S i is 1 800 to 300, and the content of S i is 2 5 to 3. The lower emulsification table is more suitable. ideal. In other words, an alkylene oxide-denatured polydimethylsiloxane containing an organic siloxane-based compound having a fluorenyl group or an alkoxy group at the terminal, a fluorine-based compound, or the like can also be used. When the polyol component is 100 parts by weight, the ideal amount of the foam stabilizer is 1 to 4 parts by weight. The mixed composition for a rigid polyurethane foam may contain additives such as an ordinary filler, a flame retardant, a reinforcing fiber, and a colorant, if necessary. Isocyanates can be used as long as they are known, and the most commonly used are toluene diisocyanate (TD I) and diphenylmethane diisocyanate (MDI). TDI can also use a mixture of isomers, that is, 2,4-isomer 100%, 2,4-isomer / 2,6-isomer = 80/20, 65/35 (weight ratio), Trade name Mitsui

Cosmonate TRC, Takenate Pharmaceutical's Takenate 404, and other crude T D I containing multifunctional tar. M D I In addition to pure products containing 4,4 / -diphenylmethane diisocyanate as the main component ', it is also possible to use Mitsui Cosmonate M-200, a trade name containing polyhedra with more than 3 cores.

Polyionic MDI by Milionate MR and others. Other aromatic or aliphatic polyfunctional isocyanates' carbamic acid-modified toluene diisocyanate represented by polymethylene polyphenyl isocyanate, 1,6-hexamethylene diisocyanate, etc. can also be used, carbodiimide Modified isocyanates such as amine-modified diphenylmethane diisocyanate. These polyfunctional isocyanates can be used alone or as a mixture of two or more. The characteristics of the isocyanate are, for example, the weight% (NC0%) of the isocyanate group in the isocyanate defined by the following formula (1). This paper size is suitable for wealth and wealth (CNS) Tiege (210x297 male f-15-'(Please read the notes on the back first)

-f 定 _ Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economy Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economy 559626 A7 __B7 V. Description of the invention (彳 3) NC〇 ％ = ([NC〇] X f (iso) / Mw (iso)) X 100 (1) [NC〇] is the molecular weight of the isocyanate group, f (is 〇) is the number of functional groups of the isocyanate group, and M w (is ο) is the molecular weight of the isocyanate. When the N C 0% of the isocyanate is less than 31, the fluidity is reduced, and when it exceeds 33, the dimensional stability is reduced. Therefore, NCO% of 3 1 ~ 3 3 can produce stable rigid polyurethane foam. The foam of the rigid polyurethane foam of the present invention is formed by a foaming agent commonly used in the industry. For example, a PU-30 foaming machine manufactured by ProMate can be used. The foaming conditions vary slightly depending on the type of foaming machine, but the ideal conditions are a liquid temperature of 18 to 30 ° C, a discharge pressure of 8 ◦ to 150 kg / cm2, and a discharge volume of 5 to 30 kg / mi. η, the temperature of the mold box is 3 5 ~ 4 5 ° C. More ideally, the liquid temperature is 20 ° C, the discharge pressure is 100kg / cm2, the discharge volume is 25kg / min, and the mold case temperature is 4 5C. The rigid polyurethane foam filled into the refrigerator and freezer prepared as described above can be used to reduce the foamed filling by using the urethane material with low density, high fluidity and high strength characteristics. Cost reduction and weight reduction. In addition, the foam body has excellent compressive strength or dimensional stability, and has high fluidity, so it can reduce the amount of heat leakage and save energy. The examples and comparative examples are compared with each other to explain the present invention in more detail. [Examples 1 to 6] This paper size applies the Chinese National Standard (CNS) A4 specification (210 × 297 mm) -16- (Please read the notes on the back first and fill in this page)-• l · Order _

559626 A7 B7___ V. Description of the invention (14) [Comparative Examples 1 to 3] Please read the notes on the back to use the epoxy resin compound and ethylene oxide added with an average of 0H 値 3 8 0 ~ 4 8 0 Toluenediamine-based polyether polyol (referred to as polyol A), a triethanolamine-based polyether polyol (referred to as polyhydric alcohol) formed by adding propylene oxide and ethylene oxide with an average of 0.30 to 400. Alcohol B), glycerol-based polyhydric polyols (referred to as polyol C) formed by adding propylene oxide with an average of 0.45 to 500, and adding propylene oxide with an average of 400 to 450. The resulting sucrose-based polyether polyol (referred to as polyol D) 'is a di-fluorinated A-based polyether polyol (referred to as polyol) added with an average ethylene oxide of 0,200 to 300. Ε) Trimethylolpropane polyether polyethers (referred to as polyhydric alcohol F) formed by adding propylene oxide with an average of 040 to 750, and ethylene oxide with an average of 0.25 to 450. 100 parts by weight of 100 parts by weight of a mixed polyol component (average 〇Η 値 is 350 ~ 450) of toluene diamine polyether polyol (referred to as polyol G) formed by addition of alkane, and 2.0 using water as a blowing agent 1 part by weight and 1 part by weight of cyclopentane (manufactured by Japanese company ZOON), trimethylamine ethyl_azine (produced by King &amp; Company), and 1.6 parts by weight with trimethylamine ethylpiperazine (Printed by the Consumer Cooperatives of the Central Standards Bureau of the Tosoh Public Surgery Ministry) 2. 4 parts by weight, diethylene glycol dipropylene glycol solution (manufactured by Tosoh Corporation), 0.4 parts by weight, organosilicone of foam stabilizer 2 parts by weight of an alkane compound (X-20-1614, manufactured by Shin-Etsu Chemical Co., Ltd.), and the isocyanate component was poly (methylene polyphenyl diisocyanate) (NC0% = 31). A rigid polyurethane foam was prepared by foaming. First, the physical properties of the heat-insulating material filled with a rigid polyurethane foam body were injected at four points as shown in Fig. 1, and the characteristic results are shown in Table 1. The physical properties and characteristics of Table 1 are shown below. This paper size applies the Chinese National Standard (CNS) A4 specification (21 ×: 297 mm) -17- 559626 A7 B7 V. Description of the invention (15) Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs Table 1 Example Comparative Example 1 2 3 4 5 6 1 2 3 Polyol A 50 45 40 50 45 40 20 30 25 Polyol B 15 20 15 15 10 10 55 45 50 Polyol C 20 15 20 15 20 15 15 5 5 — Polyol D 5 10 10 5 10 15 5 5 5 Polyol E 10 10 15 15 10 15 5 5 5 Polyol F • _ 5 Rain 10 • Polyol G _ 5. 10 Cyclops 13 13 12 12 11 10.5 11 13 18 20 Water 2.0 2.1 2.2 2.4 2.5 2.0 1.2 1.5 1.8 Water density of skin core layer (kg / m3) 34.5 34.8 35.8 35.0 34.9 36.5 42.5 41.5 41.0 Core layer density (kg / m3) 32.5 32.3 33.0 32.5 32.0 33.5 37.5 35.5 36.5 Low temperature dimensional change rate ( %) -1.1 -1.3 -1.1 -0.9 -0.8 -1.2 -2.1 -2.2 -2.3 High temperature dimensional change rate (%) 1.1 1.2 0.9 0.9 0.8 1.3 2.2 2.3 2.4 Thermal conductivity (mW / mK) 18.0 18.3 18.1 18.3 18.2 18.4 19.0 19.2 19.4 Compressive strength (MPa) 0.15 0.14 0.17 0.19 0.20 0.16 0.08 0.09 0.09 Flexural strength (MPa) 0.42 0.41 0.45 0.48 0.49 0.41 0.36 0.35 0.35 Elongation of foam 2.6 2.7 2.7 2.8 2.9 2.6 2.3 2.4 2.5 Air bubble pore size distribution (mm) 0.2 ~ 0.3 0.2 ~ 0.4 (Please read the note on the back first: write this page), 1T

This paper size applies Chinese National Standard (CNS) Λ4 specification (210X297 mm) -18- 559626 A7 B7 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (16) The overall density of the surface layer: at least The weight of the surface-containing foam (A) was measured at 5 Omni X 5 Omm x 3 5 t mm of the heat-insulating material part filled with urethane over the ester injection port of 5000 mm or more. In a beaker, adjust the distilled water and the foam attached to the metal needle with the balance to zero. Measure the volume (B) when the foam is sunk with the metal needle, and divide the weight (A) by the volume (B). To evaluate. Core layer density: Measured from at least 50 Omm above the urethane injection port of the thermal insulation material filled with urethane. 2 0 Omm X 2 0 Ommx 2 0 ~ 2 5 t mm foam The dimensional stability and weight were evaluated by dividing the weight by the volume. The examples and comparative examples of the present invention will be described with reference to the production contents of a rigid polyurethane foam body filled with a refrigerator and an ice box outside the box and the inner box. Fig. 1 is a schematic diagram showing the flow state of a hard-filled polyurethane foam-filled carcass by injecting 4 points, and taking a foam to measure a sample. First, the iron outer box and the plastic inner box are assembled, and the polyurethane foam carcass filled in the refrigerator is made before being foamed. The polyurethane foam carcass is installed on the polyurethane foam carcass and then preheated to heat the rigid polyurethane foam carcass. The foam is filled in the void portion (polyol mixture and mixed composition pre-mixed with water, cyclopentane, catalyst, foam stabilizer and isocyanate). At this time, the polyol of the polyurethane foam is chemically reacted with the isocyanate, and the foamed polyurethane foam is injected into the refrigerator box to form a heat-insulating box by applying pressure from the foaming pressure. Set the urethane materials of Examples 1 to 6 and Comparative Examples 1 to 3 to the minimum injection amount required for actual charging, and then for the charging rate (please read the precautions on the back first)

Order ·% This paper size applies the Chinese National Standard (CNS) A4 (210X297 mm) 559626 A 7 B7 V. Description of the invention (17) 1 1 10% of the refrigerator in the box, ... Part of the heat-insulating material of the urethane-filled urethane filled with an ester injection port of 500 mm or more was sampled with foam, and various physical properties and characteristics were evaluated. The temperature at the time of injection was about 45 ° C, and the liquid temperature of the polyol liquid and the isocyanate liquid was about 20 ° C. The results are shown in Table 1. The insect table 1 knows that when comparing the heat insulation material of the example of the present invention with the heat insulation material of the comparative example, the surface layer density and core layer density of the heat insulation material of the present invention are both low, and the dimensional change rate at low temperature and The air bubble pore size distribution is also small, in addition, the thermal conductivity is reduced, the compressive strength and bending strength are also enhanced, and the amount of elongation of the bubble body is increased. Furthermore, using a refrigerator with an internal volume of about 150 to 180 L in the inner space of the cabinet wall to evaluate the amino acids of Examples 1 and 2 and Comparative Examples 1 and 2 at a charge rate of 110% The actual charge of the ester. Although the results differ depending on the model, for a refrigerator with an internal volume of about 180 L, Comparative Examples 1 and 2 require a charge of 6.35 to 6.60 kg, while Example 1 The urethane material of 2 is only required to be 5.45 ~ 5.90kg. For refrigerators with a volume printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs within about 150L, the amount of tritium of the urethane materials in Comparative Examples 1 and 2 was slightly reduced by 5 · 3 5 ~ 5 · 6 5 kg, while Example 1 and 2 were reduced to 4.65 ~ 5. 00kg, which can save about 10 ~ 18% of the urethane material. When the refrigerating cycle parts (compressor / condenser / gasifier) were replaced in a refrigerator containing a heat insulating material and the heat leakage amount was measured, it was found that the heat leakage amount in Examples 1 and 2 was reduced by 3 to 6% compared to Comparative Examples 1 and 2. It can save power consumption by about 1 ~ 2 kwh / month. This shows that the rigid polyurethane foam of the present invention has both low density, high fluidity and high strength characteristics. -20- (Please read the precautions on the back first to fill out this note)

This paper size applies to Chinese National Standard (CNS) A4 (210 X 297 mm) 559626 Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention (18) Therefore, it can reduce the cost of filling Or light weight, and the compressive strength or dimensional stability of the foam body is also excellent 'and can save energy due to the effect of reducing the amount of heat leakage. Physical properties and characteristics of rigid polyurethane foamed body (surface density, core layer density, dimensional change rate, cell pore size distribution, thermal conductivity, compressive strength, flexural strength, foamed body elongation) ° The examples provide low density, high Flowable and high-strength rigid polyurethane foamed foamed insulation box, using the reduction of urethane foam to reduce cost or light weight, and the compressive strength of the foam Or high-quality refrigerators and freezers with excellent dimensional stability and energy saving due to the reduction in heat leakage. Low-temperature dimensional change rate: evaluated from at least 500 mm above the urethane injection port, the thermal insulation material filled with urethane is 15 Ommx 300mm x 2 ◦ ~ 2 5 t mm The dimensional change of thickness of the foam after being left at 20 ° C for 24 hours. High-temperature dimensional change rate: Partially evaluated at least 50 mm from the urethane injection port, the thermal insulation material filled with urethane is filled with a foam body of 50 mm x 300 mm x 20 to 25 tmm and placed at 70 t 2 Dimensional change in thickness after 4 hours. Thermal conductivity: At least 500 mm away from the urethane injection port, the thermal insulation material filled with urethane is HC-1 0 7 3 (heat flow meter method, average temperature 1) 〇 ° C) Evaluation of vesicles of 200 mm x 200 mm x 20 to 25 tmm. Compressive strength: at least 500 m from the urethane injection port (please read the notes on the back first and fill in this page) * fbn—V ·· · τ

This paper size applies to Chinese National Standard (CNS) A4 specification (210 × 297 mm) -21-559626 A7 B7 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. The description of invention (19) is filled with urethane The heat-insulating material part is subjected to a load of 50 mmx50mmx20 to 25 tmm at a delivery speed of 4 mm / mi η, and is evaluated by dividing the load at the time of deformation by 10% by the number of original compression areas. Bending strength: at least 500 mm from the urethane injection port, the thermal insulation material part filled with urethane is fed at a speed of 4mm / mi η to make a bubble of 80mmx25mmx20 to 25 tmm Carcass load is evaluated by dividing the load at the time when the foam body is broken by the number obtained by the square of the width and thickness of the foam body. Foam elongation: When foaming occurred in the reverse L panel of 5 5 Ommx 5 8 Ommx 3 5 t mm, the foam carcass elongation of the urethane plutonium charge was evaluated. The reason why the distance from the urethane injection port of the filled heat-insulating material to the position where the urethane characteristics are evaluated is set to 5000 m or more is shown in FIG. 2. Fig. 2 is a graph showing the relationship between the distance between the inlet of the heat insulating material and the density of the heat insulating material. As shown in the figure, the distance from the injection port is in a small area, and the density of the heat insulation material changes greatly with respect to the distance, so the density appears unstable. This is because the thermal insulation material that has just been injected is poorly mixed, and the fluidity of the thermal insulation material is low, so the resinized portion (called the surface layer) of the thermal insulation material is increased. In the present invention, the properties of the heat-insulating material are evaluated at a portion more than 500 mm from the injection port where a small portion (referred to as a core layer) of the resinized portion where the density is stable. [Examples 7 to 12] (Please read the cautions on the back and write this page first)

、 1T% This paper size applies the Chinese National Standard (CNS) Λ4 specification (210X297 mm) -22- Printed by the Employee Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 559626 A7 ______B7_ V. Description of the Invention (20) [Comparative Examples 4 to 6] Toluene diamine-based polyether polyol (referred to as polyol A) formed by adding propylene oxide and ethylene oxide with an average of 0.380 to 480 is used. Triethanolamine-based polyether polyol (referred to as polyol B) formed by addition of propylene oxide and ethylene oxide with an average of 0.45 to 500 Glycerin-based polyether polyol (referred to as polyol C) is an sucrose-based polyether polyol (referred to as polyol D) formed by adding propylene oxide with an average of 400 to 450. The bisphenol A-based polyether polyol (referred to as polyol E) formed by addition of ethylene oxide of ~ 300%, and trimethylol formed by addition of propylene oxide on average of 400 ~ 750. Propane-based polyether polyols (referred to as polyols F), toluene diamine-based polyether polyols (referred to as ethylene oxide with an average of 250-450) 100% by weight of a mixed polyol component (average 0 to 350-450), using 2.0 to 2.5 parts by weight of water of a foaming agent, and cyclopentane (manufactured by Japan Zeon Corporation) 10. 4〜14 重量 份 ， Trimethylamine ethylpiperazine (made by Kao Corporation) 1.6 parts by weight with trimethylamine ethylpiperazine formate (manufactured by Tosoh Corporation) Parts, 2 parts by weight of organopolysiloxane (X _ 2 0 — 1 6 1 4, manufactured by Shin-Etsu Chemical Co., Ltd.), the isocyanate component is polymethylene polyphenyl diisocyanate (NC0% di 3 1) , The hard polyurethane foam is made by foam filling. First, the physical properties of the heat insulating material of the door body shown in FIG. 3 were filled with a rigid polyurethane foam body, and the characteristic results are shown in Table 2. The physical properties and characteristics of Table 2 are shown below. This paper size applies to China National Standard (CNS) Α4 size (210X297 male thin) (Please read the precautions on the back and fill in this page first) Order

-23- 559626 A7 B7 V. Description of the invention (21 Printed by the Consumer Cooperatives of the Central Standards Bureau, Ministry of Economic Affairs, Table 2 Example Comparative Example 7 8 9 10 11 12 4 5 6 Polyol A 50 45 40 50 45 40 20 30 25 Multivariate Alcohol B 15 20 15 15 10 10 55 45 50 Polyol C 20 15 20 15 20 15 15 5 5 Polyol D 5 10 10 5 10 15 5 5 5 Polyol E 10 10 15 15 10 15 5 5 5 Polyol F • _ 5 10 Polyol G Fiber _ 5 _ _ 10 Cyclopentane 13 14 12 11 10.5 11 13 18 20 Water 2.0 2.1 2.2 2.4 2.5 2.0 1.2 1.5 1.8 Water density of the skin core layer (kg / m3) 34.2 35.8 36.3 35.5 36 37.1 42.7 41.8 41.2 Core layer density (kg / m3) 32.7 32.5 33.5 32.9 32.8 34.1 37.8 35.7 36.8 Low temperature dimensional change rate (%) -1.1 -1.3 -1.1 -0.9 -0.8 -1.2 -2.1 -2.2 -2.3 High temperature dimensional change Rate (%) 1.1 1.2 0.9 0.9 0.8 1.3 2.2 2.3 2.4 Thermal conductivity (mW / mK) 18.0 18.3 18.1 18.3 18.2 18.7 19.2 19.4 19.6 Compressive strength (MPa) 0.15 0.14 0.17 0.19 0.20 0.16 0.08 0.09 0.09 Flexural strength (MPa) 0.42 0.41 0.45 0.48 0.49 0.41 0.36 0.35 0.35 Elongation of corpus callosum 2.6 2.7 2.7 2.8 2.9 2.6 2.3 2.4 2.5 Air bubble pore size distribution (mm) 0.2 ～ 0.3 0.2 ～ 0.4 (Please read the precautions on the back first- ^ Fill in this page)

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This paper size applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) -24- Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 559626 A7 B7 V. Description of the invention (22)

Overall surface layer density: The weight of the surface-containing foam (50) x 50 mm x 50 mm x 3 5 tmm is determined from the part of the thermal insulation material filled with urethane at least 50 mm from the outer side of the door. . In a beaker, adjust the distilled water and the foam attached to the metal needle with the balance to zero, and measure the volume (B) when the foam body is submerged in the water with the metal needle. Divide the weight (A) by the volume (B).値 to evaluate. ^ Density of core layer: Measured from at least 50 mm away from the outer side of the door, the thermal insulation material filled with urethane is 2 0 mm × 2 0 0 mm X · 2 0 ~ 2 5 t mm foam The dimensional stability and weight of the body were evaluated by dividing the weight by the volume. Low-temperature dimensional change rate: The foam body filled with urethane at a distance of 50 mm or more from the outer side of the door is evaluated to be 150 mm x 300 mm x 20 to 25 tmm. (: Dimensional change rate of thickness after standing for 24 hours. High-temperature dimensional change rate: Evaluation of 150 mm X 3 〇〇 from the thermal insulation material filled with urethane at least 50 mm away from the outer side of the door mmx 2 0 ~ 2 5 t mm The dimensional change of the thickness of the foamed carcass after being left at 70 ° C for 24 hours. Thermal conductivity: It is filled with urethane at least 50 mm from the outer side of the door. For the heat insulating material, HC — 0 7 3 (heat flow meter method, average temperature 10 ° C) manufactured by Hidehiro Seiki Co., Ltd. was used to evaluate a foam body of 20 mm X 2 0 Ommx 2 0 to 2 5 tmm. Compression strength: At least 50 mm away from the outer side of the door, the heat-insulating material part filled with ammonium-carbamate has a delivery speed of 4 mm / m 1 η, so that this paper size applies the Chinese National Standard (CNS) Λ4 specification (21〇 × ： Z97mm） IΓ I ~ --- (Please read the notice on the back to fill in this page} D-f% 559626 A7 B7 V. Description of the invention (23 5 Ommx 50mm 2mm ~ 2 5 tmm foam The load generated by the body is evaluated by dividing the load at 10% deformation by the original compression area. Please read the note on the back first Yishi ft write this page Bending strength: at least 50 mm away from the outer side of the door, the thermal insulation material filled with urethane is delivered at a speed of 10 mm / mi η to 80 mm x 25 mm 2 to 25 The load generated by the foam body at tmm is evaluated by dividing the load when the foam body is broken by the number obtained by the square of the width and thickness of the foam body. Elongation of the foam body: at 5 5 Ommx 5 8 Ommx 3 The 5 t mm anti-L panel evaluates the carcass extension of the urethane charge when foaming occurs. Order% Printed by the Consumers Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs Printed on the iron sheet of the door outside the refrigerator and freezer The following describes the following examples and comparative examples of the present invention with the production content of hard polyurethane foam filled with the inner space of the inner door wall. Fig. 3 shows a foam body filled with hard polyurethane foam filled with a heat-insulating door. First, assemble the outer door made of iron and the inner door made of plastic, and make the vegetable room door, refrigerator door, freezer door filled with polyurethane foam filled in the refrigerator door, and then installed in the refrigerator door. Polyurethane foam is then preheated to hard polymer The foam of the ester foam is filled in the void portion (polyol mixture and premixed water, cyclopentane, catalyst, foam stabilizer, and isocyanate). At this time, the polyol and isocyanate of the polyurethane foam A chemical reaction is performed, and the foaming polyurethane foam is injected into the wall of the refrigerator door to form a heat-insulating door by applying pressure from the foaming pressure. The urethane materials of Examples 7 to 12 and Comparative Examples 4 to 6 were used. Set the minimum injection amount required for actual filling, and then apply the Chinese National Standard (CNS) A4 specification (210X297 mm) to the paper size at the filling rate. -26- Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 559626 A7 ____ B7 V. Description of the invention (24) 1 15% ~ 120% Injected refrigerator: taken from the part of the insulation material filled with urethane at least 50 mm away from the outer side of the door Foam samples were evaluated for various physical properties and characteristics. The temperature at the time of injection is about 45 ° C. The liquid temperature of the 'polyol liquid and isocyanate liquid is about 20 ° C. The results are shown in Table 1. It is known from Table 1 that when comparing the heat insulation material of the embodiment of the present invention with the heat insulation material of the comparative example, the surface layer density and core layer density of the heat insulation material of the present invention are both low, the dimensional change rate at low temperature, the dimensional change rate at high temperature, and The air bubble pore size distribution is also small, in addition, the thermal conductivity is reduced, the compressive strength and bending strength are also enhanced, and the amount of elongation of the bubble body is increased. Furthermore, the refrigerator door with an internal volume of about 12 to 20 liters was used to evaluate Example 1, and the actual charge of the urethane at a charge rate of 115 to 120%塡 Charge. The results vary depending on the model, but for refrigerator doors with an internal volume of about 20 L, Comparative Examples 1 and 2 require a filling amount of 0.90 to 1.5 kg, while Example 1 The urethane material of 2 is only required to have a filling amount of 0.776 to 1.05 kg. Also for a refrigerator door having an internal volume of about 12 L, the tritium charge of the urethane material of Comparative Examples 4, 5 was slightly reduced by 0.5 · 5 9 ~ 0 · 6 8 kg, while Example 7 was, 8 is reduced to 0.47 to 52 kg, which can save about 10 to 18% of the urethane material. Refrigerating cycle parts (compressor / condenser / gasifier) are assembled in a refrigerator containing a heat insulating material, and a door is installed to measure the heat leakage amount. As a result, the heat leakage amount of Examples 7 and 8 was found to be higher than that of Comparative Examples 4 and 5. A reduction of 3 to 6% can save power consumption of about 1 to 2 kwh / month. It is known that the rigid polyurethane foam of the present invention has both low density, high fluidity and high strength (please read the notes on the back first and fill in this page).% This paper size applies to China National Standard (CNS) A4 specification (210X297 (Mm) -27- 559626 A7 —__ B7 V. Description of the invention (25) degree characteristics, so it can reduce the cost and weight of the filling capacity, and the compressive strength or dimensional stability of the foam is also excellent. The effect of reducing heat leakage can save energy. Physical properties and characteristics of rigid polyurethane foams (surface density, core density, dimensional change rate, cell pore size distribution, thermal conductivity, compressive strength, flexural strength, foam extension). The embodiment is to provide a low-density, high-fluidity and high-strength rigid polyurethane foam foam insulation filling door, using the reduction of urethane filling to reduce cost or weight, and The compressive strength or dimensional stability of the foam body is also excellent, and high-quality refrigerators and freezers that can save energy due to the effect of reducing the amount of heat leakage. The area where the insulation material is 50 mm or more from the outer side of the door (end surface of the door) is the same as the insulation box. The insulation material near the end surface of the door has low fluidity, and there are many resinized parts. The formation of the surface layer and the heat-insulating material is more stable, so that various characteristics can be evaluated. (Please read the notes on the back _fill out this page)

Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs This paper is sized to the Chinese National Standard (CNS) A4 (210X297 mm) • 28-

Claims (1)

559626 Α8 Β8 C8 D8 VI. Scope of patent application Annex 2 Announcement Month B Rev. Ml Printed by the Intellectual Property Bureau Employee Consumer Cooperative of the Ministry of Economic Affairs Printed No. 87121914 Patent f Application jUl Chinese Patent Application Amendment Amended on July 10, 1992 1. A heat-insulating box for a refrigerator, which is filled in a space formed between an outer box and an inner box of a refrigerator and filled with a rigid polyurethane foam using a cyclopentane and water mixed foaming agent. The heat insulation box is characterized in that the rigid polyurethane foam body contains 60% by weight or more of a polyol component: 40-50% by weight of toluenediamine, 15-20% by weight of glycerol, and 5-10% by weight Sucrose, 10 to 15% by weight of bisphenol A, a component with lower solubility of cyclopentane, and at least 500 mm from the injection port of the rigid polyurethane foam body, the overall density of the surface layer of the rigid polyurethane foam body Materials that are 3 4 to 3 7 kg / m3 and have a compressive strength of 0.1 Mp a or more and a flexural strength of 0 · 4Mp a or more, at least from the plane and part of 500 mm above the polyurethane injection port Its thickness is about 20 ~ 2 5mm The thermal conductivity of the core insulation material is at an average temperature of lOt: 18 · 0 ~ 18 _ 5mW / mK, the core density is 3 2 ~ 3 4 kg / m3 and 7 (KC and -20 ° C in air) Insulation material with a dimensional change rate of 2% or less at room temperature for 2 to 4 hours and having a fluidity of more than 2 · 6mm / g in the unit of resin foam elongation. For the internal volume, inject 3 0 ~ 3 5 g / L of this heat insulation material. 2 · As the heat insulation box of the refrigerator in item 1 of the patent application scope, it is a polyol component using rigid polyurethane foam body consisting of ethylene oxide and The paper size of 0.38 to 4880 obtained by adding propylene oxide to toluene diamine is applicable to the Chinese National Standard (CNS) A4 specification (210 × 297 mm) (Please read the precautions on the back before filling this page ) 559626 A8 B8 C8 __D8 6. Scope of patent application (please read the notes on the back before filling this page) Polyol 40 ~ 50% by weight, ethylene oxide and propylene oxide are added to triethanolamine.値 3 0 0 ~ 4 0 0 polyol 1 0 ~ 2 0% by weight, propylene oxide is added to glycerol 〇Η 値4 5 0 to 5 0 0 of polyhydric alcohols 1 5 to 2 5 wt%, 0 to 4 0 0 to 4 50 0 of polyhydric alcohols obtained by adding propylene oxide to sucrose, ethylene oxide It is composed of a mixture of 5% to 15% by weight of a polyhydric alcohol of 0 to 2 0 to 3 0 0 obtained by adding to bisphenol A, and the average polyhydric alcohol of the polyhydric alcohol is 3 to 50 to 4 5 0. Thermal insulation of polyurethane foam. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs of the People's Republic of China 3. A kind of insulated door for refrigerators, which is located outside the refrigerator and the freezer. The heat insulation door of a refrigerator made of a rigid polyurethane foam body is characterized by using the following thermal insulation material. The heat insulation material is a rigid polyurethane foam body. The polyol component contains ethylene oxide and / or propylene oxide. 0.38 0 to 4 8 0 of polyhydric alcohol 40 to 50% by weight added to toluene diamine, 0.30 to 30% by weight of ethylene oxide and / or propylene oxide added to triethylamine 0 ~ 4 0 0 polyol 1 0 ~ 2 0% by weight, propylene oxide added to glycerol 0.45 0 ~ 50 0 0 polyol 1 5 ~ 2 5% by weight, propylene oxide added to 0 ~ 4 0 0 ~ 4 50 0% by weight of polyol obtained from sucrose, 0 ~ 2 0 0 ~ 3 0 0 by 5% of polyol obtained by adding ethylene oxide to bisphenol A It is composed of 5% by weight of the mixture, and the average alcohol content of the polyhydric alcohol is 3 50 ~ 4 50, which is at least 50 mm from the outer side of the door. The surface density of the rigid polyurethane foam carcass is 3 5 ~ 3 8 kg / m3 and the compressive strength is 0. IMpa or more, and the bending strength is more than 0.4Mpa '-2-This paper size is applicable to China National Standard (CNS) A4 Specifications (210X297 mm) 559626 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs A8 B8 C8 D8 6. The scope of patent application is at least 50 mm from the outer side of the door. The thickness of the urethane filling part is about 20 ~ The thermal conductivity of the core insulation material of 2 5mm is 18. 0 ~ 19. OmW / mK at an average temperature of 10 ° C, and the core density is 32 · 5 ~ 34 · 5kg / m3 and 70 ° C and -20 At a temperature of ° C, the dimensional change rate is 2% or less after 24 hours of degradation. The resin unit extension is a heat-insulating material with a flowability of 2.6 mm / g or more. 3 6 ~ 4 2 g / L of heat insulation material for filling the space inside the door wall. 4. The heat insulation door of the refrigerator according to item 3 of the application for a patent, which is provided with a heat insulation door containing the following heat insulation material, the heat insulation material is the above-mentioned rigid polyurethane foam, and the polyol component contains ethylene oxide and 0.38 0 ~ 4 8 0 polyols obtained by adding propylene oxide to toluene diamine 4 0-50% by weight, ethylene oxide and propylene oxide added by triethanolamine 0Η 値 3 0 〇〜4〇0 Polyol 10 ～ 20% by weight, propylene oxide added to glycerol 504 ～ 50 ～ 50 0% Polyol 1-5 ～ 25% by weight, propylene oxide added 5 to 10% by weight of the polyhydric alcohol of 4,000 to 4 to 50 obtained from sucrose, and 5 to 15% by weight of the polyhydric alcohol of 200 to 300 obtained by adding ethylene oxide to bisphenol A A heat insulating material composed of a mixture and using a rigid polyurethane foam body with an average Η 値 of the polyol ranging from 350 to 450. (Please read the precautions on the back before filling out this page) The paper size applies to Chinese National Standard (CNS) Α4 specification (210 × 297 mm) -3-