JP2001050478A - Heat insulating panel for ultra-low temperature, and its manufacture - Google Patents

Abstract

PROBLEM TO BE SOLVED: To manufacture a heat insulating panel for ultra-low temperature formed in fixed thickness in which a high rigidity plate face material and a flexible sheet face material, preferably non-permeable flexible sheet face material are adhered on a glass fiber reinforced hard polyurethane foam with high strength without using an adhesive, and which requires neither polishing process nor bonding process in particular. SOLUTION: One side of hard polyurethane foam of this adiabatic panel is coated with a permeable plate face material and the other side is coated with a flexible sheet face material. In this case, hard polyurethane foam is the glass fiber reinforced hard polyurethane foam including a glass fiber material. The permeable plate face material and the flexible sheet face material can be layered on the glass fiber reinforced hard polyurethane foam by foam- hardening reaction of an undiluted solution composite for foaming of hard polyurethane foam without using adhesive.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to heat insulation panels for ultra-low temperatures, and more particularly, to heat insulation of storage equipment for storing low-temperature, normal-temperature gaseous substances such as LNG, liquefied helium, and liquefied nitrogen, particularly preferably LNG. It relates to a suitable heat insulating panel.

[0002]

2. Description of the Related Art Insulation materials for ultra-low temperatures in storage facilities for liquefying and storing low-boiling room-temperature gaseous substances such as LNG, liquefied helium, and liquefied nitrogen are used as vaporized storage gases, especially combustible L.
To provide a sandwich panel by providing a gas-impermeable material layer to prevent leakage of vaporized LNG when NG is stored and a high-rigidity plate-like material layer to reinforce panel-like heat insulating material, physical strength For the heat insulating layer portion which is mainly required, it is required to form a sandwich panel in which both surfaces are made of a highly rigid plate-like face material layer.

[0003] Such an ultra-low temperature heat insulating panel has excellent heat insulating performance, that is, it has a low thermal conductivity and a predetermined physical strength as a whole of the heat insulating panel. In order to prevent the heat insulating effect of the entire heat insulating layer from being lowered, the following characteristics are required.

(1) The heat insulating material itself has strength enough to withstand distortion and stress caused by a temperature difference between the inside of the storage container and the outside world and not to cause cracks. (2) The heat insulating panel has a strong adhesive strength with the face material that can withstand a stress that destroys the bond between the face material and the face material generated by the strain caused by the temperature difference between the inside of the storage container and the outside. (3) Extremely high thickness accuracy, specifically, a high accuracy of ± 0.5 mm or less as the thickness tolerance of the storage facility, which enables the formation of a heat insulating layer of storage equipment by stacking a plurality of heat insulating panels without gaps. Insulation panel to have.

[0005] Rigid polyurethane foam has excellent low-temperature insulation performance, and is used as an ultra-low-temperature insulation material for the above-mentioned liquefied storage facility for room temperature gaseous substances. Such a known ultra-low temperature heat insulating material is a hard polyurethane foam as a heat insulating material, in order to have a strength capable of withstanding the strain and stress caused by the temperature difference between the inside and outside of the storage facility as described above, in order to harden the glass fiber long fiber mat. Exist in a polyurethane foam to make a glass fiber reinforced rigid polyurethane foam,
It is manufactured as a heat insulating panel in which wood plywood is bonded on one side and a non-breathable sheet including an aluminum sheet or wood plywood is bonded and covered with an adhesive on the other side. A heat insulating layer is formed.

[0006]

The above-mentioned conventional heat insulating material of glass fiber-containing rigid polyurethane foam has been produced by a known method of producing a rigid polyurethane foam heat insulating panel. That is, as shown in FIG. 1, a paper sheet material 11L is supplied onto the conveyors 7 and 8, and a glass fiber mat 9 as a glass fiber material for reinforcement is continuously supplied from the raw material and placed thereon. After casting the rigid polyurethane foam foaming stock solution M supplied from the head 3 of the foaming machine, the paper surface material 11U is continuously supplied from the upper portion to form a sandwich, and the rigid polyurethane foam foaming stock solution composition is formed by the nip roll 13. After fully impregnating the glass fiber mat, double conveyor 17U,
The glass fiber-reinforced rigid polyurethane foam B having a certain degree of thickness accuracy is prepared by sending the mixture to a heating oven 19 equipped with 17 L and foaming and curing.

In this conventional production method, the obtained glass fiber reinforced rigid polyurethane foam is difficult to improve the accuracy of the interval between the double conveyors 17U and 17L as it is, and the length of the heating oven is limited. Thus, it was impossible to produce a panel in which the polymerization and curing reaction was completed and the dimensional change no longer occurred, and did not satisfy the dimensional accuracy required for the heat insulating panel for ultra-low temperature heat insulation. Therefore, the obtained glass fiber reinforced rigid polyurethane foam is cut in the width and length directions,
Furthermore, both sides including the paper surface material are cut and polished to obtain a glass fiber reinforced rigid polyurethane foam panel of a predetermined thickness,
A plywood, which is a predetermined surface material, and an aluminum sheet-containing surface material are bonded to each other using an adhesive, whereby an ultra-low temperature insulating panel having a thickness accuracy matching a specified thickness tolerance has been manufactured.

According to such a method, a high-precision polishing and finishing step for making the glass fiber-reinforced rigid polyurethane foam to a specified thickness, and the necessary equipment and bonding step are required. there were.

In the above-mentioned conventional method for producing a glass fiber reinforced rigid polyurethane foam panel, instead of a paper surface material,
Glass fiber reinforced rigid polyurethane foam (hereinafter RP
A method of supplying a plywood as a predetermined surface material and a non-breathable flexible sheet surface material during the production of UF or simply a foam), and supplying a glass fiber mat and a rigid polyurethane foam foam stock solution therebetween. However, in order to supply the rigid polyurethane foam foam stock solution composition (hereinafter referred to as the foam stock solution), a space for installing the supply device (head of the foaming machine, 3 in FIG. 1) is required,
In addition, it is necessary to continuously supply the upper surface material immediately after spraying the foaming undiluted solution and pass it through the nip roll. For that purpose, it is also possible to manufacture by a method of supplying a plywood as a lower surface material and a flexible non-breathable flexible sheet surface material as an upper surface material.

When the heat insulating panel is manufactured by the above method, when the non-breathable flexible sheet face material is used as the upper surface material at the time of manufacturing, the shear line is provided near the interface between the non-breathable flexible sheet face material and the RPUF. A thin layer in which gas components are concentrated may be formed, and as a result, under severe conditions, for example, when the temperature difference between inside and outside such as a storage facility in a high-temperature area is large, a non-breathable flexible sheet is used. Face material and RP
In some cases, the heat insulating panel may have insufficient bonding strength with the UF, and may not be used stably depending on the application.

[0011] It is an object of the present invention to provide a highly rigid plate-like face material and a flexible sheet face material, preferably a non-breathable flexible sheet face material, which are bonded to RPUF with high strength without using an adhesive. A stable heat-insulating layer can be formed even under severe conditions, and a heat-insulating panel for ultra-low temperature molded to a predetermined thickness and a face material adhered to one side for bonding and laminating to the panel to form a multi-layer panel. It is an object of the present invention to provide a method of manufacturing a heat insulating panel for an ultra low temperature that is not yet provided, and a heat insulating panel capable of manufacturing the heat insulating panel for an ultra low temperature without separately providing a polishing step and a bonding step.

[0012]

SUMMARY OF THE INVENTION The present invention provides an ultra-low-temperature hard polyurethane foam coated on one side with a permeable plate-like surface material and the other surface with a flexible sheet or permeable plate-like surface material. A heat insulating panel for use, wherein the rigid polyurethane foam is a glass fiber reinforced rigid polyurethane foam containing a glass fiber material, and the breathable plate-like face material and the flexible sheet face material are rigid without using an adhesive. It is characterized in that the polyurethane foam foam stock solution composition is laminated with the glass fiber reinforced rigid polyurethane foam by a foam hardening reaction.

The glass fiber reinforced rigid polyurethane foam layer and the highly rigid air-permeable plate-like surface material and the flexible or air-permeable plate-like surface material are subjected to a foam-curing reaction of the rigid polyurethane foam foam stock solution composition. By bonding, distortion caused by the temperature difference between the inside and the outside, which is the storage container side of the ultra-low temperature required as a heat insulation panel for ultra-low temperature insulation,
It is possible to obtain a heat insulating panel having a strength of the heat insulating material itself capable of withstanding the stress, a strong adhesive strength between the face material and the foam capable of withstanding the stress that breaks the bond between the face material generated by the distortion, and the like.

Here, the term “lamination” means a state including a state of being adhered or releasably bonded. In the case of a breathable plate-like surface material or a normal flexible sheet surface material, it means adhesion and a flexible sheet. When a release paper surface-treated with a silicon compound, a paraffin compound, a polyolefin or the like is used among the face materials, it is a peelable bond.

For a panel using release paper as one face material, the release paper is peeled off, and the rigid polyurethane foam surface is bonded to a panel having face material layers on both sides using an adhesive to form a multi-layer panel. Can be.

In the heat insulating panel, the adhesive strength between the glass fiber-reinforced rigid polyurethane foam / the air-permeable plate-like face material and the adhesive strength between the glass fiber-reinforced hard polyurethane foam / the flexible sheet face material are all the same. When it is 12 kgf / cm ² or more, the adhesive strength is sufficient as a heat insulating panel for ultra-low temperature, and it is preferable. The bonding strength with the face material must satisfy this bonding strength on both sides of the panel.On the other hand, if the bonding strength is low due to the presence of a share line or the like, peeling occurs on that surface, and the air layer is formed. Since the heat insulating effect occurs and the heat insulating effect is reduced, the characteristics required for the heat insulating panel for ultra-low temperature are not satisfied.

Here, the adhesive strength between the face material and the glass fiber reinforced rigid polyurethane foam is a strength required for peeling the two, but in actuality, the interface peeling and the material destruction of the plywood which is a plate-like face material are not affected. This is the strength at which RPUF does not occur and the material breaks down. If a shear line is generated near the interface between the foam and the face material, breakage occurs at this share line,
The adhesive strength is greatly reduced to less than 12 kgf / cm ² .

In the heat insulating panel for ultra low temperature of the present invention,
It is preferable that the air-permeable plate material is a wood plywood.
It has high strength, is relatively lightweight, has a lower thermal conductivity than metals and the like, and is strongly adhered to by contact when foaming a rigid polyurethane foam.

It is preferable that the flexible sheet surface material is a non-breathable flexible surface material in order to prevent the leakage of the stored substance and the dew condensation due to the invasion of moisture from the outside.

In particular, the non-breathable flexible surface material is an aluminum sheet, a glass cloth and a resin composite sheet.
As an ultra-low temperature insulation panel for a storage device containing LNG, strength, reactive adhesion with rigid polyurethane foam,
The gas leakage prevention performance is excellent and preferable.

The glass fiber material is a continuous glass fiber continuous strand mat. The glass fiber as a reinforcing material can be uniformly present in the rigid polyurethane foam, and a high-strength glass fiber reinforced rigid polyurethane foam is formed. It is preferred.

In the heat insulation panel of the present invention, the thickness of the glass fiber reinforced rigid polyurethane foam layer is preferably 50 to 400 mm.

The present invention relates to a method for producing an ultra-low temperature insulating panel in which one side of a rigid polyurethane foam is covered with a permeable plate-like surface material and the other surface is covered with a flexible sheet surface material or a permeable plate-like surface material. A raw material supply step of placing the glass fiber material and the rigid polyurethane foam foam stock solution composition on the flexible sheet face material or the gas permeable plate material, and supplying and placing the gas permeable plate material from the top Foaming and laminating the breathable plate-like surface material and the flexible sheet-like surface material or the gas-permeable plate-like surface material simultaneously with the formation of the rigid polyurethane foam by foaming the rigid polyurethane foam foaming stock solution composition. It is characterized by having a process. In foaming, it is a preferable embodiment to perform temperature control or heating.

The step of supplying a highly rigid, air-permeable plate-like material having no flexibility and completely different from the prior art from the top of the rigid polyurethane foam foaming stock solution composition causes generation of a shear line. This ensures that the adhesive strength of the face materials on both sides can stably satisfy the characteristics required for the ultra-low temperature heat insulating panel at the same time even under particularly severe conditions. Moreover, according to such a method, a polishing step and a separate bonding step are not required at all, and it has become possible to manufacture a heat insulating panel at a much lower cost than before.

Conventionally, when a large flat panel is placed on the surface of a liquid, an air layer enters the contact surface, and the R
Although it is considered that the adhesive strength between the PUF and the plate-like surface material is not sufficiently obtained, the inventors of the present invention make it possible for the adhesive strength of the upper and lower materials and the RPUF to simultaneously satisfy the requirement as a heat insulating panel for ultra-low temperature by the above method. Thus, the present invention has been completed.

In the above-mentioned manufacturing method, it is a preferable embodiment that a nip step for further pressing between upper and lower face materials is provided between the upper face material supply step and the foam lamination step. The nip process is a process that performs an operation that presses the upper and lower face materials from the outside and makes it stiff, improves the penetration of the undiluted foam solution into the glass fiber material, improves the contact, and discharges air, preventing the occurrence of air voids, Consequently, it has the effect of improving the thickness accuracy.

As a device used in the nip step, any known means such as a cylinder and a roller can be used without limitation, but the use of a nip roller is preferable because the device is simple and continuous nip can be performed. .

As a means for improving the thickness accuracy, a spacer having a predetermined size is used, and a RPUF
It is a preferable embodiment to provide a curing step in which pressure is applied until the curing reaction is completely completed. The curing step is particularly preferable to be accompanied by heating because the step time can be shortened.

In the method for producing a heat insulating panel for ultra-low temperature according to the present invention, the pack ratio is preferably 105 to 120%. When the pack ratio is less than 105%, the thickness accuracy decreases, and when the pack ratio exceeds 120%, the strength of the obtained panel decreases.

The pack rate and, when the foam height was foamed without compression t _f, the compressed foam height was t, pack rate P is determined at _{P = 100 (t f / t} ) Is set by adjusting the amount of the foaming stock solution to be supplied.

Also in the above-mentioned production method, the flexible surface material is preferably a non-permeable flexible surface material, particularly preferably an aluminum sheet, a glass cloth and a resin composite flexible sheet.

[0032]

BEST MODE FOR CARRYING OUT THE INVENTION The heat insulating panel of the present invention comprises at least a glass fiber reinforced RPUF, a highly rigid air-permeable plate-like panel,
A flexible sheet facing, preferably a non-breathable flexible sheet facing, is a component.

RPUF is formed using a known rigid polyurethane foam stock solution having excellent low-temperature insulation performance.
The rigid polyurethane foam stock solution uses a component (R component) containing an active hydrogen-containing compound, a foaming agent, a catalyst, and the like, and a component (P component) containing a polyisocyanate compound as a main component. , R component are mixed and provided as a foaming stock solution composition for forming a heat insulating panel.

As the polyisocyanate compound constituting the P component, all di- or polyisocyanate compounds well-known in the technical field of polyurethane can be used, and specific examples include the following compounds.

Aromatic diisocyanate compound: 4,4'-diphenylmethane diisocyanate, 2,
Aliphatic diisocyanate compounds such as 4-toluene diisocyanate, 2,6-toluene diisocyanate, and naphthalene diisocyanate ・ aliphatic diisocyanates such as ethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, and 1,6-hexamethylene diisocyanate (HDI) -Hydrogenated 4,4'-diphenylmethane diisocyanate (HMDI, trade name Hylen-W, manufactured by Huls),
1,4-cyclohexane diisocyanate (CHD
I), methylcyclohexylene diisocyanate, isophorone diisocyanate (IPDI), hydrogenated m-
Alicyclic diisocyanates such as xylylene diisocyanate (HXDI), norbornane diisocyanate, etc. ・ Xylylene diisocyanate (XDI), tetramethyl xylylene diisocyanate (TMXDI), etc. Trifunctional or higher polyisocyanate ・ Crude MDI (44V-10,44V) -20, etc. (manufactured by Bayer))-MDI containing uretonimine (liquid MDI) (Millionate MTL; manufactured by Nippon Polyurethane Industry) The above polyisocyanate compounds may be used alone or in combination of two or more. . Among the above-mentioned polyisocyanate compounds, use of crude MDI is most preferable because of ease of handling, speed of reaction, excellent physical properties of RPUF obtained, low cost, and the like.

As the active hydrogen group-containing compound as a main component of the R component, a compound generally known as a polyol compound can be used. Particularly, as polyols for rigid polyurethane foams, aliphatic polyols, aromatic polyols, amine polyols and the like exemplified below are known.

An aliphatic polyol polyfunctional active hydrogen compound, that is, an aliphatic or alicyclic polyfunctional active hydrogen compound as a polyol initiator, an alkylene oxide, specifically, propylene oxide (P
O), cyclic ethers such as ethylene oxide (EO), styrene oxide (SO), and tetrahydrofuran.
Polyfunctional oligomers obtained by ring-opening addition polymerization of one or more species are exemplified.

Examples of the polyol initiator include glycols such as ethylene glycol, propylene glycol, 1,4-butanediol, 1,3-butanediol, 1,6-hexanediol and neopentyl glycol, trimethylolpropane, glycerin and the like. And trifunctional alcohols such as pentaerythritol, polyhydric alcohols such as sorbitol and sucrose, and water.

Instead of the alkylene oxide, or together with the alkylene oxide, a polyol compound obtained by ring-opening polymerization of a lactone such as ε-caprolactone can be used.

Amine-based polyol As a polyol initiator, a primary or secondary amine is used as an alkylene oxide, specifically one or more of propylene oxide (PO), ethylene oxide (EO), styrene oxide (SO), tetrahydrofuran and the like. Is a polyfunctional polyol compound obtained by ring-opening addition polymerization of

Examples of the initiator include amines such as ethylenediamine, toluenediamine and diphenylmethanediamine, and alkanolamines such as monoethanolamine and diethanolamine.

Aromatic polyol Examples of the method include adding the above-described alkylene oxide to a polyfunctional active hydrogen compound having an aromatic ring in the molecule, and an ester of an aromatic polycarboxylic acid and a polyhydric alcohol.

Examples of the polyol compound obtained by adding the above-mentioned alkylene oxide to a polyfunctional active hydrogen compound include hydroquinone, bisphenol A, etc.
Compounds obtained by ring-opening addition of at least one of O and SO are specifically exemplified.

Specific examples of the ester of an aromatic polycarboxylic acid and a polyhydric alcohol include ester polyols at the hydroxyl group end of terephthalic acid, phthalic acid, isophthalic acid and the like with ethylene glycol and diethylene glycol.

The above polyol compound has a hydroxyl value of 2
It is preferable that the average number of functional groups is 2 to 6 at 00 to 600 mgKOH / g.

The above polyol compounds may be used alone or in combination of two or more to form RPUF having more preferable characteristics.

In producing the rigid polyurethane foam of the present invention, a catalyst, a flame retardant, a foaming agent, a coloring agent, an antioxidant and the like well known to those skilled in the art can be used.

As the foaming agent, a chlorofluorocarbon compound having a small ozone depletion coefficient, for example, HCFC-141b, HFC-
134a, fluorine-containing compounds such as HFC-245fa,
Aliphatic or alicyclic hydrocarbons such as cyclopentane and n-pentane, and other water can be used without limitation. In particular, use of HCFC-141b is preferred because of its excellent low-temperature insulation performance.

As a catalyst, triethylenediamine, N
-Methylmorpholine, N, N, N ', N'-hexamethylethylenediamine, tertiary amines such as DBU, and metal catalysts such as dibutyltin dilaurate, dibutyltin diacetate and tin octylate as urethanization reaction catalysts Is exemplified. When water is used as one component of the blowing agent, the use of a tertiary amine catalyst is preferred because the organotin-based catalyst is hydrolyzed and deteriorated.

It is also preferable to use a catalyst that forms an isocyanurate bond that contributes to the improvement of flame retardancy in the structure of the polyurethane molecule. Examples thereof include potassium acetate and potassium octylate. Some of the above tertiary amine catalysts also promote the isocyanurate ring formation reaction. A catalyst that promotes isocyanurate bond formation and a catalyst that promotes urethane bond formation may be used in combination.

In the present invention, it is also a preferred embodiment to further add a flame retardant.
Examples include metal compounds such as halogen-containing compounds, organic phosphates, antimony trioxide, and aluminum hydroxide.

However, in these flame retardants, for example, when an organic phosphoric acid ester is excessively added, the physical properties of the obtained rigid polyurethane foam may deteriorate, and when a metal compound powder such as antimony trioxide is excessively added. This may cause problems such as affecting the foaming behavior of the foam, and the amount of addition is limited to a range that does not cause such problems.

The rigid polyurethane foam of the present invention comprises
It is preferable to use a plasticizer as needed. Such plasticizers also preferably contribute to flame retardancy, and halogenated alkyl esters of phosphoric acid, alkyl phosphates, aryl phosphates, phosphonates, and the like can be used. Specifically, tris ( β-chloroethyl) phosphate (TCEP, manufactured by Daihachi Chemical),
Tris (β-chloropropyl) phosphate (TMCP
P, manufactured by Daihachi Chemical Co., Ltd.), tributyl phosphate, triethyl phosphate, cresyl phenyl phosphate, dimethyl methyl phosphonate and the like, and one or more of these can be used. The added amount of the plasticizer is preferably 5 to 30 parts by weight based on 100 parts by weight of the polyol component. If the ratio exceeds this range, problems may occur such that a sufficient plasticizing effect cannot be obtained or physical properties of the foam deteriorate.

As the stock solution for forming the rigid polyurethane foam, a commercially available stock solution using a component selected from the above-mentioned components can be used. Specifically, Sofran R115-90F, Sofran R 115-90H (Manufactured by Toyo Tire & Rubber Co., Ltd.).

As the highly rigid air-permeable plate-like surface material, known surface materials can be used, and examples thereof include gypsum board, wood plywood, calcium silicate board and the like. The use of wood plywood is most preferred because of its good reaction adhesive strength and low thermal conductivity. The configuration, size, and the like of the wood plywood are not particularly limited as long as the rigidity meets the purpose. Generally 8 to 20 m thick commercially available as architectural plywood
m, preferably 9-12 mm plywood is also cost-effective.

Examples of the flexible surface material include known flexible surface materials such as a paper surface material, a resin laminated paper surface material, an aluminum sheet, a steel plate, and a resin film, and may be used without limitation. The composite material with aluminum sheet, glass cloth and resin coating layer has good mechanical strength, does not corrode even if dew condensation water is generated, and has good adhesive strength with reactive polyurethane foam. Use is most preferred. As such a composite material, a surface material obtained by laminating a resin layer containing a glass cloth on both surfaces of an aluminum sheet because of its excellent adhesion to a foam and a small coefficient of linear expansion (for example, a trade name: Triplex (manufactured by HUTCHINSON)); The use of Trigit (produced by Unitika Ltd.) is particularly preferred.

Among the above-mentioned surface materials, paper materials having high polarity and high hygroscopicity, gypsum board, wood plywood, calcium silicate board and the like, especially wood plywood, are dried in a state of low moisture content to form a panel. It is preferable to provide for production. If the moisture content of the face material is high, the reaction balance between the isocyanate groups and the active hydrogen groups on the adhesive surface may be lost, and the adhesive strength may decrease.

The heat insulating panel for ultra-low temperature of the present invention has a high rigidity air-permeable plate-like material / glass fiber reinforced hard polyurethane foam / aluminum sheet composite surface material / glass fiber-reinforced hard polyurethane foam / high rigid air-permeable plate-like surface. It is also preferable to use it in a configuration of a material. The heat-insulating panel having such a structure includes a heat-insulating panel having a structure of high-rigidity air-permeable plate-like material / glass fiber-reinforced hard polyurethane foam / aluminum sheet composite surface material, and a glass fiber-reinforced hard polyurethane foam / high-rigidity air-permeable plate-like material. It is manufactured by bonding an insulating panel having a structure of a face material to an aluminum sheet composite face material and a glass fiber reinforced rigid polyurethane foam surface using an adhesive. The heat insulating panel having a configuration of glass fiber reinforced rigid polyurethane foam / high-rigid air-permeable plate-like material used here can be manufactured by using a release paper surface material and a gas-permeable plate-like material. More specifically, a sandwich panel of glass fiber reinforced rigid polyurethane foam is manufactured using a breathable plate-like surface material as a lower surface material at the time of manufacture, and a release paper surface material as an upper surface material, and peeling off the release paper. R formed by removal
It is obtained by surface-coating a PUF skin layer.

The glass fiber material used to reinforce the RPUF is preferably a glass fiber having a large aspect ratio. As a preferable material, a mat-like product of long glass fiber, specifically, a chop strand mat, continuous A strand mat or the like is exemplified. The use of a continuous strand mat is most preferable because of its excellent impregnating properties of the RPUF foaming stock solution and foam reinforcing properties.

A manufacturing method suitable for manufacturing the heat insulating panel for ultra-low temperature of the present invention will be described by taking as an example the manufacturing of a heat insulating panel provided with a breathable plate-like surface material and an aluminum composite surface material. Reinforced by cutting the triplex, which is an aluminum composite surface material, on the conveyor to the same length as the air-permeable plate-like surface material, which is one of the surface materials, and then pulling it out from the raw material and cutting it to the same length as the plywood The glass fiber material (continuous strand mat) is supplied and placed, and the rigid polyurethane foam foaming stock solution composition supplied from the head of the foaming machine,
After moving the face material and the glass fiber material uniformly over the entire face, an air-permeable plate-like face material is supplied from above and placed to form an unfoamed panel. At this time, it is preferable to sufficiently impregnate the glass fiber mat with the rigid polyurethane foam foam stock solution composition using a nip roll.

Next, the unfoamed panel is pressed by a press having a spacer having a predetermined thickness to cause foaming and curing reactions, thereby producing a desired heat insulating panel. The press may heat the surface plate, or may only keep the temperature without heating. It is particularly preferable to provide an annealing step of maintaining the foam panel at a predetermined temperature for a predetermined time after the foam panel is cured, since the warpage of the heat insulating panel can be reduced. Also in the annealing step, it is preferable to maintain the thickness at a predetermined value as in the curing step.

The placement of the air-permeable plate-like material is preferably performed by a device combining a suction cup and an actuator.

In the above-mentioned manufacturing method, it is also possible to adopt a manufacturing method in which a triplex which is an aluminum composite face material and a glass fiber material for reinforcement are continuously supplied onto a conveyor.

[0064]

EXAMPLES Examples of the present invention will be described below based on experimental examples. (Examples, Comparative Examples) Sofran R 115-90H (manufactured by Toyo Tire & Rubber Co., Ltd.) was used as a rigid polyurethane foam stock solution composition, and a continuous strand mat UNIFILO U801 was used as a glass fiber mat.
(VETROTEX Co., Ltd.), as a flexible surface material, a 1.0 mm thick surface material (triplex) in which a resin layer containing glass cloth is laminated on both sides of an aluminum sheet, as a highly rigid air-permeable plate-like surface material Wooden plywood SCHAU
MAN WISA (SCHAUMAN WOOD OY
Using the above-described manufacturing method, a heat-insulating panel having a thickness of 100 mm of a rigid polyurethane foam layer having a face material continuously adhered to both surfaces under the conditions shown in Table 1 below was manufactured. It was cut to 1000 mm and 3000 mm in length.

[0065]

[Table 1] In addition, conditions other than the above were implemented by the structure suitable for this invention.

(Evaluation) [Adhesive Strength] A sample for measuring the adhesive strength having the shape shown in FIG. 2 was prepared, pulled in the direction of the arrow, and the peel adhesive strength was measured. As the adhesive strength measurement sample, the rigid polyurethane foam layer of the heat insulating panel was cut to a thickness of 20 mm, and a plywood / rigid polyurethane foam layer adhesion evaluation sample and a triplex / rigid polyurethane foam layer adhesion evaluation sample were prepared. The tensile jig and the foam, the tensile jig and the plywood, and the tensile jig and the triplex were bonded using a two-component curing type polyurethane adhesive. The measurement was performed using an autograph AG1000E as a tensile tester.
(Manufactured by Shimadzu Corporation) with a crosshead speed of 2
mm / min, and the test environment temperature was 23 ° C.

[Thickness Accuracy] The manufactured panel is cut into a plurality of strips in the width direction or the length direction, and the thickness is measured at a plurality of portions in the length direction of the strip using calipers, and the thickness is measured and statistically processed. Accuracy was required.

[Warpage] In the state shown in FIG. 3, the lifting d of the end due to the warpage was measured, and the warpage value per 1 m was obtained.

(Evaluation Results) The evaluation results of the obtained heat insulating panels are shown in Table 2 with respect to thickness accuracy and warpage. The bond strength between wood plywood and RPUF, triplex and RP
The adhesive strength of UF was as follows. Adhesive strength of wood plywood / RPUF: 15kgf / c
Adhesive strength of m ² triplex / RPUF: 15 kgf / c
m ² These each a required characteristics 12 kgf / cm ²
It is excellent.

[0070]

[Table 2] As is clear from the above results, according to the present invention, it is clear that an ultra-low temperature heat insulating panel that satisfies the standard values can be obtained.

[Brief description of the drawings]

FIG. 1 is a diagram showing a conventional apparatus for manufacturing a glass fiber-reinforced rigid polyurethane foam for an insulating panel.

FIG. 2 is a diagram showing a shape of an adhesion test sample.

FIG. 3 is a side view showing a method for measuring the warpage of the panel.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Kazuhiko Kamezaki, 1-2-1, Marunouchi, Chiyoda-ku, Tokyo, Japan Nihon Kokan Co., Ltd. (72) Yasuo Komatsu 1-2-1, Marunouchi, Chiyoda-ku, Tokyo, Japan (72) Inventor Motoya Daitoku 1-17-18 Edobori, Nishi-ku, Osaka-shi, Osaka Toyo Tire & Rubber Co., Ltd. (72) Inventor Takeshi 1-17-18 Edobori, Nishi-ku, Osaka-shi, Osaka Toyo Rubber Industry Co., Ltd. (72) Inventor Ishino Politics 1-17-18, Edobori, Nishi-ku, Osaka-shi, Osaka Toyo Rubber Industry Co., Ltd. F-term (reference) 3H036 AA09 AB18 AB25 AC01 AE13

Claims (11)

[Claims] 1. An ultra-low-temperature insulating panel, wherein one side of a rigid polyurethane foam is covered with a permeable plate-like surface material and the other surface is covered with a flexible sheet surface material or a permeable plate-like surface material, respectively. The rigid polyurethane foam is a glass fiber reinforced rigid polyurethane foam containing a glass fiber material, and the breathable plate-like face material, the flexible sheet face material is a rigid polyurethane foam foaming stock solution composition without using an adhesive. An ultra-low temperature insulating panel laminated with the glass fiber reinforced rigid polyurethane foam by a foaming curing reaction. 2. The adhesive strength of the glass fiber-reinforced rigid polyurethane foam / the air-permeable plate-like face material and the adhesive strength of the glass fiber-reinforced rigid polyurethane foam / the flexible sheet face material are all 12 kgf / cm ² or more. The heat insulating panel for ultra-low temperature according to claim 1, wherein 3. The heat insulating panel for cryogenic use according to claim 1, wherein the air-permeable plate-like material is a wood plywood. 4. The ultra-low temperature heat insulating panel according to claim 1, wherein the flexible sheet surface material is a non-breathable flexible surface material. 5. The heat insulating panel for ultra-low temperature according to claim 4, wherein the non-breathable flexible sheet surface material is a composite sheet of an aluminum sheet, a glass cloth and a resin. 6. The ultra-low temperature heat insulating panel according to claim 1, wherein the glass fiber material is a continuous glass fiber continuous strand mat. 7. A method for producing an ultra-low-temperature insulating panel in which one surface of a rigid polyurethane foam is covered with a gas-permeable plate-like material on one side and the other surface is covered with a flexible sheet-like material or a gas-permeable plate-like material. A raw material supply step of placing a glass fiber material and a hard polyurethane foam foaming stock solution composition on the flexible sheet face material or the gas permeable sheet material, and supplying and mounting the gas permeable sheet material from the top. The air-permeable plate-like surface material and the flexible sheet-like surface material or the gas-permeable plate-like surface material are laminated at the same time as the upper surface material supply step to be placed and the formation of the rigid polyurethane foam by foaming the rigid polyurethane foam foaming stock solution composition. A method for manufacturing an ultra-low temperature heat insulating panel having a foam laminating step. 8. The method according to claim 7, further comprising a nip step of pressing between upper and lower face materials between the upper face material supply step and the foam lamination step. 9. The method according to claim 7, further comprising a curing step of performing a curing reaction under pressure at a predetermined thickness. 10. The method according to claim 7, wherein the packing ratio is 105% to 120%. 11. The method according to claim 7, wherein the flexible sheet surface material is an air-impermeable flexible surface material.