JPH10226016A - Insulation panel and concrete curing room using this panel - Google Patents

Abstract

(57) [Problem] To provide an insulating panel capable of easily dissipating water-containing moisture even when used in a high-temperature, high-humidity atmosphere such as a concrete curing room. SOLUTION: In a heat insulating panel in which metal plates are laminated on both sides of a plate-like styrene-maleic anhydride copolymer resin foam, at least one metal plate has an opening.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a heat insulating panel suitable for use in a concrete curing room and a concrete curing room using the panel.

[0002]

2. Description of the Related Art Conventionally, expandable resin particles made of a styrene-maleic anhydride copolymer are pre-expanded, and the pre-expanded particles are filled in a mold in which a metal plate for lamination is previously arranged, and heated and foamed. A method for producing a metal-foamed resin laminate which forms a foam by fusing foamable resin particles to the surface of the above-mentioned metal plate for lamination is known (Japanese Patent Publication No. Sho 62-46343).
Reference). Further, as a method for producing the expandable resin particles, a styrene-maleic anhydride copolymer resin particle is suspended in an aqueous medium, and the maleic anhydride group is reacted with a compound containing an active hydroxy group. Attached,
A method for producing expandable resin particles is known in which the resin particles are impregnated with a volatile foaming agent before, during, or after the reaction to obtain expandable resin particles (Japanese Patent Publication No. Sho 6 (1988)).
0-49217).

[0003]

The laminated panel of a metal plate and a foamed resin plate manufactured by the above method is made of a foamable resin made of a styrene-maleic anhydride copolymer having high heat resistance. It can exhibit sufficient heat resistance. However, when used in a high-temperature, high-humidity atmosphere such as a concrete curing room, water vapor enters the foamed resin plate forming the intermediate layer from the seam between the laminated panels, and thereafter, when this water vapor condenses, The foamed resin plate contains water. If the foamed resin plate containing water in such a manner is used as it is, there arises a problem that the heat insulating property is extremely lowered and the weight is considerably increased. Further, once the panel of the concrete curing room containing water is laminated on both sides with metal plates, the moisture cannot be easily diffused. The present invention has been made in view of the above problems, that is, the object of the present invention, when used in a high-temperature, high-humidity atmosphere such as a concrete curing room, even if it contains water, easily remove the water. An object of the present invention is to provide a heat insulating panel having a structure capable of dissipating heat, and to provide a concrete curing room using the heat insulating panel.

[0004]

The heat insulation panel of the present invention comprises:
A heat insulating panel in which a metal plate is laminated on both sides of a plate-like styrene-maleic anhydride copolymer resin foam, wherein at least one of the metal plates has an opening. . In particular, the heat insulating panel in which the area of the opening provided in the metal plate is in the range of 20 to 70% with respect to the surface area of one side of the plate-like styrene-maleic anhydride copolymer resin foam, has heat resistance and heat insulation. It also has excellent properties and mechanical strength. Further, even if the water vapor enters the heat insulating panel, the opening not covered with the metal plate is provided in the metal plate, so that the water vapor can be radiated before being condensed. Therefore, it is possible to suppress a decrease in heat insulating properties due to water content and also suppress an increase in weight.

[0005] Since the heat insulating panel of the present invention uses a styrene-maleic anhydride copolymer resin having excellent thermal adhesion to a metal plate, the metal plate is attached to a molding die to form a molding die. The mold is closed, expandable particles made of a styrene-maleic anhydride copolymer resin are filled in a mold, and then the expandable particles are heated and expanded to form a formed foam, and at the same time, an adhesive or the like is formed. It can be manufactured by being integrally joined to a metal plate without using it.

A metal plate having substantially the same area as the plate-like foam is laminated on one surface of the plate-like styrene-maleic anhydride copolymer resin foam, and an opening is provided on the other surface. A concrete curing room in which a metal plate with an opening and a metal plate with a laminated metal plate facing the outside is excellent in heat insulation and water vapor barrier properties, especially when water vapor enters the heat insulation panel for some reason. Even in the case, water vapor can be effectively radiated from the metal plate opening that is not laminated with the metal plate, the decrease in the heat insulation of the entire concrete curing room can be suppressed, and the increase in the weight of the heat insulation panel can also be suppressed. Can be. In particular, the area of the opening provided in the metal plate is preferably in the range of 20 to 70% with respect to the surface area of one side of the styrene-maleic anhydride copolymer resin foam in the form of a plate.

[0007]

DESCRIPTION OF THE PREFERRED EMBODIMENTS A heat insulation panel according to the present invention will be described. The method for producing the styrene-maleic anhydride copolymer resin constituting the heat insulating panel of the present invention is as follows. Styrene-maleic anhydride copolysynthetic resin particles are suspended in an aqueous medium.
By subjecting the resin particles to a reaction with 50 mol% of a compound containing 2 to 4 active hydroxy groups and impregnating the resin particles with a volatile foaming agent during or after the reaction, the adhesion to metal is improved. Is obtained. The resin used in the present invention is preferably a styrene-maleic anhydride copolymer resin containing 2 to 25% by weight of maleic anhydride and having an average degree of polymerization of 500 to 4000. The resin pellet is obtained by, for example, pelletizing a commercially available styrene-maleic anhydride copolymer with an extruder or the like. When the content of maleic anhydride in the resin is 2% by weight or less, the heat resistance is not excellent, and the adhesiveness to metal becomes insufficient. If it is more than 25% by weight, impregnation with a blowing agent will be difficult. If the average degree of polymerization of the resin is 500 or less, the resin blocks at the time of impregnation with a foaming agent, and the heat resistance is poor. If it is 4000 or more, the brittleness increases, which is not preferable as a foam-formed product.

More preferably, the copolymer resin particles of the present invention have a maleic anhydride content of 5 to 15% by weight and an average degree of polymerization of 900 to 2,000. In producing expandable resin particles using the styrene-maleic anhydride copolymer resin particles, the copolymer resin particles are usually suspended in an aqueous medium. The aqueous medium is composed of water and a suitable amount of a dispersant. As this dispersant,
Partially saponified polyvinyl alcohol, polyacrylate, polyvinylpyrrolidone, carboxymethylcellulose, methylcellulose, calcium stearate, organic compounds such as ethylenebisstearamide, calcium pyrophosphate, calcium phosphate, calcium carbonate, magnesium carbonate, magnesium phosphate, Inorganic compounds and the like made of fine powder insoluble in water such as magnesium pyrophosphate and magnesium oxide are used. In the present invention, when an inorganic compound is used as a dispersant, it is preferable to use a surfactant such as sodium dodecylbenzenesulfonate in combination. These dispersants are generally 0.0
It is used by adding 1 to 5% by weight.

In the present invention, "a compound having at least two active hydroxy groups" (hereinafter referred to as "hydroxy compound") refers to a compound having two hydroxy groups capable of reacting with a maleic anhydride group of a styrene-maleic anhydride copolymer resin. Means more than one compound. It is particularly preferred that the number of active hydroxy groups is two. Compounds having two active hydroxy groups include aliphatic dioxy compounds,
Examples thereof include an aromatic dioxy compound, an aliphatic dioxy compound containing an aromatic ring, and an aliphatic diethanolamide. This will be described in more detail below. (I) Aliphatic dioxy compound: Here, the aliphatic residue includes those having various structures such as a structure containing a saturated or unsaturated linear, branched, cyclic or alicyclic residue. Specific examples include the following compounds. (A) In the general formula HO- (CH ₂ ) -nOH, n is 2
And compounds such as ethylene glycol and propylene glycol. (B) In formula H- (OR) -nOH, n is 2
6 is a compound wherein R is an alkene group, for example, diethylene glycol, dipropylene glycol, tetraethylene glycol, tetrapropylene glycol and the like. (C) In addition to the above, represented by the following formulas [formula 1] to
The compound of the formula [4] can also be used.

[0010]

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[0011]

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[0012]

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[0013]

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(II) Aromatic dioxy compounds (a) Polyhydric phenols: hydroquinone, disorcin,
Examples include compounds having two hydroxy groups on the aromatic nucleus or the substituted aromatic nucleus, such as catechol and lower alkyl or chloro substituted derivatives thereof, pyrogallol-1-methyl ether, pyrogallol-2-methyl ether, and the like. (B) a compound represented by the following general formula:

[0015]

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Particularly preferred of this group of compounds is bisphenol A [2,2-bis (4'-hydroxyphenyl) propane].

(III) Aliphatic dioxy compounds containing an aromatic ring: Compounds belonging to this category include, for example, those represented by the general formula H
N in _{O- (CH 2) -nR'- (CH} 2) -nOH
Is 1 or 2 and R 'is a group as follows:

[0018]

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(IV) Fatty acid diethanolamide: The aliphatic residue of the fatty acid includes those having various structures such as a structure containing a linear, branched, cyclic or alicyclic residue.
In this case, the fatty acid may be a mixed fatty acid of various fatty acids having different numbers of carbon atoms. A preferred specific example is diethanolamide of coconut oil fatty acid. Examples of the compound having three or more active hydroxy groups include glycerin and pentaerythritol. The hydroxy compound is used in an amount of 2. based on the total amount of maleic anhydride groups in the styrene-maleic anhydride copolymer resin.
It is added in an amount of 5 mol% or more. Generally, it may be added in amounts up to 150%. If the addition amount is less than 2.5 mol%, a good foam-formed product cannot be obtained unless the pre-expanded particles from the obtained expandable particles are overfilled, and the object of the invention cannot be achieved. . Also, the use of a large excess of the hydroxy compound relative to the content of the anhydrous substance may not be meaningful from an economic or technical point of view. The reaction between the styrene-maleic anhydride copolymer resin particles and the hydroxy compound is carried out at 80 ° C to 150 ° C, preferably 90 ° C.
The reaction is carried out by heating and stirring at a temperature of １１０110 ° C. (depending on the reaction temperature and the size of the copolymer particles) for 3 to 60 hours.

The hydroxy group of the above hydroxy compound is
It is believed that the acid anhydride groups in the molecular chain of the styrene-maleic anhydride copolymer are attacked to open the ring and form a half-ester bond. At this time, it is considered that the two hydroxy groups of the hydroxy compound react with the acid anhydride groups of the different copolymers to form a half ester bond and also to form a kind of crosslinked structure. Thereby, when the foaming agent is impregnated into pre-expanded particles, the secondary foaming power is increased, and various effects such as a reduction in the heat shrinkage of the obtained foam molded article are considered to be exhibited. Can be

The impregnation of the particles of the styrene-maleic anhydride copolymer resin with the volatile blowing agent may be carried out during or after the reaction. However, it is most preferable in industrial practice that the hydroxy compound and the volatile blowing agent are added to the same reaction system, and the esterification reaction and the impregnation with the blowing agent are performed in the same treatment.

As the volatile foaming agent in the present invention,
For example, aliphatic hydrocarbons such as propane, n-butane, i-butane, n-pentane, i-pentane, and n-hexane;
Examples thereof include cycloaliphatic hydrocarbons such as cyclopentane and cyclohexane, and halogenated hydrocarbons such as methyl chloride, ethyl chloride, dichlorodifluoromethane, chlorodifluoromethane, and trichlorofluoromethane. Of these blowing agents, it is preferred to use propane or n-butane or i-butane, and mixtures thereof. These blowing agents are generally used at a ratio of 3 to 40% by weight based on the polymer resin particles.

In the present invention, it is preferable to add a solvent that dissolves the styrene-maleic anhydride copolymer resin particles when adding the foaming agent. This solvent is preferably stirred and dispersed, for example, in an aqueous suspension in advance so as to sufficiently impregnate the styrene-maleic anhydride copolymer resin particles. Such solvents include aromatic hydrocarbons such as benzene, toluene, xylene and ethylbenzene, esters such as methyl acetate and ethyl acetate, halogenated hydrocarbons such as dichloroethane, trichloroethane, tetrachloroethane, trichloroethylene and tetrachloroethylene, cyclohexane and cycloheptane. And hydrocarbons such as n-hexane and n-heptane. The base resin of the expandable resin particles of the present invention may contain various additives such as a filler, a plasticizer, a lubricant, a colorant, a flame retardant, an ultraviolet absorber, and an antioxidant. .

The styrene-maleic anhydride copolymer resin expandable particles are expanded 10 to 50 times with heated steam to obtain pre-expanded particles, and the obtained pre-expanded particles are used as plate-like foams used for lamination. A metal plate having substantially the same area as the above, and a metal plate having an opening are filled in a pre-arranged mold, and are molded by heating, thereby forming one of a plate-like styrene-maleic anhydride copolymer resin foam. A heat insulation panel can be manufactured in which a metal plate is laminated on the entire surface and a metal plate having an opening is laminated on the other surface. The opening area of the metal plate is preferably 20 to 70% of the surface area of one surface of the plate-like styrene-maleic anhydride copolymer resin foam. An even more preferred range is 30 to 50%. When the opening ratio is less than 20%, the water content in the heat insulating panel (metal-foam resin laminate) increases, and when the opening ratio exceeds 70%, the rigidity difference between the metal and the foaming resin causes deformation of the heat insulating panel. And the commercial value is reduced. The metal is, for example, aluminum, iron, stainless steel, copper, nickel, zinc-iron, or the like.

The metal plate having an opening used in the present invention may be a metal plate having an opening formed in advance, or a combination of a plurality of metal plates. When an opening is formed in a metal plate in advance, the opening may have any geometric shape such as a rectangle or a circle, and the number of openings may be one or more. May be appropriately determined within a range of 20 to 70%. Especially,
When a plurality of metal plates are combined, it is preferable in terms of strength of the heat insulating panel to arrange the metal plates in a frame shape on the outer peripheral portion of the styrene-maleic anhydride copolymer resin foam. Further, as described above, the styrene-maleic anhydride copolymer resin foam used for the heat insulation panel is obtained by expanding the pre-expanded particles of the styrene-maleic anhydride copolymer resin in the mold at the same time as the metal plate. It may be molded or styrene-
A pre-expanded particle of a maleic anhydride copolymer resin may be cut into a plate shape from a block formed in advance into a block shape, and then heat-sealed. Further, they may be bonded via an adhesive.

Next, a concrete curing room using the heat insulating panel of the present invention is shown in FIG. The concrete curing room divided into three rooms has a heat insulating panel on its wall, ceiling, etc.
And the surface on which the metal plate having the opening 11 is laminated is arranged facing the outside of the heated steam. Reference numeral 12 in the figure denotes a steam pipe for sending steam to the concrete curing room, which is connected to a boiler (not shown). Therefore, the concrete curing room of the present invention is excellent in heat insulation and water vapor barrier properties, and is a metal plate having an opening arranged so as to be outside the concrete curing room even when water vapor enters the heat insulation panel. Since the water vapor can be radiated through the opening, it is possible to suppress a decrease in heat insulation and an increase in weight.

[0027]

【Example】

(Example 1) In an autoclave having an internal volume of 50 liters, 28 kg of water and metathesis method magnesium pyrophosphate 1 were added.
24 g, sodium dodecylbenzenesulfonate 4 g
And then a styrene-maleic anhydride copolymer [trade name: Dailac 2 having a maleic anhydride content of 8.0% by weight and an average degree of polymerization of 1200 as a copolymerization component].
32 (manufactured by Mitsui Toatsu Chemicals Co., Ltd.)] and suspended therein, and then 80 g of 1,4-butanediol and 640 of toluene
g, and then 1760 g of butane as a blowing agent was injected while stirring in a closed state. Thereafter, the temperature was raised to 100 ° C. and maintained at this temperature for 5 hours. Thereafter, the temperature was cooled to 30 ° C., and the foaming resin particles impregnated with the foaming agent were taken out.

After the particles were washed, dehydrated and dried, they were placed in a closed container and kept at a temperature of 15 ° C. for 72 hours to produce expandable resin particles. The particles were heated with steam at 98 ° C. for 5 minutes to obtain pre-expanded particles having a bulk specific gravity of 0.015.
The bulk specific gravity of the pre-expanded particles was adjusted to 0.033, and the depth 25
3,000 cc in a 3000 cc mold
And the foam was molded by heating with 1.0 kg / cm ² (gauge pressure) water vapor for 40 seconds to obtain a good foam molded article with a fusion bond of 90%. After annealing the obtained foam molded article at 50 ° C. for 24 hours, it was left in an oven at 90 ° C. for 7 days.
% Shrinkage. Further, when the foamed molded product was subjected to infrared analysis, an absorption peak based on an ester bond was observed.
Further, when the expandable resin particles were immersed in toluene, a swollen insoluble material (approximately 15
wt%) remained. This insoluble matter is considered to be a product due to cross-linking. On the other hand, the average degree of polymerization of toluene
500.

The bulk specific gravity of the pre-expanded particles was adjusted to 0.025, and Teflon-treated at a depth of 35 mm and a height of 1000 m.
m, 2000 mm (35 × 1000 × 2000) in a mold, 400 mm long and 1400 mm wide (40 mm) at the center
0.3 mm thick, 999 mm long, and 1998 mm wide (0.3 × 1400) having an opening (opening ratio 28%) of 0 × 1400).
999 × 1998) stainless steel plate is placed in advance, and 70,000 cc of the pre-expanded particles are filled thereon, and the thickness of the pre-expanded particles is 0.3 mm, 999 mm in height, 19 mm in width.
A 98 mm (0.3 × 999 × 1998) stainless steel plate is placed on the plate and steamed at 1.0 kg / cm ² (gauge pressure).
It was molded by heating for 0 seconds. FIG. 2 shows a perspective view of the obtained heat insulating panel. In a water tank of 15 cm in depth, 1 m in height and 2 m in width, put water until the depth becomes 10 cm, set it in the water and set the heater, so that the metal plate having the opening of the obtained heat insulating panel becomes the upper surface. And used as a lid to cover the top of the aquarium. The temperature of the water tank was controlled to 75 ° C., and after heating for 5 hours, the power of the heater was turned off and the outside air temperature (20
(〜25 ° C.) for 19 hours, and then the water temperature was raised to 75 ° C. again. This process is defined as one cycle, and the heating and moisture absorption
0 cycles were performed. After 20 cycles, the heat insulating panel contained 70 g of water.

(Example 2) This example was carried out in exactly the same manner as in Example 1 except that only the size of the opening of the stainless steel plate was changed. 700 vertical in the center of the stainless plate
mm, an opening having a width of 1700 mm (an opening ratio of 59.5%). After performing 20 cycles of the heating / moisture absorption test in the same manner as in Example 1, the heat insulating panel contained 25 g of water.

(Example 3) This example was carried out in exactly the same manner as in Example 1 except that only the size of the opening of the stainless steel plate was changed. 800 vertically in the center of the stainless plate
mm, an opening of 1700 mm in width (opening ratio 68%). After performing the heating / moisture absorption test for 20 cycles in the same manner as in Example 1, the heat insulating panel contained 20 g of water.

Example 4 This example was carried out in exactly the same manner as in Example 2 except that the method of forming the openings in the metal plate was changed. 0.3mm thick in the longitudinal direction of mold bottom, 1 vertical
Two 50 mm, 1998 mm wide stainless steel plates a and b are arranged vertically, and the thickness is 0.3 m in the width direction of the bottom of the mold.
Two stainless steel plates c and d having a length of m, a length of 150 mm and a width of 699 mm were arranged on the left and right sides, and the metal plates were arranged in a frame shape. The pre-expanded particles were filled with 70,000 cc, and 0.3 mm thick, 99
Place a 9 mm, 1998 mm wide stainless steel plate,
The foam was molded by heating with steam of kg / cm ² (gauge pressure) for 90 seconds. FIG. 3 shows a perspective view of the obtained heat insulating panel. The aperture ratio of the metal plate is 59.5%. After performing the heating / moisture absorption test for 20 cycles in the same manner as in Example 1,
The insulation panel contained 25 g of water.

Example 5 This example was performed in the same manner as in Example 2 except that a metal plate having a plurality of punched holes (opening ratio: 59.5%) in the opening of the stainless steel plate was used. . FIG. 4 shows a perspective view of the obtained heat insulating panel. As in Example 1, after performing the heating / moisture absorption test for 20 cycles, the heat insulating panel contained 26 g of water.

[0034]

[Comparative example]

(Comparative Example 1) In Comparative Example 1, a heat insulating panel in which both surfaces were laminated with a metal plate having no opening was used. Therefore, the aperture ratio of the metal plate is 0%. As in Example 1,
After performing the heating / moisture absorption test for 20 cycles, the heat insulating panel contained 278 g of water.

[0035]

As described above, the heat insulating panel of the present invention is:
It is excellent in heat resistance, heat insulation, and mechanical strength, and can dissipate water vapor that has entered the heat insulation panel through an opening that is not laminated with a metal plate, so that the water content can be suppressed. Therefore, a decrease in heat insulation can be suppressed, and an increase in weight can be suppressed. In addition, the concrete curing room in which the surface on which the metal plate having no opening is laminated is disposed on the side in contact with the heated steam has excellent heat insulation and water vapor blocking properties,
Even if the water vapor enters the heat insulating panel, the water vapor can be radiated through the opening of the metal plate having the opening arranged outside the concrete curing room, so that the heat insulating property is reduced. And increase in weight can be suppressed. In particular, the opening area of the metal plate is 20 to 70% of the surface area of one side of the plate-like styrene-maleic anhydride copolymer resin foam, and the concrete curing room using this panel has water vapor. Even if the heat enters the heat insulating panel, water vapor can be radiated through the opening of the metal plate having the opening, so that a decrease in heat insulation can be suppressed and an increase in weight can be suppressed.

[Brief description of the drawings]

FIG. 1 is a reference perspective view of a concrete curing room.

FIG. 2 is a perspective view of a heat insulating panel obtained in Example 1.

FIG. 3 is a perspective view of a heat insulating panel obtained in Example 4.

FIG. 4 is a perspective view of a heat insulating panel obtained in Example 5.

Claims (4)

[Claims] 1. A heat insulation panel comprising a plate-shaped styrene-maleic anhydride copolymer resin foam and a metal plate having substantially the same area as the plate-shaped foam laminated on both surfaces of the foam. Is a heat insulating panel provided with an opening. 2. The opening area of the metal plate is 2% of the surface area of one side of the plate-like styrene-maleic anhydride copolymer resin foam.
The heat insulating panel according to claim 1, wherein the heat insulating panel has a content of 0 to 70%. 3. A plate-shaped styrene-maleic anhydride copolymer resin foam is laminated on one surface with a metal plate having substantially the same area as the plate-like foam, and an opening is provided on the other surface. A concrete curing room characterized in that a heat insulating panel in which laminated metal plates are stacked is disposed such that a metal plate surface provided with an opening faces an outdoor side. 4. The area of the opening provided in the metal plate is 20 to 70% with respect to the surface area of one side of the styrene-maleic anhydride copolymer resin foam in the form of a plate. 3. The concrete curing room according to 3.