JP2002086460A - Method for manufacturing heat insulating panel - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for manufacturing a heat insulating panel which is free from the triggering of environmental destruction because of the non-use of a chlorofluorocarbon as a foaming agent and is of high strength and not brittle and further, can be securely bonded to a surface material. SOLUTION: A polyisocyanate mixture 1 is prepared by blending a trimerization catalyst of a polyisocyanate, a polyol and an isocyanate with pentane as the foaming agent. The heat insulating, material 4 is obtained by supplying the polyisocyanate mixture 1 to the surface of the surface material 2 and expanding the former.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a heat insulating panel using a polyisocyanurate foam such as a urethane-modified polyisocyanurate foam as a heat insulating material.

[0002]

2. Description of the Related Art Conventionally, a heat insulating material formed of a polyisocyanurate foam is filled between surface materials formed of a metal plate or the like to form a heat insulating panel. As a method for producing a polyisocyanurate foam to be used, there is known a method for producing a polyisocyanurate foam using a trimerization catalyst and a carbodiimidation catalyst in combination with a polyisocyanate and a polyol in the presence of a foaming agent (for example, See Japanese Patent Publication No. 46-5991). A method for producing a polyisocyanurate foam using a polyisocyanate and a polyol in combination with methanol, furfuryl alcohol or phosphorene oxide (carbodiimidization catalyst) and an alkali metal salt (trimerization catalyst) in the presence of a blowing agent. (US Pat. No. 4,166,164, JP-A-2-245).
No. 013). Further, Japanese Patent Application Laid-Open No. 50-95397
JP-A-50-124997, JP-A-50-124997, JP-A-50-124997
-75799, JP-A-51-76395,
JP-A-51-80393, JP-A-51-1020
No. 98, etc., a method of obtaining a polyisocyanurate foam using a tertiary amine and an alcohol such as an amino alcohol as a cocatalyst, a method of using a Mannich polyol or a phosphorus-containing polyol as a catalyst, s-triazine and phenol The method of using is reported.

[0003] In the production of such polyisocyanurate foams, flon is generally used as a blowing agent. However, CFCs have a problem of depletion of the ozone layer, and their use is restricted.

Therefore, a method has been proposed in which carbon dioxide generated by the reaction between water and isocyanate is used as a substitute for CFCs. The method for producing a polyisocyanurate foam using carbon dioxide gas generated by the reaction between water and isocyanate is described in US Pat.
+ H2O → R-NHC (O) NH-R + CO2 to generate carbon dioxide gas and use this carbon dioxide gas as a foaming agent. This makes it possible to use a polyisocyanurate foam without using freon. The polyisocyanurate foam can be used as a heat insulating material.

[0005]

However, in the reaction between water and isocyanate, a urea bond is simultaneously formed with the generation of carbon dioxide, and this urea bond is uniformly dispersed in the polyisocyanurate foam. However, there is a problem that an aggregate (domain) is formed, and this aggregate makes the polyisocyanurate foam fragile and lowers the strength. In addition, when this polyisocyanurate foam is used as a heat insulating material for a heat insulating panel, the adhesiveness between the heat insulating material and the surface material is reduced due to the influence of the above-described aggregate, and the surface material and the heat insulating material cannot be firmly bonded. There was a problem. In particular, in order to reduce the density of the heat insulating material (to obtain a highly foamed material), it is necessary to increase the amount of water used. The above problems have been significant. In addition, the heat insulating material of the conventional polyisocyanurate foam generally has a high crosslink density, which causes a problem that the heat insulating material of the polyisocyanurate foam is brittle. In particular, when foaming with water as described above, urea bonds are generated, and there is a problem that the brittleness of the heat insulating material of the polyisocyanurate foam further increases.

[0006] The present invention has been made in view of the above points, does not cause environmental destruction without using chlorofluorocarbon as a foaming agent, furthermore, has a high strength of the heat insulating material, is not brittle, and has a surface material. It is an object of the present invention to provide a method for manufacturing a heat insulating panel capable of firmly bonding a heat insulating material and a heat insulating material.

[0007]

According to a first aspect of the present invention, there is provided a method for producing a heat insulating panel, comprising the steps of: mixing a polyisocyanate, a polyol, a trimerization catalyst of isocyanate, and pentane as a blowing agent; Is prepared and foamed by supplying the polyisocyanate mixture 1 to the surface material 2 to form the heat insulating material 4. By using pentane as a foaming agent, flon and water are not used. And prevent environmental destruction, and
By preventing urea bonds from being generated, the heat insulating material has high strength and is not brittle, and the surface material and the heat insulating material can be firmly bonded.

According to a second aspect of the present invention, there is provided a method of manufacturing the heat insulating panel A, wherein the pentane is n-pentane.

A third aspect of the present invention is directed to a method of manufacturing the heat insulating panel A, wherein, in addition to the constitution of the first or second aspect, after mixing the polyisocyanate and the pentane, this is mixed with the polyol. Things.

[0010]

Embodiments of the present invention will be described below.

The polyisocyanate used as a raw material in the present invention is an organic polyisocyanate, and may be any type of aliphatic, alicyclic, aromatic, and a mixture thereof. Those conventionally used in the production of polyurethane and polyisocyanurate can be used in the same manner.

Specifically, aromatic diisocyanates such as 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, crude tolylene diisocyanate, methylene diphenyl diisocyanate, and crude methylene diphenyl diisocyanate; Aromatic triisocyanates such as "-triphenylmethane triisocyanate and 2,4,6-tolylene triisocyanate; 4,4'-dimethyldiphenylmethane-2,2'-
Aromatic tetraisocyanates such as 5,5'-tetraisocyanate; aliphatic isocyanates such as hexamethylene-1,6-diisocyanate; alicyclic isocyanates such as hydrogenated methylene diphenyl diisocyanate; m-phenylene diisocyanate and naphthylene-1 , 5-Diisocyanate, 1-methoxyphenyl-2,4-diisocyanate, 4,4'-biphenylenediisocyanate, 3,3'-dimethoxy-4,4'-
Biphenyl diisocyanate, 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate and the like can be mentioned.

The above polyisocyanates can be used alone or in combination of two or more.

Among the above polyisocyanates, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, crude tolylene diisocyanate,
Preferred are methylene diphenyl diisocyanate, crude methylene diphenyl diisocyanate, hexamethylene-1,6-diisocyanate, hydrogenated methylene diphenyl diisocyanate, and the like.

[0015] The polyol used in the present invention includes:
Polyether polyols, polyester polyols, castor oil, and other compounds having two or more hydroxyl groups in one molecule, such as aliphatic, sugar, and aromatic compounds, and mixtures thereof, are included. What is used at the time can also be used. Further, such a polyol may have either a low molecular weight or a high molecular weight.

More specifically, examples of the polyether polyol include compounds having a structure in which an alkylene oxide is added to an active hydrogen-containing compound such as a polyhydric alcohol, a polyhydric phenol, an amine, or a polycarboxylic acid.

Examples of the polyhydric alcohol include dihydric alcohols such as ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol and neopentyl glycol; glycerin, pentaerythritol, and sucrose. And the like.

Examples of polyhydric phenols include pyrogallol, hydroquinone, bisphenols such as bisphenol A, and condensates of phenol and formaldehyde.

Examples of the amines include alkanolamines such as ammonia, monoethanolamine, diethanolamine, and triethanolamine, isopropanolamine, and aminoethylethanolamine;
22 alkyl amines, alkylene diamines having 2 to 6 carbon atoms, polyalkylene polyamines, aniline, phenylene diamine, diamino toluene, xylylene diamine, aromatic amines such as diphenyl ether diamine, isophorone diamine cyclohexylene diamine, etc. Alicyclic amines, heterocyclic amines and the like.

Examples of the polycarboxylic acid include aliphatic carboxylic acids such as succinic acid, adipic acid, sebacic acid, maleic acid, and dimer acid; and aromatic polycarboxylic acids such as phthalic acid, terephthalic acid, trimellitic acid, and pyromellitic acid. Carboxylic acid and the like can be mentioned.

Two or more active hydrogen-containing compounds such as polyhydric alcohols, polyhydric phenols, amines, and polycarboxylic acids can be used.

Examples of the alkylene oxide to be added to the active hydrogen-containing compound include propylene oxide, ethylene oxide, butylene oxide, and tetrahydrofuran. These alkylene oxides may be used alone or in combination of two or more kinds. In the latter case, they may be added by block addition or random addition.

Further, as the polyester polyol,
For example, a condensation polyester polyol obtained by reacting a polyhydric alcohol (the above dihydric alcohol, trimethylolpropane, glycerin, etc.) with a carboxylic acid (the above polycarboxylic acid, etc.), a polyester polyol obtained by ring-opening polymerization of lactone And a polyester obtained by adding an ethylene oxide adduct of nonylphenol to a recovered polyester.

Among the above polyols, aliphatic,
Aromatic, aliphatic or aromatic amine, pentaerythritol and sucrose polyether polyols; aromatic or aliphatic carboxylic polyester polyols; lactone polyester polyols and the like are preferred.

The above polyols can be used alone or in combination of two or more. In addition, the polyols as described above are generally 20 to
600 mgKOH / g, preferably 25-500 mgK
OH / g, more preferably 50 to 400 mg KOH /
It can have a hydroxyl value in the range of g.

As the isocyanate trimerization catalyst used in the present invention, for example, a hydroxyalkyl quaternary ammonium compound represented by the general formula (I) can be used, such as polyisocyanurate and polyurethane-polyisocyanurate resin. The catalyst used in the production of is known per se (for example, JP-B-61-23214), and specific examples thereof include those represented by formulas (I-1) to (I-12). .

[0027]

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[0028]

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[0029]

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[0030]

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[0031]

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[0032]

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[0033]

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[0034]

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[0035]

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[0036]

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[0037]

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[0038]

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[0039]

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Of the above hydroxyalkyl quaternary ammonium compounds, those of (I-1), (I-2) and (I-12) are preferably used.

As the isocyanate trimerization catalyst, DBU (1,8-diazabicyclo [5,
4,0] undecene-7), tertiary amines such as 1,3,5-tris (N, N-dimethylaminopropyl) -s-triazine and 2,4,6-tris (dimethylaminomethyl) phenol Can also be used as appropriate.
Further, an alkali metal salt of an aliphatic monocarboxylic acid represented by the formula (II) can be exemplified.

[0042]

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As the above-mentioned alkali metal salt of aliphatic monocarboxylic acid, potassium 2-ethylhexanoate, sodium acetate and the like can be preferably used.

The above trimerization catalysts can be used alone or in combination of two or more.

The blowing agent used in the present invention includes n-
Pentane such as pentane, cyclopentane and 2-methylpentane can be exemplified. These pentanes can be used alone or in combination of two or more. Among them, n-pentane is preferably used. By using n-pentane as the foaming agent, the unreacted portion of the polyisocyanate and the polyol can be reduced, and the unreacted portion of the polyisocyanate and the polyol does not react after the formation of the heat insulating panel A. Can be prevented from swelling.

Further, in the method of the present invention, if necessary, a urethane-ureaization catalyst (for example, triethylenediamine, dimethylethanolamine, triethylamine, trimethylaminoethylethanolamine, dimethylaminoethylether, pentamethyldiethylenetriamine, N -Methylmorpholine, dibutyltin dilaurate, tin octoate, lead octoate, etc.), crosslinkers (e.g., ethylene glycol, propylene glycol, 1,
4-butanediol, 1,6-hexanediol, diethylene glycol, triethanolamine, diethanolamine, ethylenediamine, toluenediamine, etc., a foam stabilizer (eg, dimethylsiloxane-polyether block copolymer, etc.), a flame retardant (eg, triphenyl) Phosphate, triethyl phosphate,
Trimethyl phosphate, cresyl diphenyl phosphate, triscresyl phosphate, trischloroethyl phosphate, trisdichloropropyl phosphate, tris-β-chloropropyl phosphate, tris-β-chloroethyl phosphate, tris (2, 3-Dibromopropyl) phosphate, tris (bromocresyl) phosphate, melamine, antimony trioxide, and the like, a colorant, and other additives can be used in commonly used amounts.

The polyisocyanate mixture 1 of the present invention comprises
The polyisocyanate, the polyol, the foaming agent, the trimerization catalyst, and other raw materials can be prepared by blending them in predetermined amounts and mixing. At this time, after mixing the polyisocyanate and pentane as a blowing agent first,
It is preferred to mix the polyol with this mixture. Pentane (n-pentane) is a special flammable substance stipulated by the Fire Services Act, and is handled at general handling sites (see Article 19 of the Cabinet Order on the Regulation of Dangerous Goods and Article 28 of the Regulations on the Regulation of Dangerous Goods). Needs to establish a holding place, but by mixing with polyisocyanate as described above, this mixture including pentane can be treated as the first petroleum, and therefore, the entire production line described later is sent to a general handling place. Therefore, it is possible to clear the standards of the Fire Service Law without having to make a vacant lot. Moreover, pentane (n-pentane) has poor compatibility with the polyol, but has better compatibility with the isocyanate than the polyol. Therefore, the polyol is mixed after the polyisocyanate and pentane are mixed first. By doing so, the polyisocyanate, pentane and polyol can be uniformly mixed, and the occurrence of voids due to the foaming agent bumping at the time of foaming of the polyisocyanate mixture 1 (at the time of foaming) can be prevented.

The blending ratio of the polyisocyanate and the polyol is not strictly limited, and can be varied over a wide range according to the physical properties and use desired for the heat insulating material 5, but in general, the NCO / OH equivalent Isocyanate index represented by the ratio is 1.8 or more, preferably 1.8 to
It is preferable to mix and react the above components so as to be 5.0, particularly 2.0 to 4.0.

The amount of the trimerization catalyst is not strictly limited, and can be varied over a wide range according to the desired physical properties and application of the heat insulating material 4. 0.1 to 10% by mass, preferably 0.5 to 5% by mass. The amount of the foaming agent can be adjusted according to the density and the like desired for the heat insulating material 4. In particular, the present invention has a major feature in that a product having a high expansion ratio can be produced only with n-pentane without using chlorofluorocarbon, and according to the method of the present invention, for example, the total amount of polyisocyanate and polyol 0.3 to 20% by mass, preferably 0.5% by mass
A foaming agent in a range of 10 to 10% by mass is blended. This makes it possible to easily produce an isocyanurate foam having a high expansion ratio of generally 50 kg / m ³ or less in free foam density.

FIG. 1 shows an example of an apparatus for manufacturing the heat insulating panel A of the present invention. This manufacturing apparatus includes a surface material forming section 40, a filling section 41, a pre-mixing section 42, and a finishing section 43. The surface material forming section 40 is a portion where the surface material 2 is formed from a strip-shaped metal plate 5 such as a colored zinc-iron plate, a colored aluminum plate, a colored aluminum-zinc alloy-plated steel plate, a stainless steel plate, a titanium steel plate, and a double-sided colored zinc-iron plate. A pair of strip-shaped metal plates 5 arranged vertically from 10a, 10b are pulled out by pinch rollers 12a, 12b,
Forming machines 11a, 1
By forming the male and female fitting portions 30 and 32 by folding back at 1b, and providing irregularities over the entire surface of the strip-shaped metal plate 5 as necessary to form the surface pattern of the heat insulating panel A. A pair of long surface materials 2 can be formed. The surface plate 2 thus formed is continuously advanced and conveyed to the filling section 41 by conveying means such as the support roller 13. In addition, as the surface material 2, paper, a plastic sheet, etc. other than a metal plate can be used. Reference numeral 9 in the figure is a shear.

The filling section 41 is a place where the polyisocyanate mixture 1 is prepared and the polyisocyanate mixture 1 is filled between a pair of surface materials 2, 2. Surface material 2 at an optimum temperature of 30 to 30
The pre-heater 15 for pre-heating to 80 ° C. and the polyisocyanate mixture 1 are injected between the surface materials 2, which are reciprocated in the width direction (transverse direction) of the surface material 2, and are vertically arranged. A gantry 16 provided with a spray nozzle 25 for uniformly spraying at 60 kg / m ³ , a double conveyor 17 for setting the interval between the surface materials 2 and 2 arranged above and below to a predetermined size, and a double conveyor 17 And a mixer 50 for preparing the polyisocyanate mixture 1 and supplying it to the spray nozzle 25.
And

As shown in FIG. 2, the double conveyor 17 has a pair of upper and lower conveyors 17a and 17b, and the conveyors 17a and 17b are formed to be vertically movable by a hydraulic cylinder or the like. In order to set the upper and lower intervals of the surface material 2 to a predetermined size using the double conveyor 17, a pair of upper and lower surface materials 2 and 2 are introduced between the conveyors 17a and 17b, and the conveyors 17a and 17b are respectively moved up and down. By moving and changing the vertical distance, the surface materials 2 and 2 are pressed, and the vertical distance between the surface materials 2 is changed. Therefore, the double conveyor 17 has a structure that can withstand the foaming pressure of the polyisocyanate mixture 1 so as not to be damaged by the foaming of the polyisocyanate mixture 1.

The mixer 50 includes a mixing tank 51 for mixing the raw materials of the polyisocyanate mixture 1 to prepare the polyisocyanate mixture 1, a supply amount of the polyisocyanate mixture 1 from the spray nozzle 25, and a mixing tank for the polyisocyanate mixture 1. A metering device 52 for controlling and managing the temperature and the like is provided, and the raw materials are mixed at a high pressure by a mixing valve or the like to prepare the polyisocyanate mixture 1.

As shown in FIG. 3, the pre-mixing section 42
Is provided with a premixer 54 for mixing the blowing agent of the polyisocyanate mixture 1 and a part of other raw materials to prepare a premix, and a raw material tank 53 for storing the raw material of the polyisocyanate mixture 1. It is formed. Other raw materials such as a foam stabilizer and a flame retardant are mixed with the polyol in the polyol tank 53c. The blowing agent tank 53a and the premixer 54 are connected by a blowing agent pipe 55, and an intermediate tank 56 and a pump 57 are provided in the middle of the blowing agent pipe 55. The isocyanate tank 53b and the premixer 54 are connected by an isocyanate pipe 58, and a pump 59 is provided in the middle of the isocyanate pipe 58. The pre-mixer 54 and the mixing tank 51 of the mixer 50 are connected by a pre-mixture pipe 60 and the polyol tank 5
3c and the mixing tank 51 of the mixer 50 are the polyol piping 6
1 connected.

The finishing section 43 is a section for finishing the heat insulating panel A from the heat insulating panel original sheet 7 formed by the filling section 41, and is a width and thickness meter for measuring the width and thickness of the heat insulating panel original sheet 7. 19, a cutting machine 20 for cutting the heat insulating panel original plate 7 to a predetermined size controlled by the process computer, and a reject for controlling and stacking the heat insulating panel A according to its length and the number of packages. A piler 22 and a piler 24 are provided.

In the above-described apparatus for manufacturing the heat insulating panel A,
A partition 65 is provided between the pre-mixing section 42 and other parts (the surface material forming section 40, the filling section 41, and the finishing section 43).
Is provided. Gantry 16 in filling section 41
And the mixer 50 is a general handling place for dangerous goods, and in principle, it is necessary to provide a holding space of 3 to 5 m around this general handling place. 65, the safety is ensured, and the provision of possessed vacant land is reduced. However, this exemption is excluded when handling special flammables in the gantry 16 and the mixer 50. Therefore, when pentane, which is a special flammable, is used as a blowing agent, the above-mentioned exemption measures cannot be taken. If the entire insulated panel manufacturing equipment is made a general handling place, exemption measures can be taken, but in that case, all internal electrical equipment must be explosion-proof and some are technically impossible.

Therefore, the partition 65 is provided as described above to separate the premixing portion 42 from the other portions, and the foaming agent and the polyisocyanate are preliminarily mixed in the premixing portion 42 to prepare a premix. Thereafter, the pre-mix is supplied to the mixer 50. By mixing the blowing agent and the polyisocyanate in this way,
By raising the boiling point of the pre-mixture (pentane), it can be converted into first petroleum, and the firefighting panel can be safely manufactured by clearing the standards of the Fire Service Law without making the entire heat insulation panel production equipment a general handling place. Is what you can do.

Then, the manufacturing of the heat insulating panel is performed as follows. First, a pre-mixture, a polyol and other raw materials are mixed in a mixing tank 51 of a mixer 50 to prepare a polyisocyanate mixture 1, and stored in the mixing tank 51 while heating to a predetermined temperature (18 to 40 ° C). The pre-mix is prepared by the pre-mixer 54 of the pre-mixing unit 42 and is supplied from the pre-mixer 54 to the mixing tank 51 of the mixer 50 through the pre-mix pipe 54. In addition, the polyol and other raw materials mixed therein are supplied from the polyol tank 53c of the pre-mixing section 42 to the mixing tank 5 of the mixer 50 through the polyol pipe 61.
1 is supplied.

The pre-mix can be prepared by mixing pentane and polyisocyanate. That is, the foaming agent is supplied from the foaming agent tank 53 a to the intermediate tank 56 through the foaming agent pipe 55 by the operation of the pump 57, and the foaming agent is supplied from the intermediate tank 56 to the premixer 54 through the foaming agent pipe 55. By supplying the polyisocyanate from the isocyanate tank 53b to the premixer 54 through the isocyanate pipe 58, and mixing the polyisocyanate and the foaming agent with the premixer 54, a premix can be prepared. The pre-mixture is supplied from the pre-mixer 54 to the mixing tank 5 of the mixer 50 through the pre-mixture pipe 60.
1 and mixed with a polyol or the like as described above to prepare a polyisocyanate mixture 1.

On the other hand, as described above, the surface material forming section 40
The pair of upper and lower surface materials 2, 2 formed in the step (1) are introduced into the filling portion 41, and are first heated in the preheater 15. next,
The heated surface materials 2 and 2 are introduced to the lower side of the gantry 16, where the polyisocyanate mixture 1 prepared by the mixer 50 is sprayed from the spray nozzle 25 provided in the gantry 16 as shown in FIG. It is supplied by being injected between the materials 2 and 2. Thereafter, with the polyisocyanate mixture 1 interposed therebetween, the surface materials 2 and 2 are connected to the upper and lower conveyors 17.
a and 17b, and continuously heated to 40 to 50 ° C. by the heating device 8 via the double conveyor 17. Here, the polyisocyanate and the polyol in the polyisocyanate mixture 1 react in the presence of a trimerization catalyst, and are foamed and cured by a foaming agent, thereby forming a polyisocyanurate foam between the surface materials 2 and 2. The heat insulating material 4 is formed by bonding to the surface of the surface material 2,
The heat insulating panel original plate 7 in which the heat insulating material 4 is filled between the surface materials 2 and 2 is continuously formed.

The filling section 41 includes a double conveyor 17.
Seal conveyor (not shown) that operates in synchronism with
The side materials 2, 2 introduced into the double conveyor 17 are adjusted in the width direction by the side seal conveyor. The side seal conveyor supplies a band-shaped seal packing 31 to the female fitting portion 30 of the surface material 2 and a moisture-proof paper strip (not shown) to the male fitting portion 32 continuously. It is like
The seal packing 31 and the moisture-proof paper band prevent the polyisocyanate mixture 1 during foaming and hardening from flowing out between the upper and lower surface materials 2 and 2.

Thereafter, the heat insulating panel original plate 7 is
Will be introduced. Here, the heat insulating panel original plate 7 is a width thickness meter 1
The dimensions are measured by 9 and cut into predetermined dimensions by the running cutter 20 controlled by the process computer, thereby forming the heat insulating panel A as shown in FIG. After that, the heat insulation panel A is rejected
The length and the number of packs are controlled by an automatic loading device such as a stacker 2 and a piler 24 to stack the sheets.
The line speed (speed at which the surface material 2 is fed) of the above-described manufacturing apparatus is preferably set to 5.0 to 15.0 m / min. Further, by performing the heat insulating panel A thus formed, the male fitting portion 32 and the female fitting portion 30 are fitted as shown in FIG. 4B. Further, in the above, the heat insulating material 4 of the polyisocyanurate foam was used by filling it between the two surface materials 2 and 2. However, the present invention is not limited to this.
The sizing material may be formed by forming the heat insulating material 4 as a backing material on one surface material 2 (one surface of the surface material 2).

[0063]

The present invention will be described below in detail with reference to examples.

(Examples 1 to 3 and Comparative Examples 1 to 3) A heat insulating panel A was manufactured using the manufacturing apparatus shown in FIGS. The polyisocyanate mixture 1 was prepared by mixing a polyisocyanate, a polyol, a foaming agent, a trimerization catalyst, a foam stabilizer, and a flame retardant in predetermined amounts (units by mass) shown in the table. The surface material 2 was formed from a double-sided colored zinc iron plate having a thickness of 0.5 mm. The line speed was 8 m / min. The temperature of the surface material 2 at the time of filling the polyisocyanate mixture 1 was 40 to 50 ° C.
Was set to 50 kg / m ³ . And the thickness is 35
A long heat insulating panel A having a width of 910 mm and a width of 910 mm was manufactured.

The continuous heat-insulating panel A was cut into a sample of 100 × 100 × 35 mm to obtain a sample, which had a compressive strength of 10%, an adhesive strength with a surface material, brittleness and dimensional stability. Properties, cutting properties at low temperature (10 ° C.), and outdoor exposure test (6 months).

(1) Free foaming density: Free foaming in a wooden frame of 200 mm square, and after one day, 100
It was cut into mm squares and the density was calculated.

(2) The 10% compressive strength is in accordance with JIS A9
514.

(3) The adhesive strength is JIS K 6848
The adhesive strength between the heat insulating material 4 and the surface material 2 was measured according to the standard.

(4) The dimensional stability was measured by measuring the dimensional change of the heat insulating panel A when the heat insulating panel A was held at a high temperature (80 ° C.) or a low temperature (−20 ° C.) for 3 hours.

Table 1 shows the measurement results of (1) to (4).
Shown in

The following materials were used as raw materials for the polyisocyanate mixture 1. Polyisocyanate:
"MR-200" (trade name) (Crude MDI manufactured by Nippon Polyurethane Industry Co., Ltd.) Polyol A: phthalic anhydride-based polyester polyol (OHV = 260, viscosity 6000 mPa.s at 25 ° C.) Polyol B: phthalic anhydride-based polyester polyol (OHV) = 250, viscosity 4000 mPa.s 25 ° C) Polyol C: phthalic anhydride polyester polyol (OHV = 315, viscosity 2600 mPa.s 25 ° C) Polyol D: shoe-closed polyether polyol (OHV = 400, viscosity 12000 mPa.s25)
Polyol E: phthalic anhydride-based polyester polyol (OHV = 205, viscosity 1500 mPa.s 25 ° C.) Polyol F: phthalic anhydride-based polyester polyol (OHV = 185, viscosity 1100 mPa.s 25 ° C.) Trimerization catalyst: “DABCO TMR” (Trade name) (manufactured by Air Products and having the structural formula of formula (V-1)) Trimerization catalyst: "DABCO K-15" (trade name) (potassium 2-ethylhexanoate manufactured by Air Products) Trimerization catalyst: "Polycat 46" (trade name) (a solution of potassium acetate in ethylene glycol manufactured by Air Products) Trimerization catalyst: "Kaolyzer No. 1" (trade name) (tetramethylhexanediamine manufactured by Kao Corporation) Blowing agent : N-pentane manufactured by Maruzen Yuka Blowing agent: Freon Blowing agent: Water Flame retardant: "TMC P "(trade name) (Tris (beta-chloropropyl) phosphate manufactured by Daihachi Chemical Co., Ltd.) Foam stabilizer:" SH-193 "(trade name) (dimethylsiloxane-polyether manufactured by Dow Corning Toray Silicone Co., Ltd.) Block copolymer)

[0072]

[Table 1]

As is evident from Table 1, the performance of Examples 1 to 3 is higher than those of Comparative Examples 1 and 2 using only water as the blowing agent, and is equal to or higher than Comparative Example 3 using CFC as the blowing agent. Could be formed.

[0074]

As described above, according to the first aspect of the present invention, a polyisocyanate mixture is prepared by blending a polyisocyanate, a polyol, a trimerization catalyst for isocyanate, and pentane as a blowing agent. Since a heat insulating material is formed by supplying and foaming a polyisocyanate mixture to the above, by using pentane as a foaming agent, it is possible to avoid using CFCs and water and prevent environmental destruction. In addition, the strength of the heat insulating material is high and not brittle so that no urea bond is generated, and the surface material and the heat insulating material can be firmly bonded.

Further, according to the invention of claim 2 of the present invention, since pentane is n-pentane, the unreacted portion of the polyisocyanate and the polyol can be reduced, and the polyisocyanate and the polyol can be formed after the heat insulating panel is formed. The unreacted portion does not react, so that the heat insulating material does not swell.

In the invention according to claim 3 of the present invention, the polyisocyanate and pentane are mixed and then mixed with the polyol, so that this mixture containing pentane can be treated as the first petroleum, It does not require the entire line to be a general handling office and does not require the establishment of possessed vacant lots, and can meet the standards of the Fire Service Law. Moreover, after mixing pentane and polyol first,
Rather than mixing with polyisocyanate, polyisocyanate, pentane and polyol can be more uniformly mixed, and the occurrence of voids due to foaming agent bumping during foaming of the polyisocyanate mixture can be prevented.

[Brief description of the drawings]

FIG. 1 is a schematic view showing an example of an apparatus used in the present invention.

FIG. 2 is a perspective view showing a part of the above device.

FIG. 3 is a plan view showing another part of the above device.

FIG. 4A is a side view showing the heat insulating panel of the above.
(B) is a side view which shows the joining state of the heat insulation panel.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Polyisocyanate mixture 2 Surface material 4 Heat insulation material A Heat insulation panel

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme court ゛ (Reference) B29K 105: 04 B29K 105: 04 B29L 9:00 B29L 9:00 31:00 31:00 (72) Inventor Koichi Shibata 3-2-1, Minase, Shinsemachi, Amagasaki, Hyogo Prefecture Inside Daido Steel Sheet Co., Ltd. (72) Inventor Hajime Nonomura 196 BSF Finoac Polyurethane Co., Ltd. Person Ryo Kojima 1-196, Motomiya-do, Shinjo-shi, Aichi Pref. F-term (reference) in BESF INOAC Polyurethane Co., Ltd. 2E001 DD01 GA12 GA42 HD01 JD02 4F074 AA78 AA85 BA35 DA08 DA20 DA32 4F204 AA42 AB02 AB05 AB20 AD03 AD08 AD08 AG03 AG20 AH47 AH48 EA01 EA04 EB02 EB13 EF02 EK04 4J034 CA04 CC03 DA01 DB03 DB04 DC02 DC12 DC14 DC50 DF01 DF14 DG01 DG02 DG08 DG09 DG23 HA01 HA02 HA06 HA07 HC03 HC12 HC13 HC64 HC71 JA01 KA01 KB03 KE02 NA06 QB16 QC01 QD03 RA05 RA19

Claims (3)

[Claims] 1. A polyisocyanate mixture is prepared by blending a polyisocyanate, a polyol, a trimerization catalyst of isocyanate, and pentane as a foaming agent, and a polyisocyanate mixture is supplied to a surface material to foam the insulating material. A method for manufacturing a heat-insulating panel, characterized by being formed. 2. The method according to claim 1, wherein the pentane is n-pentane. 3. The method for producing a heat insulating panel according to claim 1, wherein the polyisocyanate and pentane are mixed and then mixed with a polyol.