KR20100074376A - Polyisocianurate foams using polyether-ester hybrid polyol - Google Patents

Abstract

PURPOSE: A polyisocyanurate form is provided to have superior heat resistance, flame-retardant property, drug resistance, soundproof property, and workability and to be used as a raw material for a constructional insulator. CONSTITUTION: Polyisocyanurate foams are manufactured by foaming a mixture of 100.0 parts by weight of polyol having polyether-ester hybrid polyol as a main component and 100-200 parts by weight of polyisocyanurate. The polyol has an average OH value is 150-300 and NCO% of the polyisocyanurate is 29-32. The number of functional groups of the polyisocyanurate is 2.5-3.0. The polyisocyanurate is polymeric MDI.

Description

Polyisocyanurate foam using polyether-ester hybrid polyol {POLYISOCIANURATE FOAMS USING POLYETHER-ESTER HYBRID POLYOL}

The present invention relates to a polyisocyanurate foam and a building panel using the same. More particularly, the present invention relates to a polyisocyanurate foam and a thermosetting plastic foam (foam) in which a poly (ether-ester) polyol having a chemically stable property is foamed. The present invention relates to a polyisocyanurate foam having excellent low smokeability and a polyisocyanurate foam thereof as an intermediate material of a building panel, and to an adhesive panel having excellent dimensional stability while increasing adhesive strength on the upper and lower surfaces thereof.

The present invention relates to a flame retardant insulation panel used as a material for insulation construction of various buildings, including refrigerated warehouses, industrial buildings, insulated houses, container boxes and ship interiors.

Polyisocyanurate foams used as internal insulation are generally prepared by reacting a polyol component with an isocyanate component in the presence of a blowing agent, catalyst, foam stabilizer and other additives. Conventionally, there has been a heat insulating material filled with a flame retardant formed of a modified polyisocyanurate foam between a surface material formed of a metal plate or the like, which generally has a high crosslinking density, but a heat insulating material made of a polyisocyanurate foam has a problem of being broken.

Japanese Patent Publication No. 46-4591 discloses a method for producing a modified polyisocyanurate foam in which an organic polyisocyanate and a polyol are used as a heat insulating material using a trimerization catalyst and a carbodiimide catalyst in the presence of a blowing agent. Known.

Korean Patent No. 278,365 discloses a technique for a polyisocyanurate foam in which a polyol obtained by adding propylene oxide and ethylene oxide to polymeric MDI and terephthalic acid and a heat insulating material using the same are disclosed.

US 5164422 describes the use of isocyanate prepolymers with CFC-11 as blowing agent to improve the thermal insulation of foams.

EP 320134 describes the use of isocyanate prepolymers with R-11 as blowing agent to improve the compatibility of component A and component B.

Likewise, US 5254600 shows improved processability as a result of the use of isocyanate prepolymers.

Improved thermal conductivity of rigid foams as a result of the use of isocyanate prepolymers is given in EP 394736. JP 2000-264945 describes sandwich surfaces of good surfaces produced using isocyanate prepolymers.

WO 240566 describes the use of isocyanate prepolymers to improve flame retardancy and the mechanics of rigid polyurethane and polyisocyanurate foams.

However, this is only a method for overcoming the poor adhesion of the polyisocyanurate foam and the low miscibility of the ether polyol and the ester polyol, which is a disadvantage of the polyol system. There can be.

It is an object of the present invention to provide a novel isocyanurate foam with improved flame retardancy, heat resistance, heat insulation, chemical resistance and processability.

Another object of the present invention is to provide a method for producing a novel isocyanurate foam having improved flame retardancy, heat resistance, heat insulation, chemical resistance, and processability.

Still another object of the present invention is to provide a heat insulation panel made of a novel isocyanurate foam having improved flame retardancy, heat resistance, heat insulation, chemical resistance, and processability.

Another object of the present invention has been made in view of the above-described prior art, and maximizes the miscibility of ether polyols and ester polyols in a polyol system to promote overall system stability and thus reaction with polymeric MDI as a curing agent. The purpose of the present invention is to provide polyisocyanurate foam panel for building, which has increased the miscibility and maximizes product stability by increasing foam property and adhesion with steel plate, and thus improves flame retardancy, heat resistance, heat resistance, chemical resistance and processability.

In order to achieve the above object, the polyisocyanurate foam of the present invention is produced by mixing and foaming 100 parts by weight of a polyol having a polyether-ester mixed polyol as a main component and 100 to 200 parts by weight of a polyisocyanate.

In the present invention, the polyether-ester hybrid polyol is for increasing the miscibility of the polyol system for the purpose of improving the miscibility of the polyisocyanurate foam, and the dicarboxylic acid component and the polyvalent poly (alkylene oxide) Prepared by condensation of polyols. In one embodiment of the invention, the condensation process may optionally include a diol component or a polyfunctional compound in addition to the dicarboxylic acid component and the poly (alkylene oxide) component.

In a preferred embodiment of the present invention, the polyether-ester hybrid polyol is 5 to 40% by weight of the dicarboxylic acid component, 60 to 95% by weight of the poly (alkylene oxide) polyol in order to increase adhesion and miscibility. It is good to be included. When the dicarboxylic acid component is less than 10% by weight, there is a problem that the adhesive strength is lowered, and when the dicarboxylic acid component is more than 30% by weight, there is a problem of poor compatibility, and because of the cost burden, it is preferably 10 to 30% by weight, such as For this reason, it is preferable that the component of a poly (alkylene oxide) polyol is also 60 to 95 weight%. More preferably, the dicarboxylic acid component is 10 to 30% by weight, and the component of the poly (alkylene oxide) polyol is preferably 70 to 90% by weight.

In the present invention, as the dicarboxylic acid component, for example, phthalic acid, naphthalene carboxylic acid, sodium dicarboxylic benzene sulfonic acid, adipic acid, suberic acid, sebacic acid, aliphatic cyclo 1,1 carboxyl Acids, or mixtures thereof, and the like, and examples of the polyvalent poly (alkylene oxide) polyol include alkylene oxide, for example, ethylene oxide, propylene oxide, styrene oxide, butylene oxide, epichlorohydrin, and the like. have.

In the present invention, the diol component is ethylene glycol, 1,2-propylene glycol, triethylene glycol, butanediol, neopentylene glycol, 1,4-cyclohexanediol, 1,4-cyclohexanedimentanol, di Ethylene glycol, 1,5-pentanediol, polyethylene glycol, and the like. In the practice of the present invention, the diol component is preferably included in 10% by weight or less in the hybrid polyol.

In the present invention, as the multifunctional compound, for example, trimethylolpropane, triglycidyl ether, trimethylolpropane, diglycidyl ether, glycerol diglycidyl ether, glycerol triglycidyl ether, sorbitol diglycol Sorbitol polyglycidyl ethers such as cylyl ether, triglycidyl ether, tetraglycidyl ether, triepoxypropyl isocyanurate, neopentylglycol diglycidyl ether, ethylene glycol diglycidyl ether, polyethylene And compounds containing glycidyl ether terminals such as glycol diglycidyl ether and the like.

In the present invention, as the catalyst used in the preparation of the polyether-ester hybrid polyol, tetraalkyl titanate may be used or mixed with magnesium or calcium acetate. In addition, an alcohol compound of an alkali earth metal and an ester compound of titanate may be used. A titanate complex such as Mg [HTi (OR) 5] 2 produced from an inorganic titanate compound such as titanium titanate, a mixture of calcium acetate and antimonytrioxide, lithium or magnesium acetate, an organotin compound, or Mixtures of organotin compounds and organotitanium compounds also exhibit excellent performance as polymerization catalysts.

In the present invention, the polyether-ester hybrid polyol may impart chemical crosslinking to improve heat resistance and mechanical properties.

In one embodiment of the invention, a trifunctional or higher poly (alkylene oxide) polyol can be obtained by an ester reaction or a polycondensation reaction with a bifunctional acid. Therefore, in the present invention, a polyfunctional poly (alkylene oxide) polyol is prepared by an addition polymerization reaction of an alkylene oxide and an organic compound having two or more active structures. In this case, as an initial material having two or more active hydrogen atoms, For example, propylene glycol, glycerin, pentaerythritol, ethylenediamine, sorbitol, and the like, and alkylene oxides include, for example, ethylene oxide, propylene oxide, styrene oxide, butylene oxide and epichlorohydrin.

In another embodiment of the present invention, since there is no chemical crosslinking point when a bifunctional ether and a bifunctional ester are used, a multi-tube having three or more functional groups capable of reacting with ester-forming functional groups in the transesterification and polycondensation reactions. By adding the functional mixture, chemical crosslinking of the poly (ether-ester) polyol can be induced to improve not only heat resistance but also mechanical properties of the final polymer.

Therefore, in the present invention, as a multifunctional compound, trimethylolpropane, triglycidyl ether, trimethylolpropane, diglycidyl ether, glycerol diglycidyl ether, glycerol triglycidyl ether, sorbitol diglycidyl ether, triglycidyl Sorbitol polyglycidyl ether such as ether, tetraglycidyl ether, triepoxypropyl isocyanurate, neopentyl glycol diglycidyl ether, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, etc. By using a compound containing a glycidyl ether terminal such as, it is possible to induce chemical crosslinking in the polymer to achieve the object of the present invention. The polyfunctional compound including glycidyl ether terminal is not only excellent in reactivity with carboxyl terminal than hydroxyl terminal, but also advantageous in terms of physical properties of the final polymer.

The polyfunctional compound as described above, which can induce a chemical bond to the polyether-ester hybrid polyol, is added in an amount of 0.1 to 5.0% by weight based on the acid component of the polyether-ester hybrid polyol. Improved polyurethane foams can be produced. In this case, when the polyfunctional compound is added in an amount of 0.1 wt% or less, it is impossible to prepare a polyisocyanurate foam in which desired heat resistance and mechanical properties are improved, and in the case of adding and using 5.0 wt% or more of poly (ether- Ester) As the viscosity of the polyol rises sharply, it is not preferable because the workability is very bad and the mechanical properties are lowered.

On the other hand, the polymerization of the polyether-ester hybrid polyol according to the present invention is prepared by using a conventional method of reacting by simultaneously adding a polymerization component, a catalyst, and a reaction aid including the multifunctional compound, and having excellent elastic performance. Ester mixed polyols can be prepared.

In the present invention, the polyol contains the polyether-ester hybrid polyol as a main component, preferably 50% by weight or more, more preferably 60% by weight or more, and most preferably the polyether-ester hybrid polyol. Contains at least 80% by weight.

In the present invention, the polyol is a variety of known polyols, such as polyether polyol, polyester polyol, or mixtures thereof in order to supplement the dimensional stability, flame retardancy, or viscosity performance of the polyisocyanurate foam Polyols.

In the practice of the present invention, the polyetherpolyol may be prepared in a conventional manner to add alkylene oxides such as ethylene oxide or propyline oxide to the polyol, preferably obtained by adding propylene oxide to sorbitol or Ether polyols obtained by adding propylene oxide and ethylene oxide to the loose can be used, and commercially available from polyol manufacturers, for example, PPG-482 grade of Kumho Petrochemical.

In the practice of the present invention, the polyester polyol may be prepared in a conventional manner by adding diethylene glycol or propylene glycol to phthalic anhydride, and may be purchased commercially. Preferably, it is AK-3001 grade of Aekyung Chemical.

In a preferred embodiment of the invention, the polyol is a polyol comprising 5-50 parts by weight of polyol selected from 50-95% by weight of polyether-ester mixed polyol, polyetherpolyol, polyesterpolyol, or mixtures thereof, and Preferably it is a mixture of 80 weight part of polyether ester interpolyols and 20 weight part of polyether polyols.

In one embodiment of the present invention, the polyol is 5-30% by weight of an ether polyol obtained by adding propylene oxide to sorbitol, 0-30% by weight of an ether polyol obtained by adding propylene oxide and ethylene oxide to sucrose, and phthalic anhydride. Mixed polyol composition containing 10 to 45 weight% of ester polyol obtained by adding diethylene glycol and propylene glycol to 50 to 85 weight% of linear or branched, non-crosslinked polyfunctional polyether-ester mixed polyol having ester end groups Can be.

In the present invention, in order to maintain the mechanical strength of the product of the polyol and the dimensional stability at low temperature, it is preferable to use a polyol having an average OH value of 150 to 300. If the average OH value of the polyol composition is 150 or less, the mechanical strength and low-temperature dimensional stability of the product is inferior, and if the average OH value exceeds 300, the flame retardancy and heat insulation are lowered, resulting in a failure of the product and productivity is lowered.

In the present invention, the polyisocyanate may be of any form such as aliphatic, aromatic, and mixtures thereof, but preferably includes urethane.

In more detail, the aliphatic polyisocyanate includes hexamethylene diisocyanate, dimethyl diisocyanate, isophorone diisocyanate, methylene biscyclohexyl isocyanate, methyl isocyanate, and the like, and the aromatic polyisocyanate is 2,4-toluene diisocyanate, 2 Diisocyanates such as, 6-toluene diisocyanate and methylene diphenyl diisocyanate, and aromatic isocyanates such as 4,4 ', 4-triphenylmethane triisocyanate and 2,4,6-tolylene triisocyanate. Preferably it is polymeric MDI.

In the present invention, the polyisocyanate component to be reacted with the polyol composition is a polymeric MDI having 2 or more functional groups and preferably 2.5 to 3.0. If the average number of functional groups of the isocyanate component is 2.5 or less, the dimensional stability is poor at the time of forming the polyisocyanurate foam, and if the number of the functional groups is 3.0 or more, the viscosity is greatly increased and fluidity is inferior. Therefore, the average number of functional groups of the isocyanate component is preferably 2.5 to 3.0 for producing a stable polyisocyanurate foam.

In the present invention, the isocyanate component preferably has an average NCO% of 29 to 32%. At this time, fluidity | liquidity falls that the average NCO% of the said isocyanate component is 29% or less, and low temperature dimensional stability falls when it is 32% or more. Therefore, the average NCO% of the isocyanate component is preferably 29 to 32 for producing a stable polyisocyanurate foam.

The reaction ratio of the polyisocyanate component and the polyol component should have an equivalent ratio of polyisocyanate and polyol of 1: 2.0 to 1: 4.0. The equivalent ratio of 1: 2.0 means that the NCO of the polymeric MDI is 200% of the OH component in the polyol system.As the average NCO% is lower, the adhesion and the compressive strength increase to a certain range, but the polyisocyanurate foam is unique. The flame retardancy of the resin is reduced, and the higher the average NCO%, the higher the polyisocyanurate synthesis, the more the foam is brittle, the low temperature dimensional stability is lowered, and the adhesive strength with the iron plate is reduced. It is preferable to adjust to 1: 4.0.

In the present invention, the polyol is mixed with a catalyst, foam stabilizer, flame retardant or other additives, for example, a nucleating agent or a surfactant to form a resin solution, blended with a polyisocyanate component, foamed with a foaming agent, and adhesive performance and flame retardancy It is made from this excellent polyisocyanurate foam.

In the present invention, the resin stock solution may include a flame retardant for the flame retardancy of the final product. The flame retardant may be a non-halogen type, a halogen type, a mineral type, or the like. Preferably, a phosphorus flame retardant, a bromine flame retardant, or a mixture thereof is suitable. In particular, it is preferable to use phosphorus-based flame retardants because phosphorus-based flame retardants containing phosphorus compounds are less harmful to the human body, have excellent environmental friendliness and have high flame retardant efficiency.

In the case of the polyisocyanurate foam, the phosphorus-based flame retardant functions to prevent the conversion of the combustible material into a gas in a combustible state because the phosphorus compound increases the carbonization yield.

Inorganic phosphorus flame retardants include tricresyl phosphate, ammonium phosphate, ammonium poly phosphate, and the like, and organophosphorous flame retardants include melamine phosphate, dimelamine phosphate, triethylene phosphate, and the like, and halogen phosphate includes bromine phosphate. In comparison to other flame retardants, phosphorus-based flame retardants are generally known to be harmless or exhibit only slight toxicity.

The brominated based flame retardants include tribromer neopentyl alcohol, dibromer neopentyl glycol, decabromer diphenyloxide, penta bromer diphenyl oxide, and the like, and liquid brominated is particularly preferable. Do.

As for the flame retardant total amount used for this invention, 1-40 weight part is preferable with respect to 100 weight part of polyol components, More preferably, it is 5-25 weight part. If the amount is less than 1 part by weight, the flame retardant effect of the addition of the flame retardant is insignificant. If it is more than 40 parts by weight, the flame retardant effect of the flame retardant is not observed. Deformation, flowability, processability, and the like have a problem of deterioration. Therefore, it is preferable that it is 5-40 weight part of phosphorus flame retardants, a bromine flame retardant, or the mixture of a phosphorus flame retardant and a bromine flame retardant with respect to 100 weight part of polyol and polyisocyanate mixtures.

In addition, the reaction catalyst used in the present invention is a typical catalyst that can be used to obtain a polyisocyanurate foam, for example triethylamine, tripropylamine, triisopropanolamine, tributylamine, trioctylamine, hexadecyl Dimethylamine, N-methylmorpholine, N-ethylmorpholine, N-octadecylmorpholine, monoethanolamine, diethanolamine, dimethylethanolamine, triethanolamine, N-methyldiethanolamine, N, N-dimethylethanol Amine, diethylenetriamine, N, N, N ', N'-tetramethylbutanediamine, N, N, N', N'-tetramethyl-1.3-butanediamine, N, N, N ', N'- Tetraethylhexamethylenediamine, bis [2- (N, N-dimethylamino) ethyl] ether, N, N-dimethylbenzylamine, N, N-dimethylcyclohexylamine, N, N, N ', N', N Pentamethyldiethylenetriamine, triethylenediamine, formic acid and other salts of triethylenediamine, amino groups and oxyalkylene adducts of the first and second amines, N Amine-type urethanization catalysts, such as azacyclic compounds, such as N-dialkyl piperazine, and the beta aminocarbonyl catalyst of various N, N ', N "-trialkylaminoalkylhexahydrotriazines.

In particular, the isocyanate trimerization catalyst used in the present invention is a hydroxy alkyl ammonium compound, 1,3,5-tris (N, N-dimethylaminopropyl) -S-triazine, 2,4,6-tris (dimethyl amino Amines such as methyl) phenol, and aliphatic monocarboxylic acid alkali metal salts.

Tertiary amine catalysts include dimethylcyclohexylamine (DMCHA), dimethylethanol amine (DMEA), pentamethyldiethylenetriamine (PMDETA), tetramethylhexamethylenediamine (TMHMDA), and the like.

The catalyst controls the trimer primary and secondary reactions and affects the productivity, processability, and polyisocyanurate conversion of the polyisocyanurate, in particular by mixing the trimerization catalyst with the tertiary amine catalyst. It is desirable to.

These catalysts are used individually or in mixture, The usage-amount is preferable 0.5-10 weight part with respect to 100 weight part of polyol components, More preferably, it is 1-5 weight part. When the total weight of the tertiary amine catalyst, trimerization catalyst or mixture of tertiary amine catalyst and trimerization catalyst is less than 0.5 parts by weight, there is a problem that the rate of the trimerization reaction is slowed. Accelerated effect of the reaction rate is not seen, and because of the cost burden problem is preferably 0.5 to 10 parts by weight.

As the foam stabilizer, a polyalkylene glycol silicone copolymer is used as the organic silicone compound generally used in polyurethane foam production. The amount of foam stabilizer to be used is preferably 0.5 to 5.0 parts by weight, more preferably 1.5 to 3.0 parts by weight based on 100 parts by weight of the polyol component.

The blowing agent includes trichloromonofluoromethane or dichloromonofluoroethane, which is a fluorocarbon blowing agent. The blowing agent affects the density and the density should be more than 35kg / m3 according to KMS 3809. The total amount of the blowing agent to be used is preferably 5 to 50 parts by weight, more preferably 5 to 40 parts by weight based on 100 parts by weight of the polyol component. When it is 5 parts by weight or less with respect to 100 parts by weight, there is a problem that foaming is difficult, and when it is 40 parts by weight or more, there is a problem that adversely affect the physical properties of the foam, such as thickness strain, compressive strength, 5 to 50 parts by weight desirable.

In addition, a nucleating agent may be used to make the size of the cell fine for the purpose of improving the thermal insulation of the polyisocyanurate foam of the present invention. Nucleating agents used in the present invention include perfluorocarbons, titanium oxide, titanium oxide compounds, carbon black and the like. When using a nucleating agent, the usage-amount is 0-10 weight part with respect to 100 weight part of polyol components, More preferably, it is 0-5 weight part. Here, that the amount of nucleating agent is 0 parts by weight with respect to 100 parts by weight of the polyol component indicates that the nucleating agent is not used.

In one aspect, the polyisocyanurate foam obtained by the present invention has a density of 30-50 kg / m 3, a thermal conductivity of 0.0180 kcal / m · hr · ° C. or less, an independent bubble ratio of 90% or more, and low temperature dimensional stability at −40 ° C. -0.1%, room temperature adhesive strength of more than 5kg / ㎠ shows excellent mechanical properties.

The inner plate and the outer plate of the present invention include a zinc iron plate, aluminum plate, colored zinc iron plate, color aluminum zinc alloy plated steel sheet, stainless steel plate, titanium steel plate and the like. The thickness of the steel sheet will be readily determined by one skilled in the art and will vary depending on the use of the panel, but is preferably 0.5 mm.

Hereinafter, the present invention will be described in more detail based on the following examples. However, the following examples are only intended to illustrate specific embodiments, and the scope of the present invention is not limited by the examples, and therefore should not be construed as limiting the protection scope.

"Part" and "%" are by weight unless there is particular notice in an Example and a comparative example below.

As described above, the polyisocyanurate foam building panel using the polyether-ester hybrid polyol of the present invention uses polyisocyanurate foam as its inner heat insulating material, so that the strength of the inner heat insulating material is high so that it is not deformed or deteriorated by external impact. Not only that, but also excellent in flame retardancy and heat resistance. Therefore, it is possible to extinguish the fire at the early stage by preventing the combustion of the building and the rapid progress of the fire in case of fire, and there is less harmful to the human body, and it has excellent environment-friendly effect, so it is excellent for buildings such as multi-use facilities and apartment houses. It is a flame retardant insulation panel.

In addition, the polyisocyanurate foam, which is an internal insulation of the flame retardant insulation panel of the present invention, can be continuously produced within 2% of a thickness strain, and a decrease in adhesive strength is excellent by as much as 15% compared to a conventional polyurethane foam.

The average OH value is 450 to 550, and the condensation of 20 parts by weight of a polyol having propylene oxide added to sorbitol having a molecular weight of 700, adipic acid, phthalic anhydride and an ether polyol having propylene oxide added to propylene glycol results in an average OH value of 200 1 part by weight of water as a blowing agent, 30 parts by weight of trichloromonofluoromethane, 3 parts by weight of ammonium salt as a trimerization catalyst, in 100 parts by weight of a mixed polyol component comprising 80% by weight of a polyether-ester mixed polyol having a molecular weight of 700 and 1 part by weight of tertiary amine catalyst, 20 parts by weight of tricresyl phosphate as phosphorus flame retardant, and 10 parts by weight of tribromer neopentyl alcohol as bromine-based flame retardant, wherein the average MCO% is 31% and the functional group number is 2.7. 150 parts by weight of Mitsui's M-200) is discharged to the bottom surface of the panel in the molding facility, and foamed to the top surface of the present invention while Riyi isocyanurate foam was created, the foam was prepared in an internal density 45kg / ㎥ is compression molded around a stainless steel plate with a thickness of 0.5㎜, the back plate is polyisocyanurate sandwich panels having a thickness in 50㎜ configuration.

[Example 2]

10 weight percent polyol with propylene oxide added to sucrose with an average OH value of 350 to 450, molecular weight 700, 10 weight polyol with propylene oxide added to a sorbitol having an average OH value of 350 to 450 and molecular weight of 600 %, 60% by weight of a polyether-ester mixed polyol prepared by condensing an ether polyol having propylene oxide added to phthalic anhydride and propylene glycol with an average OH value of 250 and a molecular weight of 1000, anhydrous having an average OH value of 250 to 350 100 parts by weight of a mixed polyol component consisting of 20% by weight of polyol prepared by condensing diethylene glycol on phthalic acid, 1 part by weight of water as a blowing agent, 30 parts by weight of trichloromonofluoromethane, 3 parts by weight of ammonium salt as a trimerization catalyst and tertiary amine 1 part by weight of catalyst, 15 parts by weight of tricresyl phosphate as a phosphorus-based flame retardant, with an average NCO% of 31% and a functional number of 2.7 MDI (Kumho Mitsui) Using the M-200) 200 parts by weight of the discharging to the panel bottom surface in the molding facility, the foam is filled up to the top surface to form a polyisocyanurate foam of the present invention, the foam is compressed to an internal density of 45kg / ㎥ 50 mm thick polyisocyanurate sandwich panel was formed by forming a front and rear plate of a 0.5 mm thick stainless steel sheet.

Example 3

5 weight% polyol with propylene oxide added to sucrose with an average OH value of 350 to 450, molecular weight 500, 15 weight polyol with propylene oxide added to sorbitol having an average OH value of 450 to 550 and a molecular weight of 700 %, 70% by weight of a polyether-ester mixed polyol prepared by condensing an ether polyol having propylene oxide added to phthalic anhydride and propylene glycol with an average OH value of 250 and a molecular weight of 1000, and an average OH value of 250 to 350 100 parts by weight of a mixed polyol component consisting of 10% by weight of a polyol prepared by condensing diethylene glycol with phthalic acid and benzoic acid, 1 part by weight of water as a blowing agent, 30 parts by weight of trichloromonofluoromethane, 3 parts by weight of ammonium salt as a trimerization catalyst, and 1 part by weight of tertiary amine catalyst, 20 parts by weight of tricresyl phosphate as a phosphorus-based flame retardant, with an average NCO% of 31% and a functional group of 2.7 By using the 250 parts by weight of Tsui M-200) discharged to the lower surface of the panel in the molding facility, the polyisocyanurate foam of the present invention was produced while being filled and foamed to the upper surface, the foam is an internal density of 45kg / ㎥ The polyisocyanurate sandwich panel having a thickness of 50 mm in which the front and back plates were made of a stainless steel plate having a thickness of 0.5 mm was formed by compression molding.

Comparative Example 1

30 weight% of polyol with propylene oxide added to sucrose with an average OH value of 350 to 450, molecular weight 700, 10 weight of polyol with propylene oxide added to sorbitol with an average OH value of 450 to 550 %, 50% by weight of polyol prepared by condensing diethylene glycol and dipropylene glycol in adipic acid and terephthalic acid having an average OH value of 250 to 350, and diethylene glycol in phthalic anhydride having an average OH value of 250 to 350 100 parts by weight of a mixed polyol component consisting of 10% by weight of polyol condensed, 1 part by weight of water as a blowing agent, 30 parts by weight of trichloromonofluoromethane, 3 parts by weight of ammonium salt as a trimerization catalyst and 1 part by weight of tertiary amine catalyst, phosphorus-based As the flame retardant, 20 parts by weight of tricresyl phosphate, 31% of average NCO%, and 250 parts by weight of polymeric MDI (M-200 from Kumho Mitsui Co., Ltd.) having a functional number of 2.7 The polyisocyanurate foam of the present invention was produced while being discharged to the bottom surface of the board and foamed up to the top surface, and the foam was compression molded to an internal density of 45 kg / m 3, and the front and rear plates were made of a stainless steel plate having a thickness of 0.5 mm. 50 mm thick polyisocyanurate sandwich panel was prepared.

Comparative Example 2

10 weight percent polyol with propylene oxide added to sucrose with an average OH value of 350 to 450, molecular weight 700, 10 weight polyol with propylene oxide added to a sorbitol having an average OH value of 350 to 450 and molecular weight of 600 %, 70% by weight of polyol prepared by condensation of diethylene glycol and dipropylene glycol on terephthalic acid having an average OH value of 200 to 300, and prepared by condensation of diethylene glycol on phthalic anhydride having an average OH value of 250 to 350 100 parts by weight of a mixed polyol component consisting of 10% by weight of polyol, 1 part by weight of water as a blowing agent, 30 parts by weight of trichloromonofluoromethane, 3 parts by weight of ammonium salt as trimerization catalyst, 1 part by weight of tertiary amine catalyst, and tricre as a phosphorus flame retardant. 20 parts by weight of sil phosphate and 0 parts by weight of tribromer neopentyl alcohol as a bromine-based flame retardant, and an average NCO% of 31% and a functional group of 2.7 functional MDI (M-Kumho Mitsui's M- 200) by discharging to the lower surface of the panel in the molding equipment using 250 parts by weight, the polyisocyanurate foam of the present invention was produced while being filled and foamed to the upper surface, the foam is compression molded to an internal density of 45kg / ㎥ thickness 50 mm thick polyisocyanurate sandwich panel having the front and rear plates was made of a 0.5 mm stainless steel sheet.

Comparative Example 3

Polyol 70 prepared by condensation of diethylene glycol and dipropylene glycol on terephthalic acid having an average OH value of 350 to 450, a molecular weight of 600, a polyol added with propylene oxide to sorbitol, and an average OH value of 200 to 300. 100 parts by weight of a mixed polyol component consisting of 10% by weight of a polyol prepared by condensing diethylene glycol on phthalic anhydride having a weight% and an average OH value of 250 to 350, and 1 part by weight of water as a blowing agent and 30 parts by weight of trichloromono fluoromethane Parts, 3 parts by weight of ammonium salt as trimerization catalyst and 1 part by weight of tertiary amine catalyst, 20 parts by weight of tricresyl phosphate as phosphorus flame retardant and 0 parts by weight of tribromer neopentyl alcohol as bromine-based flame retardant, with an average NCO% of 31 %, 250 parts by weight of polymeric MDI (M-200, Kumho Mitsui Co., Ltd.) having a functional number of 2.7 are discharged to the lower surface of the panel in the molding facility, and foamed to the upper surface. The polyisocyanurate foam of the present invention was produced, and the foam was compression molded to an internal density of 45 kg / m 3 to form a 0.5 mm thick stainless steel sheet, and a 50 mm thick polyisocyanurate sandwich panel having a rear plate. Manufactured.

Test Methods:

[Adhesion test method] KSM-3718

[Dimensional Stability Test Method] ASTM D2126-99

[Flame retardancy test method] KSF-2271 flame retardant class 3

Property comparison unit Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 density kg / ㎥ 45 46 44 47 46 45 Adhesion kgf 25 23 22 11 9 10 Dimensional stability vol.% 1.0 1.2 1.5 2.9 3.3 3.5 Flame retardant class 3 - pass pass pass fail fail fail

As can be seen above, polyisocyanurate foam building panels using poly (ether-ester) polyols used in the polyisocyanurate sandwich panels of Examples 1 to 3 of the present invention are generally used in the comparative examples under the same internal density. Compared to the polyisocyanurate building panel using polyether polyol and polyester polyol, the adhesion and the dimensional stability were much better, and the polyisocyanurate foam building panel of the present invention was further described in Examples 1 to 3 in flame retardancy. Passed the KSF-2271 flame retardant class 3 which is a 'test method for flame retardancy of building materials and structure of building', and is a polyisocyanurate foam building panel using the poly (ether-ester) polyol of the present invention. , The dimensional stability has been proved and excellent in Example 1 ~ All 3 have no problem in use, and the conventional polyisocyanurate foam used for the polyisocyanurate building panel using the general polyether polyol and polyester polyol, which are comparative examples, has problems in adhesion, dimensional stability, and flame retardant properties. It turned out to be.

Claims (11)

A polyisocyanurate foam characterized by mixing and foaming 100 parts by weight of a polyol having a polyether-ester mixed polyol as a main component and 100 to 200 parts by weight of a polyisocyanate. The polyisocyanurate foam according to claim 1, wherein the polyol has an average OH value of 150-300 and NCO% of polyisocyanate is 29-32. The polyisocyanurate foam according to claim 1 or 2, wherein the number of functional groups of the polyisocyanate is 2.5-3.0. The polyisocyanurate foam according to claim 1 or 2, wherein the polyisocyanate is polymeric MDI. The polyisocyanurate foam according to claim 1 or 2, wherein the polyether-ester hybrid polyol is 50% by weight or more. The polyol according to claim 1 or 2, wherein the polyol comprises 50-95% by weight of a polyether-ester mixed polyol and 5-50% by weight of a polyetherpolyol, a polyesterpolyol, or a mixture thereof. Sociaurate foam. The polyisocyanurate foam according to claim 1 or 2, wherein the polyether-ester hybrid polyol is prepared by condensing a dicarboxylic acid component with a polyvalent poly (alkylene oxide) polyol. According to claim 1 or 2, wherein the polyisocyanurate foam is 0.5 to 10 parts by weight of catalyst, 5 to 50 parts by weight of blowing agent, 5 to 40 parts by weight of flame retardant, 0.5 to 5 parts by weight of foaming agent, based on 100 parts by weight of polyol. Polyisocyanurate foam characterized in that the foam is further mixed with the foam. The polyisocyanurate foam according to claim 1 or 2, wherein the polyisocyanurate foam has a density of 30 to 50 kg / m 3, a thermal conductivity of 0.0180 kcal / m · hr · ° C. or less, and an independent bubble ratio of 90% or more. Form. The polyisocyanurate foam according to claim 1 or 2, wherein the equivalent ratio of polyisocyanate to polyol is 1: 2.0 to 1: 4.0. An insulation panel comprising the polyisocyanurate foam according to claim 1.