KR100316326B1 - Composition for Rigid P.I.R Polyurethane Foam forming by Sprayer - Google Patents

Abstract

The present invention is a mixed polyol 44 ~ 67 mixture of 90 to 50 weight ratio of polyester polyol having a functional group of 2 to 4 and a molecular weight of 300 to 800 and 10 to 50 weight ratio of a polyether polyol having a functional group of 3 to 6 and a molecular weight of 300 to 800 48 to 52% by weight of a resin premix containing 1 part by weight, 5 to 15 parts by weight of flame retardant, 0.00 to 2.0 parts by weight of crosslinking agent, 1.0 to 2.0 parts by weight of amine urethane catalyst, 0.1 to 3.0 parts by weight of water and 15 to 25 parts by weight of blowing agent. The present invention relates to a composition for producing a hard P.I.polyurethane foam for spraying, comprising 30 to 33% by weight of isocyanate groups and 52 to 48 parts by weight of polyisocyanates having an isocyanate index of 2.0 to 3.5.

The rigid polyurethane foam composition for spraying of the present invention comprises a resin premix having a mixed polyol of a polyester polyol and a polyether polyol and a polyisocyanate having an isocyanate index of 2.0 to 3.0 as a metal trimerization catalyst in forming a urethane foam. By making it react with each other, the isocyanurate functional group is formed relatively more than the urethane functional group inside the foam, so that the combustibility is reduced as compared to the conventional rigid polyurethane foam, and the flame retardancy is added to facilitate the initial suppression in case of fire. Has

Description

Composition for preparing rigid P.I.polyurethane foam for spraying {Composition for Rigid P.I.R Polyurethane Foam forming by Sprayer}

The present invention relates to a composition for the production of polyurethane foams useful as thermal insulation for cold warehouses and cold storage warehouses.

In general, the insulation method of a building using a synthetic resin foam can be roughly divided into two. First of all, polystyrene foam (aka: Styrofoam) or rigid polyurethane board processed to a certain size is inserted into the middle of the building to maintain insulation. This has the disadvantage of showing poor results. However, there is an advantage in the work environment because it uses a commercialized product. Second, it is used in general buildings to maintain polyurethane insulation on the site by using spray foaming machine. It is mainly used for low temperature warehouses and frozen warehouses for agricultural products. Insulation by spray foaming has the advantage of quick workability and the use of liquid resin premix and isocyanate, so it can work in a certain shape regardless of surface condition bending. Another disadvantage is that space must be secured.

Hard spray foaming isocyanate and resin premixes are stored in their respective drums, and the air pressure 5 ~ 7Kgf / cm after maintaining the temperature of the stock solution at 40 ℃ ~ 60 ℃ while passing the long hose of the foamer using the dedicated sprayer. ^{It means} to cure to a solid state within a few seconds while spraying through a spray gun to about ² degrees. The hard polyurethane for spraying thus formed is classified into various uses and its use, and the field of use is applied to general warehouses, gymnasiums, storage warehouses of agricultural and livestock products, and freezing warehouses.

The present invention relates to a hard P.I.polyurethane foam composition for spraying used as a heat insulating material for cold storage warehouses and cold storage warehouses, and more particularly, polyester polyols and sugars formed from phthalic esters or terephthalic acid. In a hard P.I.polyurethane foam composition for spraying a polyol mixed with a polyether polyol made from glycerin, a resin premix consisting of a flame retardant, a foaming agent, a foaming agent, a urethane reaction catalyst, a trimerization catalyst, a crosslinking agent, and a polyisocyanate. It is about.

Herein, the P. I. urethane foam refers to an isocyanate group (-NCO) in the urethane foam forming a hexagonal cyclic structure to form polyisocyanurate.

In general, the rigid polyurethane foam composition contains about 8 to 10% of the urethane functional group and is generally called urethane, and various functional groups such as urea, biuret, allophanate, and isocyanurate are formed. Are mixed to form a rigid foam. At this time, the thermal stability of the formed functional groups is the most excellent isocyanurate, and then the urea, urethane, biuret, allophanate tends to be worse. Therefore, based on this theory, the method of forming a relatively large number of isocyanuret functional groups in the rigid urethane foam was studied.

Conventional rigid polyurethane foam for spraying has the equivalent equivalence ratio of resin premix and isocyanate, and the mixed polyether polyol ratio in resin premix is 100 ~ 80%, and the polyisocyanate index is 1.0 ~ 1.1. Due to the formation of rigid P.I.polyurethane foams, the surface area exceeded 2-3 times the standard value and the thermal stability was very poor. Therefore, there is a need for the development of a new rigid P. polyurethane foam manufacturing technology that can significantly reduce fire resistance and property loss. (S.M CLIFT and J.GRIMMINGER and K.MUHA. 1994 Proceeding of the SPI 35th Annual Technical / Marketing Conference, pp 546-560)

In general, rigid polyurethane foams are used as insulation materials for buildings, so the Korean Industrial Standards specify the physical properties suitable for each application.Thermal conductivity is directly related to fuel consumption and self-extinguishing and flame retardant As required, the thermal conductivity, self-extinguishing and flame retardant properties of the insulating foam are the main properties. The present inventors have studied various methods for improving the thermal stability of rigid polyurethane foams prepared using conventional polyether polyols. As a result, the present invention has been made from polyester polyols formed from phthalic esters or terephthalic acid, sugars and glycerin. The polyether polyol formed is mixed with a polyol, a flame retardant, a crosslinking agent, an amine urethane reaction catalyst, a metal trimerization catalyst, a foam stabilizer, a resin premix including an blowing agent and an isocyanate at a constant ratio, thereby improving the thermal insulation of the foam and the resin premix. The present invention was completed by confirming that an increase in the ratio of organic polyisocyanate reacted with (2.0 to 3.5 times) and thus a metal trimerization catalyst at a constant ratio can obtain a foam capable of taking thermal stability without changing physical properties. Could All. This is known to improve thermal conductivity and thermal stability when the metal-based trimerization catalyst reacts with an excess of polyisocyanate to form a hexagonal ring with a urethane group structure of -NCO.

Therefore, in the present invention, the reaction ratio of polyisocyanate and resin premix is 50/50% by weight due to the characteristics of spray foaming, and the thermal stability of the rigid P.I.polyurethane foam for spraying is based on inorganic addition method. By adjusting the use ratio of the metal-based trimerization catalyst and the amount of polyisocyanate used at a constant ratio, the present invention provides a composition which can be improved by remarkable differentiation from the existing rigid foam, and also maintains the self-extinguishing property of the polyurethane foam. In addition, the aim of the present invention is to provide a rigid polyurethane foam composition for spraying, which has a significantly improved criterion, which is based on a fire method, with a base value of 50 cm ² or less.

The present invention is a mixed polyol 67 ~ 44 weight ratio of 90 to 50 weight ratio of polyester polyol having a functional group of 2 to 4 and a molecular weight of 300 to 800 and a polyether polyol of 3 to 6 and a molecular weight of 300 to 800 in a 10 to 50 weight ratio 5 to 15 parts by weight of flame retardant and 0.00 to 2.0 parts by weight of amine or glycol crosslinking agent, 0.5 to 2.0 parts by weight of tertiary amine catalyst, 0.1 to 3.0 parts by weight of water, 2.0 to 7.0 parts by weight of metal trimerization catalyst and silicone 0.5-2.0 parts by weight of oil foam stabilizer, 48-52 parts by weight of resin premixed with 15-25 parts by weight of blowing agent and 48-52% by weight of polyisocyanate containing 30-33% by weight of isocyanate group are reacted in an equivalent ratio. It consists of the composition for manufacturing the hard P.I.polyurethane foam for spraying by adjusting the index of polyisocyanate to 2.0-3.5.

The present invention is described in more detail as follows.

In the present invention, a large amount of isocyanate groups are formed in the urethane functional group by reacting the resin premix and the organic polyisocyanate, thereby improving resistance to fire without adding an additional inorganic material or surface treatment, thereby facilitating initial suppression in case of fire and reducing property damage. It is characterized by the production of rigid P.I.polyurethane foam for spraying, which can minimize economic losses and reduce human injury.

The foam composition of the present invention consists of a resin premix and a polyisocyanate, and the resin premix is a flame retardant, a crosslinking agent, an amine catalyst, a metal trimerization catalyst, an organosilicon foam stabilizer, and a mixed polyol in which a polyester polyol and a polyether polyol are mixed. It is prepared by containing a blowing agent.

The mixed polyol constituting such a resin premix has a functional group of 2 to 4, 90 to 50 weight ratio of a polyester polyol having a molecular weight of 300 to 800, and a 10 to 50 weight ratio of a polyether polyol having a molecular weight of 3 to 6 and a molecular weight of 300 to 1,000. It can be obtained by mixing. If the mixing ratio is out of the above range, there is a problem that the hardness, moldability, physical properties of the polyurethane foam is deteriorated. Preferred mixing ratio is mixing at a weight ratio of 85:15 to 70:30.

A resin premix including a flame retardant, a crosslinking agent, an amine catalyst, a metal trimerization catalyst, an organosilicon foam stabilizer and a blowing agent is prepared in the mixed polyol as described above.

Flame retardants may include tris (chloroisopropyl) phosphate, tris (2-chloroethyl) phosphate, and the like, and the crosslinking agent may be contained in an amount of 5 to 15% by weight in the total resin premix. If the weight is less than 5% by weight, the density of the foam is reduced and the thermal stability of the foam is poor, and when the weight is more than 15% by weight, the density is increased, resulting in a decrease in production efficiency.

As the crosslinking agent, glycol or amine may be used, and for example, ethylene glycol, diethyl glycol, triethylene glycol, ditropylene glycol, 1,4-butanediol, 1,6-hexanediol, pentaerythritol, di Ethanolamine, triethanolamine, ethylenediamine, triethylenetetraamine, methyleneorthochloraniline, 4,4-diphenylmethanediamine, 2,6-dichloro-4,4-diphenylmethanediamine, 2,4-toluenediamine, 2,6-toluenediamine, etc. may be included, and such a crosslinking agent may be contained in an amount of 0.0 to 2.0% by weight in the total resin premix. If the content of the crosslinking agent exceeds 2.0% by weight, the density of the foam increases, causing economic problems.

In addition, two types of urethane reaction catalysts used in the present invention are used.

Firstly, it is possible to use those conventionally used for the rigid polyurethane foam for spraying, and there is no particular limitation, but it is preferable to use a tertiary amine catalyst, for example triethylamine, N, N, N as a resination catalyst. One or more selected from ', N'tetramethyl-n-hexyldiamine, N, N'-dimethylcyclohexylamine, and quinnusamine (1,4-ethylene piperadine) may be used in combination. It is preferable that such catalyst is contained in the total resin premix at 0.5 to 2.0% by weight. If the content is less than 0.5% by weight, the reaction is delayed, resulting in poor curing and poor production efficiency and quality. The internal heat of reaction may increase, so that the phenomenon of skipping may occur, and foam may be formed in the spray foamer, which may affect workability. Secondly, one of the important points of the present invention is to use a metal-based trimerization catalyst which allows relatively more isocyanurate functional groups to be formed inside the rigid polyurethane foam, for example, fibioctate, tin octet, Potassium Octate, Calcium Octate, Dibutyl Tin Dilaurate, Diethyl Tin Dilaurate, Dibutyl Tin Dimercaptide, Dibutyl Tin Diacetate, N-Hydroxy-alkyl Quaterierammonium Carbosyrate, Tris (dimethyl One or more selected from aminomethyl) phenol, Quetereri ammonium salt, potassium acetate, 1,3,5-tris (3- (dimethylamino) propyl) hexahydro-s-triazine can be used. have. Here, the trimerization catalyst refers to a catalyst used to form a hexagonal N-C-O structure in the urethane foam. It is preferable that such a catalyst is contained in the total resin premix at 2.0 to 7.0% by weight. If the content is less than 2.0% by weight, the reaction is delayed and the formation of isocyaninate, which increases thermal stability, is insufficient. The resistance becomes weak, and if the weight exceeds 7.0% by weight, the internal reaction heat of the foam increases, so that the phenomenon of squeezing may occur, and the hardness of the foam is weakened by forming an excess isocyanurate functional group.

The foam stabilizer reacts with isocyanate and water in the resin premix to generate carbon dioxide, and when the generated gas expands by the heat of reaction to form a cell in the foam, it prevents the resulting cells from coalescing and destroying. It serves to adjust to form, the type is usually used for the production of a rigid polyurethane foam for spraying can be used alone or in combination, it is good to contain 0.1 to 2.0% by weight in the total resin premix.

In addition, there are two kinds of blowing agents, and chemical blowing agents are preferably used in water and 0.1 to 3.0% by weight of the total resin premix. If less than 0.1% by weight is used, the strength of the foam is weakened. If it exceeds 3.0% by weight, the surface of the foam is very swelling, weakening the adhesion to the face. As the physical blowing agent, it is preferable to use florotrichloromethane and dichloro-1-fluoroethane, and it is preferable to contain 15-25% by weight of the total resin premix, and if it is used below 15% by weight, the foam hardens quickly. Failure to dissipate internally generated heat results in severe skipping and increased density resulting in poor productivity. If more than 25% by weight is used, the curing of the foam becomes very slow.

In the present invention, if necessary, stabilizers, fillers, colorants, antibacterial agents, and the like suitable for the purpose can be used together.

In the present invention, the resin premix and the organic polyisocyanate of 30 to 33% by weight of the isocyanate group are controlled by reacting by mixing and mixing with indes 2.0 to 3.5 to prepare a hard P.I.polyurethane foam for spray, The organopolyisocyanate index applied at this time is very important. When the index is 2.0 or less, urethane functional groups are formed more than isocyanurate functional groups, and thus exhibit weak physical properties to fire. When the index is 3.5 or more, curing of the foam is slowed and workability is impaired.

The hard P.R.polyurethane foam for spraying produced by the present invention is similar in physical properties to the hard polyurethane foam for spraying, but the foam structure is characterized in that it has the form of P.R. Due to its shape, the flammability for firearms has been greatly improved, and the surface area has been significantly reduced, which is suitable for the flame retardant performance of building interior materials.

The test method for the impact area was conducted according to the Ministry of Government Administration and Home Affairs (No. 1994-88), and the applicability of specific buildings was determined according to the results. The test method for combustibility was conducted according to KS M 3809.

Hard P.I.polyurethane foam for spray is mixed with resin premix and organic polyisocyanate index of 2.0 ~ 3.5 and adjusted to have P.I.al form on foam and foamed with spray foam to insulate the interior of building It is mainly used as.

The term index is commonly used in the manufacture of foams, which is an index of the equivalent of the compound with active hydrogen groups contained in the resin premix and the stoichiometric amount of isocyanate reacting with the active hydrogen. The index of this isocyanate is calculated by the following formula.

The equivalents of each substance having an active hydrogen group in the resin premix are calculated to determine the total equivalents and the amount of isocyanate required for the reaction.

Where OHV is the OH value.

Resin premix and organic polyisocyanate are mixed, and the mixture is stirred and put into an open wooden box of 200 × 200 × 200mm for free foaming, and the density is measured by cutting 100 × 100 × 100mm at the center of the next day. . In addition, the test of hard P.I.polyurethane foam for spraying does not burn well against fire, and it was cut into 290 × 190 × 30 ^t mm, and the test equipment equipped with propane gas and McKell burner was used for about 800 ~ 900 The raw material was heated for 120 seconds to compare and evaluate the results of the combustion state of the foam, the burn area, and the like. Combustion conditions and surface area of hard P.I.polyurethane foam for spraying can be used as a measure of ease of initial suppression, prevention of spreading and economic loss in case of fire.

As a result of experiments on the rigid P.I.polyurethane foam for spraying prepared according to the present invention as described above, the thermal stability against fire is not a method of adding inorganic materials and increasing the amount of flame retardant, but controlling the amount of metal catalyst used and polyiso By controlling the cyanate index and using the maximum amount of polyester polyol to have a P.E. form in the foam, it is effective to significantly increase the stability to fire.

The present invention will be described in detail with reference to Examples. However, the present invention is not limited to Examples, and the spray foaming makes the reaction ratio of polyisocyanate and resin premix 50/50% by weight due to the characteristics of the foaming machine. In principle, this reaction rate is also a feature of the present invention.

Examples 1-6

As polyisocyanate, the isocyanate group content is 31.5 weight% and the viscosity used 50-150 cps / 25 degreeC.

And polypropylene glycol, flame retardant, water, catalyst, crosslinking agent, organosilicon foam stabilizer, blowing agent was mixed in the composition shown in Table 1 to prepare a resin premix. Then, 150 g of resin premix adjusted to 15 ± 1 ° C. and 150 g of organic polyisocyanate adjusted to 15 ± 1 ° C. were mixed and vigorously stirred for 1-2 seconds, then injected into a 200 × 200 × 200 mm wooden box to react. The rigid polyurethane foam was molded using a spraying machine, cut to 290 × 190 × 30 ^t mm the next day, and processed to a burn area and 150 × 50 × 13 ^t mm to measure the combustibility. 1 is shown.

As a result of measuring the combustibility while changing the flame retardant in the resin premix composition, it was found to have self-extinguishing overall, and to decrease in proportion to the amount of the flame retardant in the carbon screen area.

division Example One 2 3 4 5 6 Resin premix (part by weight) Polyol A ¹⁾ 350 350 350 350 350 350 Polyol B ²⁾ 150 150 150 150 150 150 Flame retardant ³⁾ 5 30 50 80 100 120 Water ⁴⁾ 1.0 1.0 1.0 1.0 1.0 1.0 L-5420 ⁵⁾ 7.5 7.5 7.5 7.5 7.5 7.5 DABCO K-15 ⁶⁾ 40 40 40 40 40 40 DABCO 33LV ⁷⁾ 7.5 7.5 7.5 7.5 7.5 7.5 DEOA ⁸⁾ 0.0 0.0 0.0 0.0 0.0 0.0 CFC-11 ⁹⁾ 165 165 165 165 165 165 Isocyanate (parts by weight) M-100 ¹⁰⁾ 726.0 751.0 771.0 801.0 821.0 841.0 Density (Kg / m ³ ) 29.8 29.2 29.4 29.7 29.9 30.2 Combustion area (Cm ² ) 35.0 32.0 30.0 30.5 27.5 25.5 Combustibility (self-extinguishing) has exist has exist has exist has exist has exist has exist 1) Polyether obtained by condensation reaction of terephthalic acid with an initiator (called polypropylin glycol), OHv 250 mgKOH / g2) Polyether obtained by addition polymerization of propylene oxide with sugar and glycerin as an initiator Polyol, OHv 360 mgKOH / g3) Flame retardant: Tris (chloroisopropyl) phosphate (brand name of flame retardant from Sungbo Chemical Co., Ltd.) 4) Distilled or ion-exchanged water 5) Foaming agent: Silicone oil (L-5420 is Witco's silicone oil 6) Trimerization catalyst: Potassium Octate (DABCOK-15 is a trade name of Air Products) 7) Catalyst: Triethylamine (DABCO 33LV is a trade name of Air Products) 8) Crosslinking agent: Ethanolamine 9) Foaming agent: Florotrichloromethane 10) Polymethyldiphenyl diisocyanate containing 31.5% by weight of NCO

Examples 7-12

A resin premix was prepared by mixing polypropylene glycol, flame retardant, water, catalyst, crosslinking agent and blowing agent in the composition shown in Table 2 below. Then, 150 g of resin premix adjusted to 15 ± 1 ° C. and 150 g of polyisocyanate adjusted to 15 ± 1 ° C. were mixed, stirred vigorously for 1 to 2 seconds, and then injected into a 200 × 200 × 200 mm wooden box for reactivity. Using a spraying machine, the rigid polyurethane foam was molded and cut to 290 × 190 × 30 ^t mm the next day and processed to a burn area and 150 × 50 × 13 ^t mm to measure the combustibility. Indicated on

In general, it is known that it is very difficult to completely reduce the carbon surface area of the organic compound to the fire, because the organic material itself is burned, but the inorganic material may not be carbonized on the contrary. Therefore, although minerals may be added in response to the situation, problems are more likely to occur due to problems in the work equipment and storage properties of the resin premix, thereby avoiding their use.

As a result of comparing the amount of crosslinking agent in the resin premix composition, it was determined that the amount of crosslinking agent was not significantly affected as the amount of crosslinking agent was increased. Was measured.

division Example 7 8 9 10 11 12 Resin premix (part by weight) Polyol A ¹⁾ 420 420 420 420 420 420 Polyol B ²⁾ 180 180 180 180 180 180 Flame retardant ³⁾ 60 60 60 60 60 60 Water ⁴⁾ 1.2 1.2 1.2 1.2 1.2 1.2 L-5420 ⁵⁾ 9.0 9.0 9.0 9.0 9.0 9.0 DABCO K-15 ⁶⁾ 48 48 48 33 48 63 DABCO 33LV ⁷⁾ 9.0 9.0 9.0 9.0 9.0 9.0 DEOA ⁸⁾ 3.0 6.0 12 3.0 3.0 3.0 CFC-11 ⁹⁾ 198 198 198 198 198 198 Isocyanate (parts by weight) M-100 ¹⁰⁾ 928.2 931.2 937.2 913.2 928.2 943.2 Free Density (Kg / m ³ ) 29.8 30.1 30.4 29.8 30.2 31.0 Combustion area (Cm ² ) 30.0 29.5 29.5 30.0 30.2 28.5 Combustibility (self-extinguishing) has exist has exist has exist has exist has exist has exist 1) Polyether obtained by condensation reaction of terephthalic acid with an initiator (called polypropylin glycol), OHv 250 mgKOH / g2) Polyether obtained by addition polymerization of propylene oxide as an initiator with sugar and glycerin Polyol, OHv 360 mgKOH / g3) Tris (chloroisopropyl) phosphate, Sungbo chemicals 4) Distilled or ion-exchanged water 5) Silicone oil, Whitcosa product 6) Potassium octate, Air product company 7) Triethylamine, Air Products Co., Ltd. 8) Dietanolamine, Korea Polyol Co., Ltd. 9) Florotrichloromethane, Ulsan Chemical Co., Ltd. 10) Polymethyldiphenyl diisocyanate containing 31.5 wt% NCO

Examples 13-18

A resin premix was prepared by mixing polypropylene glycol, flame retardant, water, catalyst, crosslinking agent, organosilicon foam stabilizer, and blowing agent in the composition shown in Table 3 below. Then 150 g of resin premix adjusted to 15 ± 1 ° C. and 150 g of organic polyisocyanate adjusted to 15 ± 1 ° C. were mixed and vigorously stirred for 1-2 seconds, then injected into a 200 × 200 × 200 mm wooden box to react. The rigid polyurethane foam was molded using a spraying machine, cut to 290 × 190 × 30 ^t mm the next day, and processed to a burn area and 150 × 50 × 13 ^t mm to measure the combustibility. 3 is shown.

As a result of the measurement by changing to organic polyisocyanate with high NCO wt%, the flame retardant tends to decrease as more flame retardant is added. It showed digestibility but increased surface area.

division Example 13 14 15 16 17 18 Resin premix (part by weight) Polyol A ¹⁾ 210 210 210 210 210 210 Polyol B ²⁾ 90 90 90 90 90 90 Flame retardant ³⁾ 3 30 66 30 30 30 Water ⁴⁾ 0.6 0.6 0.6 0.6 0.9 2.1 L-5420 ⁵⁾ 4.5 4.5 4.5 4.5 4.5 4.5 DABCO K-15 ⁶⁾ 24 24 24 24 24 24 DABCO 33LV ⁷⁾ 4.5 4.5 4.5 4.5 4.5 4.5 DEOA ⁸⁾ 0.0 0.0 0.0 0.0 0.0 0.0 CFC-11 ⁹⁾ 99 93 99 99 99 99 Isocyanate (parts by weight) M-80 ¹⁰⁾ 429.6 462.5 498.6 - - - M-100 ¹¹⁾ - - - 462.6 462.9 464.1 Free Density (Kg / m ³ ) 29.5 30.1 30.9 30.2 29.7 29.4 Combustion area (Cm ² ) 32.0 30.5 25.0 33.0 36.0 37.0 Combustibility (self-extinguishing) has exist has exist has exist has exist has exist has exist 1) Polyether obtained by condensation reaction of terephthalic acid with an initiator (called polypropylin glycol), OHv 250 mgKOH / g2) Polyether obtained by addition polymerization of propylene oxide with sugar and glycerin as an initiator Polyol, OHv 360 mg KOH / g3) Tris (chloroisopropyl) phosphate, Sungbo Chemicals: Flame retardant 4) Distilled or ion-exchanged water 5) Silicone oil, Whitco Inc. 6) Potassium Octate, Air Products Inc. 7) Tree Ethylamine, manufactured by Air Products, Inc. 8) Dietanolamine, manufactured by Poriol, Korea 9) Florotrichloromethane, Ulsan Chemicals, 10) Polymethyldiphenyldiisocyanate containing 31.7% by weight of NCO11) 31.5% by weight of NCO Polymethyldiphenyl diisocyanate containing

Examples 19-24

A resin premix was prepared by mixing polypropylglycol, flame retardant, water, catalyst, crosslinking agent, organosilicon foam stabilizer, and blowing agent in the composition shown in Table 4 below. Then 150 g of resin premix adjusted to 15 ± 1 ° C. and 150 g of organic polyisocyanate adjusted to 15 ± 1 ° C. were mixed and vigorously stirred for 1-2 seconds, then injected into a 200 × 200 × 200 mm wooden box to react. The rigid polyurethane foam was molded using a spraying machine, cut to 290 × 190 × 30 ^t mm the next day, and processed to a burn area and 150 × 50 × 13 ^t mm to measure the combustibility. 4 is shown.

The content of the polyether polyol in the mixed polyol was sequentially increased, and equivalent physical properties and combustion conditions were measured by replacing the physical blowing agent, florotrichloromethane, with dichloro-1-fluoroethane.

As the component of the polyether polyol increases, the carbon surface area increases accordingly, and when the physical blowing agent is changed, the amount of dichloro-1-fluoroethane decreases by the molar ratio and the carbon area decreases.

division Example 19 20 21 22 23 24 Resin premix (part by weight) Polyol A ¹⁾ 270 240 180 150 210 210 Polyol B ²⁾ 30 60 120 150 90 90 Flame retardant ³⁾ 30 30 30 30 30 30 Water ⁴⁾ 0.6 0.6 0.6 0.6 0.6 2.4 L-5420 ⁵⁾ 4.5 4.5 4.5 4.5 4.5 4.5 DABCO K-15 ⁶⁾ 24 24 24 24 24 24 DABCO 33LV ⁷⁾ 4.5 4.5 4.5 4.5 4.5 4.5 DEOA ⁸⁾ 0.0 0.0 0.0 0.0 0.0 0.0 CFC-11 ⁹⁾ 99 99 99 99 - - HCFC-141b ¹⁰⁾ - - - - 84 60 Isocyanate (parts by weight) M-100 ¹¹⁾ 462.6 462.6 462.6 462.6 447.6 425.4 Free Density (Kg / m ³ ) 30.5 30.2 29.6 29.4 29.5 29.8 Combustion area (Cm ² ) 28.2 30.8 34.5 35.0 32.0 35.0 Combustibility (self-extinguishing) has exist has exist has exist has exist has exist has exist 1) Polyether obtained by condensation reaction of terephthalic acid with an initiator (called polypropylin glycol), OHv 250 mgKOH / g2) Polyether obtained by addition polymerization of propylene oxide as an initiator with sugar and glycerin Polyol, OHv 360 mgKOH / g3) Tris (chloroisopropyl) phosphate 4) Distilled or ion-exchanged water 5) Silicone oil, Whitco Inc. 6) Potium Octate 7) Triethylamine, Air Products Inc. 8) Ethanolamine 9) Plorotrichloromethane, Ulsan Chemical Co., Ltd. 10) Dichloro-1-fluoroethane11) Polymethyldiphenyl diisocyanate containing 31.5% by weight of NCO.

Examples 25-30

As the organopolyisocyanate, an isocyanate group content of 31.5 wt% and a viscosity of 50 to 150 cps / 25 ° C were used.

And polypropylene glycol, flame retardant, water, catalyst, crosslinking agent, organosilicon foam stabilizer, foaming agent was mixed in the composition shown in Table 5 to prepare a resin premix. Then, 150 g of resin premix adjusted to 15 ± 1 ° C. and 150 g of organic polyisocyanate adjusted to 15 ± 1 ° C. were mixed and vigorously stirred for 1-2 seconds, then injected into a 200 × 200 × 200 mm wooden box to react. The rigid polyurethane foam was molded using a spraying machine, cut to 290 × 190 × 30 ^t mm the next day, and processed to a burn area and 150 × 50 × 13 ^t mm to measure the combustibility. 5 is shown.

As a result of measuring the combustibility while changing the index and the foaming quantity in the resin premix composition, it showed that it had overall self-extinguishing, and that the index was higher and the foaming quantity was smaller, the smaller the burnt area was.

division Example 25 26 27 28 29 30 Resin premix (part by weight) Polyol A ¹⁾ 490 490 490 490 490 490 Polyol B ²⁾ 210 210 210 210 210 210 Flame retardant ³⁾ 7 112 168 70 70 70 Water ⁴⁾ 1.4 1.4 1.4 1.4 1.4 1.4 L-5420 ⁵⁾ 10.5 10.5 10.5 10.5 10.5 10.5 DABCO K-15 ⁶⁾ 56 56 56 56 56 56 DABCO 33LV ⁷⁾ 10.5 10.5 10.5 10.5 10.5 10.5 DEOA ⁸⁾ 0.0 0.0 0.0 0.0 0.0 0.0 CFC-11 ⁹⁾ 231 231 231 231 238 266 Isocyanate (parts by weight) M-100 ¹⁰⁾ 1016.4 1121.4 1177.4 1079.4 1086.4 1114.4 index 2.1 2.3 2.4 - - - Free Density (Kg / m ³ ) 29.8 29.7 30.2 29.4 29.3 28.9 Combustion area (Cm ² ) 35.0 30.5 25.5 30.5 33.5 37.5 Combustibility (self-extinguishing) has exist has exist has exist has exist has exist has exist 1) Polyether obtained by condensation reaction of terephthalic acid with an initiator (called polypropylin glycol), OHv 250 mgKOH / g2) Polyether obtained by addition polymerization of propylene oxide as an initiator with sugar and glycerin Polyol, OHv 360 mgKOH / g3) Tris (chloroisopropyl) phosphate, Sungbo Chemicals 4) Distilled or ion-exchanged water 5) Silicone oil, Whitcosa 6) Potassium Octate, Air Products 7) Triethylamine, 8) diethanolamine 9) fluorotrichloromethane 10) polymethyldiphenyl diisocyanate containing 31.5% by weight of NCO

In the rigid polyurethane foam composition for spraying of the present invention, a urethane foam is formed, and a resin premix having a mixed polyol of polyester polyol and a polyether polyol and a polyisocyanate having an isocyanate index of 2.0 to 3.0 as a metal-based trimerization catalyst are used. By making it react with each other, the isocyanurate functional group is formed relatively more than the urethane functional group inside the foam, so that the combustibility is reduced as compared to the conventional rigid polyurethane foam, and the flame retardancy is added to facilitate the initial suppression in case of fire. Has

Claims (2)

In the composition for preparing rigid polyurethane foam for spraying comprising polyisocyanate, polyol, reaction catalyst, foaming agent and foam stabilizer, 90 to 50 weight ratio of polyester polyol having a functional group of 2 to 4 and a molecular weight of 300 to 800 and a functional group of 3 to 6 44 to 67 parts by weight of mixed polyol mixed at 10 to 50 weight ratio of polyether polyol having a molecular weight of 300 to 800, 5 to 15 parts by weight of flame retardant, 0.00 to 2.0 parts by weight of crosslinking agent, 1.0 to 2.0 parts by weight of amine urethane catalyst It contains 48 to 52% by weight of resin premixes containing 2.0 to 7.0 parts by weight of trimerization catalyst, 1.0 to 2.0 parts by weight of silicone oil, 0.1 to 3.0 parts by weight of water, and 15 to 25 parts by weight of blowing agent, and 30 to 33% by weight of isocyanate groups. Composition for the production of hard P.I.polyurethane foam for spraying composed of 52 to 48% by weight of polyisocyanate having an isocyanate index of 2.0 to 3.5. The hard P.I.poly poly for spraying according to claim 1, wherein an average OH value of the mixed polyol is 150 to 400 mgKOH / g, and the blowing agent is composed of difluoro-1-fluoroethane or fluorotrichloromethane and water. Composition for preparing urethane foam.