JP6776279B2 - Rigid urethane resin composition - Google Patents

Description

The present invention relates to a rigid urethane resin composition capable of obtaining a rigid urethane foam having good flame retardancy.

Conventionally, hard urethane foam heat insulating materials have been widely used in many buildings for reasons such as high heat insulation and economy.

Further, it is being studied to improve the flame retardancy (fire resistance) of the rigid urethane foam itself.
Patent Document 1 includes a trimerization catalyst that promotes the trimerization reaction of isocyanate groups contained in urethane resin, requires red phosphorus as a flame retardant, and contains a phosphate ester, a phosphate-containing flame retardant, and a bromine-containing difficulty. A technique for improving the fire resistance of a rigid urethane resin has been shown by adding at least two selected from the group consisting of a flame retardant, a boron-containing flame retardant and an antimony-containing flame retardant.

As another method for increasing the flame retardancy, there is also a method of adding a powdery flame retardant such as ammonium polyphosphate, expanded graphite, and aluminum hydroxide.

Patent Document 2 discloses a flame-retardant composition in which a boron compound and a saccharide are used in combination (Patent Document 2).
Patent Document 3 describes a flame retardant in which a polyhydric phenol compound, a saccharide compound, and a sulfonic acid compound of alkylbenzene or a metal salt thereof are mixed. When the saccharide compound is present in the resin, the saccharide compound is present at a high temperature in combustion. It has been shown that the hydroxyl groups dehydrate and release water to exert a cooling effect, and at the same time, generate char (carbohydrate layer) to form a heat insulating film.

JP-A-2014-193995 Japanese Unexamined Patent Publication No. 2011-162734 Japanese Patent No. 4833564

However, the conventional technique of adding a flame retardant to urethane resin to improve fire resistance requires a large amount of flame retardant to realize high flame retardancy, and there is a problem that various physical properties are significantly deteriorated in exchange for flame retardancy. is there.

Further, it is difficult to uniformly disperse a powder (solid) flame retardant such as red phosphorus in a raw material of a urethane resin, and there is a problem that the flame retardancy of a molded product is lowered due to poor dispersion of the flame retardant. Further, the raw material containing the powder flame retardant tends to cause poor dispersion of the flame retardant during storage, and there is a problem of the storability of the raw material.

On the other hand, when the boron compound and the saccharide are used in combination, the characteristics of the urethane resin may be impaired depending on the blending amount of the boron compound.
Further, in the conventional flame retardant used for urethane resin, since char is only incompletely generated, the film of char is thin and the strength is weak, so that there is a problem that the flame retardant effect cannot be sufficiently exhibited.

The present invention has been made in view of the above points, and an object of the present invention is to provide a rigid urethane resin composition capable of improving the dispersion stability of a powder flame retardant and obtaining good flame retardancy.

The invention of claim 1 is a rigid urethane resin composition containing a polyol compound, a polyisocyanate, a foaming agent, a catalyst and an additive, wherein the additive contains a flame retardant and a dispersion stabilizer, and the low temperature flame retardant and the above. The medium temperature flame retardant is a phosphorus-containing liquid, the high temperature flame retardant is a powder, and the amount added is 2 to 3 parts by weight with respect to 100 parts by weight of the total amount of the polyol compound and polyisocyanate. , The dispersion stabilizer is characterized by being composed of a saccharide compound.

In the invention of claim 2, the total amount of the liquid low temperature flame retardant, the liquid medium temperature flame retardant, and the powder high temperature flame retardant added is the polyol compound and the poly. 20 to 30 parts by weight per 100 parts by weight of the total amount of the isocyanate, the amount of the saccharide compound is 100 parts by weight of the total amount of the polyol compound and the polyisocyanate is 0.1 to 10 parts by weight It is characterized by.

According to the present invention, as the flame retardant, a low temperature flame retardant having a decomposition temperature of less than 250 ° C., a medium temperature flame retardant having a decomposition temperature of 250 ° C. or higher and lower than 400 ° C., and a high temperature having a decomposition temperature of 400 ° C. or higher. Since it contains three types of region flame retardants, good flame retardancy can be obtained even if the amount of the powder flame retardant (for example, when the powder flame retardant is used as the high temperature region flame retardant) is reduced. Further, the dispersion stabilizer enables the powder flame retardant to be uniformly dispersed in the rigid urethane resin composition by suppressing the sedimentation of the powder flame retardant due to aging, resulting in good storability and good flame retardancy. Hard urethane foam can be obtained.

It is a table which shows the formulation and the measurement result of Example , Reference Example and Comparative Example.

Hereinafter, embodiments of the present invention will be described. The present invention comprises a rigid urethane resin composition containing a polyol compound, a polyisocyanate, a foaming agent, a catalyst and an additive.

As the polyol compound, a polyol for urethane foam is used, and is not particularly limited, and may be any of a polyether polyol, a polyester polyol, and a polyether ester polyol, and one or more of them may be used. Good.

Polyether polyols include, for example, ethylene oxide (EO) in polyhydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, butylene glycol, neopentyl glycol, glycerin, pentaerythritol, trimethylolpropane, sorbitol, and shoe cloth. ), Polyether polyol to which alkylene oxide such as propylene oxide (PO) is added.

The polyester polyol is polycondensed from, for example, an aliphatic carboxylic acid such as malonic acid, succinic acid, or adipic acid, an aromatic carboxylic acid such as phthalic acid, and an aliphatic glycol such as ethylene glycol, diethylene glycol, or propylene glycol. The polyester polyol obtained in the above can be mentioned.
In addition, examples of the polyether ester polyol include those obtained by reacting the polyether polyol with a polybasic acid to form a polyester, or those having both a polyether and a polyester segment in one molecule.

As the polyisocyanate, an aliphatic or aromatic polyisocyanate having two or more isocyanate groups, a mixture thereof, and a modified polyisocyanate obtained by modifying them can be used. Examples of the aliphatic polyisocyanate include hexamethylene diisocyanate, isophorone diisocyanate, and dicyclohexamethane diisocyanate, and examples of the aromatic polyisocyanate include toluene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), naphthalenediocyanate, and xylyl. Examples thereof include range isocyanate and polypeptide polyisocyanate (crude MDI). In addition, other prepolymers can also be used.

The isocyanate index is preferably 300 or more, more preferably 300 to 400. If the isocyanate index is less than 300, the flame retardancy is lowered due to the decrease in the nurateization rate. The isocyanate index is a value obtained by dividing the number of moles of isocyanate groups in polyisocyanate by the total number of moles of active hydrogen groups such as hydroxyl groups of polyol and multiplying by 100. [NCO equivalent of polyisocyanate / active hydrogen equivalent × 100 ] Is calculated.

As the foaming agent, hydrocarbons such as water, CFC substitutes or pentane can be used alone or in combination. For water, the carbon dioxide gas generated during the reaction of the polyol with a polyisocyanate, foaming is carried out by the carbon dioxide. The amount of water as a blowing agent, 0-10 parts by weight per 100 parts by weight of the total amount of the polyol compound and polyisocyanate is preferable. Further, the amount of other blowing agents when used in combination with other blowing agents with water are appropriately determined, preferably in the range of 5 to 50 parts by weight per 100 parts by weight of the total amount of the polyol compound and polyisocyanate.

As the catalyst, a quantifier catalyst is used. The trimerization catalyst is a catalyst that reacts an isocyanate group to triquantize it and promotes the formation of an isocyanurate ring. As the trimerization catalyst, a known trimerization catalyst can be used, for example, 2,4,6-tris (dimethylaminomethyl) phenol, 2,4-bis (dimethylaminomethyl) phenol, 2,4,6. -Tris (dialkylaminoalkyl) hexahydro-S-triazine, potassium acetate, potassium 2-ethylhexanoate, potassium octylate and the like can be used. Three the amount of dimerization catalyst is appropriately determined, preferably in the range of 0.5 to 5 parts by weight per 100 parts by weight of the total amount of the polyol compound and polyisocyanate. If it is less than 0.5 parts by weight, the flame retardancy decreases due to the decrease in the nurateization rate.

A known urethanization catalyst can be used in combination with the trimerization catalyst. Examples of catalysts that can be used in combination with the trimerization catalyst include amine catalysts such as triethylamine, triethylenediamine, diethanolamine, dimethylaminomorpholine, N-ethylmorpholine, and tetramethylguanidine, and tin catalysts such as stanas octoate and dibutyltin dilaurate. Examples thereof include metal catalysts such as phenylmercury propionate and lead octate (also referred to as organic metal catalysts). In order to increase the nurateization rate and improve the flame retardancy, it is preferable to reduce the amount of the urethanization catalyst used in combination. Further, by setting the isocyanate index to 300 or more, the flame retardancy is further improved.

Examples of the additive include a flame retardant and a dispersion stabilizer.
The flame retardant includes a low temperature flame retardant having a decomposition temperature of less than 250 ° C., a medium temperature flame retardant having a decomposition temperature of 250 ° C. or higher and lower than 400 ° C., and a high temperature flame retardant having a decomposition temperature of 400 ° C. or higher. Is done. The reason why three types of flame retardants with different decomposition temperatures are included is that in the thermal decomposition behavior of hard urethane foam (nurate foam) during combustion, each combustion assumes the combustion process of the initial stage of heating, the growth stage of heating, and the final stage of heating. By blending a flame retardant in a temperature range having a decomposition temperature in the process, it is intended to exhibit good flame retardancy. The decomposition temperature is a temperature measured using a thermogravimetric measuring device in a dry air atmosphere based on a 10% weight loss temperature at a heating rate of 10 ° C./min.

A low temperature flame retardant having a decomposition temperature of less than 250 ° C. is a flame retardant that decomposes at less than 250 ° C. and exhibits flame retardancy. The low temperature flame retardant is added to match its pyrolysis temperature with the pyrolysis behavior of the urethane bond. By diluting the combustion gas in combustion in the low temperature range, combustion is suppressed as a low calorific value. Examples of low temperature flame retardants having a decomposition temperature of less than 250 ° C. include tris (β-chloropropyl) phosphate (liquid, decomposition temperature 184 ° C.), triethyl phosphate (liquid, decomposition temperature 95 ° C.), [[bis (2--). Hydroxyl ethyl) amino] methyl] diethyl phosphonate (liquid, decomposition temperature 95 ° C.) and the like can be mentioned. The low temperature flame retardant is preferably a liquid, and is not limited to one type, and a plurality of types may be used in combination. The amount of low temperature range flame retardant is preferably 2 to 20 parts by weight per 100 parts by weight of the total amount of the polyol compound and a polyisocyanate, and more preferably 3 to 15 parts by weight.

A medium temperature flame retardant having a decomposition temperature of 250 ° C. or higher and lower than 400 ° C. is a flame retardant that decomposes at 250 ° C. or higher and lower than 400 ° C. and exhibits flame retardancy. The thermal decomposition behavior of the medium temperature flame retardant is matched by setting the thermal decomposition temperature to be close to the decomposition temperature of the nurate ring. Similar to combustion in the low temperature range, the medium temperature flame retardant also dilutes the combustion gas to reduce the calorific value and suppress combustion. It also promotes the formation of char by slowing the burning rate and gaining time. Examples of the medium temperature flame retardant having a decomposition temperature of 250 ° C. or higher and lower than 400 ° C. include a condensate of phosphoryl trichloride with phenol and resorcinol (liquid, decomposition temperature 383 ° C.), and a cyclophosphazene compound (powder, decomposition temperature). 397 ° C.), ammonium polyphosphate (II) (powder, decomposition temperature 357 ° C.) and the like. The medium temperature flame retardant is preferably a liquid, and is not limited to one type, and a plurality of types may be used in combination. The amount of intermediate temperature flame retardant is preferably 2 to 20 parts by weight per 100 parts by weight of the total amount of the polyol compound and a polyisocyanate, and more preferably 3 to 15 parts by weight.

A high temperature flame retardant having a decomposition temperature of 400 ° C. or higher is a flame retardant that decomposes at 400 ° C. or higher and exhibits flame retardancy. The thermal decomposition behavior in the high temperature region forms char by the dehydration reaction of the surface of the burning polymer. The high temperature zone flame retardant having a 400 ° C. above the decomposition temperature, for example, red phosphorus (powder, decomposition temperature 490 ° C.), zinc borate _{(4ZnO · B 2 0 3 ·} H 2 O, powder, dehydration temperature 415 ℃) and the like. As the high temperature flame retardant, powder can be used, and the flame retardant is not limited to one type, and a plurality of types may be used in combination. The amount of high-temperature range flame retardant powder is preferably 1 to 7 parts by weight per 100 parts by weight of the total amount of the polyol compound and the polyisocyanate, more preferably 2 to 3 parts by weight. If the amount of the high-temperature flame retardant in the powder is too small, the flame retardancy is low, and if it is too large, the dispersion tends to be uneven.

In the present invention, the flame retardant (low temperature range flame retardant, intermediate temperature range flame retardant, high temperature range flame retardant) the total amount of, for below 50 parts by weight per 100 parts by weight of the total amount of the polyol compound and a polyisocyanate Is preferable in terms of the effect of the flame retardant, more preferably 5 to 47 parts by weight, still more preferably 20 to 30 parts by weight.

As the dispersion stabilizer, a saccharide compound is used. The saccharide compound is not limited, and examples thereof include monosaccharides, disaccharides, oligosaccharides, polysaccharides, and saccharide derivatives. The saccharide compound is not limited to one type alone, and two or more types can be used in combination. Examples of monosaccharides include glucose (dextrose), fructose (fructose), galactose, mannose and the like. Examples of the disaccharide include maltose (maltose), sucrose (sucrose), lactose (lactose), and serobis. The oligosaccharide is a combination of about 3 to 10 monosaccharides, and is also called an oligosaccharide, and is not particularly limited. Examples of polysaccharides include starch and cellulose. Examples of the saccharide derivative include those obtained by esterifying a part of the hydroxyl groups of the saccharide. Among these, starch and cellulose are preferable, and microcellulose and cellulose nanofibers are more preferable. The amount of saccharide compound is preferably 0.1 to 10 parts by weight per 100 parts by weight of the total amount of the polyol compound and polyisocyanate. If the blending amount is too large, the calorific value at the time of combustion increases, and if the blending amount is too small, the dispersion stabilizing effect cannot be obtained. While the dispersion stabilizer has a hydroxyl group, it has a polymer chain that exhibits hydrophobicity, and thus exhibits a surface-active action between the polyol and the high-temperature flame retardant that is a powder. Shown. Furthermore, by combining with low, medium and high temperature flame retardants, it promotes the formation of stronger char.

Further, as an additive, it is preferable to contain a hindered amine compound (abbreviated as HALS). Usually, a hindered amine compound (HALS) is used as a light stabilizer, a photoantioxidant, and a resin additive. This time, focusing on the capture of active radicals, by including this hindered amine compound, the effect of suppressing the generation of combustion gas during combustion and the effect of suppressing combustion can be obtained when used in combination with other flame retardants. Examples of the hindered amine compound include bissebacate (1,2,2,6,6-pentamethyl-4-piperidyl) and 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate. .. The amount of hindered amine compound is 0.1 to 3 parts by weight per 100 parts by weight of the total amount of the polyol compound and a polyisocyanate, more preferably 0.3 to 3 parts by weight. The hindered amine compound is preferably a liquid.

Moreover, it is preferable to contain a foam stabilizer as an additive. Examples of the defoaming agent include surfactants such as a polyoxyalkylene defoaming agent and a silicone defoaming agent.
As other additives, known additives such as antioxidants, ultraviolet absorbers, and antibacterial agents can be added.

As a method for producing a rigid urethane foam using the rigid urethane resin composition of the present invention, a liquid A component in which a polyol compound, a foaming agent, a catalyst and an additive are mixed and a liquid B component containing a polyisocyanate are mixed by a foaming machine. It can be carried out by discharging the material. It is also possible to foam-mold a molded product having a predetermined shape by injecting it from a foaming machine into a mold having a cavity having a predetermined product shape. The rigid urethane foam produced by using the rigid urethane resin composition of the present invention contains an isocyanurate ring, and is also referred to as an isocyanurate foam.

Using the following raw materials, hard urethane resin compositions of Examples , Reference Examples and Comparative Examples having the formulations shown in the table of FIG. 1 were prepared. Each embodiment, polyol compounds in Reference Examples and Comparative Examples, foam stabilizer, a catalyst, for blowing agent and polyisocyanate, have the same formulation. The blending amount of each raw material in Table 1 is a part by weight.

-Polycarbonate compound: hydroxyl value 235-265 mgKOH / g, number average molecular weight 380, product name; Fantall 6301, manufactured by Hitachi Kasei Polymer Co., Ltd. Catalyst: 33% dipropylene glycol solution of triethylenediamine (urethaneization catalyst), product name: Dabco33LV, manufactured by Air Products, and potassium octylate (trimerization catalyst), product name: DabcoK-15, manufactured by Air Products, 1: 1. Mix in a ratio of 2.
Foaming agent 1: water Foaming agent 2: (Z)-1,1,1,4,4,4-hexafluoro-2-butene, product name; HFO-1336mzz, Opteon 1100, Chemours Corp. Polyisocyanate: Polymeric MDI, product name; MR200, manufactured by Nippon Polyurethane Industry Co., Ltd.

-Low temperature range-Liquid flame retardant: Monophosphate ester, Tris (chloropill) phosphate (TMCPP, decomposition temperature 184 ° C, liquid), manufactured by Daihachi Chemical Co., Ltd.-Medium temperature range-Liquid flame retardant: Condensed phosphate ester, product name; PFR ( Decomposition temperature 383 ° C, liquid), ADEKA, medium temperature range, powder flame retardant: polyphosphazene derivative, product name; R-17-11 (decomposition temperature, 382 ° C, powder), Miki Riken Kogyo Co., Ltd., high temperature range, Powder flame retardant: Red phosphorus, Product name; Nova Excel 140 (decomposition temperature 490 ° C, powder), manufactured by Phosphor Chemical Industry Co., Ltd. ・ HALS (hindered amine compound): Bis (1,2,2,6,6-pentamethyl- 4-Piperidil) = Decandioate and Methyl = 1,2,2,6,6-pentamethyl-4-piperidyl = Sevacart mixture, product name; LA-72 (decomposition temperature 274 ° C, liquid), manufactured by ADEKA

・ Sugar compound 1: Sucrose benzoic acid ester, product name; Monopet SB, manufactured by Daiichi Kogyo Seiyaku Co., Ltd. ・ Sugar compound 2: Sucrose acetic acid ester, product name; Monopet SOA, manufactured by Daiichi Kogyo Seiyaku Co., Ltd. ・ Sugar compound 3: Cellulous microfiber, product name; UFC100, manufactured by Lettenmeier, sugar compound 4: cellulose nanofiber, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.

The rigid urethane resin compositions of each Example, Reference Example and Comparative Example were foamed as follows to prepare a rigid urethane foam.
The polyol compound, low temperature flame retardant, medium temperature flame retardant, high temperature flame retardant, HALS (hindered amine compound) and saccharide compound were weighed in a cup and stirred at room temperature with a laboratory mixer. Then, a foam stabilizer, a catalyst and a foaming agent were added, and the mixture was stirred at room temperature with a laboratory mixer. Further, the polyisocyanate was added, and stirred at laboratory mixer at room temperature to prepare a rigid polyurethane foam (isocyanurate foams) by free foaming.

Each example, with respect to reference examples and comparative examples, to determine the dispersibility of the powder in the raw material before the polyisocyanate formulation was carried sedimentary tested as follows. The polyol compound, low temperature flame retardant, medium temperature flame retardant, high temperature flame retardant, HALS (hindered amine compound) and saccharide compound were weighed in a cup and stirred at room temperature with a laboratory mixer. After that, a foam stabilizer, a catalyst, and a foaming agent were added, and the mixture was stirred at room temperature with a laboratory mixer. 15 ml of the obtained mixed solution was placed in a test tube and allowed to stand for 3 days, and the total height of the liquid and the height of the sedimented portion were increased. The ratio (%) occupied by the height of the settling portion was calculated and used as the settling rate. The smaller the sedimentation rate value, the better the dispersibility, indicating that the dispersion is uniform.

Density (JIS K7222), compression hardness (JIS K7220), and cone calorimeter test were performed on the hard urethane foams of each of the prepared Examples , Reference Examples, and Comparative Examples.

In the cone calorimeter test, a test sample having a thickness of 10 cm × 10 cm × 5 cm was cut out from the rigid urethane foam of each example , reference example and each comparative example, and in accordance with ISO5660, the radiant heat intensity was 20 at 50 kW / m ² . The total calorific value when heated for 1 minute was measured. In addition, the state of the sample after 20 minutes was confirmed, and the presence or absence of cracks and through holes penetrating to the back surface was examined. Furthermore, it was confirmed whether or not the sample was deformed during combustion and was in contact with the spark plug of the testing machine set above the sample. The evaluation was indicated by [○] when there was no crack, through hole, and plug contact, and was indicated by “x” when there was.

The measurement results will be described for each Example , Reference Example, and Comparative Example.
In Example 1, the low temperature region / liquid flame retardant was 13.8 parts by weight, the medium temperature region / liquid flame retardant was 6.9 parts by weight, the high temperature region / powder flame retardant was 2.8 parts by weight, and HALS was 0.7. parts by weight, saccharide compound 1 is 0.5 part by weight, the addition amount of the powder additives to 100 parts by weight of the total amount of the polyol compound and the polyisocyanate are examples of 2.8 parts by weight. In Example 1, the density was 36 kg / m ³ , the compression hardness was 216 kPa, the sedimentation rate was 0%, the total calorific value in the cone calorimeter test was 7.1 MJ / m ² , and the cracks, through holes, and plug contacts were all “○”. Yes, the dispersion of the powder flame retardant was uniform in the high temperature range, and the flame retardant was high.

Example 2 is the same example as in Example 1 except that 0.5 part by weight of the saccharide compound 2 was added instead of the saccharide compound 1 in the first example. In Example 2, the density was 40 kg / m ³ , the compression hardness was 220 kPa, the sedimentation rate was 0%, the total calorific value in the cone calorimeter test was 6.3 MJ / m ² , and the cracks, through holes, and plug contacts were all “○”. Yes, the dispersion of the powder flame retardant was uniform in the high temperature range, and the flame retardant was high.

Example 3 is the same example as in Example 1 except that 0.5 part by weight of the saccharide compound 3 was added instead of the saccharide compound 1 in the first example. In Example 3, the density was 39 kg / m ³ , the compression hardness was 248 kPa, the sedimentation rate was 0%, the total calorific value in the cone calorimeter test was 6.9 MJ / m ² , and the cracks, through holes, and plug contacts were all “○”. Yes, the dispersion of the powder flame retardant was uniform in the high temperature range, and the flame retardant was high.

Example 4 is the same example as in Example 1 except that 0.5 part by weight of the saccharide compound 4 was added instead of the saccharide compound 1 in the first example. In Example 4, the density was 36 kg / m ³ , the compression hardness was 258 kPa, the sedimentation rate was 0%, the total calorific value in the cone calorimeter test was 7.2 MJ / m ² , and the cracks, through holes, and plug contacts were all “○”. Yes, the dispersion of the powder flame retardant was uniform in the high temperature range, and the flame retardant was high.

Reference example, except for using 6.9 parts by weight of a high temperature range, the powder flame retardants in Example 3 is an example similar to Example 3, powder added to the total amount 100 parts by weight of the polyol compound and polyisocyanate The amount of the agent added is 6.9 parts by weight. In Example 5, the density was 35 kg / m ³ , the compression hardness was 267 kPa, the sedimentation rate was 0%, the total calorific value in the cone calorimeter test was 4.3 MJ / m ² , and the cracks, through holes, and plug contacts were all “〇”. The dispersion of the powder flame retardant was uniform in the high temperature range, and the flame retardant was high.

Comparative Example 1 is the same example as in Example 1 except that the saccharide compound 1 was 0 parts by weight and none of the saccharide compounds 1 to 4 was added. In Comparative Example 1, the density was 37 kg / m ³ , the compression hardness was 187 kPa, the sedimentation rate was 23%, the total calorific value in the cone calorimeter test was 9.8 MJ / m ² , and the cracks, through holes, and plug contact were all "○". there were. In Comparative Example 1, since the saccharide compound was not blended, the value of the precipitation rate was as high as 23%, and the dispersion of the powder flame retardant in the high temperature range was non-uniform. As a result, the total calorific value of the cone calorimeter was 9.8 MJ / m ² , and the flame retardancy was lower than that of Example 1 in which the saccharide compound 1 was blended.

Comparative Example 2 is the same example as in Example 3 except that the medium temperature range / liquid flame retardant and the high temperature range / powder flame retardant and HALS are all set to 0 parts by weight, and the polyol compound and poly The amount of the powder additive added to 100 parts by weight of the total amount of isocyanate is 0 parts by weight. Since the amount of the powder additive added was 0 parts by weight, the sedimentation test was not performed. In Comparative Example 2, the density was 38 kg / m ³ , the compression hardness was 251 kPa, the total calorific value in the cone calorimeter test was 14.8 MJ / m ² , and there were both cracks and through holes, which was “x”. In Comparative Example 2, since the amount of the powder flame retardant added in the high temperature region was 0, the cone calorimeter test result was poor and the flame retardancy was low.

In Comparative Example 3, in Example 3, the low temperature range / liquid flame retardant, the medium temperature range / liquid flame retardant, and HALS were all set to 0 parts by weight, and the high temperature range / powder flame retardant was increased to 6.9 parts by weight. is an example similar to example 3, the addition amount of the powder additives to 100 parts by weight of the total amount of the polyol compound and the polyisocyanate is 6.9 parts by weight. Comparative Example 3 has a density of 40 kg / m ³ , a compression hardness of 237 kPa, a sedimentation rate of 0%, a total calorific value of 15.6 MJ / m ² in the cone calorimeter test, a crack and a through hole “○”, and a plug contact “×”. there were. In Comparative Example 3, since neither the low temperature range / liquid flame retardant nor the medium temperature range / liquid flame retardant was added, the total calorific value in the cone calorimeter test was large, and the contact with the plug was low. It was a thing.

Comparative Example 4 is the same example as in Example 3 except that 4.1 parts by weight of (medium temperature range / powder flame retardant) was added in place of the high temperature range / powder flame retardant, and the polyol compound. and the addition amount of the powder additives to 100 parts by weight of the total amount of the polyisocyanate is 4.1 parts by weight. In Comparative Example 4, the density was 38 kg / m ³ , the compression hardness was 233 kPa, the sedimentation rate was 0%, the total calorific value in the cone calorimeter test was 8.3 MJ / m ² , and the cracks, through holes, and plug contacts were all “○”. there were. In Comparative Example 4, the value of the total calorific value of the cone calorimeter became large at 8.3 MJ / m ² by not adding the high temperature region / powder flame retardant, and the high temperature region / powder flame retardant was added. The flame retardancy was lower than that of Example 3.

Comparative Example 5 is the same as Comparative Example 4 except that the amount of the saccharide compound 3 added was 0 parts by weight in Comparative Example 4. Comparative Example 5 has a density of 37 kg / m ³ , a compression hardness of 207 kPa, a sedimentation rate of 28%, a total calorific value of 13.8 MJ / m ² in the cone calorimeter test, cracks and through holes “○”, and plug contact “×”. there were. In Comparative Example 5, by not adding the saccharide compound, the value of the sedimentation rate was as high as 28%, and the dispersion of the medium temperature range / powder flame retardant was non-uniform. Further, in Comparative Example 5, the total calorific value of the cone calorimeter test was 13.8 MJ due to the non-uniform dispersion of the medium temperature range / powder flame retardant and the absence of the addition of the high temperature range / powder flame retardant. The flame retardancy was as high as / m ² and the plug contact was “x”, and the flame retardancy was further lowered as compared with Comparative Example 4.

Further, as a result of performing the spraying work by the general-purpose spray system using the rigid urethane resin compositions of Examples 1 to 4 and the reference example , the spraying work could be performed well without any problems such as nozzle clogging.

As described above, the rigid urethane resin composition of the present invention is decomposed into a low temperature flame retardant that decomposes in a low temperature range (less than 250 ° C.) and exhibits flame retardancy and a medium temperature range (250 ° C. or higher and lower than 400 ° C.). It is composed of a medium temperature flame retardant that exhibits flame retardancy and a high temperature flame retardant that decomposes in a high temperature range (400 ° C or higher) and exhibits flame retardancy, and also contains a saccharide compound as a dispersion stabilizer. As a result, the dispersion of the powder flame retardant becomes uniform, the storage stability of the raw material becomes good, and good flame retardancy can be obtained even if the amount of the powder flame retardant added is small. In the examples, high flame retardancy could be exhibited by setting the isocyanate index to 300 or more using a trimerization catalyst.

Claims (2)

In a rigid urethane resin composition containing a polyol compound, a polyisocyanate, a foaming agent, a catalyst and an additive,
The additive comprises a flame retardant and a dispersion stabilizer.
The flame retardant is a low temperature flame retardant having a decomposition temperature of less than 250 ° C., a medium temperature flame retardant having a decomposition temperature of 250 ° C. or higher and lower than 400 ° C., and a high temperature flame retardant having a decomposition temperature of 400 ° C. or higher. Including 3 types
The low temperature flame retardant and the medium temperature flame retardant are phosphorus-containing liquids.
The high temperature flame retardant is a powder, and the amount added is 2 to 3 parts by weight with respect to 100 parts by weight of the total amount of the polyol compound and polyisocyanate.
A rigid urethane resin composition, wherein the dispersion stabilizer is composed of a saccharide compound. The total amount of the liquid low temperature flame retardant, the liquid medium temperature flame retardant, and the powder high temperature flame retardant added is 20 to 100 parts by weight based on the total amount of the polyol compound and polyisocyanate. 30 parts by weight
The amount of the saccharide compound, the polyol compound and the rigid urethane resin composition according to claim 1, characterized in that 0.1 to 10 parts by weight per 100 parts by weight of the total amount of the polyisocyanate.

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