JP2019119825A - Hard urethane resin composition - Google Patents

Abstract

An object of the present invention is to provide a rigid urethane resin composition capable of suppressing sedimentation of a powdery flame retardant due to changes over time, uniformly dispersing the powdery flame retardant, and achieving good flame retardancy. A rigid urethane resin composition comprising a polyol compound, an isocyanate, a blowing agent, a catalyst and an additive, wherein the additive comprises a flame retardant and a dispersion stabilizer, and the flame retardant has a decomposition temperature of less than 250°C. Contains three types: a low-temperature flame retardant, a medium-temperature flame retardant having a decomposition temperature of 250° C. or more and less than 400° C., and a powder high-temperature flame retardant having a decomposition temperature of 400° C. or more, and the dispersion stabilizer is a sugar. compound. [Selection drawing] Fig. 1

Description

  The present invention relates to a hard urethane resin composition from which a hard polyurethane foam having good flame retardancy can be obtained.

  In the past, rigid urethane foam insulation has been widely used in many buildings for reasons such as high insulation and economy.

In addition, it has been studied to improve the flame retardancy (fire resistance) of the hard urethane foam itself.
Patent Document 1 includes a trimerization catalyst for promoting trimerization reaction of isocyanate groups contained in a urethane resin, and as a flame retardant, red phosphorus is essential, and a phosphate ester, a phosphate-containing flame retardant, a bromine-containing flame retardant 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, a technique for improving the fire resistance of a hard urethane resin has been shown.

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

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 discloses a flame retardant comprising a polyhydric phenol compound, a saccharide compound, and a sulfonic acid compound of alkylbenzene or a metal salt thereof, and when the saccharide compound is present in a resin, the saccharide compound is at 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, a char (carbonized layer) is formed to form a thermal barrier coating.

JP, 2014-193995, A JP, 2011-162743, A Patent No. 4833564

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

  In addition, powder (solid) flame retardants such as red phosphorus are difficult to uniformly disperse in the raw material of urethane resin, and there is a problem that the flame retardancy of molded articles is reduced due to poor dispersion of the flame retardant. Moreover, the raw material containing a powder flame retardant tends to produce the dispersion | distribution defect of a flame retardant during storage, and there exists a problem of the storability of a raw material.

On the other hand, in the combined use of a boron compound and a saccharide, the properties of the urethane resin may be impaired depending on the compounding amount of the boron compound.
Further, in the conventional flame retardants used for the urethane resin, since the char is only generated incompletely, the film of the char is thin and the strength is weak, so there is a problem that the flame retardant effect can not be sufficiently exhibited.

  The present invention is made in view of the above-mentioned point, and aims at providing a hard urethane resin composition which improves the dispersion stability of a powder flame retardant and can obtain good flame retardancy.

  The invention according to claim 1 is a hard urethane resin composition containing a polyol compound, an isocyanate, a blowing agent, a catalyst and an additive, wherein the additive contains a flame retardant and a dispersion stabilizer, and the flame retardant is less than 250 ° C. Containing three kinds of low temperature range flame retardant having decomposition temperature, medium temperature range flame retardant having decomposition temperature of 250 ° C. or more and less than 400 ° C., and high temperature range flame retardant having decomposition temperature of 400 ° C. or more The agent is characterized in that it comprises a saccharide compound.

  In the invention of claim 2, in the claim 1, the amount of the high-temperature range flame retardant is 1 to 7 parts by weight with respect to 100 parts by weight of the total amount of the polyol compound and isocyanate, and the amount of the saccharide compound is the polyol It is characterized in that it is 0.1 to 10 parts by weight with respect to 100 parts by weight of the total amount of the compound and the isocyanate.

  According to the present invention, as a flame retardant, a low temperature range flame retardant having a decomposition temperature of less than 250 ° C., a medium temperature range flame retardant having a decomposition temperature of 250 ° C. to less than 400 ° C., and a high temperature having a decomposition temperature of 400 ° C. or more Since three types of flame retardants are included, good flame retardancy can be obtained even if the compounding amount of the powder flame retardant (for example, when the powder flame retardant is used as the high temperature flame retardant) is reduced. Furthermore, with the dispersion stabilizer, the powder flame retardant can be uniformly dispersed in the hard urethane resin composition by suppressing the sedimentation of the powder flame retardant due to the temporal change, the storage property becomes good, and the flame retardancy is good. Hard urethane foam can be obtained.

It is a table | surface which shows the mixing | blending and measurement result of an Example and a comparative example.

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

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

  Examples of polyether polyols include ethylene oxide (EO) (polyethylene glycol) such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, butylene glycol, neopentyl glycol, glycerin, pentaerythritol, trimethylolpropane, sorbitol, sucrose, etc. And polyether polyols to which alkylene oxides such as propylene oxide (PO) are added.

Examples of polyester polyols include polycondensed from aliphatic carboxylic acids such as malonic acid, succinic acid and adipic acid, and aromatic carboxylic acids such as phthalic acid and aliphatic glycols such as ethylene glycol, diethylene glycol and propylene glycol And polyester polyols obtained by
Further, examples of the polyether ester polyol include those obtained by reacting the above-mentioned polyether polyol with a polybasic acid to form a polyester, or those having both a segment of a polyether and a polyester in one molecule.

  As the isocyanate, 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 aliphatic polyisocyanates include hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexamethane diisocyanate and the like, and examples of aromatic polyisocyanates include toluene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), naphthalene diisocyanate, and xylyl diisocyanate. There may be mentioned diisocyanate, polymeric polyisocyanate (crude MDI) and the like. 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 reduced due to the decrease in the rate of nuration. The isocyanate index is a value obtained by dividing the number of moles of isocyanate groups in the polyisocyanate by the total number of moles of active hydrogen groups such as hydroxyl groups of the polyol times 100. [NCO equivalent of polyisocyanate / active hydrogen equivalent × 100 Calculated with].

  As the blowing agent, water, a fluorocarbon substitute, or a hydrocarbon such as pentane can be used alone or in combination. In the case of water, carbon dioxide gas is generated during the reaction of the polyol and the isocyanate, and the carbon dioxide gas causes foaming. The amount of water as a foaming agent is preferably 0 to 10 parts by weight based on 100 parts by weight of the total amount of the polyol compound and the isocyanate. Further, the amount of the other foaming agent in the case of using another foaming agent in combination with water is appropriately determined, but the range of 5 to 50 parts by weight is preferable with respect to 100 parts by weight of the total amount of the polyol compound and the isocyanate.

  As a catalyst, a trimerization catalyst is used. A trimerization catalyst is a catalyst which reacts an isocyanate group to trimerize and promotes formation of an isocyanurate ring. As the trimerization catalyst, known trimerization catalysts 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. Although the quantity of a trimerization catalyst is determined suitably, the range of 0.5-5 weight part is preferable with respect to 100 weight part of total amounts of a polyol compound and an isocyanate. If the amount is less than 0.5 parts by weight, the flame retardancy is reduced due to the decrease in the rate of desalting.

  A known urethanization catalyst can be used in combination with the trimerization catalyst. Examples of the catalyst which 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 Mention may be made of metal catalysts such as phenylmercuric propionate or lead octenoate (also referred to as organometallic catalysts). In order to raise a nuration rate and to improve a flame retardance, it is preferable to decrease the addition amount of the urethanization catalyst to be used together. Furthermore, the flame retardancy is further improved by setting the isocyanate index to 300 or more.

The additives include flame retardants and dispersion stabilizers.
The flame retardant includes a low temperature range flame retardant having a decomposition temperature of less than 250 ° C., a medium temperature range flame retardant having a decomposition temperature of 250 ° C. to less than 400 ° C., and a high temperature range flame retardant having a decomposition temperature of 400 ° C. or more Be The reason for including three types of flame retardants with different decomposition temperatures is that in the thermal decomposition behavior of hard urethane foam (nurate foam) at the time of combustion, assuming the combustion process of the initial heating stage, 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 based on a 10% weight loss temperature at a temperature rising rate of 10 ° C./min in a dry air atmosphere using a thermogravimetry apparatus.

  A low temperature range flame retardant having a decomposition temperature of less than 250 ° C. is a flame retardant that decomposes at less than 250 ° C. to exhibit flame retardancy. Low temperature flame retardants are added to match their thermal decomposition temperature with the thermal decomposition behavior of urethane bonds. The combustion is suppressed as a low calorific value by diluting the combustion gas in the combustion in the low temperature range. As a low temperature range flame retardant having a decomposition temperature of less than 250 ° C., for example, tris (β-chloropropyl) phosphate (liquid, decomposition temperature 184 ° C.), triethyl phosphate (liquid, decomposition temperature 95 ° C.), [bis (2- Examples include hydroxyethyl) amino] methyl] phosphonate diethyl (liquid, decomposition temperature 95 ° C.) and the like. The low temperature range 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 the low temperature range flame retardant is preferably 2 to 20 parts by weight, and more preferably 3 to 15 parts by weight with respect to 100 parts by weight of the total amount of the polyol compound and the isocyanate.

  The mid-temperature range flame retardant having a decomposition temperature of 250 ° C. or more and less than 400 ° C. is a flame retardant that decomposes at 250 ° C. or more and less than 400 ° C. to exhibit flame retardancy. The medium temperature flame retardant makes the thermal decomposition behavior coincide by setting the thermal decomposition temperature near the decomposition temperature of the nurate ring. As in the case of low temperature combustion, medium temperature range flame retardants dilute combustion gas and suppress combustion with a low calorific value. In addition, by delaying the burning rate and earning time, the high temperature range flame retardant promotes formation of char. As a medium-temperature range flame retardant having a decomposition temperature of 250 ° C. to less than 400 ° C., for example, a condensate of phosphoryl trichloride with phenol and resorcinol (liquid, decomposition temperature 383 ° C.), cyclophosphazene compound (powder, decomposition temperature 397 ° C.), ammonium polyphosphate (II) (powder, decomposition temperature 357 ° C.), and the like. The medium-temperature range 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 the medium temperature range flame retardant is preferably 2 to 20 parts by weight, more preferably 3 to 15 parts by weight with respect to 100 parts by weight of the total amount of the polyol compound and the isocyanate.

A high temperature range flame retardant having a decomposition temperature of 400 ° C. or higher is a flame retardant that decomposes at 400 ° C. or higher to exhibit flame retardancy. The thermal decomposition behavior in the high temperature region forms a char by the dehydration reaction of the burning polymer surface. As a high temperature range flame retardant having a decomposition temperature of 400 ° C. or higher, for example, red phosphorus (powder, decomposition temperature 490 ° C.), zinc borate (4ZnO · B ₂ O ₃ · H ₂ O, powder, dehydration temperature 415 C) etc. can be mentioned. The high temperature range flame retardant may use powder, and is not limited to one type, and plural types may be used in combination. The amount of the high-temperature region flame retardant in powder is preferably 1 to 7 parts by weight, and more preferably 2 to 3 parts by weight with respect to 100 parts by weight of the total amount of the polyol compound and the isocyanate. If the blending amount of the high-temperature range flame retardant in powder is too small, the flame retardancy decreases, and if too large, the dispersion tends to be uneven.

  In the present invention, the total amount of the flame retardant (low temperature range flame retardant, medium temperature range flame retardant, high temperature range flame retardant) is 50 parts by weight or less with respect to 100 parts by weight of the total amount of the polyol compound and isocyanate. It is preferable at the point of the effect of a flame retardant, More preferably, it is 5 to 47 weight part, Still more preferably, it is 20 to 30 weight part.

  As the dispersion stabilizer, a saccharide compound is used. The saccharide compound is not limited, and may include monosaccharides, disaccharides, oligosaccharides, polysaccharides, saccharide derivatives and the like. The saccharide compound is not limited to one type of single use, and two or more types may be used in combination. Examples of monosaccharides include glucose (glucose), fructose (fructose), galactose, mannose and the like. Examples of disaccharides include maltose (malt sugar), sucrose (sucrose), lactose (lactose), cerevis and the like. Oligosaccharides are those in which about 3 to 10 monosaccharides are linked, and are also referred to as oligosaccharides, and are not particularly limited. Examples of polysaccharides include starch and cellulose. Examples of the saccharide derivative include those obtained by esterifying part of hydroxyl groups of saccharides. Among these, starch and cellulose are preferable, and microcellulose and cellulose nanofibers are more preferable. The amount of the saccharide compound is preferably 0.1 to 10 parts by weight with respect to 100 parts by weight of the total amount of the polyol compound and the isocyanate. If the compounding amount is too large, the calorific value at the time of combustion will increase, and if too small, the dispersion stabilizing effect can not be obtained. The dispersion stabilizer has a hydroxyl group, while having a polymer chain exhibiting hydrophobicity, exhibits a surface active action between the polyol and the high temperature flame retardant which is a powder, so that the sedimentation and dispersion stability is improved. Show. Furthermore, the combination with low, middle and high temperature flame retardants promotes the formation of stronger char.

  Furthermore, it is preferable to contain a hindered amine compound (abbr. HALS) as an additive. Generally, hindered amine compounds (HALS) are used as additives for resins as light stabilizers and light antioxidants. This time, focusing on the capture of active radicals and containing this hindered amine compound, combined with other flame retardants, the effect of suppressing the generation of combustion gas and the effect of suppressing combustion can be obtained at the time of combustion. Examples of hindered amine compounds include bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate, and the like. . The amount of the hindered amine compound is 0.1 to 3 parts by weight, more preferably 0.3 to 3 parts by weight, based on 100 parts by weight of the total amount of the polyol compound and the isocyanate. The hindered amine compound is preferably a liquid.

Moreover, it is preferable to include a foam stabilizer as an additive. As a foam control agent, surfactant, such as a polyoxyalkylene foam control agent and a silicone foam control agent, is mentioned.
As other additives, those known as additives such as antioxidants, ultraviolet light 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 component A mixed with a polyol compound, a foaming agent, a catalyst and an additive, and a liquid component B containing isocyanate are mixed with a foaming machine It can be done by Alternatively, a molded article having a predetermined shape can be foam-formed by injecting from a foaming machine into a mold having a cavity of a predetermined product shape. In addition, the rigid urethane foam manufactured using the rigid urethane resin composition of this invention contains an isocyanurate ring, and is also called an isocyanurate foam.

  The rigid urethane resin composition of each Example and each comparative example which consists of a mixing | blending shown to the table | surface of FIG. 1 using the following raw materials was created. About the polyol compound in each Example and each comparative example, a foam stabilizer, a catalyst, a foaming agent, and an isocyanate, it becomes the same mixing | blending. The blending amounts of the respective raw materials in Table 1 are parts by weight.

-Polyol compound: Hydroxyl value 235 to 265 mg KOH / g, Number average molecular weight 380, Product name: Fantoll 6301, manufactured by Hitachi Chemical Polymer Co., Ltd.-Foam regulating agent: Silicone foam regulating agent, Product name; SF-2937F, produced by Toray Dow Corning- Catalyst: 33% dipropylene glycol solution of triethylenediamine (urethanization catalyst), product name: Dabco 33 LV, manufactured by Air Products, and potassium octylate (trimerization catalyst), product name: Dabco K-15, manufactured by Air Products: 1: Mix at a ratio of two.
· Blowing agent 1: Water · Blowing agent 2: (Z) -1,1,1,4,4,4-hexafluoro-2-butene, Product name: HFO-1336mzz, Opteon 1100, Chemours, Inc. Isocyanate: Polymeric MDI, product name: MR200, manufactured by Nippon Polyurethane Industry Co., Ltd.

・ Low temperature range ・ Liquid flame retardant: Monophosphate, tris (chloropyr) phosphate (TMCPP, decomposition temperature: 184 ° C, liquid), Daihachi Chemical Co., Ltd. ・ Medium temperature range, liquid flame retardant: Condensed phosphate ester, product name: PFR Decomposition temperature: 383 ° C, liquid), made by ADEKA, medium temperature range, powder flame retardant: Product name: R-17-11 (decomposition temperature: 382 ° C, powder), Miki manufactured by Riken Kogyo Co., Ltd. High temperature range Powder flame retardant: Red phosphorus, product name; Nova Excel 140 (decomposition temperature: 490 ° C, powder), HALS (hindered amine compound) manufactured by Phosphorus Chemical Industry Co., Ltd .: Bis (1,2,2,6,6-pentamethyl- 4-piperidyl) = mixture of decandioate and methyl = 1,2,2,6,6-pentamethyl-4-piperidyl = sebacato, product name; LA-72 (decomposition temperature 274 ° C, liquid) ADEKA Co., Ltd.

Sugar compound 1: Sucrose benzoate, product name: Monopet SB, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd. Sugar compound 2: sucrose acetate, product name: Monopet SOA, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd. Sugar compound 3: Cellulose microfiber, product name: UFC 100, manufactured by Rettmeier, saccharide compound 4: cellulose nanofiber, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.

The rigid urethane resin compositions of the respective Examples and Comparative Examples were foamed as follows to prepare rigid urethane foams.
The polyol compound, the low temperature range flame retardant, the medium temperature range flame retardant, the high temperature range flame retardant, the HALS (hindered amine compound) and the saccharide compound were weighed in a cup and stirred with a lab mixer at room temperature. Then, a foam stabilizer, a catalyst, and a foaming agent were added, and it stirred by the lab mixer at room temperature. Furthermore, the isocyanate was added and it stirred by the lab mixer at room temperature, and produced the rigid urethane foam (isocyanurate foam) by free foaming.

  In order to judge the dispersibility of the powder in the raw material before isocyanate mixing with respect to each Example and each comparative example, the sedimentation test was done as follows. The polyol compound, the low temperature range flame retardant, the medium temperature range flame retardant, the high temperature range flame retardant, the HALS (hindered amine compound) and the saccharide compound were weighed in a cup and stirred with a lab mixer at room temperature. After that, a foam stabilizer, a catalyst and a foaming agent are added, the mixture is stirred with a lab mixer at room temperature, 15 ml of the mixture obtained is put into a test tube, and allowed to stand for 3 days. The sedimentation rate was calculated by measuring the proportion (%) of the height of the precipitation portion. The smaller the value of the sedimentation rate, the better the dispersibility, indicating that the particles are uniformly dispersed.

  The measurement of density (JIS K7222), the measurement of compression hardness (JIS K7220), and the cone calorimeter test were performed with respect to the rigid urethane foam of each produced Example and each comparative example.

In the corn calorimeter test, a test sample of 10 cm × 10 cm × 5 cm thickness was cut out from the rigid urethane foam of each example and each comparative example, and heated for 20 minutes at a radiation heat intensity of 50 kw / m ² according to ISO 5660 The total calorific value of time was measured. In addition, the state of the sample after 20 minutes was confirmed, and the presence or absence of a crack and a through hole penetrating to the back surface was examined. Furthermore, it was checked whether the sample deformed during combustion and was in contact with the spark plug of the tester set above the sample. In the evaluation, the crack, the through hole, and the plug contact are indicated by [O] in the absence of each of them, and indicated by "x" in the presence of the cracks.

Measurement results will be described for each example and each comparative example.
In Example 1, 13.8 parts by weight of the low-temperature liquid flame retardant, 6.9 parts by weight of the medium-temperature liquid flame retardant, 2.8 parts by weight of the high-temperature powder flame retardant, and 0.7 of the HALS It is an example that the addition amount of the powder additive is 2.8 parts by weight with respect to 100 parts by weight of the total amount of the polyol compound and the isocyanate in which the weight of the saccharide compound 1 is 0.5 parts by weight. Example 1 has a density of 36 kg / m ³ , a compression hardness of 216 kPa, a sedimentation rate of 0%, a total calorific value of 7.1 MJ / m ² in a cone calorimeter test, and all cracks, through holes and plug contacts are “〇” The high temperature area, the dispersion of the powder flame retardant was uniform, and the flame retardancy was high.

Example 2 is an example similar to Example 1 except that 0.5 parts by weight of the sugar compound 2 is added instead of the sugar compound 1 in Example 1. Example 2 has a density of 40 kg / m ³ , a compression hardness of 220 kPa, a sedimentation rate of 0%, a total calorific value of 6.3 MJ / m ² in a corn calorimeter test, and all cracks, through holes and plug contacts are “「 ” The high temperature area, the dispersion of the powder flame retardant was uniform, and the flame retardancy was high.

Example 3 is an example similar to Example 1 except that 0.5 parts by weight of the saccharide compound 3 is added instead of the saccharide compound 1 in Example 1. Example 3 has a density of 39 kg / m ³ , a compression hardness of 248 kPa, a sedimentation rate of 0%, a total calorific value of 6.9 MJ / m ² in a cone calorimeter test, and all cracks, through holes and plug contacts are “〇”. The high temperature area, the dispersion of the powder flame retardant was uniform, and the flame retardancy was high.

Example 4 is an example similar to Example 1 except that 0.5 parts by weight of a sugar compound 4 is added instead of the sugar compound 1 in Example 1. Example 4 has a density of 36 kg / m ³ , a compression hardness of 258 kPa, a sedimentation rate of 0%, a total calorific value of 7.2 MJ / m ² in a corn calorimeter test, and all cracks, through holes and plug contacts are “〇” The high temperature area, the dispersion of the powder flame retardant was uniform, and the flame retardancy was high.

Example 5 is the same example as Example 3 except that the high-temperature region / powder flame retardant in Example 3 is 6.9 parts by weight, and the powder addition with respect to the total amount of the polyol compound and the isocyanate of 100 parts by weight The addition amount of the agent is 6.9 parts by weight. Example 5 has a density of 35 kg / m ³ , a compression hardness of 267 kPa, a sedimentation rate of 0%, a total calorific value of 4.3 MJ / m ² in a corn calorimeter test, and all of the cracks, through holes and plug contacts are “〇” The high temperature range, the dispersion of the powder flame retardant was uniform, and the flame retardancy was high.

Comparative Example 1 is an example similar to Example 1 except that in Example 1, 0 parts by weight of the sugar compound 1 is added and none of the sugar compounds 1 to 4 is added. Comparative Example 1 has a density of 37 kg / m ³ , a compressive hardness of 187 kPa, a sedimentation rate of 23%, a total calorific value of 9.8 MJ / m ² in a cone calorimeter test, and all cracks, through holes and plug contacts are “o”. there were. In Comparative Example 1, by not blending the saccharide compound, the value of the sedimentation rate was as high as 23%, and the dispersion of the high-temperature region and the powder flame retardant became uneven. Thereby, the value of the total calorific value of a corn calorimeter was 9.8 MJ / m < ² > and the flame retardance became low compared with Example 1 with which the saccharide compound 1 was mix | blended.

The comparative example 2 is an example similar to the example 3 except that each of the medium temperature area / liquid flame retardant, the high temperature area / powder flame retardant and the HALS is made to be 0 parts by weight in the example 3, the polyol compound and the isocyanate The addition amount of the powder additive is 0 parts by weight with respect to 100 parts by weight of the total amount of No sedimentation test was conducted because the additive amount of the powder additive was 0 parts by weight. Comparative Example 2 had a density of 38 kg / m ³ , a compression hardness of 251 kPa, a total calorific value of 14.8 MJ / m ² in a cone calorimeter test, and both cracks and through holes, resulting in “x”. In Comparative Example 2, the addition amount of the high-temperature region / powder flame retardant was 0, so that the corn calorimeter test result was bad and the flame retardancy was low.

Comparative Example 3 is the same as Example 3 except that each of the low temperature region liquid flame retardant, the medium temperature region liquid flame retardant, and the HALS is 0 parts by weight and the high temperature region powder flame retardant is 6.9 parts by weight. Is an example similar to Example 3, and the addition amount of the powder additive is 6.9 parts by weight with respect to 100 parts by weight of the total amount of the polyol compound and the isocyanate. 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 a cone calorimeter test, a crack and a through hole “o”, a plug contact “x” there were. In Comparative Example 3, since neither the low temperature region liquid flame retardant nor the medium temperature region liquid flame retardant is added, the total calorific value in the corn calorimeter test becomes large, and the plug contacts the plug, and the flame retardancy is low. It was a thing.

Comparative Example 4 is an example similar to Example 3 except that, in Example 3, 4.1 parts by weight of a medium temperature zone, powder flame retardant) is added instead of the high temperature zone, powder flame retardant, and a polyol compound is obtained. The addition amount of the powder additive is 4.1 parts by weight with respect to 100 parts by weight in total of the above and the isocyanate. Comparative Example 4 has a density of 38 kg / m ³ , a compression hardness of 233 kPa, a sedimentation rate of 0%, a total calorific value of 8.3 MJ / m ² in a corn calorimeter test, and all of the cracks, through holes and plug contacts are “o”. there were. In Comparative Example 4, by not adding the high-temperature region / powder flame retardant, the value of the total calorific value of the corn calorimeter became 8.3 MJ / m ² , and the high-temperature region / powder flame retardant was added. The flame retardancy was lower compared to Example 3.

The comparative example 5 is an example similar to the comparative example 4 except that the addition amount of the saccharide compound 3 is 0 parts by weight in the 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 a cone calorimeter test, a crack and a through hole “o”, a plug contact “x” 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 and the powder flame retardant became uneven. Moreover, the comparative example 5 has a value of the total calorific value of a corn calorimeter test of 13.8 MJ, because the dispersion of the medium temperature range and the powder flame retardant is not uniform, and the high temperature range and the powder flame retardant are not added. As compared with Comparative Example 4, the flame retardancy was further lowered, as high as / m ² and the plug contact “x”.

  Moreover, as a result of using the hard urethane resin composition of Examples 1-5 and performing spray construction by a general purpose spray system, it was able to perform spraying operation favorably, without problems, such as clogging of a nozzle.

  Thus, the hard urethane resin composition of the present invention decomposes in the low temperature range (250 ° C. or more but less than 400 ° C.) with the low temperature range flame retardant which decomposes in the low temperature range (less than 250 ° C.) to exhibit flame retardancy. Containing a medium temperature range flame retardant that exhibits flame retardancy and a high temperature range flame retardant that decomposes in a high temperature range (400 ° C. or higher) to exhibit flame retardancy, and contains a saccharide compound as a dispersion stabilizer As a result, the dispersion of the powder flame retardant becomes uniform and the storability 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 addition, the example was able to express high flame retardance by making an isocyanate index into 300 or more using a trimerization catalyst.

Claims (2)

In a hard urethane resin composition comprising a polyol compound, an isocyanate, a blowing agent, a catalyst and an additive,
The additive includes a flame retardant and a dispersion stabilizer,
The flame retardant comprises a low temperature range flame retardant having a decomposition temperature of less than 250 ° C., a medium temperature range flame retardant having a decomposition temperature of 250 ° C. to less than 400 ° C., and a high temperature range flame retardant having a decomposition temperature of 400 ° C. or greater Including three types,
The hard urethane resin composition, wherein the dispersion stabilizer comprises a saccharide compound. The amount of the high temperature range flame retardant is 1 to 7 parts by weight with respect to 100 parts by weight of the total amount of the polyol compound and the isocyanate,
The hard urethane resin composition according to claim 1, wherein the amount of the saccharide compound is 0.1 to 10 parts by weight with respect to 100 parts by weight of the total amount of the polyol compound and the isocyanate.

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