JP2018172597A - Flame-retardant thermosetting polyurethane foam - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a flame-retardant thermosetting polyurethane foam that forms a char layer on a foam surface during firing and has excellent shape retention after the firing.SOLUTION: A salen type copper complex represented by general formula (1) in the figure is used as a flame-retardant thermosetting polyurethane foam, where Rand Reach independently represent a hydrogen atom or C1-6 alkyl group, and R, R, Rand Rare groups selected from the group consisting of a hydrogen atom, a hydroxy group, a C1-6 alkyl group and a C1-6 alkoxy group.SELECTED DRAWING: None

Description

  The present invention relates to a flame retardant thermosetting polyurethane foam containing a salen type copper complex.

  Polyurethane foams are produced mainly by the reaction of polyisocyanates and polyols, and are used in a wide range of applications such as cushioning materials for vehicles and furniture, heat insulating materials and structural materials in buildings, storage tanks, ships and the like. In recent years, polyurethane foam particularly for building materials has been required to have improved flame retardancy related to the Building Standard Law. Conventionally, in order to make a polyurethane foam flame retardant, the flame retardancy of the polyurethane itself has been improved and a flame retardant has been added and used. As the flame retardant, a flame retardant that is liquid at room temperature represented by a phosphate ester monomer has been mainly used.

  However, in general, when a phosphoric acid ester monomer that is liquid at room temperature is used as a flame retardant for polyurethane foam, there is a plasticizing effect, so as the amount of flame retardant used increases, the mechanical properties of polyurethane foam decrease in strength and shrinkage. There was a problem that it was easy to cause a decrease. For this reason, reduction of the usage-amount of a phosphate ester type flame retardant and the substitution to the other flame retardant which does not have a bad influence on a physical property were calculated | required.

  On the other hand, in the case of using only a low molecular weight phosphate ester as a flame retardant in a heat generation evaluation test using a cone calorimeter test based on ISO 5660, which is one of the combustion tests for evaluating the flame retardant performance of foams In some cases, radiant heating may cause a crack in the sample surface or a decrease in foam thickness (thinning). Cracks cause the spread of fire to the inside of the sample, and the thin skin causes spread of fire to the back of the sample, leading to expansion of combustion. As a result, the calorific value increases, causing a reduction in flame retardancy. For this reason, in order to ensure flame retardancy, a flame retardant polyurethane foam excellent in shape retention property that forms a smooth carbonized layer on the combustion surface is desired. Therefore, as a specific required characteristic index, there is a demand for further reduction of the heat generation rate, which is one of the evaluation items of flame retardancy, and improvement of shape retention for a long time of 10 minutes or more.

  As a polyurethane foam having excellent shape retention, for example, Patent Document 1 discloses the flame retardancy of a rigid polyurethane foam using a specific phenol resin-based polyol, and the remaining in a heat generation evaluation test using a corn calorimeter test. Mention is made about charcoal rate and flame retardancy. However, only exothermicity in a short time of 5 minutes has been evaluated.

  Moreover, although there exists a report that the addition of a salen type copper complex is effective for the flame retardance of a thermoplastic urethane resin (refer nonpatent literature 1), there is no description regarding a thermosetting urethane resin. A thermosetting polyurethane foam containing a salen-type copper complex is not known.

Japanese Patent No. 5412018

Gael Fontaine; Thomas Turf; Serge Bourbigot; ACS Symposium Series, 2009, 1013, 329-340

  The present invention has been made in view of the above problems, and an object thereof is to provide a flame-retardant thermosetting polyurethane foam which forms a smooth carbonized layer on the combustion surface and is excellent in shape retention after the test. It is in.

As a result of intensive studies to solve the above problems, the present inventor has included a salen-type copper complex in a flame-retardant thermosetting polyurethane foam, so that when the polyurethane foam is burned, the combustion surface is smoothed. The present invention was completed by finding a good carbonized layer and having excellent shape retention. That is, the present invention
(I) General formula (1)

(In the formula, R ¹ and R ² each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. R ³ , R ⁴ , R ⁵ and R ⁶ are a hydrogen atom, a hydroxyl group, and 1 carbon atom. A group selected from the group consisting of an alkyl group of ˜6 and an alkoxy group of 1 to 6 carbon atoms.)
A flame retardant thermosetting polyurethane foam comprising a salen type copper complex represented by:
(II) The above item characterized by foam-molding by stirring and mixing a polyol, a catalyst, a foaming agent, a foam stabilizer, a flame retardant, a salen-type copper complex represented by the general formula (1) and a polyisocyanate. A process for producing a flame retardant thermosetting polyurethane foam according to I);
(III) Polyisocyanate is added to a polyol, a catalyst, a foaming agent, a foam stabilizer, a flame retardant, and a salen-type copper complex represented by the above general formula (1), and the mixture is stirred and mixed to perform foam molding. A method for producing a flame retardant thermosetting polyurethane foam according to item (I) or (II);
About.

  According to the present invention, by containing a salen type copper complex in a thermosetting polyurethane foam, when the polyurethane foam is burned, a uniform carbonized layer is formed on the combustion surface, and the shape retention after the test is excellent. A flammable thermosetting polyurethane foam can be obtained.

4 is an enlarged image of the surface after the test of Example 3. FIG. 6 is an enlarged image of a cross section after the test of Example 3. FIG. 2 is an enlarged image of the surface after the test of Comparative Example 1. 2 is an enlarged image of a cross section after a test of Comparative Example 1;

  Hereinafter, the present invention will be described in detail.

First, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ^{6 in the} salen-type copper complex (1) contained in the flame-retardant thermosetting polyurethane foam of the present invention will be described.

The alkyl group having 1 to 6 carbon atoms represented by R ¹ and R ² may be linear, branched or cyclic, and specifically includes a methyl group, an ethyl group, a propyl group, and isopropyl. Group, cyclopropyl group, butyl group, 2-methyl-1-propyl group, 1-methyl-1-propyl group, t-butyl group, pentyl group, cyclopentyl group, 1-methylbutyl group, 2-methylbutyl group, 3- Examples thereof include a methylbutyl group, 1,1-dimethylpropyl group, 1,2-dimethylpropyl group, hexyl group, cyclohexyl group, 1-methyl-1-pentyl group, 4-methyl-1-pentyl group and the like.

In the salen-type copper complex (1) contained in the flame-retardant thermosetting polyurethane foam of the present invention, R ¹ and R ² are hydrogen atoms in that good shape retention results are obtained in the flame-retardant test. It is preferable.

Examples of the alkyl group having 1 to 6 carbon atoms represented by R ³ , R ⁴ , R ⁵ and R ⁶ include methyl group, ethyl group, propyl group, isopropyl group, cyclopropyl group, butyl group, 2-methyl-1 -Propyl group, 1-methyl-1-propyl group, t-butyl group, pentyl group, cyclopentyl group, 1-methylbutyl group, 2-methylbutyl group, 3-methylbutyl group, 1,1-dimethylpropyl group, 1,2 Examples include -dimethylpropyl group, hexyl group, cyclohexyl group, 1-methyl-1-pentyl group, 4-methyl-1-pentyl group and the like.

Examples of the alkoxy group having 1 to 6 carbon atoms represented by R ³ , R ⁴ , R ⁵ and R ⁶ include a methoxy group, an ethoxy group, a propyloxy group, a 1-methyl-1-ethyloxy group, and 1,1-dimethyl group. Examples thereof include an ethyloxy group, a pentyloxy group, and a hexyloxy group.

R ³ , R ⁴ , R ⁵ and R ⁶ are each a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 or 2 carbon atoms in that it gives good results in a flame retardancy test. It is preferable that a hydrogen atom, a hydroxyl group, a methyl group, an ethyl group, a t-butyl group, a methoxy group, or an ethoxy group is more preferable.

As a preferable example of the salen type copper complex (1) contained in the flame retardant thermosetting polyurethane foam of the present invention, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are all hydrogen atoms. unsubstituted salen-type copper complex (salen copper ^{complex), R 1, R 2,} R 4, R 5 and ^{R 6} are hydrogen atom ^{R 3} is a hydroxyl 3,3'-dihydroxy-salen copper ^{complex, R} 1, 3,3′-dimethoxysalen copper complex in which R ² , R ⁴ , R ⁵ and R ⁶ are hydrogen atoms and R ³ is a methoxy group, R ¹ , R ² , R ⁴ , R ⁵ and R ⁶ are hydrogen atoms And 3,3′-diethoxysalen copper complex in which R ³ is an ethoxy group, ^{3, 3 ′ in} which R ¹ , R ² , R ⁴ , R ⁵ and R ⁶ are hydrogen atoms and R ³ is a methyl group - dimethyl salen copper ^{complex, R 1, R 2, R} 4, R 5 and ^{R 6} Ah hydrogen atom 3,3′-diethylsalen copper complex in which R ³ is an ethyl group, ^{3, 3 ′ in} which R ¹ , R ² , R ⁴ , R ⁵ and R ⁶ are hydrogen atoms and R ³ is a t-butyl group A di-t-butylsalen copper complex, a 4,4′-dihydroxysalen copper complex in which R ¹ , R ² , R ³ , R ⁵ and R ⁶ are hydrogen atoms and R ⁴ is a hydroxyl group, R ¹ , R ² , 4,4′-dimethoxysalen copper complex in which R ³ , R ⁵ and R ⁶ are hydrogen atoms and R ⁴ is a methoxy group, R ¹ , R ² , R ³ , R ⁵ and R ⁶ are hydrogen atoms and R 4,4′-diethoxysalen copper complex in which ⁴ is an ethoxy group, 4,4′-dimethylsalen in which R ¹ , R ² , R ³ , R ⁵ and R ⁶ are hydrogen atoms and R ⁴ is a methyl group copper ^{complex, R 1, R 2, R} 3, R 5 and ^{R 6} are hydrogen atoms 4, 4 ^{R 4} is an ethyl group ' Diethyl salen copper ^{complex, R 1, R 2, R} 3, R 5 and ^{R 6} are hydrogen atoms ^{R 4} is a t- butyl group 4,4' -t- Buchirusaren copper ^{complex, R} 1, R 2,5'-dihydroxysalen copper complex in which ² , R ³ , R ⁴ and R ⁶ are hydrogen atoms and R ⁵ is a hydroxyl group, R ¹ , R ² , R ³ , R ⁴ and R ⁶ are hydrogen atoms 5,5′-dimethoxysalen copper complex in which R ⁴ is a methoxy group, 5,5′-diethoxy in which R ¹ , R ² , R ³ , R ⁴ and R ⁶ are hydrogen atoms and R ⁴ is an ethoxy group Salen copper complex, 5,5′-dimethylsalen copper complex, R ¹ , R ² , R ³ , R ⁶ , wherein R ¹ , R ² , R ³ , R ⁴ and R ⁶ are hydrogen atoms and R ⁴ is a methyl group ⁴ and ^{R 6} are hydrogen atoms ^{R 4} is an ethyl group 5,5'-diethyl salen copper ^{complex, R} 1, ^{2, R} 3, ^{R 4} and ^{R 6} are hydrogen atoms ^{R 5} is a t- butyl group 5,5'-di -t- Buchirusaren copper complexes.

In the salen type copper complex (1) contained in the flame retardant thermosetting polyurethane foam of the present invention, R ¹ , R ² , R ³ , R are provided in that good shape retention results are obtained in the flame retardant test. ⁴ , R ⁵ and R ⁶ are all hydrogen atoms salen copper complex, R ¹ , R ² , R ³ , R ⁵ and R ⁶ are hydrogen atoms and R ⁴ is a hydroxyl group 4,4′-dihydroxysalen copper 4,4′-dimethoxysalen copper complex, R ¹ , R ² , R ³ , R ⁵ and R ⁶ , wherein R ¹ , R ² , R ³ , R ⁵ and R ⁶ are hydrogen atoms and R ⁴ is a methoxy group 4,4′-diethoxysalen copper complex in which ⁶ is a hydrogen atom and R ⁴ is an ethoxy group, R ¹ , R ² , R ³ , R ⁴ and R ⁶ are hydrogen atoms and R ⁵ is a hydroxyl group '-Dihydroxysalen copper complex etc. are preferred. In, unsubstituted salen copper complex from R ¹ R ⁶ is a hydrogen atom, it is more preferable.

  The salen-type copper complex (1) contained in the flame-retardant thermosetting polyurethane foam of the present invention can be synthesized, for example, by a synthesis method described in Non-Patent Document 1 (Skateboel et al., Tetrahedron Letters, 2005, Vol. 46). , P. 3829) is applied mutatis mutandis to produce a salen-type ligand from salicylaldehyde or a substituted product thereof and ethylenediamine or a substituted product thereof (formula 1), and then a reaction with a copper salt (formula 2). It can be manufactured easily.

(Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ represent the same meaning as described above).

  Next, a method for producing the flame-retardant thermosetting polyurethane foam of the present invention (hereinafter referred to as the production method of the present invention) will be described. The flame-retardant thermosetting polyurethane foam of the present invention is obtained by stirring and mixing a polyol, a catalyst, a foaming agent, a foam stabilizer, a flame retardant, a salen-type copper complex (1), and a polyisocyanate and foam-molding. Furthermore, the flame retardant thermosetting polyurethane foam of the present invention comprises a step of preparing a polyol composition by mixing a polyol, a catalyst, a foaming agent, a foam stabilizer, a flame retardant and a salen type copper complex (1), The polyol composition prepared in step 1 can be produced by a production method comprising step 2 in which polyisocyanate is added, mixed by stirring and foamed. Hereinafter, each process will be described in detail.

  The salen-type copper complex (1) used in step 1 in the production method of the present invention may be one or a mixture of two or more salen-type copper complexes (1) having different substituents.

  Although the addition amount of the salen type copper complex (1) used in the step 1 is not particularly limited, the proportion of the salen type copper complex (1) in the flame retardant thermosetting polyurethane foam of the present invention is in the range of 1 to 20% by weight. Preferably, it is in the range of 2 to 15% by weight, more preferably in the range of 3 to 10% by weight. When the salen-type copper complex (1) in the flame-retardant thermosetting polyurethane foam of the present invention is less than 1% by weight, the resulting thermosetting polyurethane foam may have insufficient flame retardancy. On the other hand, if it exceeds 20% by weight, it may be difficult to handle these compositions in uniform mixing or foaming treatment due to a decrease in fluidity accompanying an increase in the solid content of the salen-type copper complex (1).

  Although it does not specifically limit as a polyol used for the process 1 in the manufacturing method of this invention, The commercially available polyol etc. which are used for manufacture of a polyurethane are mentioned, For example, polyether polyols obtained by ring-opening polymerization etc. of alkylene oxide, Polymer polyols obtained by radical polymerization of vinyl monomers in polyether polyols, polyester polyols obtained by polycondensation of polyhydric alcohols and polycarboxylic acids, polyhydric alcohols, polycarboxylic acids and amino alcohols Polyester amide polyols obtained by polycondensation with lactones, polylactone polyols obtained by ring-opening polymerization of lactones, polycarbonate polyols obtained by polycondensation of polyhydric alcohols and carbonates, acrylic polyols, poly Tadiene polyols and hydrogenated products thereof, polyisoprene polyols and hydrogenated products thereof, partially saponified ethylene-vinyl acetate copolymers, natural oil-based polyols such as soybean oil and castor oil, halogen and / or phosphorus-based polyols, Examples thereof include phenol-based polyols. Of these, polyester polyols, polyether polyols, halogen and / or phosphorus polyols, and phenol polyols are more preferable because of excellent flame retardancy. These polyols may be used alone or in combination.

  Specific examples of the polyester polyols include polyester polyols obtained by polycondensation of a polyhydric alcohol and a divalent carboxylic acid (dibasic acid). The polyester polyols are not particularly limited, but polyester polyols derived from adipic acid, orthophthalic acid, terephthalic acid, isophthalic acid, phthalic anhydride, succinic acid, azelaic acid, sebacic acid, linocyl acid, dimethyl terephthalate, polyethylene terephthalate Examples include polyethylene terephthalate waste, dimethyl terephthalate process waste, nylon waste, trimethylolpropane and pentaerythritol waste, and polyester polyols made from phthalate polyester waste. . Also included are lactone-based polyester polyols obtained by ring-opening polymerization of cyclic esters such as ε-caprolactone and methylvalerolactone.

  Of these, aromatic polyester polyols are preferred because of their high flame retardancy. As a ratio of the polyester polyol in the polyol used in Step 1, the ratio in the polyol composition is preferably 100% by weight or less, and more preferably in the range of 50 to 100% by weight.

  Specific examples of the polyether polyols are obtained by, for example, ring-opening addition polymerization of alkylene oxides such as ethylene oxide and propylene oxide with respect to initiators such as ethylenediamine, tolylenediamine, sucrose, amino alcohol, and diethylene glycol. Examples include polyether polyols. If the proportion of the polyether polyol in the polyol used in Step 1 is too large, the flame retardancy may be lowered. Therefore, the proportion of the polyol used in Step 1 is preferably 70% by weight or less.

  Specific examples of the halogen and / or phosphorus polyol include, for example, halogen-containing polyols obtained by ring-opening polymerization of epichlorohydrin and trichlorobutylene oxide, brominated pentaerythritol / sucrose polyols, and tetrabromophthalic acid polyesters. And halogen-based polyols such as phosphoric acid polyols obtained by adding alkylene oxides to phosphoric acid compounds. In addition, if the proportion of the halogen and / or phosphorus polyol in the polyol used in Step 1 is too large, the foaming reactivity may decrease, so the proportion in the polyol composition is in the range of 70% by weight or less. preferable.

  Specific examples of the phenol-based polyol include, for example, a phenol derivative such as unsubstituted phenol or nonylphenol, which is modified with Mannich using formaldehyde and a primary or secondary amine such as diethanolamine, and further ethylene oxide or Examples include Mannich polyols obtained by ring-opening addition polymerization of alkylene oxides such as propylene oxide. If the proportion of the phenolic polyol in the polyol used in Step 1 is too large, the foaming reactivity may be lowered. Therefore, the proportion in the polyol composition is preferably in the range of 70% by weight or less.

  The polyol used in Step 1 preferably has a hydroxyl value of 1 to 2000 (mgKOH / g), more preferably in the range of 10 to 800 (mgKOH / g) when molding a flame retardant thermosetting polyurethane foam. It is preferable because excellent properties such as moldability and strength are easily exhibited. The hydroxyl value can be calculated according to the method of JIS K1557.

  Examples of the catalyst used in Step 1 in the production method of the present invention include commercially available catalysts used for the production of polyurethane. Although not particularly limited, examples thereof include tertiary amines, quaternary ammonium salts, alkali metal salts of carboxylic acids having 2 to 12 carbon atoms, and metal catalysts.

  Specific examples of the tertiary amines include, for example, triethylenediamine, dimethylcyclohexylamine, N, N, N ′, N′-tetramethylethylenediamine, N, N, N ′, N ″, N ″ -pentamethyl. Diethylenetriamine, N, N, N ′, N ″, N ″ ′, N ″ ′-hexamethyltriethylenetetramine, bis (dimethylaminoethyl) ether, 1,3,5-tris (N, N-dimethylaminopropyl) Hexahydro-S-triazine, 2,4,6-tris (dimethylaminomethyl) phenol, 2,4-bis (dimethylaminomethyl) phenol, N-dimethylaminoethyl-N′-methylpiperazine, N, N, N ′ , N′-tetramethylhexamethylenediamine, 1,2-dimethylimidazole, N, N-dimethylaminopropyla , Amine compounds such as bis (dimethylaminopropyl) amine, N, N-dimethylaminoethanol, N, N, N′-trimethylaminoethylethanolamine, 2- (2-dimethylaminoethoxy) ethanol, N, N , N′-trimethyl-N′-hydroxyethylbisaminoethyl ether, N- (3-dimethylaminopropyl) -N, N-diisopropanolamine, N- (2-hydroxyethyl) -N′-methylpiperazine, N , N-dimethylaminohexanol, alkanolamines such as 5-dimethylamino-3-methyl-1-pentanol, and the like.

  Specific examples of the quaternary ammonium salts include, for example, tetraalkylammonium organic acid salts and hydroxyalkyl-based quaternary ammonium organic acid salts. Specifically, tetramethylammonium acetate, tetramethylammonium formic acid. Examples thereof include salts, tetraethylammonium acetate, tetraethylammonium formate, tetramethylammonium 2-ethylhexanoate, 2-hydroxypropyltrimethylammonium formate, 2-hydroxypropyltrimethylammonium 2-ethylhexanoate and the like.

  Specific examples of the alkali metal salt of the carboxylic acid having 2 to 12 carbon atoms include sodium acetate, potassium acetate, potassium 2-ethylhexanoate, sodium 2-ethylhexanoate, potassium octylate, sodium octylate and the like. Can be mentioned.

  Specific examples of the metal catalyst include, for example, stannous octoate, dibutyltin dilaurate, tin catalyst such as dibutyltin acetate, lead catalyst such as lead octylate, zinc catalyst such as zinc neodecanoate and zinc naphthenate, octanoic acid Examples thereof include bismuth catalysts such as bismuth and bismuth neodecanoate.

  The amount of the catalyst used in Step 1 is 0.01 to 10% by weight for tertiary amines, quaternary ammonium salts, and carboxylic acids having 2 to 12 carbon atoms in the flame-retardant thermosetting polyurethane foam. The range of 0.05 to 10% by weight for the alkali metal salt of an acid and 0.05 to 5% by weight for a metal catalyst are preferred.

  Although it does not specifically limit as a foaming agent used for the process 1 in the manufacturing method of this invention, A commercially available physical foaming agent and / or chemical foaming agent, etc. can be used. For example, physical blowing agents include chlorofluorocarbons, hydrochlorofluoroolefins, hydrochlorofluorocarbons, hydrofluoroolefins, hydrofluorocarbons, perfluorocarbons, halogenated hydrocarbons such as dichloromethane, pentane, etc. And alkanes such as cyclopentane, gas such as air, nitrogen and carbon dioxide, or low-temperature liquid. Examples of chemical blowing agents include water, organic acids, inorganic acids such as boric acid, alkali carbonates, cyclic carbonates, dialkyl carbonates, and those that generate gas by being reacted with polyurethane raw materials or by heat or the like. Is mentioned. Among them, since the ozone depletion potential (ODP) is small and the global warming potential (GWP) is small, HCFO-1233zd, its trans isomer, HCFO-1233xf, hydrochlorofluoroolefins such as dichloro-fluorinated propene, HCFC-141b Since the ODP is zero and the GWP is small, HFO-1234zf, E-HFO-1234ze, Z-HFO-1234ze, HFO-1234yf, E-HFO-1255ye, Z-HFO-125ye , E-HFO-1336mzz, Z-HFO-1336mzz, hydrofluoroolefins such as HFO-1438mzz, HFC-134a, HFC-245, HFC-236, HFC-356, HFC-365mfc, HFC- Hydrofluorocarbons such as 27Ea, propane, butane, pentane, hexane, alkanes cyclopentane and the like, or water is preferred.

  The amount of the foaming agent added is, in the case of hydrochlorofluorocarbons, hydrofluoroolefins or hydrofluorocarbons, 20% by weight or less in the flame-retardant thermosetting polyurethane foam of the present invention, and 10% in the case of alkanes. % Or less, and in the case of water, a range of 0.01 to 5% by weight is preferable.

  Examples of the foam stabilizer used in Step 1 in the production method of the present invention include commercially available foam stabilizers used in the production of polyurethane foam. The foam stabilizer is not particularly limited, and examples of the surfactant include organic silicone surfactants that are nonionic surfactants such as organosiloxane-polyoxyalkylene copolymers and silicone-grease copolymers. It is done. Specifically, L5420, L5340, L6188, L6877, L6889, L6900, manufactured by Momentive, B8040, B8155, B8239, B8244, B8330, B8443, B8450, B8460, B8462, B8465, B8466, B8467, B8481, B8444 , B8485, B8486, B8496, B8870, B8871, SZ-1328, SZ-1642, SZ-1677, SH-193, Toray Dow Corning, DC-193, DC5598, etc. manufactured by Air Products.

  The amount of the foam stabilizer added is preferably in the range of 0.1 to 10% by weight in the flame-retardant thermosetting polyurethane foam.

  Although it does not specifically limit as a flame retardant used for the process 1 in the manufacturing method of this invention, Generally used flame retardants, such as phosphate ester, a halogen containing organic compound, inorganic compounds, can be used. Examples of the flame retardant include tris (chloroethyl) phosphate, tris (chloropropyl) phosphate, tris (dichloropropyl) phosphate, tetrakis (2-chloroethyl) ethylene diphosphate, 2,2-bis (chloromethyl) -1, 3-propanebis (chloroethyl) phosphate, tris (2,3-dibromopropyl) phosphate, tris (tribromoneopentyl) phosphate, 2,2-bis (chloromethyl) trimethylenebis (bis (2-chloroethyl) phosphate) , Polyoxyalkylene bisdichloroalkyl phosphate, halogen-containing phosphate phosphonate oligomer ester (CR-530, CR-570, CR-509, etc. manufactured by Daihachi Chemical Industry Co., Ltd.), triphenyl phosphate, tricresyl phosphate Fate, cresyl diphenyl phosphate, tri-2-ethylhexyl phosphate, trimethyl phosphate, tributyl phosphate, trixylenyl phosphate, triethyl phosphate, trioctyl phosphate, diethylphenyl phosphate, dimethylphenyl phosphate, resorcinol diphenyl phosphate, phosphorous acid Halogenated phosphoric acid such as ethyl, diethyl phosphite, aromatic phosphoric acid oligomer ester (resorcinol bisdiphenyl phosphate, resorcinol bisdixylenyl phosphate, bisphenol A bisdiphenyl phosphate, CR-735 manufactured by Daihachi Chemical Industry Co., Ltd.) Ester or non-halogen phosphate ester and oligomer thereof, dibromopropanol, dibromoneopentylglyco And halogen-containing organic compounds such as tetrabromobisphenol A, magnesium carbonate, aluminum phosphate, red phosphorus, ammonium polyphosphate, aluminum hydroxide, magnesium hydroxide, silicate, borate, calcium hydroxide, expanded graphite, melamine Examples thereof include inorganic compounds such as resin, clay, antimony trioxide, zinc white, and calcium carbonate. Among these, halogen-based phosphate esters or non-halogen phosphate esters and oligomers thereof, red phosphorus, expanded graphite, and ammonium polyphosphate are preferable because of high flame retardancy. More preferably, from the ease of mixing, halogen-based phosphate esters and oligomers thereof having a polystyrene equivalent number average molecular weight of 1,000 or less by GPC method, or polystyrene equivalent number average molecular weight of 1,000 or less by GPC method. Non-halogen phosphates and oligomers thereof. These flame retardants may be used alone or in combination.

  As the addition amount of the flame retardant, the proportion of the flame retardant thermosetting polyurethane foam of the present invention is in the range of 1 to 20% by weight, preferably in the range of 2 to 20% by weight, more preferably. It is in the range of 5 to 15% by weight.

Next, Step 2 in which a polyisocyanate is added to the polyol composition prepared in Step 1 and mixed by stirring will be described.
The polyisocyanate used in step 2 in the production method of the present invention is not particularly limited as long as it has at least two isocyanate groups. For example, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 2 , 4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, tolidine diisocyanate, xylylene diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, lysine diisocyanate, triphenylmethane tris Isocyanate, tetramethylxylene diisocyanate, 1,6-hexamethylene diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, isophorone diisocyanate, 1 4-cyclohexane diisocyanate, norbornane diisocyanate, lysine ester triisocyanate, 1,6,11-undecane triisocyanate, 1,8-diisocyanate-4-isocyanate methyloctane, 1,3,6-hexamethylene triisocyanate, bicycloheptane triisocyanate , Trimethylhexamethylene diisocyanate and the like, and these may be used in combination. Moreover, the isocyanate containing prepolymer etc. by reaction of this polyisocyanate and a polyol can also be used. Furthermore, modified polyisocyanates (urethane modified, carbodiimide modified, allophanate modified, urea modified, burette modified, isocyanurate modified, amide modified, imide modified, uretonimine modified, uretdione modified or oxazolidone modified) and polymethylene polyphenylene. Condensates such as polyisocyanate (polymeric MDI) can also be used.

  Polymeric MDI, which is a mixture of diphenylmethane diisocyanate (MDI) and diphenylmethane diisocyanate polynuclear condensate (MDI condensate), can also be used as the polyisocyanate.

  The amount of the polyisocyanate added is preferably in the range of 20 to 80% by weight, more preferably in the range of 40 to 75% by weight, even more preferably in the flame-retardant thermosetting polyurethane foam of the present invention. Is in the range of 50-65% by weight.

In Step 2 of the production method of the present invention, specific examples of the foam molding method when the polyol composition prepared in Step 1 is stirred and mixed with polyisocyanate for foam molding include slab foaming, injection mold foaming, spraying. Well-known manufacturing methods, such as foaming and continuous production panel foaming, are mentioned. The core density of the flame retardant thermosetting polyurethane foam of the present invention prepared in Step 2 is preferably in the range of 10 to 100 kg / m ³ .

  The flame-retardant thermosetting polyurethane foam of the present invention can be used for various applications in which a flexible polyurethane foam, a semi-rigid polyurethane foam, or a rigid polyurethane foam is generally used. Although not particularly limited, for example, heat insulating materials and structural materials related to architecture, civil engineering, heat insulating materials such as freezers, refrigerators, and freezer showcases related to electrical equipment, and heat insulating materials such as LPG, LNG tankers and pipelines related to plants and ships In relation to materials and vehicles, there are applications such as cold insulation and heat insulation for cold cars. It can also be used in applications such as bedding and automobile seats, cushioning materials, sound absorbing materials, vibration damping materials, construction floor materials, and the like. Of these, construction and civil engineering related heat insulating materials and structural materials are preferred.

  The present invention will be described in more detail with reference to examples and comparative examples, but the present invention is not limited thereto.

<Preparation of salen type copper complex>
A salen-type ligand and a salen-type copper complex were prepared as follows based on the synthesis methods described in the literature.

Reference example 1
1 equivalent of ethylenediamine was mixed with 2.1 equivalent of a 2 mol / L ethanol solution of 2-hydroxybenzaldehyde and heated to reflux for 1 hour. This was allowed to cool and the precipitated crystals were collected by filtration to give unsubstituted salen as yellow crystals in a yield of 81%. The 0.2 mol / L ethanol solution of this unsubstituted salen and the copper acetate monohydrate 0.4 mol / L aqueous solution were mixed in an equivalent amount and heated to reflux for 1 hour. This was allowed to cool to room temperature, and the precipitated crystals were collected by filtration to obtain a salen copper complex (salen-type copper complex F-1) as green crystals in a yield of 83%.

Reference example 2
1 equivalent of ethylenediamine was mixed with 2.1 equivalent of a 1.4 mol / L ethanol solution of 2-hydroxy-4-methoxybenzaldehyde and heated to reflux for 1 hour. This was allowed to cool and the precipitated crystals were collected by filtration to give 2,2′-dihydroxy-4,4′-dimethoxysalen as yellow crystals in a yield of 99%. This 2,2′-dihydroxy-4,4′-dimethoxysalen 0.03 mol / L ethanol solution and copper sulfate 0.4 mol / L aqueous solution were mixed in an equivalent amount and heated to reflux for 1 hour. This was allowed to cool to room temperature, the precipitated crystals were collected by filtration, and 2,2′-dihydroxy-4,4′-dimethoxysalen copper complex (salen-type copper complex F-2) was obtained as a blue-violet crystal with a yield of 96%. Got in.

Reference example 3
1 equivalent of ethylenediamine was mixed with 2.0 equivalent of a 1.7 mol / L ethanol solution of 2,4-dihydroxybenzaldehyde and 1 equivalent of a copper sulfate 0.4 mol / L aqueous solution and heated to reflux for 1 hour. This was allowed to cool and the precipitated crystals were collected by filtration to give 4,4′-dihydroxysalen copper complex (salen-type copper complex F-3) as dark green crystals in a yield of 81%.

Examples 1-4
Polyol composition obtained by mixing polyol, catalyst, foaming agent, foam stabilizer, flame retardant and salen-type copper complex (F-1, F-2 or F-3) at room temperature (20-25 ° C). The temperature is adjusted to 20 ± 1 ° C., polyisocyanate adjusted to 20 ± 1 ° C. is added, and the mixture is stirred and mixed at a stirring speed of 6000 rpm for 4 seconds, and heated to 40 ° C. 150 × 150 × 150 mm made of top open aluminum It was poured into a container and free-foamed to obtain a polyurethane foam. Table 1 shows the composition.

As raw materials described in Table 1, the following were used.
Polyol B: phthalic acid-based polyester polyol composed of terephthalic acid as dibasic acid and DEG / TEG as polyhydric alcohol (OH value = 250 mgKOH / g)
-Salen copper complex F-1: Salen copper complex-Salen copper complex F-2: 4,4'-dimethoxysalen copper complex-Salen copper complex F-3: 4,4'-dihydroxysalen copper complex-Difficult Flame retardant G: Tris (chloropropyl) phosphate manufactured by ICL-IP (trade name: FYROL PCF)
-Foaming agent D: 1,1,1,3,3-pentafluorobutane (trade name: Solcan HFC-365mfc) manufactured by Solvay Japan
-Foam stabilizer E: Silicone surfactant (trade name: B-8465) manufactured by Evonik
・ Catalyst C-1: tertiary amine catalyst manufactured by Tosoh Corporation (trade name: TOYOCAT-DT)
・ Catalyst C-2: Quaternary ammonium salt catalyst manufactured by Tosoh Corporation (trade name: TOYOCAT-TRX)
Polyisocyanate A: Polymeric MDI manufactured by Tosoh Corporation (trade name: MR-200, NCO content = 31.0%)

Evaluation Method The foaming reactivity (cream time, gel time, rise time), core density of the foam molded product, and flame retardancy (corn calorimeter test) were measured in the following manner.

<Evaluation of foaming reactivity>
Cream time (CT): foaming start time, and the time to start foaming was measured visually.

  Gel time (GT): This is the time when the polyurethane foam begins to harden, and the time during which the stringing phenomenon occurs when a thin rod-like material is pierced into the foamed foam and pulled out, or the time when resistance was felt when pierced was measured.

  Rise time (RT): The time for the polyurethane foam to stop rising was visually measured.

<Core density of foam>
After 10 minutes from the start of stirring, the foam foamed freely in a 150 × 150 × 150 mm upper open aluminum container is removed from the mold, and the center part is cut into 120 mm × 120 mm × 120 mm dimensions. The core density was measured by measuring accurately.

<Combustion test>
After curing the core density measured sample in a 20 ° C. atmosphere for 72 hours or more, the sample was cut out from the center of the foam so that the length × width size was 99 ± 1 mm and the thickness of the foam was 25 mm. A conforming corn calorimeter test was conducted using CONE-III (manufactured by Toyo Seiki Seisakusho Co., Ltd.). The heating intensity of the heater was 50 kW / m ² and the test time was 10 minutes. Evaluation of flammability includes total calorific value, maximum heat generation rate, combustion time from ignition to flame extinction, weight retention (weight ratio% after completion of test based on weight before test), appearance after test (visual confirmation) ) Was measured.

  Appearance after test: No cracks or irregularities on the sample surface, sample thickness is 20 mm or more: good, cracks or irregularities on the sample surface, sample thickness is 15 mm or less: poor

  In Comparative Example 1, the same procedure as in Examples 1 to 4 was performed except that the salen-type copper complex was not added. Table 1 also shows the composition of the polyurethane foam prepared in Comparative Example 1.

Test Examples 1-4
The core density of Examples 1 to 4 was measured. Furthermore, these combustion tests were conducted. Combustion evaluation test results (corresponding to Test Examples 1 to 4 respectively) of polyethylene foams (Examples 1 to 4) containing a salen type copper complex are compared with the polyurethane foam prepared in Comparative Example 1, and the sample after the test The surface was smooth and the appearance after the test was good. Moreover, the total calorific value of the corn calorie test of the polyethylene foam containing the salen-type copper complex was smaller than that of Comparative Example 1, the combustion time was shorter, and the sample retention rate was higher.

  1 and 2 show enlarged images of the surface and cross section after the test of Example 3. FIG.

Comparative Test Example 1
A polyurethane foam was obtained in the same manner as in Example 1 except that the salen-type copper complex was not added. The polyurethane foam obtained in Comparative Example 1 was subjected to a combustion evaluation test (Comparative Test Example 1). It was found that cracks occurred on the sample surface of the combustion evaluation test, and that the skin was thin, the appearance was poor after the test, and the flame retardancy was insufficient.

  3 and 4 show enlarged images of the surface and cross section of the polyurethane foam obtained in Comparative Test Example 1 after the combustion test, respectively. Compared to the surface and cross section of the polyurethane foam obtained in Test Example 3 after the combustion test, irregularities are seen on the combustion surface and cross section.

Claims (3)

General formula (1)

(In the formula, ^{R 1} and ^{R 2} are ^{.R 3, R 4,} R ⁵ and ^{R 6} representing independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, a hydrogen atom, a hydroxyl group, 1 to carbon atoms 6 is a group selected from the group consisting of 6 alkyl groups and C 1-6 alkoxy groups.)
A flame retardant thermosetting polyurethane foam comprising a salen type copper complex represented by the formula: The polyol, the catalyst, the foaming agent, the foam stabilizer, the flame retardant, the salen-type copper complex represented by the general formula (1) and the polyisocyanate are mixed by stirring and foam-molded. A method for producing a flame retardant thermosetting polyurethane foam. 2. A foam, which is formed by adding a polyisocyanate to a polyol, a catalyst, a foaming agent, a foam stabilizer, a flame retardant, and a salen-type copper complex represented by the above general formula (1) and mixing them with stirring. 2. A method for producing a flame retardant thermosetting polyurethane foam according to 2.

Images