WO2015064018A1 - 難燃剤および難燃性ポリウレタン樹脂組成物 - Google Patents
難燃剤および難燃性ポリウレタン樹脂組成物 Download PDFInfo
- Publication number
- WO2015064018A1 WO2015064018A1 PCT/JP2014/005095 JP2014005095W WO2015064018A1 WO 2015064018 A1 WO2015064018 A1 WO 2015064018A1 JP 2014005095 W JP2014005095 W JP 2014005095W WO 2015064018 A1 WO2015064018 A1 WO 2015064018A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- flame retardant
- polyurethane
- raw material
- weight
- general formula
- Prior art date
Links
- 0 C*(C(*)(*)*O1)OP1(N(C)*)=O Chemical compound C*(C(*)(*)*O1)OP1(N(C)*)=O 0.000 description 1
- VPIAIVPXUZGEGN-UHFFFAOYSA-N CC(C)(CO1)COP1(N1CCCCC1)=O Chemical compound CC(C)(CO1)COP1(N1CCCCC1)=O VPIAIVPXUZGEGN-UHFFFAOYSA-N 0.000 description 1
- IPZOLVGIGPKBJL-UHFFFAOYSA-N COP(N)(OC)=O Chemical compound COP(N)(OC)=O IPZOLVGIGPKBJL-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0014—Use of organic additives
- C08J9/0038—Use of organic additives containing phosphorus
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4829—Polyethers containing at least three hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4833—Polyethers containing oxyethylene units
- C08G18/4837—Polyethers containing oxyethylene units and other oxyalkylene units
- C08G18/4845—Polyethers containing oxyethylene units and other oxyalkylene units containing oxypropylene or higher oxyalkylene end groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
- C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
- C08J9/143—Halogen containing compounds
- C08J9/144—Halogen containing compounds containing carbon, halogen and hydrogen only
- C08J9/145—Halogen containing compounds containing carbon, halogen and hydrogen only only chlorine as halogen atoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5317—Phosphonic compounds, e.g. R—P(:O)(OR')2
- C08K5/5333—Esters of phosphonic acids
- C08K5/5357—Esters of phosphonic acids cyclic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/5399—Phosphorus bound to nitrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K21/00—Fireproofing materials
- C09K21/06—Organic materials
- C09K21/12—Organic materials containing phosphorus
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2101/00—Manufacture of cellular products
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
- C08J2375/08—Polyurethanes from polyethers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
- C08L2666/66—Substances characterised by their function in the composition
- C08L2666/78—Stabilisers against oxidation, heat, light or ozone
- C08L2666/82—Phosphorus-containing stabilizers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
- C08L2666/66—Substances characterised by their function in the composition
- C08L2666/84—Flame-proofing or flame-retarding additives
Definitions
- the present invention relates to a polyurethane resin composition (for example, a flame retardant polyurethane foam composition and a flame retardant elastomer composition) excellent in flame retardancy and various performances.
- the present invention relates to a flame retardant, a flame retardant polyurethane resin composition, a raw material composition thereof, and a reaction raw material composition.
- a flame retardant polyurethane that is excellent in flame retardancy, fogging resistance (low volatility), distortion, and scorch properties, which contains a phosphoramidate compound having a specific structure as a flame retardant.
- the present invention relates to a foam raw material composition.
- Polyurethane resins are inexpensive, lightweight and easy to form, so they are widely used mainly in fields closely related to daily life, such as automobile interior materials, furniture, electrical materials, etc. It is used as However, polyurethane foam, which is a high molecular organic compound, is flammable and may cause uncontrollable combustion once ignited. If a fire occurs in a living environment, it may be a disaster that affects human life. . From this aspect, in the polyurethane foam manufacturing industry, efforts have been made to avoid a fire phenomenon by introducing flame retarding technology into the foam. In addition, today, some flame retardants are required by law depending on the application field of each polyurethane foam, such as automobile interior parts, furniture, and electric coating materials. For example, UL standards for electrical appliances in the United States and MVSS-302 flame retardant regulations for automobiles are known.
- ⁇ Halogen-containing flame retardants are widely used as flame retardants for polyurethane foam.
- halogen-containing flame retardants for polyurethane foams include tetrakis (2-chloroethyl) ethylene diphosphate (Patent Document 1), 2,2-bis (chloromethyl) -1,3-propylene-bis [bis ( 2-chloroethyl) phosphate] (Patent Document 2), tris [di (2-chloroethoxy) phosphinyl (dimethyl) methyl] phosphate, 2-chloroethylbis [di (2-chloroethoxy) phosphinyl (dimethyl) methyl] phosphate ( Patent Document 3) and oxydi-2,1-ethanediyltetrakis (2-chloro-1-methylethyl) phosphate (Patent Document 4) have been studied.
- halogen flame retardants have excellent performance, they contain halogen elements such as chlorine and bromine. Therefore, when products using polyurethane foam containing them are discarded and incinerated, There is a problem that hydrogen halide, which is a substance, is generated, and depending on the type of halogen flame retardant, halogenated dioxin, which is a substance with a greater environmental load, is generated.
- the main object of the present invention is a polyurethane foam composition and a polyurethane elastomer composition that can solve the above-mentioned problems, that is, they do not contain halogen, and are comprehensively flame retardant, fogging resistance, distortion resistance, and scorch resistance. It is to provide good flame retardant polyurethane foam compositions and polyurethane elastomer compositions.
- a phosphoramidate compound having a specific structure not containing halogen as a flame retardant for polyurethane
- a flame retardant polyurethane resin composition for example, a flame retardant polyurethane foam composition and a polyurethane elastomer composition
- a phosphoramidate compound having a specific structure is preferably used as a flame retardant for polyurethane foam or polyurethane elastomer.
- a polyurethane reaction raw material composition is obtained by mixing this flame retardant with a raw material (polyol, polyisocyanate and various additives) of a polyurethane resin.
- a curing reaction occurs to obtain a polyurethane resin composition (for example, a polyurethane foam composition or a polyurethane elastomer composition).
- the obtained polyurethane resin composition is excellent in flame retardancy and excellent in performance required for other polyurethanes (for example, performance required for polyurethane foam or polyurethane elastomer).
- the present invention provides the following flame retardant, flame retardant polyurethane foam composition, and the like.
- R 1 and R 2 are each independently an alkyl group having 1 to 3 carbon atoms
- R 11 and R 12 are each independently an alkylene group having 1 to 3 carbon atoms
- R 13 is carbon
- B 1 is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms
- A is a hydrogen atom or the general formula (II):
- R 3 and R 4 are each independently an alkyl group having 1 to 3 carbon atoms
- R 14 and R 15 are each independently an alkylene group having 1 to 3 carbon atoms
- B 2 Is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
- A is a hydrogen atom
- B 1 is an alkyl group having 1 to 6 carbon atoms
- B 1 and R 13 -A are bonded to each other, and the nitrogen to which these are bonded Together with the atoms, a nitrogen-containing heterocycle is formed.
- B 2 is an alkyl group having 1 to 6 carbon atoms
- B 1 is an alkyl group having 1 to 6 carbon atoms
- B 1 and B 2 may be bonded together to form a nitrogen-containing heterocycle together with the nitrogen atom to which they are bonded and R 13 .
- the flame retardant for polyurethane foam or polyurethane elastomer which consists of a phosphoramidate compound represented by these.
- A is an organic group represented by the general formula (II)
- R 3 and R 4 are methyl groups
- R 14 and R 15 are methylene groups. 5.
- a flame retardant polyurethane foam reaction raw material composition comprising the flame retardant according to any one of items 1 to 10, a polyol, a polyisocyanate, and a foaming agent.
- a flame retardant polyurethane foam raw material composition comprising the flame retardant according to any one of items 1 to 10 and a polyol, Here, the raw material composition is mixed with polyisocyanate immediately before performing the curing reaction. Composition.
- a method for producing a polyurethane foam comprising a step of reacting a reaction raw material composition containing the flame retardant according to any one of items 1 to 10, a polyol, a foaming agent, and a polyisocyanate.
- a flame retardant polyurethane elastomer reaction raw material composition comprising the flame retardant according to any one of items 1, 2, and 4 to 10, a polyol for elastomer, a polyisocyanate, and a foaming agent.
- a flame retardant polyurethane elastomer raw material composition comprising the flame retardant according to any one of items 1, 2 and 4 to 10 and a polyol for elastomer, Here, the raw material composition is mixed with polyisocyanate immediately before performing the curing reaction. Composition.
- the present invention uses a phosphoramidate compound having a specific structure that does not contain halogen as a flame retardant, and thus a flame retardant polyurethane foam composition excellent in flame retardancy, fogging resistance, distortion, and scorch properties And an elastomer composition.
- the phosphoramidate compound according to the present invention has a high phosphorus content, does not affect the physical properties of the product when used as a raw material, and does not contain halogen atoms such as chlorine and bromine. It can be seen that there is no environmental pollution at the time and recyclability is excellent.
- the flame retardant compound of the present invention does not contain a halogen atom, it does not generate harmful halogenated gas during combustion, and is effective in environmental protection. If the flame retardant of this invention is used, the resin composition to which the outstanding flame retardance was provided will be obtained.
- the flame retardant used in the present invention is represented by the general formula (I):
- R 1 and R 2 are each independently an alkyl group having 1 to 3 carbon atoms
- R 11 and R 12 are each independently an alkylene group having 1 to 3 carbon atoms
- R 13 is carbon
- B 1 is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms
- A is a hydrogen atom or the general formula (II):
- R 3 and R 4 are each independently an alkyl group having 1 to 3 carbon atoms
- R 14 and R 15 are each independently an alkylene group having 1 to 3 carbon atoms
- B 2 Is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
- A is a hydrogen atom
- B 1 is an alkyl group having 1 to 6 carbon atoms
- B 1 and R 13 -A are bonded to each other, and the nitrogen to which these are bonded Together with the atoms, a nitrogen-containing heterocycle is formed.
- A is an organic group represented by the general formula (II)
- B 2 is an alkyl group having 1 to 6 carbon atoms
- B 1 is an alkyl group having 1 to 6 carbon atoms
- B 1 and B 2 may be bonded together to form a nitrogen-containing heterocycle together with the nitrogen atom to which they are bonded and R 13 .
- It consists of the phosphoramidate compound represented by these.
- the “alkyl group” refers to a monovalent group generated by losing one hydrogen atom from a chain or cyclic aliphatic hydrocarbon (alkane). In the case of a chain, it is generally represented by C k H 2k + 1 ⁇ (where k is a positive integer).
- a chain alkyl may be a straight chain or branched chain.
- the cyclic alkyl may be composed only of a cyclic structure, or may be a structure in which a chain alkyl is further bonded to the cyclic structure.
- the “alkylene group” refers to a divalent group generated by losing one more hydrogen atom from an alkyl group.
- ethylene group refers to a divalent group produced by losing one more hydrogen atom from an ethyl group.
- Examples of the alkyl group having 1 to 3 carbon atoms in the general formulas (I) and (II) include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group. Among these, a methyl group and an ethyl group are preferable, and a methyl group is particularly preferable from the viewpoint of flame retardancy.
- Examples of the alkylene group having 1 to 3 carbon atoms include a methylene group, an ethylene group, an n-propylene group, and an isopropylene group. Among these, a methylene group and an ethylene group are preferable, and a methylene group is particularly preferable from the viewpoint of flame retardancy.
- alkyl group having 1 to 6 carbon atoms examples include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, n-pentyl group, and n-hexyl group. .
- a methyl group and an ethyl group are preferable, and a methyl group is particularly preferable from the viewpoint of flame retardancy.
- alkylene group having 1 to 6 carbon atoms examples include methylene group, ethylene group, n-propylene group and isopropylene group, n-butylene group, isobutylene group, tert-butylene group, n-pentylene group, and n-hexylene group. It is done. Among these, an alkylene group having 4 or less carbon atoms is preferable, and a methylene group and an ethylene group are particularly preferable from the viewpoint of flame retardancy.
- the aliphatic nitrogen-containing heterocyclic ring formed by combining B 1 and R 13 when A is a hydrogen atom is a 3- to 13-membered, preferably 4- to 8-membered, more preferably 6-membered nitrogen Is a heterocyclic ring containing one of
- the nitrogen-containing heterocyclic ring that can be formed when A is an organic group represented by the general formula (II) is 5 to 20 members, preferably 5 to 8 members, more preferably 6 or 7 members, still more preferably A 6-membered heterocycle containing two nitrogens.
- B 1 is an alkyl group having 1 to 6 carbon atoms
- A is a hydrogen atom
- B 1 and R 13 -A are bonded to each other.
- the nitrogen atom to which they are bonded together forms a nitrogen-containing heterocycle, represented by the general formula (III):
- R 1 , R 2 , R 11 , and R 12 are the same as defined in formula (I), and R 16 is an alkylene group having 2 to 12 carbon atoms, A is an organic group represented by the general formula (II), and B 1 and B 2 are each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
- R 1 , R 2 , R 11 , R 12 , and R 13 are the same as defined in the general formula (I), and R 3 , R 4 , R 14 , and R 15 are defined in the general formula (II)
- R 6 and R 7 are each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms
- B 1 is an alkyl group having 1 to 6 carbon atoms
- A is an organic group represented by the general formula (II)
- B 2 is an alkyl group having 1 to 6 carbon atoms
- B 1 and B 2 are bonded, and these are bonded Together with the nitrogen atom and R 13 form a nitrogen-containing heterocycle, general formula (V):
- R 1 , R 2 , R 11 , R 12 , and R 13 are the same as defined in the general formula (I), and R 3 , R 4 , R 14 , and R 15 are defined in the general formula (II) And R 17 is an alkylene group having 2 to 12 carbon atoms].
- Examples of the compound represented by the general formula (III) include compounds such as the following formulas (1) to (3).
- Examples of the compound represented by the general formula (IV) include compounds such as the following formulas (4) to (9).
- Examples of the compound represented by the general formula (V) include compounds such as the following formulas (10) to (14).
- a compound in which R 1 and R 2 are methyl groups and R 11 and R 12 are methylene groups is preferable from the viewpoint of flame retardancy.
- a in the general formula (I) is preferably an organic group represented by the general formula (II).
- R 3 and R 4 are methyl groups, and R 14 and R 15 are A methylene group is preferred.
- R 13 in the general formula (I) has 1 to 6 carbon atoms, preferably 1 to 5 carbon atoms, more preferably 1 to 4 carbon atoms, and more preferably 1 to 2 carbon atoms from the viewpoint of flame retardancy. More preferably.
- a in the formula (I) is an organic group represented by the formula (II)
- B 2 of B 1 of the general formula (I) (II) does not bind, flame retardant
- both B 1 and B 2 are hydrogen atoms.
- B 1 and B 2 are bonded, it is preferable that B 1 and B 2 together form an ethylene group or a propylene group. More preferably, B 1 and B 2 together form an ethylene group.
- R 1 and R 2 of the general formula (I) and R 11 and R 12 are R 3 of the general formula (II) and It is preferably the same as R 4 and R 14 and R 15 , that is, the two phosphorus-containing ring structures are the same. If the two phosphorus-containing ring structures are the same, there is an advantage that the compound can be easily synthesized.
- preferred compounds include compounds of the formulas (1), (4) to (7), (10) and (12). , (4) to (6) and (10) are more preferred, and compounds of the formulas (4) to (6) and (10) are more preferred.
- the method for synthesizing the phosphoramidate compound represented by the general formula (I) is not particularly limited. Since some of the phosphoramidate compounds represented by the general formula (I) are known and their synthesis methods are also known, they may be synthesized using the known synthesis methods as they are. Further, the known synthesis method may be modified as appropriate. Accordingly, the phosphoramidate compound represented by the general formula (I) can be synthesized by applying various known reactions with respect to the synthesis of the phosphoramidate compound.
- R 1 , R 2 , R 11 , and R 12 are the same as defined in the general formula (I), and X represents a halogen atom such as Br or Cl.
- X represents a halogen atom such as Br or Cl.
- the compound of the formula (VIa) includes, for example, phosphorus oxyhalide (for example, phosphorus oxychloride or phosphorus oxybromide) and the following formula (VIIa):
- the compound of formula (VIb) can also be obtained by the same method. That is, phosphorus oxyhalide (for example, phosphorus oxychloride or phosphorus oxybromide) and the following formula (VIIb):
- the reaction between phosphorus oxyhalide and diol can be carried out in an organic solvent, if necessary.
- organic solvent those having no reaction activity with the raw material phosphorus oxyhalide and diol can be used, and for example, toluene, xylene, chlorobenzene, dichlorobenzene, 1,4-dioxane and the like can be used.
- the phosphoramidate compound represented by the general formula (I) specifically, when the phosphoramidate compound is a compound represented by the general formula (III),
- the compound of the general formula (VIa) corresponding to the phosphorus-containing ring structure and the cyclic amine (for example, piperidine) corresponding to the nitrogen-containing ring structure of the general formula (III) can be reacted at 1: 1 (molar ratio). That's fine.
- phosphorus oxyhalide for example, phosphorus oxychloride or phosphorus oxybromide
- neopentyl glycol 2,2-dimethyl-1,3-propanediol
- the phosphoramidate compound is a compound represented by the general formula (IV) and the two phosphorus-containing rings have the same structure (that is, R 1 , R 2 , R 11 , R 12 and R 3 , R 4 , R 14 , and R 15 are the same)
- the compound of general formula (VIa) corresponding to the structure of the phosphorus-containing ring and the —N (R 6 ) —R 13 —N (R 7 ) — May be reacted with a diamine (for example, ethylenediamine) corresponding to the structure of the moiety at a ratio of 2: 1 (molar ratio).
- a diamine for example, ethylenediamine
- the compound of the general formula (VIa) corresponding to the two phosphorus-containing rings and 1: 1: 1 (molar ratio) of the compound of the general formula (VIb) and a diamine (for example, ethylenediamine) corresponding to the structure of the —N (R 6 ) —R 13 —N (R 7 ) — moiety
- a diamine for example, ethylenediamine
- the reaction may be carried out by reacting three types of compounds in one step, or after reacting the compound of general formula (VIa) with the diamine, the reaction with the compound of general formula (VIb) may be performed.
- the phosphoramidate compound is a compound represented by the general formula (V) and the two phosphorus-containing rings have the same structure (that is, R 1 , R 2 , R 11 , R 12 and R 3 , R 4 , R 14 , and R 15 are the same), a compound of the general formula (VI) corresponding to the structure of the phosphorus-containing ring and a cyclic diamine corresponding to the cyclic diamine structure portion (for example, piperazine) And 2: 1 (molar ratio).
- the phosphoramidate compound is a compound represented by the general formula (V) and the two phosphorus-containing rings have different structures
- the general formula (VIa) corresponding to the structures of the two phosphorus-containing rings
- the compound of the general formula (VIb) may be reacted with a cyclic diamine corresponding to the cyclic diamine structure portion (for example, piperazine) at 1: 1: 1 (molar ratio).
- the reaction may be carried out by reacting three types of compounds in one step, or after reacting the compound of general formula (VIa) with the diamine, the reaction with the compound of general formula (VIb) may be performed.
- phosphoramidate compounds synthesized as described above can be used as they are as flame retardants for polyurethane. You may adjust a particle size etc. as needed. Moreover, you may perform a surface treatment etc. as needed.
- the average particle size of the phosphoramidate compound when used as a flame retardant is not particularly limited, but is preferably 500 ⁇ m or less, more preferably 300 ⁇ m or less, and even more preferably 100 ⁇ m or less. Further, from the viewpoint of equipment and cost for reducing the particle size, the thickness is preferably 10 nm or more, more preferably 100 nm or more, and further preferably 1 ⁇ m or more.
- one of the various phosphoramidate compounds may be used alone, or a plurality of kinds may be used in combination.
- the amount used when the phosphoramidate compound, which is the flame retardant of the present invention, is used in a polyurethane resin is not particularly limited, but is 100 parts by weight of polyol. 0.1 parts by weight or more is preferably used, more preferably 1 part by weight or more, and even more preferably 5 parts by weight or more. If necessary, 10 parts by weight or more can be used. Moreover, it is preferable to use 60 parts by weight or less, more preferably 40 parts by weight or less, and further preferably 30 parts by weight or less. It can also be 20 weight part or less as needed. If the amount of the flame retardant used is too small, a sufficient flame retarding effect may not be obtained. On the other hand, when there is too much usage-amount, the physical characteristic of the resin composition obtained may fall.
- Polyurethane resin used in the polyurethane resin composition of the present invention will be described in detail.
- a flame retardant polyurethane resin composition can be obtained by mixing the flame retardant of the present invention with a polyurethane resin.
- the polyurethane resin may be a thermoplastic polyurethane resin or a thermosetting polyurethane resin.
- thermoplastic polyurethane resin for example, a flame retardant polyurethane resin composition can be obtained by mixing a resin and a flame retardant.
- the urethane synthesis reaction may be performed after mixing the urethane reaction raw material and the flame retardant.
- a flame retardant polyurethane resin composition may be obtained by mixing a resin and a flame retardant.
- the urethane reaction material and the flame retardant are mixed before the urethane.
- a flame retardant polyurethane resin composition is obtained by performing a synthesis reaction.
- the polyurethane resin is in the form of a polyurethane foam in one embodiment and in the form of a polyurethane elastomer in another embodiment.
- the performance required for the flame retardant for polyurethane, particularly polyurethane foam, is significantly different from the performance required for the flame retardant of other resins such as polyester and polyolefin. Therefore, in general, it is not appropriate to divert a flame retardant used for polyester or the like to polyurethane.
- compounds having an aromatic structure are selected as flame retardants used in various resins classified as polyesters and engineering plastics or polyolefins. This is because these resins are often molded at a high temperature, and the flame retardant added to these resins often requires heat resistance and mechanical strength.
- the molding processing temperature of polyester or the like is usually around 300 ° C., and the flame retardant used for the polyester is required to sufficiently withstand the molding processing temperature, and therefore has a thermal decomposition temperature of about 400 ° C.
- the compound is selected as a flame retardant for polyester.
- the flame retardant of polyurethane particularly polyurethane foam
- fogging resistance, scorch resistance and distortion are more important than heat resistance and mechanical strength.
- the processing temperature of polyurethane foam is at most about 200 ° C., it is generally a compound having a lower heat resistance than a flame retardant for polyester (for example, a compound having a thermal decomposition temperature of about 300 ° C.).
- a compound excellent in fogging resistance, scorch resistance, distortion and the like is used as a flame retardant for polyurethane foam.
- the design philosophy and chemical structure of the flame retardant are different from those of other resin flame retardants. Is different. Under such circumstances, it is common technical knowledge of those skilled in the art of flame retardants for resins that flame retardants for polyurethane foams are significantly different from flame retardants for other resins such as polyester. And because of this technical common sense, when a flame retardant for resin such as polyester is used as it is for polyurethane, especially polyurethane foam, it is considered that the flame retardant compound cannot exhibit the desired performance comprehensively. It was.
- the present invention provides a flame retardant for a special resin called polyurethane, which is required to have a performance significantly different from that of other resins. And this flame retardant has the outstanding remarkable effect that it is the performance which is favorable about the fogging resistance, scorch property, and distortion property which are requested
- an extremely excellent flame retardant is provided comprehensively for polyurethane foam.
- a resin other than polyurethane may be mixed in the flame-retardant polyurethane resin composition of the present invention.
- a polyolefin resin for example, polyethylene resin, polypropylene resin, etc.
- a polyester resin for example, polyethylene terephthalate resin, polybutylene terephthalate resin, etc.
- an acrylic resin for example, polymethyl methacrylate resin, etc.
- the amount of the resin other than polyurethane is preferably 20 parts by weight or less with respect to 100 parts by weight of the total amount of resins in the composition (that is, the sum of the amount of polyurethane resin and the amount of resin other than polyurethane). 10 parts by weight or less is more preferable, 5 parts by weight or less is more preferable, 1 part by weight or less is more preferable, 0.5 part by weight is particularly preferable, and 0.1 part by weight or less is most preferable.
- the flame-retardant polyurethane resin composition of the present invention can also be a composition that does not contain a resin other than a polyurethane resin. By not using a resin other than the polyurethane resin, the characteristics of the polyurethane resin can be exhibited to the maximum.
- polyol As the polyol used in the polyurethane resin composition of the present invention, various known polyols can be used as the polyol for the polyurethane resin. In particular, various polyols generally used in the production of polyurethane foams can be suitably used. Specifically, polyether polyol, polyester polyol, polymer-dispersed polyol, or the like can be used. Generally, it is not particularly limited as long as it is used as a raw material for forming polyurethane. Polyols containing about 2-15 hydroxyl groups per molecule are preferred, and polyols containing about 2-8 hydroxyl groups per molecule are more preferred.
- the hydroxyl value of the polyol is preferably about 25 to 70 mgKOH / g.
- the molecular weight of the polyol is from about 100 to 20000 in one embodiment and from about 250 to 6500 in a preferred embodiment. If the molecular weight is within this range, it is easy to obtain activity and viscosity suitable for urethane foam formation when used in polyurethane foam. Conversely, if the molecular weight is too large or too small, a good urethane foam can be obtained. Hateful.
- polyether polyols include, for example, glycols such as ethylene glycol or propylene glycol, triols such as glycerin or trimethylolpropane, and polyfunctional polyols such as pentaerythritol, sorbitol, or sucrose.
- polyether polyols obtained by adding alkylene oxides such as ethylene oxide or propylene oxide in a random or block form to amine compounds such as ammonia, triethanolamine, ethylenediamine, diethylenetriamine, aminoethylpiperazine or aniline.
- a polyether polyol having a hydroxyl value of about 25 to 70 mg KOH / g is preferred.
- the polyester polyol is a compound having a hydroxyl group at the terminal obtained by polycondensation of a polyfunctional carboxylic acid and a polyfunctional hydroxy compound, and preferably has a number average molecular weight of about 500 to 10,000, more preferably a number average molecular weight of 1,000 to 5,000. Something about can be used.
- adipic acid, phthalic acid, succinic acid, azelaic acid, sebacic acid and the like can be used as the polyfunctional carboxylic acid.
- glycols such as ethylene glycol, propylene glycol, butanediol and diethylene glycol
- polyhydric alcohols such as glycerin, trimethylolpropane and pentaerythritol
- the polymer-dispersed polyol is a mixture of a polyether polyol and an ethylenically unsaturated monomer. If necessary, a chain transfer agent, a dispersion stabilizer, etc. are added, and the ethylenically unsaturated monomer is added in the presence of a radical initiator. It can be obtained by radical polymerization.
- ethylenically unsaturated monomer examples include cyano group-containing monomers such as acrylonitrile and methacrylonitrile, methyl (meth) acrylate, butyl (meth) acrylate, stearyl (meth) acrylate, and hydroxyalkyl (meth) acrylate (for example, , Hydroxyethyl (meth) acrylate), dimethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate and other (meth) acrylic acid esters, acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid and other carboxyls Group-containing monomers, maleic anhydride, acid anhydride-containing monomers such as itaconic anhydride, hydrocarbon compounds such as butadiene, isoprene, 1,4-pentadiene, styrene, ⁇ -methylstyrene, phenylst
- polyol component may be used alone or in combination of two or more depending on the properties required for a desired polyurethane product such as polyurethane foam.
- the polyisocyanate to be reacted with the polyol is a compound having a plurality of isocyanate groups.
- a polyisocyanate used in any conventionally known polyurethane resin can be used as the polyisocyanate.
- a polyisocyanate compound for example, aromatic polyisocyanate, aliphatic polyisocyanate, alicyclic polyisocyanate and the like can be used, and further modified polyisocyanate obtained by modifying these polyisocyanates, etc. Can be used. Moreover, you may use the mixture of 2 or more types of polyisocyanate as needed.
- polyisocyanate examples include tolylene diisocyanate (TDI) (for example, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate), 4,4-diphenylmethane diisocyanate (MDI), 1,5- Naphthalene diisocyanate (NDI), triphenylmethane triisocyanate, xylylene diisocyanate (XDI), hexamethylene diisocyanate (HDI), dicyclohexylmethane diisocyanate, isophorone diisocyanate (IPDI), modified products of these polyisocyanates, etc. (for example, carbodiimide modified products) , Modified burette, dimer, trimer, etc.). Furthermore, the terminal isocyanate group prepolymer etc. which are obtained from these polyisocyanate and an active hydrogen compound can also be used.
- TDI tolylene diisocyanate
- MDI 4,4-diphenylmethan
- polyisocyanate a so-called block polyisocyanate type compound in which an isocyanate group is protected by a protective group may be used.
- block polyisocyanate since the reaction does not start until heating is performed after mixing with the polyol, there is an advantage that the mixture can be stored stably.
- the amount of polyisocyanate used is not particularly limited, and any amount can be used as long as polyurethane can be formed by reaction with polyol. Therefore, in consideration of the total number of moles of isocyanate groups in the polyisocyanate and the total number of moles of active hydrogen such as hydroxyl groups in the polyol and water of the blowing agent, the blending amount should be adjusted so that the urethane synthesis reaction proceeds well. It can be determined as appropriate.
- the amount of polyisocyanate used can be appropriately designed according to the performance of the target urethane.
- the isocyanate index (isocyanate index) serving as an index of the amount may be 100 or less, or may exceed 100. Preferably it is 90 or more, More preferably, it is 95 or more, More preferably, it is 100 or more, More preferably, it is 105 or more. It may be 110 or more, 115 or more, or 120 or more as required.
- the isocyanate index is preferably 130 or less, more preferably 125 or less, still more preferably 120 or less, and still more preferably 115 or less. If necessary, it can be 110 or less, 105 or less, or 100 or less.
- the isocyanate index represents the equivalent ratio of the isocyanate group of the polyisocyanate to the total amount of active hydrogen such as polyol and water in percentage. That is, it means the amount of polyisocyanate actually present in the reaction system when the amount of polyisocyanate stoichiometrically required is 100 with respect to the total amount of active hydrogen present in the reaction system. Thus, an isocyanate index exceeding 100 means that the polyisocyanate is in excess of an active hydrogen-containing compound such as a polyol.
- the amount of polyisocyanate is preferably an amount that gives an isocyanate index of about 90 to 120, and an amount that makes about 95 to 115. More preferably, the amount is about 100 to 115.
- the amount of polyisocyanate is such that the isocyanate index is about 100 to 110.
- the amount of polyisocyanate is preferably an amount such that the isocyanate index is about 180 to 300, and is about 220 to 260. It is more preferable to use the amount. When the amount of polyisocyanate is too large or too small, it is difficult to obtain a polyurethane foam having good physical properties.
- the polyurethane resin of the present invention is a polyurethane foam
- a foaming agent is added to the raw material composition and the reaction raw material composition as necessary.
- the foaming agent is used for forming a polyurethane foam during the polyurethane polymerization reaction or by foaming a polyurethane resin.
- a foaming agent is usually used.
- the foaming agent is not used, it is difficult to sufficiently foam, and it is very preferable to use the foaming agent.
- a known foaming agent used for ordinary polyurethane foam can be used as the foaming agent.
- water, pentane, cyclopentane, hexane, cyclohexane, dichloromethane, carbon dioxide gas or the like is used.
- These foaming agents may be used singly or in combination of two or more, depending on the required density of foam and other physical properties, according to known usage methods. .
- the amount of the foaming agent used is not particularly limited, but is generally preferably 0.01 parts by weight or more, more preferably 0.1 parts by weight or more with respect to 100 parts by weight of the polyol. Moreover, 50 weight part or less is preferable and 40 weight part or less is more preferable.
- a foaming agent other than water may be used in combination, depending on the required density of the foam and other physical properties.
- the amount of the foaming agent other than water is preferably 0.1 parts by weight or more and more preferably 1 part by weight or more with respect to 100 parts by weight of the polyol.
- 50 weight part or less is preferable and 30 weight part or less is more preferable.
- a catalyst is added to the polyurethane resin composition of the present invention as necessary.
- the catalyst is for accelerating the urethanization reaction between polyol and polyisocyanate.
- the catalyst used in the polyurethane resin composition of the present invention is not particularly limited, and various conventionally known catalysts for promoting the reaction for synthesizing polyurethane can be used. Roughly classified are amine catalysts and metal catalysts.
- Catalysts may be used alone or in combination of two or more.
- the amine catalyst include triethylenediamine, dimethylethanolamine, bis (2-dimethylaminoethyl) ether, N, N ′, N′-trimethylaminoethylpiperazine, N-ethylmorpholine, and the like. Tertiary amines are used.
- the organometallic compound containing various metals, such as tin, copper, zinc, cobalt, nickel, is typical, and the catalyst containing tin can be preferably used.
- the tin catalyst include, for example, tin octylate (tin octoate), dibutyltin dilaurate, and the like.
- acetates, alkali metal alcoholates and the like can be used.
- the metal catalyst is particularly preferably used when producing a slab-based flexible polyurethane foam.
- the amount of the amine catalyst used is not particularly limited, but is usually preferably 0.02 parts by weight or more, more preferably 0.05 parts by weight or more with respect to 100 parts by weight of the polyol. If necessary, it may be 0.1 parts by weight or more. Moreover, 3 weight part or less is preferable and 1 weight part or less is more preferable. If necessary, it may be 0.5 parts by weight or less.
- the amount of the metal catalyst used is not particularly limited, but is usually preferably 0.02 parts by weight or more and more preferably 0.05 parts by weight or more with respect to 100 parts by weight of the polyol. If necessary, it may be 0.1 parts by weight or more. In one embodiment, it is 1 part by weight or less, preferably 0.8 part by weight or less, and more preferably 0.5 part by weight or less. If necessary, it may be 0.3 parts by weight or less.
- the metal catalyst is not an essential component. Therefore, when a sufficient urethane synthesis reaction is performed without adding a metal catalyst, it is not necessary to add a metal catalyst.
- a metal catalyst is generally not used when producing a rigid polyurethane foam.
- the raw material for the polyurethane foam contains a foam stabilizer to facilitate foaming.
- a foam stabilizer By using a silicone foam stabilizer, mixing and emulsification of raw material components and dispersion of entrained gas are facilitated, and effects such as prevention of foam coalescence and stabilization of the cell membrane are achieved. A foam having this can be obtained.
- foam stabilizer those generally used in the production of polyurethane foams can be used.
- a silicone compound an anionic surfactant such as sodium dodecylbenzenesulfonate, sodium lauryl sulfate, polyether siloxane, a phenolic compound, or the like is used as the foam stabilizer.
- the content of the foam stabilizer is preferably 0.1 parts by weight or more, more preferably 0.5 parts by weight or more with respect to 100 parts by weight of the polyol. If necessary, the amount can be 1 part by weight or more. Moreover, 5 weight part or less is preferable and 2.5 weight part or less is more preferable. If necessary, it can be 2 parts by weight or less or 1.5 parts by weight or less.
- the content of the foam stabilizer is too small, the foam regulating action at the time of foaming of the raw material of the polyurethane foam is not sufficiently exhibited, and it may be difficult to obtain a good foam. On the other hand, when the content of the foam stabilizer is too large, the foam regulating action becomes strong, and the cell connectivity tends to decrease.
- the polyurethane resin composition of the present invention can contain an antioxidant effective amount of an antioxidant.
- the antioxidant include a hydroquinone compound and a trivalent organophosphate compound.
- the amount of the antioxidant used is preferably 0.1 parts by weight or more and more preferably 0.2 parts by weight or more with respect to 100 parts by weight of the polyurethane resin composition. Moreover, 5 weight part or less is preferable and 2 weight part or less is more preferable. When long-term storage stability is not required, it is not necessary to use an antioxidant.
- additives other than the above-mentioned various additives can be used as required within the range not impairing the properties of the target polyurethane according to the purpose of use.
- additives include, for example, colorants (eg, dyes or pigments), crosslinking agents, UV absorbers, hydrolysis inhibitors, fillers (eg, inorganic fillers), reinforcing agents (eg, glass fiber reinforcement) Material) and the like.
- colorants eg, dyes or pigments
- crosslinking agents eg, UV absorbers, hydrolysis inhibitors
- fillers eg, inorganic fillers
- reinforcing agents eg, glass fiber reinforcement
- each of these additives can be 0.01 parts by weight or more with respect to 100 parts by weight of the polyol, and is 0.1 parts by weight or more or 1 part by weight or more. And can be up to 20 parts by weight, up to 10 parts by weight or up to 5 parts by weight.
- the above-mentioned additives such as the colorant, the crosslinking agent, the ultraviolet absorber, the hydrolysis inhibitor, the filler, and the reinforcing agent are not necessarily required for the polyurethane resin composition of the present invention. It is sufficient that these additives are used in the polyurethane resin composition in the minimum amount necessary based on the performance required for the intended polyurethane resin product.
- the polyurethane resin composition of the present invention When the polyurethane resin composition of the present invention is used to produce a urethane resin product for special applications that require very high strength and very high rigidity, a large amount of fiber reinforcement (for example, , Glass fibers) and large amounts of inorganic fillers (eg glass powder, glass flakes) can be mixed to produce products with very high strength and very high stiffness. However, in normal applications other than special applications where such very high strength and very high stiffness are required, it is not necessary to mix fiber reinforcement and inorganic filler.
- fiber reinforcement for example, Glass fibers
- inorganic fillers eg glass powder, glass flakes
- the polyurethane resin composition of the present invention when used to produce urethane resin products for normal applications that require relatively high flexibility, has a large amount of fiber reinforcement and a large amount of inorganic filling. There is no need to mix the materials. Rather, in general, it is preferable that the amount of the fiber reinforcing material and the inorganic filler is small or the absence of the fiber reinforcing material and the inorganic filler is obtained in order to obtain high flexibility. And even if a fiber reinforcement and an inorganic filler do not exist, the performance calculated
- the flame retardant of the present invention can be used by mixing with a flame retardant other than the phosphoramidate compound in addition to the above-mentioned compound comprising the phosphoramidate compound, if necessary.
- an organic flame retardant other than the phosphoramidate compound or an inorganic flame retardant can be used.
- organic flame retardants other than phosphoramidate compounds include melamine flame retardants, halogen flame retardants, and phosphate ester flame retardants.
- inorganic flame retardants include antimony compounds and metal hydroxides. Specific examples of the metal hydroxide include aluminum hydroxide (alumina hydrate), magnesium hydroxide, and the like.
- the amount of flame retardant other than the phosphoramidate compound used is preferably 20 parts by weight or less, more preferably 10 parts by weight or less, and even more preferably 5 parts by weight or less based on 100 parts by weight of polyol. More preferred are parts by weight or less.
- the amount of the flame retardant other than the phosphoramidate compound used is preferably 100 parts by weight or less, more preferably 50 parts by weight or less, and 20 parts by weight with respect to 100 parts by weight of the flame retardant of the present invention. The following is more preferable, and 10 parts by weight or less is even more preferable.
- the usage-amount of flame retardants other than a phosphoramidate compound is 5 weight part or less, 1 weight part or less, 0.5 weight part or less, and 0.1 weight part or less with respect to 100 weight part of resin.
- Parts by weight, 0.05 parts by weight, 0.01 parts by weight, 0.009 parts by weight, 0.008 parts by weight, 0.005 parts by weight, 0.001 parts by weight, 0.0005 parts by weight The amount is preferably not more than parts, or not more than 0.0001 parts by weight.
- a flame retardant composed of a phosphoramidate compound is used without mixing a flame retardant other than the phosphoramidate compound.
- the flame retardant of the present invention can achieve high flame retardancy and various performances required for ordinary urethane resin products without mixing with flame retardants other than phosphoramidate compounds. Therefore, if the target urethane resin product is not a product for a special application, it is not necessary to mix a flame retardant other than the phosphoramidate compound with the flame retardant of the present invention.
- a polyurethane foam raw material composition can be obtained by mixing the flame retardant of the present invention with each raw material for the polyurethane foam described above.
- a polyurethane foam raw material composition is obtained by mixing the flame retardant of the present invention with a polyol and optionally the additives described above.
- the reaction starts at room temperature. Therefore, when it is necessary to store the polyurethane foam raw material composition in a state before the start of the reaction, the polyisocyanate and the polyol are usually stored in a state where they are not mixed.
- raw materials other than polyisocyanate are mixed and stored as a urethane raw material composition separately from polyisocyanate, and stored and reacted in a manner in which the raw material composition is mixed with polyisocyanate and reacted immediately before the reaction. May be performed.
- the raw material composition may include all raw materials other than polyisocyanate. That is, one raw material composition may contain all raw materials other than polyisocyanate. However, raw materials other than polyisocyanate may be further divided as necessary. For example, a mixture of polyol and flame retardant is prepared and stored as a raw material composition, and other additives are prepared separately, and all raw materials may be mixed before reaction with polyisocyanate. good. Further, for example, raw materials other than polyisocyanate may be prepared and stored in two or more raw material compositions. For example, a material obtained by adding a dispersant to a small amount of polyol may be prepared as one raw material composition, and the remaining polyol or the like may be separately prepared as another raw material composition.
- a raw material composition is obtained by adding a dispersant to a small amount of polyol, for example, the composition is stored and mixed with the remaining polyol before reacting and further reacted with polyisocyanate.
- the whole process can be done in the form of
- a dispersant can be added to a polyol, and the flame retardant of the present invention can be uniformly dispersed in the polyol to obtain a raw material composition.
- Phosphoramidate does not dissolve in the polyol, but a composition that does not separate over time can be obtained by adding a dispersant.
- a polyurethane foam reaction raw material composition is obtained by mixing the flame retardant of the present invention with a polyol, a polyisocyanate and, if necessary, the above-mentioned additives.
- the polyurethane foam reaction raw material composition since the reaction starts quickly, the polyurethane foam reaction raw material composition usually contains all raw materials for forming the polyurethane foam. And the target polyurethane foam can be obtained by reaction of a reaction raw material composition.
- the polyurethane foam raw material composition preferably contains substantially only materials necessary for the polyurethane foam raw material composition. That is, it is preferable that an unnecessary material is not substantially included.
- the amount of materials other than the above components (polyol, catalyst, foaming agent, foam stabilizer and antioxidant) contained in the polyurethane foam raw material composition is based on the whole raw material composition. It is preferably 10% by weight or less, more preferably 5% by weight or less, still more preferably 1% by weight or less, still more preferably 0.5% by weight or less, and 0.1% by weight. % Or less is particularly preferable.
- the polyurethane foam raw material composition may be a composition that does not substantially contain a flame retardant other than the phosphoramidate compound.
- the polyurethane foam raw material composition may be a composition that does not substantially contain an organic flame retardant other than the phosphoramidate compound.
- the polyurethane foam raw material composition may be a composition that does not substantially contain a melamine compound.
- the polyurethane foam raw material composition may be a composition that does not contain an inorganic flame retardant.
- the polyurethane foam raw material composition may be a composition that does not contain a hydroxide-based flame retardant.
- the polyurethane foam raw material composition may be a composition that does not contain alumina hydrate.
- the polyurethane foam reaction raw material composition preferably contains substantially only materials necessary for the polyurethane foam reaction raw material composition. That is, it is preferable that an unnecessary material is not substantially included.
- the amount of materials other than the above-mentioned components (polyol, polyisocyanate, catalyst, foaming agent, foam stabilizer and antioxidant) contained in the polyurethane foam reaction raw material composition is the same as that of the reaction raw material composition. Is preferably 10% by weight or less, more preferably 5% by weight or less, still more preferably 1% by weight or less, and still more preferably 0.5% by weight or less. The content is particularly preferably 0.1% by weight or less.
- the polyurethane foam reactive raw material composition can be a composition that does not substantially contain a flame retardant other than the phosphoramidate compound.
- the polyurethane foam reaction raw material composition may be a composition that does not substantially contain an organic flame retardant other than the phosphoramidate compound.
- the polyurethane foam reaction raw material composition may be a composition that does not substantially contain a melamine compound.
- the polyurethane foam reaction raw material composition may be a composition that does not contain an inorganic flame retardant.
- the polyurethane foam reaction raw material composition may be a composition that does not contain a hydroxide-based flame retardant.
- the polyurethane foam reaction raw material composition may be a composition not containing alumina hydrate.
- polyurethane foam The polyurethane foam of the present invention (hereinafter also referred to as polyurethane foam) is produced by a usual method for producing polyurethane foam except that it contains the flame retardant of the present invention. That is, it is obtained by foaming and curing by reacting a polyol and a polyisocyanate in a polyurethane foam raw material composition containing a polyol, a polyisocyanate, a flame retardant, and, if necessary, a foaming agent and a catalyst.
- the polyurethane foam may be a rigid polyurethane foam or a flexible polyurethane foam.
- the polyurethane foam preferably contains substantially only the materials necessary for the polyurethane foam. That is, it is preferable that an unnecessary material is not substantially included.
- the amount of materials other than the above-described components (polyurethane resin, catalyst, foaming agent, foam stabilizer and antioxidant) contained in the polyurethane foam is 10 with respect to the entire polyurethane foam. % By weight or less, preferably 5% by weight or less, more preferably 1% by weight or less, still more preferably 0.5% by weight or less, and 0.1% by weight or less. It is particularly preferred that
- the polyurethane foam can be made into a foam substantially free of a flame retardant other than the phosphoramidate compound.
- the polyurethane foam may be a foam that does not substantially contain an organic flame retardant other than the phosphoramidate compound.
- the polyurethane foam may be a foam that is substantially free of melamine compounds.
- the polyurethane foam may be a foam that does not contain an inorganic flame retardant.
- the polyurethane foam may be a foam that does not contain a hydroxide flame retardant.
- the polyurethane foam may be a foam that does not contain alumina hydrate.
- the polyurethane reaction raw material composition is cured.
- an active hydrogen-containing compound such as polyol
- All the raw materials may be mixed at one time to form the urethane reaction raw material composition in one step, or the respective raw materials may be sequentially mixed to form the urethane reaction raw material composition in a plurality of steps.
- components other than polyisocyanate may be stirred and mixed to form a urethane raw material composition, and polyisocyanate may be added immediately before the curing reaction.
- Urethane foam can be cured and foamed by any conventionally known method. By performing curing and foaming using the urethane reaction raw material composition containing the flame retardant of the present invention, a polyurethane foam composition is obtained.
- the flame retardant of the present invention can be a flame retardant for polyurethane elastomers.
- a polyurethane elastomer refers to a polyurethane elastic synthetic material used in the rubber field.
- the polyurethane elastomer may be a thermoplastic polyurethane elastomer or a thermosetting polyurethane elastomer.
- the polyurethane elastomer may be a polyurethane foam elastomer in which the polyurethane is foamed, or may be an elastomer in which the polyurethane is not foamed.
- the flame retardant polyurethane elastomer composition can be obtained by mixing the thermoplastic polyurethane elastomer and the flame retardant of the present invention.
- the thermoplastic polyurethane elastomer any conventionally known thermoplastic polyurethane elastomer can be used.
- the flame retardant of the present invention is used for the thermosetting polyurethane elastomer
- the flame retardant of the present invention is mixed with the reaction raw material of the thermosetting polyurethane elastomer, and then the curing reaction is performed.
- a urethane reaction raw material composition is prepared by mixing the flame retardant of the present invention, a polyol for elastomer, polyisocyanate, and various additives as required, and this reaction raw material composition can be reacted.
- a flame retardant elastomer composition can be obtained.
- any polyol conventionally used for polyurethane elastomers can be used.
- the various polyols described above can be used.
- the polyol for elastomer preferably contains a glycol called a chain extender. By introducing a chain extender, appropriate elasticity can be imparted to the elastomer.
- the chain extender include lower alkylene glycols such as ethylene glycol and propylene glycol. The carbon number of the lower alkylene glycol may be 1, 2, 3, 4, 5 or 6, for example.
- the same additives as those described for the polyurethane foam described above can be used in the same amount and in the same manner.
- the polyurethane elastomer is an unfoamed elastomer, it is not necessary to use a foaming agent and a foam stabilizer. Therefore, among the various additives described above, the foaming agent is not used.
- the reaction raw material composition is prepared using additives other than the foam stabilizer.
- reaction starts at room temperature when polyisocyanate and polyol are mixed. Therefore, when it is necessary to store the polyurethane elastomer raw material composition in a state before the start of the reaction, the polyisocyanate and the polyol are usually stored in a state where they are not mixed.
- raw materials other than polyisocyanate are mixed and stored as a urethane raw material composition separately from polyisocyanate, and stored and reacted in a manner in which the raw material composition is mixed with polyisocyanate and reacted immediately before the reaction. May be performed.
- the raw material composition may include all raw materials other than polyisocyanate. That is, one raw material composition may contain all raw materials other than polyisocyanate. However, raw materials other than polyisocyanate may be further divided as necessary. For example, a mixture of polyol and flame retardant is prepared and stored as a raw material composition, and other additives are prepared separately, and all raw materials may be mixed before reaction with polyisocyanate. good. Further, for example, raw materials other than polyisocyanate may be prepared and stored in two or more raw material compositions. For example, a material obtained by adding a dispersant to a small amount of polyol may be prepared as one raw material composition, and the remaining polyol or the like may be separately prepared as another raw material composition.
- a raw material composition is obtained by adding a dispersant to a small amount of polyol, for example, the composition is stored and mixed with the remaining polyol before reacting and further reacted with polyisocyanate.
- the whole process can be done in the form of
- a dispersant can be added to a polyol, and the flame retardant of the present invention can be uniformly dispersed in the polyol to obtain a raw material composition.
- Phosphoramidate does not dissolve in the polyol, but a composition that does not separate over time can be obtained by adding a dispersant.
- a polyurethane elastomer reaction raw material composition is obtained by mixing the flame retardant of the present invention with a polyol, a polyisocyanate and, if necessary, the above-mentioned additives.
- a polyol suitable for an elastomer containing a chain extender is preferably used as the polyol.
- the polyurethane elastomer reaction raw material composition usually contains all the raw materials for forming the polyurethane elastomer.
- the target polyurethane elastomer can be obtained by reaction of a reaction raw material composition.
- the polyurethane elastomer raw material composition preferably contains substantially only materials necessary for the polyurethane elastomer raw material composition. That is, it is preferable that an unnecessary material is not substantially included.
- the amount of materials other than the above-mentioned components (polyol, catalyst, foaming agent, foam stabilizer and antioxidant) contained in the polyurethane elastomer raw material composition is based on the whole raw material composition. It is preferably 10% by weight or less, more preferably 5% by weight or less, still more preferably 1% by weight or less, still more preferably 0.5% by weight or less, It is particularly preferable that the amount is not more than wt%.
- the flame retardant of the present invention can achieve high flame retardancy and various performances required for ordinary urethane resin products without mixing with flame retardants other than phosphoramidate compounds. is there. Therefore, the polyurethane elastomer raw material composition can be a composition that does not substantially contain a flame retardant other than the phosphoramidate compound.
- the polyurethane elastomer raw material composition may be a composition that does not substantially contain an organic flame retardant other than the phosphoramidate compound.
- the polyurethane elastomer raw material composition may be a composition that does not substantially contain a melamine compound.
- the polyurethane elastomer raw material composition may be a composition that does not contain an inorganic flame retardant.
- the polyurethane elastomer raw material composition may be a composition that does not contain a hydroxide-based flame retardant. Further, for example, the polyurethane elastomer raw material composition may be a composition containing no alumina hydrate.
- the polyurethane elastomer reaction raw material composition preferably contains only materials necessary for the polyurethane elastomer reaction raw material composition. That is, it is preferable that an unnecessary material is not substantially included.
- the amount of materials other than the above-described components (polyol, polyisocyanate, catalyst, foaming agent, foam stabilizer and antioxidant) contained in the polyurethane elastomer reaction raw material composition is the same as the reaction raw material composition. It is preferably 10% by weight or less, more preferably 5% by weight or less, still more preferably 1% by weight or less, and further preferably 0.5% by weight or less, based on the entire product. The content is preferably 0.1% by weight or less.
- the polyurethane elastomer reactive raw material composition can be a composition that does not substantially contain a flame retardant other than the phosphoramidate compound.
- the polyurethane elastomer reaction raw material composition can be a composition that does not substantially contain an organic flame retardant other than the phosphoramidate compound.
- the polyurethane elastomer reaction raw material composition may be a composition that does not substantially contain a melamine compound.
- the polyurethane elastomer reaction raw material composition may be a composition that does not contain an inorganic flame retardant.
- the polyurethane elastomer reaction raw material composition may be a composition that does not contain a hydroxide-based flame retardant.
- the polyurethane elastomer reaction raw material composition may be a composition not containing alumina hydrate.
- the polyurethane elastomer of the present invention is produced by an ordinary method for producing a polyurethane elastomer except that it contains the flame retardant of the present invention. That is, an elastomer can be obtained by reacting a polyol and a polyisocyanate in a polyurethane elastomer reaction raw material composition containing a polyol, a polyisocyanate, a flame retardant, and, if necessary, a catalyst and other additives. .
- thermosetting polyurethane elastomer When the flame retardant of the present invention is used for a thermosetting polyurethane elastomer, there is an advantage that it is excellent in flame retardancy and performance as a polyurethane elastomer.
- the polyurethane elastomer preferably contains substantially only materials necessary for the polyurethane elastomer. That is, it is preferable that an unnecessary material is not substantially included.
- the amount of materials other than the above-mentioned components (polyurethane resin, catalyst, foaming agent, foam stabilizer and antioxidant) contained in the polyurethane elastomer is 10 with respect to the whole polyurethane elastomer. % By weight or less, preferably 5% by weight or less, more preferably 1% by weight or less, still more preferably 0.5% by weight or less, and 0.1% by weight or less. It is particularly preferred that
- the polyurethane elastomer can be made into an elastomer substantially free of a flame retardant other than the phosphoramidate compound.
- the polyurethane elastomer may be an elastomer that does not substantially contain an organic flame retardant other than the phosphoramidate compound.
- the polyurethane elastomer may be an elastomer that is substantially free of melamine compounds.
- the polyurethane elastomer can be an elastomer that does not contain an inorganic flame retardant.
- the polyurethane elastomer may be an elastomer that does not contain a hydroxide flame retardant.
- the polyurethane elastomer may be an elastomer that does not contain alumina hydrate.
- the method of using the flame retardant of the present invention is described in detail particularly for polyurethane foams and polyurethane elastomers. This is because the effects of the flame retardant of the present invention are extremely advantageous in these uses.
- the use of the flame retardant of the present invention is not limited to these. It is also possible to use polyurethanes other than foam or elastomer. Furthermore, it can be used for resins other than polyurethane, for example, various thermoplastic resins other than thermoplastic polyurethane, and can also be used for thermosetting resins other than thermosetting polyurethane.
- the back coating agent obtained above was uniformly applied to the back surface of a polyester knit of 250 g / m 2 so as to have a dry weight of 60 g / m 2, and then dried at 150 ° C. for 3 minutes to obtain a flame-retardant fiber fabric.
- Comparative Example 1 Difficulty in the same manner as in Reference Example 1 except that 20 parts by weight of a polyphosphate flame retardant ammonium polyphosphate silane-coated product (Budenheim, FRCROS486, hereinafter referred to as “APP”) was used as the flame retardant compound. A flammable fiber fabric was obtained.
- a polyphosphate flame retardant ammonium polyphosphate silane-coated product Budenheim, FRCROS486, hereinafter referred to as “APP”
- a flame-retardant fiber fabric was obtained in the same manner as in Reference Example 1 except that 20 parts by weight of a compound having a succinamide was used.
- the fiber fabrics of Reference Examples 1 and 2 are considered to contribute to flame retardancy, although the phosphorus content and nitrogen content in the flame retardant compound are low compared to the fiber fabric of Comparative Example 1, Shows good flame retardancy. Further, it can be seen that the flame retardant compounds used in the fiber fabrics of Reference Examples 1 and 2 have low hot water solubility that causes wrinkles. On the other hand, Comparative Example 1 using APP as the flame retardant compound passes the flame retardant test, but is prone to flicker because of its high hot water solubility.
- Kiwatsuki means that the water-soluble component of the flame retardant dissolves when high-temperature steam used in the manufacture of wheel seats and moisture such as rain, sweat, etc. adhere to the surface of the textile product, and later when it is dried. A phenomenon in which a wet part becomes white spots or stains.
- the flame retardant compound of Comparative Example 2 is a phosphate ester having a structure similar to the flame retardant compound of Reference Example 1, and the phosphorus content is also equivalent to the flame retardant compound of Reference Example 1.
- the flame retardant compound of Comparative Example 2 has low flame retardancy and high hot water solubility, and is not suitable as a flame retardant for backcoat. From these, it can be seen that the backcoat agent containing the phosphoramidate represented by the general formula (I) is very effective as a flame retardant backcoat agent.
- the above-mentioned resin composition solution for forming the skin layer is applied to a release paper (Dai Nippon Printing Co., Ltd., DE 73) with an applicator set to 320 ⁇ m, dried at 110 ° C. for 4 minutes, and the average film thickness after drying is 40 ⁇ m.
- a coating film for the skin layer was prepared.
- polyurethane material for bonding made by DIC, Crisbon 4010, nonvolatile content 50% by weight
- isocyanate-based crosslinking agent made by DIC, Bernock D-750, nonvolatile content 75% by weight
- crosslinking accelerator 3 parts by weight of DIC, Crisbon A
- the adhesive layer forming resin composition was applied to the upper surface of the skin layer coating film with an applicator set to 320 ⁇ m, and a base fabric (polyester knit, basis weight 250 g / m 2 ) was layered thereon and pressure-bonded. . Heating was performed at 110 ° C. for 4 minutes to accelerate the curing and the solvent was removed. Further, aging was performed at 25 ° C. for 3 days to complete the curing of the adhesive layer, and the release paper was peeled off to complete a flame-retardant synthetic leather. The thickness of the adhesive layer was 150 ⁇ m.
- Example 1 (Production method) In the formulation shown in Table 3, polyol, silicone foam stabilizer, amine-based catalyst, tin-based catalyst, foaming agent and flame retardant A are mixed and stirred with a stirrer at 3000 rpm for 1 minute to make the blend uniform Then, polyisocyanate was added, and the mixture was stirred at 3000 rpm for 5 to 7 seconds. Immediately, the contents were poured into a cube (height about 200 mm) ball box with a square bottom (about 200 mm on one side).
- the obtained foam was allowed to stand in an oven at 80 ° C. for 30 minutes and cured to obtain a polyurethane foam (foam).
- the obtained foam had a white soft open-cell structure.
- the flame retardancy, fogging resistance, compression residual strain, and scorch properties were evaluated by the following methods.
- Test method FMVSS-302 method (Test method for safety standards for automobile interior parts) Horizontal burning test of polyurethane foam Test conditions: The air permeability was adjusted to 200 ml / cm 2 / sec.
- Test conditions Using a windscreen fogging tester (manufactured by Suga Test Instruments Co., Ltd.), a sample of polyurethane foam (diameter 80 mm, thickness 10 mm) was placed at the bottom of the container, and the sample was heated at 100 ° C. for 16 hours. The amount of scattered matter adhering to the aluminum foil at the top of the container was measured as the amount of aluminum adhering (mg).
- Examples 2 to 5 and Comparative Examples 5 and 6 As shown in Table 3, a foam was produced in the same manner as in Example 1 except that flame retardant B, C, D, E, F or G was used instead of flame retardant A. The fogging resistance, compression residual strain, and scorch resistance were evaluated. The results are shown in Table 3.
- Examples 2A-5A, 2B-5B and Comparative Examples 5B and 6B As shown in Table 4 and Table 5, a foam was produced in the same manner as in Example 1 except that the type and amount of the flame retardant were changed, and its flame retardancy, fogging resistance, compression residual strain, scorch property. Evaluated. The results are shown in Table 4 and Table 5.
- Example 3A the flame retardancy was determined to be SE instead of NB, but the combustion distance was 43 mm, so this level is not a problem unless it is a special application that requires extremely high flame retardancy.
- Comparative Examples 5B and 6B the flame retardancy was determined to be SE, but the combustion distance of Comparative Examples 5B and 6B was 87 to 88 mm, and the flame retardancy of Example 3A was Comparative Examples 5B and 6B. Is significantly better than.
- Example 2 In Examples 2 to 5, 2A to 5A, and 2B to 5B, the fogging resistance was very good, and almost no scattering component was observed. Particularly in Examples 2 to 3, 2A to 3A and 2B to 3B (flame retardants B and C), the fogging resistance value “ ⁇ 0.1”, the compression residual strain value 5 or less, and the scorch resistance value 5 or less. It was confirmed that the performance was extremely high overall.
- the fogging resistance is slightly lower than those in Comparative Examples 5 to 6, and the scorch is also slightly lower than that in Comparative Example 5.
- the fogging resistance and the scorch are not special applications that require extremely high performance. This is not a problem level for general applications. For example, some conventionally known flame retardants have results that are worse than the first embodiment in terms of fogging resistance.
- Example 1 As for the scorch, the result of Example 1 is better than that of Comparative Example 6. Therefore, as a comprehensive evaluation including flame retardancy and compression residual strain, Example 1 is better than Comparative Examples 5 to 6, and the flame retardant of Example 1 is more comprehensive than the conventional flame retardant. Can be evaluated as excellent. In Examples 4, 5, 4A, 5A, 4B, and 5B, the scorch property value is slightly high, but it is sufficient for general applications other than special applications that require very high performance for scorch property. Can be used.
- the compound used as a flame retardant in Comparative Examples 5, 6, 5B and 6B is a type of compound that has been conventionally known to have high flame retardancy. It was confirmed that the flame retardant of the present invention has very high performance as compared with the conventional flame retardant known as such a high-performance flame retardant.
- a flame retardant polyurethane foam excellent in flame retardancy, fogging resistance, distortion and scorch properties Compositions and elastomer compositions are provided.
- the urethane foam using the flame retardant of the present invention is excellent in flame retardancy and various performances required for the urethane foam, and can be used for various applications in which the conventional urethane foam has been used.
- the urethane elastomer using the flame retardant of the present invention is excellent in flame retardancy and various performances required for the urethane elastomer, and can be used for various applications in which the urethane elastomer has been conventionally used.
Abstract
Description
ここで、Aが水素原子である場合には、B1が炭素数1~6のアルキル基であって、そして、B1とR13-Aとが結合して、これらが結合している窒素原子と一緒になって含窒素複素環を形成する。
Aが一般式(II)で表される有機基であって、B2が炭素数1~6のアルキル基であり、且つB1が炭素数1~6のアルキル基である場合には、B1とB2とが結合して、これらが結合している窒素原子及びR13と一緒になって含窒素複素環を形成してもよい。]で表されるホスホロアミデート化合物からなるポリウレタンフォームまたはポリウレタンエラストマー用難燃剤。
ここで、該原料組成物は、硬化反応を行う直前にポリイソシアネートと混合されるものである、
組成物。
ここで、該原料組成物は、硬化反応を行う直前にポリイソシアネートと混合されるものである、
組成物。
ここで、Aが水素原子である場合には、B1が炭素数1~6のアルキル基であって、そして、B1とR13-Aとが結合して、これらが結合している窒素原子と一緒になって含窒素複素環を形成する。
Aが一般式(II)で表される有機基であって、B2が炭素数1~6のアルキル基であり、且つB1が炭素数1~6のアルキル基である場合には、B1とB2とが結合して、これらが結合している窒素原子及びR13と一緒になって含窒素複素環を形成してもよい。]
で表されるホスホロアミデート化合物からなる。
Aが一般式(II)で表される有機基であり、B1およびB2がそれぞれ独立して水素原子または炭素数1~6のアルキル基である、一般式(IV):
B1が炭素数1~6のアルキル基であり、且つAが一般式(II)で表される有機基であって、B2が炭素数1~6のアルキル基であり、B1とB2とが結合して、これらが結合している窒素原子及びR13と一緒になって含窒素複素環を形成している、一般式(V):
一般式(I)で表されるホスホロアミデート化合物を合成する方法は特に限定されない。一般式(I)で表されるホスホロアミデート化合物のうちいくつかは公知であり、その合成方法も公知であるので、その公知の合成方法をそのまま用いて合成してもよい。また、その公知の合成方法を適宜改変しても良い。従って、一般式(I)で表されるホスホロアミデート化合物は、ホスホロアミデート化合物の合成に関して公知の各種反応を応用して合成することができる。
各種ホスホロアミデート化合物は、上述した方法で合成されたものをそのまま、ポリウレタン用難燃剤として使用することができる。必要に応じて、粒径の調整等を行っても良い。また、必要に応じて、表面処理等を行ってもよい。
以下、本発明のポリウレタン樹脂組成物に用いられるポリウレタン樹脂について詳細に説明する。
本発明の難燃性ポリウレタン樹脂組成物には、必要に応じて、ポリウレタン以外の樹脂が混合されていても良い。例えば、ポリオレフィン系樹脂(例えば、ポリエチレン樹脂、ポリプロピレン樹脂等)、ポリエステル系樹脂(例えば、ポリエチレンテレフタレート樹脂、ポリブチレンテレフタレート樹脂等)、アクリル系樹脂(例えば、ポリメチルメタクリレート樹脂等)などをポリウレタン樹脂に混合することができる。
本発明のポリウレタン樹脂組成物に用いられるポリオールとしては、ポリウレタン樹脂用のポリオールとして公知の各種のポリオールが使用可能である。特に、ポリウレタン発泡体の製造に一般的に使用されている各種ポリオールが好適に使用可能である。具体的には、ポリエーテルポリオール、ポリエステルポリオール、ポリマー分散ポリオールなどを用いることができる。一般にポリウレタン形成の原料として使用されるものであれば特に限定されない。一分子当たり約2~15個の水酸基を含有するポリオールが好ましく、1分子当り約2~8個の水酸基を含有するポリオールがより好ましい。ポリオールの水酸基価は、1つの実施形態では、25~70mgKOH/g程度が好ましい。ポリオールの分子量は、1つの実施形態では約100~20000であり、好ましい実施形態では約250~6500である。分子量がこの範囲であれば、ポリウレタンフォームに用いた場合にウレタンフォーム形成に適した活性と粘度が得られやすく、逆に分子量が大きすぎる場合または小さすぎる場合には、良好なウレタンフォームが得られにくい。
前記ポリオールと反応させるポリイソシアネートはイソシアネート基を複数個有する化合物である。本発明のポリウレタン樹脂組成物において、ポリイソシアネートとしては、従来公知の任意のポリウレタン樹脂に使用されるポリイソシアネートを使用することができる。この様なポリイソシアネート化合物としては、例えば、芳香族ポリイソシアネート、脂肪族ポリイソシアネート、脂環式ポリイソシアネート等を用いることができ、更に、これらのポリイソシアネートを変性して得られる変性ポリイソシアネート等を用いることができる。また、必要に応じて、2種類以上のポリイソシアネートの混合物を用いてもよい。
本発明のポリウレタン樹脂がポリウレタンフォームである場合、その原料組成物および反応原料組成物には、必要に応じて発泡剤が添加される。発泡剤は、ポリウレタン重合反応の際またはポリウレタン樹脂を発泡させてポリウレタン発泡体とするためのものである。ポリウレタンフォームを工業的に製造する際には、通常、発泡剤が使用される。発泡剤を用いない場合には、充分に発泡させることが困難になりやすいので、発泡剤を用いることが非常に好ましい。
本発明のポリウレタン樹脂組成物には、必要に応じて触媒が添加される。触媒はポリオールとポリイソシアネートとのウレタン化反応を促進するためのものである。本発明のポリウレタン樹脂組成物に用いられる触媒に特に限定はなく、ポリウレタンを合成する反応を促進するための従来公知の各種の触媒を使用することができる。大別してアミン触媒と金属触媒が挙げられる。
ポリウレタン樹脂がポリウレタンフォームである場合、ポリウレタン発泡体の原料には、発泡を円滑に行うために、整泡剤を含有することが好ましい。シリコーン整泡剤を使用することにより、原料成分の混合乳化および巻き込みガスの分散が容易になると共に、泡の合一防止、セル膜の安定化等の効果が奏されて、より良好な特性を有するフォームを得ることができる。
本発明のポリウレタン樹脂組成物には、必要に応じて、酸化防止有効量の酸化防止剤を含有させることができる。ここで酸化防止剤の例としては、ヒドロキノン化合物及び3価の有機リン酸化合物が挙げられる。
更に、本発明のポリウレタン用組成物には、必要に応じて、その使用目的に応じ、目的とするポリウレタンの物性を損なわない範囲内で、上記各種添加剤以外の添加剤を使用することができる。そのような添加剤としては、例えば、着色剤(例えば、染料または顔料)、架橋剤、紫外線吸収剤、加水分解防止剤、充填剤(例えば、無機充填材)、強化剤(例えば、ガラス繊維強化材)等を配合することができる。これらの添加剤の種類及び添加量については特に限定はなく、通常用いられている添加剤を、通常の使用量の範囲において使用できる。具体的には、例えば、これらの添加剤のそれぞれについて、ポリオール100重量部に対して0.01重量部以上とすることが可能であり、0.1重量部以上または1重量部以上とすることも可能であり、そして20重量部以下とすることが可能であり、10重量部以下または5重量部以下とすることが可能である。
本発明の難燃剤は、必要に応じて、上記ホスホロアミデート化合物からなる化合物に加えて、ホスホロアミデート化合物以外の難燃剤と混合して使用することもできる。
本発明の難燃剤を、上述したポリウレタンフォームのための各原料と混合することにより、ポリウレタンフォーム原料組成物が得られる。1つの実施形態においては、本発明の難燃剤を、ポリオールおよび必要に応じて上述した添加剤と混合することにより、ポリウレタンフォーム原料組成物が得られる。
本発明のポリウレタンフォーム(以下、ポリウレタン発泡体ともいう)は、本発明の難燃剤を含有すること以外は通常のポリウレタンフォームの製造方法によって製造される。すなわち、ポリオール、ポリイソシアネート、および難燃剤、ならびに必要に応じて発泡剤及び触媒等を含有するポリウレタン発泡体原料組成物においてポリオールとポリイソシアネートとを反応させることにより、発泡及び硬化させて得られる。
ポリイソシアネートとポリオールなどの活性水素含有化合物との反応により、ポリウレタン反応原料組成物が硬化する。硬化を行う際の各原料の混合方法およびその順序は特に限定されず、任意の方法および順序が可能である。すべての原料を一度に混合して上記ウレタン反応原料組成物を1工程で形成してもよく、あるいは、各原料を逐次混合して上記ウレタン反応原料組成物を複数工程で形成しても良い。例えば、ポリイソシアネート以外の成分を攪拌混合してウレタン原料組成物を形成しておき、硬化反応させる直前にポリイソシアネートを添加しても良い。ただし、ポリイソシアネートとポリオールまたは水等の活性水素を含有する化合物とを混合すると室温でも反応が開始するので、ポリイソシアネートとポリオールまたは水等の活性水素を含有する化合物とを混合する際にすべての原料が混合されるような手順で各原料の混合を行うことが好ましい。
1つの実施形態において、本発明の難燃剤は、ポリウレタンエラストマー用の難燃剤とすることができる。ポリウレタンエラストマーとは、ゴム分野に使用されるポリウレタン弾性合成物質をいう。
本発明のポリウレタンエラストマーは、本発明の難燃剤を含有すること以外は通常のポリウレタンエラストマーの製造方法によって製造される。すなわち、ポリオール、ポリイソシアネート、および難燃剤、ならびに必要に応じて触媒およびその他の添加剤等を含有するポリウレタンエラストマー反応原料組成物においてポリオールとポリイソシアネートとを反応させることにより、エラストマーを得ることができる。
本明細書においては、特に、ポリウレタンフォームおよびポリウレタンエラストマーについて詳細に本発明の難燃剤の使用方法を説明している。これらの用途において、本発明の難燃剤の効果が極めて有利であるからである。しかしながら、本発明の難燃剤の用途はこれらに限定される訳ではない。フォームまたはエラストマーの形態以外の形態のポリウレタンに用いることも可能である。さらに、ポリウレタン以外の樹脂、例えば、熱可塑性ポリウレタン以外の各種熱可塑性樹脂に用いることも可能であり、熱硬化性ポリウレタン以外の熱硬化性樹脂に用いることも可能である。
(合成例1)
式(1)の化合物の合成
式(4)の化合物の合成
式(10)の化合物の合成
下記式で表されるホスホロアミデート化合物(式(5)の化合物)
下記式で表されるホスホロアミデート化合物(式(6)の化合物)
合成例2で得られた難燃化合物20重量部、イオン交換水20重量部、市販のアクリル樹脂エマルジョン(DIC製ボンコートAB-886:固形分50%)40重量部、及び28%アンモニア水溶液0.4重量部に、増粘剤としてSNシックナーA-812(サンノブコ株式会社製)0.7重量部を加え、ホモジナイザーで均一化し、粘度15000mPa・s(BM型粘度計4号ローター12rpm)のバックコート剤を得た。
難燃化合物として、合成例3で得られた難燃化合物20重量部を用いた以外は参考例1と同じ方法で難燃性繊維布帛を得た。
難燃化合物として、ポリリン酸系難燃剤であるポリリン酸アンモニウムのシランコート物(ブーデンハイム社製、FRCROS486、以下「APP」と称する)20重量部を用いた以外は参考例1と同じ方法で難燃性繊維布帛を得た。
難燃化合物として、リン酸エステル系難燃剤である以下の構造:
難燃性試験は、米国自動車安全基準FMVSS302の試験方法に準じて行った。縦横5回ずつ試験を行い、その全てが、1)A標線(38mm)前に自消、2)A標線後の燃焼距離50mm以下かつ燃焼時間60秒以下、3)A標線後の燃焼速度80mm/分以下、のいずれかに該当するものを難燃性ありと判断し、合格とした。
合成例2および3の難燃化合物、ならびに比較例1および2の難燃化合物のそれぞれの5重量部を水45重量部に加え、90℃にて1時間撹拝し、熱時濾過した溶液中のリン含有量を測定することで90℃での熱水溶解度を測定した。なお、難燃化合物が完全に溶解した場合には、熱水溶解度を「>10%」とした。
[表皮層の作成]
ポリウレタン材料(DIC製、クリスボンMP120、不揮発分30重量%)100重量部をトルエン30重量部の割合で混合して溶液とし、表皮層形成用樹脂組成物を調製した。
接着用ポリウレタン材料(DIC製、クリスボン4010、不揮発分50重量%)を100重量部、イソシアネート系架橋剤(DIC製、バーノックD-750、不揮発分75重量%)を10重量部、架橋促進剤(DIC製、クリスボンアクセルHM、不揮発分15重量%)を3重量部、難燃剤として合成例2の難燃化合物(不揮発分100重量%)を6.45重量部、及びトルエンを22.8重量部用いて接着層形成用樹脂組成物を調製した。
上記接着層形成用樹脂組成物を、前記表皮層用塗膜のさらに上面に、320μmに設定したアプリケーターで塗布し、その上に基布(ポリエステルニット、目付250g/m2)を重ね、圧着した。110℃で4分間加熱し、硬化を促進させるとともに溶剤を除去し、さらに25℃で3日間熟成して接着層の硬化を完了させ、離型紙を剥離して難燃性合成皮革を完成した。接着層の厚みは150μmであった。
上記難燃性合成皮革の難燃性試験は、米国自動車安全基準FMVSS302の試験方法に準じて行った。5回試験を行い、その全てがA標線(38mm)前に自消したものを難燃性ありと判断し、合格とした。結果を表2に示す。
難燃剤として、合成例3の難燃化合物を用いた以外は参考例3と同様に合成皮革を得て、難燃性を測定した。結果を表2に示す。
難燃剤として、比較例2で用いたリン酸エステル難燃化合物を用いた以外は参考例3と同様に合成皮革を得て、難燃性を測定した。結果を表2に示す。
難燃剤として、樹脂用に広く使用されているリン酸エステルである、テトラキス(2,6-ジメチルフェニル)-m-フェニレンビスホスフェートを20重量部及びトルエンを39.2重量部用いた以外は参考例3と同様に合成皮革を得て、難燃性を測定した。結果を表2に示す。
以下の実施例において、原料は下記を使用した。
(1)ポリオール:グリセリンおよびプロピレンオキサイドをベースにしたポリエーテルタイプのトリオール、分子量約3000、水酸基価56.0、三井化学株式会社製、商品名:アクトコールT-3000
(2)シリコーン整泡剤:モメンティブ・パフォーマンス・マテリアルズ・ジャパン合同会社製、商品名:Niax Silicone L-638J
(3)アミン系触媒:
エア・プロダクツ・アンド・ケミカル社製、商品名:DABCO 33LV
エア・プロダクツ・アンド・ケミカル社製、商品名:DABCO BL-11
(4)錫系触媒:
エア・プロダクツ・アンド・ケミカル社製、商品名:DABCO T-9)
(5)発泡剤:水
ジクロロメタン
(6)ポリイソシアネート:トリレンジイソシアネート(TDI)
(三井化学株式会社製、商品名:コスモネートT-80)
(2,4体/2,6体=80/20(重量%))
(7)難燃剤:以下の難燃剤A~Gを用いた。
下記式で表されるホスホロアミデート化合物(式(1)の化合物)
下記式で表されるホスホロアミデート化合物(式(4)の化合物)
下記式で表されるホスホロアミデート化合物(式(10)の化合物)
下記式で表されるホスホロアミデート化合物(式(5)の化合物)
下記式で表されるホスホロアミデート化合物(式(6)の化合物)
ホスホリックアシッド,オキシジ-2,1-エタンジイルテトラキス(2-クロロ-1-メチルエチル)エステル
(難燃剤G) Antiblaze V-66 (アルベマール社製)
主成分:2,2-ビス(クロロメチル)-1,3,-プロパンジオールビス〔ビス(2-クロロエチル)ホスフェート〕。
(製造方法)
表3に示す処方で、ポリオール、シリコーン整泡剤、アミン系触媒、錫系触媒、発泡剤および難燃剤Aを混合し、撹拌機を用いて回転数3000rpmで1分間攪拌して配合物を均一に混和した後、さらにポリイソシアネートを加え、回転数3000rpmで5~7秒間攪拌し、直ちに内容物を、底面が正方形(一辺約200mm)の立方体(高さ約200mm)のボール箱に注いだ。
得られた発泡体から試料を切り取り、下記の条件で燃焼試験を行なった。
ポリウレタンフォームの水平燃焼試験
試験条件:通気度200ml/cm2/secになるように調整した。
試料 :縦160mm、横70mm、厚み13mm
評価基準:NB:燃焼距離38mm以下
SE:燃焼距離39mm以上88mm以下
BN:燃焼距離89mm以上。
得られた発泡体から試料を切り取り、下記の条件で耐フォギング試験を行なった。
圧縮残留歪み(%)を、JISK6400-4:2004に準じて測定した。
得られた発泡体を電子レンジで3分、その後70℃で4.5分保持後、温度の高い発泡体の中心部分と温度の低い側面部分について色差計(日本電色Color MeterZE2000)を用いて黄変度(白色度)を測定し、それらの色差をΔYIで示した。
表3に示すとおり、難燃剤Aの代わりに難燃剤B、C、D、E、FまたはGを用いたこと以外は、実施例1と同様にして発泡体を製造し、その難燃性、耐フォギング性、圧縮残留歪み、スコーチ性を評価した。結果を表3に示す。
表4および表5に示すとおり、難燃剤の種類および量を変更したこと以外は、実施例1と同様にして発泡体を製造し、その難燃性、耐フォギング性、圧縮残留歪み、スコーチ性を評価した。結果を表4および表5に示す。
Claims (18)
- 一般式(I):
[式中、R1及びR2はそれぞれ独立して炭素数1~3のアルキル基であり、R11及びR12はそれぞれ独立して炭素数1~3のアルキレン基であり、R13は炭素数1~6のアルキレン基であり、B1は水素原子又は炭素数1~6のアルキル基であり、Aは水素原子又は一般式(II):
(式中、R3及びR4はそれぞれ独立して炭素数が1~3のアルキル基であり、R14及びR15はそれぞれ独立して炭素数が1~3のアルキレン基であり、B2は水素原子又は炭素数1~6のアルキル基である)で表される有機基である。
ここで、Aが水素原子である場合には、B1が炭素数1~6のアルキル基であって、そして、B1とR13-Aとが結合して、これらが結合している窒素原子と一緒になって含窒素複素環を形成する。
Aが一般式(II)で表される有機基であって、B2が炭素数1~6のアルキル基であり、且つB1が炭素数1~6のアルキル基である場合には、B1とB2とが結合して、これらが結合している窒素原子及びR13と一緒になって含窒素複素環を形成してもよい。]で表されるホスホロアミデート化合物からなるポリウレタンフォームまたはポリウレタンエラストマー用難燃剤。 - 前記一般式(I)において、Aが一般式(II)で表される有機基である、請求項1に記載の難燃剤。
- ポリウレタンフォーム用である、請求項1または2に記載の難燃剤。
- 前記一般式(I)において、R1及びR2がメチル基であり、R11及びR12がメチレン基である請求項1~3のいずれか1項に記載の難燃剤。
- 前記一般式(I)において、Aが一般式(II)で表される有機基であり、R3及びR4がメチル基であり、R14及びR15がメチレン基である請求項1~4のいずれか1項に記載の難燃剤。
- 前記一般式(I)において、R13が炭素数1~4のアルキレン基である請求項5に記載の難燃剤。
- 前記一般式(I)において、R13が炭素数1~2のアルキレン基である請求項6に記載の難燃剤。
- 前記一般式(I)において、B1及びB2が水素原子である請求項5~7のいずれか1項に記載の難燃剤。
- 前記一般式(I)において、B1とB2とが結合して、これらが結合している窒素原子及びR13と一緒になって5~8員の含窒素複素環を形成している請求項5~7のいずれか1項に記載の難燃剤。
- 前記一般式(I)において、B1とB2とが結合して、これらが結合している窒素原子及びR13と一緒になって6員の含窒素複素環を形成している請求項9に記載の難燃剤。
- 請求項1~10のいずれか1項に記載の難燃剤、ポリオール、及びポリイソシアネートならびに発泡剤を含有する難燃性ポリウレタンフォーム反応原料組成物。
- 請求項1~10のいずれか1項に記載の難燃剤およびポリオールを含む難燃性ポリウレタンフォーム原料組成物であって、
ここで、該原料組成物は、硬化反応を行う直前にポリイソシアネートと混合されるものである、
組成物。 - 請求項1~10のいずれか1項に記載の難燃剤を含むポリウレタンフォーム。
- 請求項1~10のいずれか1項に記載の難燃剤、ポリオール、発泡剤およびポリイソシアネートを含む反応原料組成物を反応させる工程を包含する、ポリウレタンフォームの製造方法。
- 請求項1、2および4~10のいずれか1項に記載の難燃剤、エラストマー用ポリオール、及びポリイソシアネートならびに発泡剤を含有する難燃性ポリウレタンエラストマー反応原料組成物。
- 請求項1、2および4~10のいずれか1項に記載の難燃剤およびエラストマー用ポリオールを含む難燃性ポリウレタンエラストマー原料組成物であって、
ここで、該原料組成物は、硬化反応を行う直前にポリイソシアネートと混合されるものである、
組成物。 - 請求項1、2および4~10のいずれか1項に記載の難燃剤を含むポリウレタンエラストマー。
- 請求項1、2および4~10のいずれか1項に記載の難燃剤、エラストマー用ポリオール、発泡剤およびポリイソシアネートを含む反応原料組成物を反応させる工程を包含する、ポリウレタンエラストマーの製造方法。
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR1020167013304A KR102295291B1 (ko) | 2013-10-31 | 2014-10-07 | 난연제 및 난연성 폴리우레탄 수지 조성물 |
US15/027,672 US9988510B2 (en) | 2013-10-31 | 2014-10-07 | Flame retardant and flame retardant polyurethane resin composition |
JP2015544776A JP6513571B2 (ja) | 2013-10-31 | 2014-10-07 | 難燃剤および難燃性ポリウレタン樹脂組成物 |
CN201480058762.5A CN105683337B (zh) | 2013-10-31 | 2014-10-07 | 阻燃剂和阻燃性聚氨酯树脂组合物 |
MX2016005544A MX2016005544A (es) | 2013-10-31 | 2014-10-07 | Retardante de llama y composicion de resina de poliuretano retardante de llama. |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2013-227044 | 2013-10-31 | ||
JP2013227044 | 2013-10-31 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2015064018A1 true WO2015064018A1 (ja) | 2015-05-07 |
Family
ID=53003652
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2014/005095 WO2015064018A1 (ja) | 2013-10-31 | 2014-10-07 | 難燃剤および難燃性ポリウレタン樹脂組成物 |
Country Status (7)
Country | Link |
---|---|
US (1) | US9988510B2 (ja) |
JP (1) | JP6513571B2 (ja) |
KR (1) | KR102295291B1 (ja) |
CN (1) | CN105683337B (ja) |
MX (1) | MX2016005544A (ja) |
TW (1) | TWI631131B (ja) |
WO (1) | WO2015064018A1 (ja) |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2019093066A1 (ja) * | 2017-11-10 | 2019-05-16 | 大八化学工業株式会社 | 難燃剤組成物および該難燃剤組成物を含む難燃性熱可塑性樹脂組成物 |
JP2020063439A (ja) * | 2018-10-16 | 2020-04-23 | 株式会社エフコンサルタント | 硬化性組成物 |
WO2021132597A1 (ja) * | 2019-12-27 | 2021-07-01 | 大八化学工業株式会社 | 難燃剤組成物および該難燃剤組成物を含む難燃性熱可塑性樹脂組成物 |
CN115010992A (zh) * | 2022-07-08 | 2022-09-06 | 威海海润新材料科技有限公司 | 一种含磷阻燃剂及其合成与应用 |
JP7421900B2 (ja) | 2018-10-24 | 2024-01-25 | 株式会社エフコンサルタント | 断熱サンドイッチパネル及びそれに用いる硬化性組成物 |
Families Citing this family (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109790268A (zh) * | 2016-08-05 | 2019-05-21 | 东曹株式会社 | 软质聚氨酯泡沫成形用多元醇组合物以及软质聚氨酯泡沫 |
CN106634523A (zh) * | 2017-01-05 | 2017-05-10 | 华北科技学院 | 一种环境友好聚氨酯阻燃涂料及其制备方法 |
KR101985111B1 (ko) * | 2017-12-14 | 2019-05-31 | 서울시립대학교 산학협력단 | 폴리우레탄 조성물, 이를 포함하는 흡음재 및 폴리우레탄 폼의 제조방법 |
CN108766647A (zh) * | 2018-05-21 | 2018-11-06 | 浙江嘉泽电缆有限公司 | 一种防水电缆 |
CN108986964B (zh) * | 2018-07-23 | 2019-05-28 | 广州开创天虹电气有限公司 | 一种超高阻燃耐候性电缆 |
EP4010450A4 (en) * | 2019-08-09 | 2023-05-03 | Daihachi Chemical Industry Co., Ltd. | FLAME RETARDANT COMPOSITION AND FLAME RETARDANT THERMOPLASTIC POLYURETHANE COMPOSITION |
CN115011104B (zh) * | 2021-11-25 | 2023-12-22 | 上海联景高分子材料有限公司 | 一种阻燃性能优异的热塑性聚氨酯的制备方法及其应用 |
KR20230080668A (ko) | 2021-11-30 | 2023-06-07 | 롯데케미칼 주식회사 | 폴리우레탄 수지 조성물 및 이의 경화물을 포함하는 폴리우레탄 폼 |
KR20230081448A (ko) | 2021-11-30 | 2023-06-07 | 롯데케미칼 주식회사 | 유무기 하이브리드 폴리올 조성물 및 이의 제조방법 |
CN113980264B (zh) * | 2021-11-30 | 2023-02-28 | 江苏钟山新材料有限公司 | 一种阻燃聚醚多元醇的制备方法及其应用 |
CN114395100A (zh) * | 2022-01-21 | 2022-04-26 | 中国科学技术大学 | 一种防火阻燃聚氨酯泡沫材料及其制备方法 |
CN116284649B (zh) * | 2023-04-10 | 2024-04-05 | 上海玓墨节能科技有限公司 | 一种防火封堵聚氨酯泡沫及其制备方法和应用 |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5017463A (ja) * | 1973-06-18 | 1975-02-24 | ||
WO2008085926A1 (en) * | 2007-01-04 | 2008-07-17 | Supresta Llc | Phosphoramide ester flame retardant and resins containing same |
CN101608348A (zh) * | 2009-06-16 | 2009-12-23 | 天津工业大学 | 一种阻燃纤维素纤维及其制备方法 |
WO2014002958A1 (ja) * | 2012-06-28 | 2014-01-03 | 大八化学工業株式会社 | 難燃剤、該難燃剤を含有する難燃性水性樹脂組成物及び難燃性ウレタン樹脂組成物、並びにそれらの用途 |
Family Cites Families (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
BE790849Q (fr) | 1970-02-02 | 1973-04-30 | Olin Corp | Nouveaux polyesters phosphoriques halogenes retardateurs d'inflammationet mousse de polyurethanne contenant ces polyesters |
US3887655A (en) * | 1972-05-12 | 1975-06-03 | Stauffer Chemical Co | Phosphoramidate esters of dibromoneopentylglycol |
US3867320A (en) | 1972-11-29 | 1975-02-18 | Olin Corp | Flame retardant densified polyurethane foam |
JPS5419919A (en) * | 1977-07-14 | 1979-02-15 | Mitsubishi Rayon Co Ltd | Novel phosphoric acid amide, its preparation, and flame-retardants consisting of the compound |
JPS5636512A (en) | 1979-08-31 | 1981-04-09 | Daihachi Kagaku Kogyosho:Kk | Flame retardant for polyurethane foam |
JP3113228B2 (ja) | 1998-06-01 | 2000-11-27 | 大八化学工業株式会社 | 難燃性ポリウレタンフォーム組成物 |
US7115677B2 (en) * | 2001-11-30 | 2006-10-03 | Polyplastics Co., Ltd. | Flame-retardant resin composition |
US6617379B2 (en) * | 2001-12-04 | 2003-09-09 | Albemarle Corporation | Flame retardant polymer compositions |
JP4469167B2 (ja) * | 2003-12-03 | 2010-05-26 | ポリプラスチックス株式会社 | 難燃性樹脂組成物 |
-
2014
- 2014-10-07 KR KR1020167013304A patent/KR102295291B1/ko active IP Right Grant
- 2014-10-07 CN CN201480058762.5A patent/CN105683337B/zh active Active
- 2014-10-07 US US15/027,672 patent/US9988510B2/en active Active
- 2014-10-07 JP JP2015544776A patent/JP6513571B2/ja active Active
- 2014-10-07 MX MX2016005544A patent/MX2016005544A/es unknown
- 2014-10-07 WO PCT/JP2014/005095 patent/WO2015064018A1/ja active Application Filing
- 2014-10-30 TW TW103137663A patent/TWI631131B/zh active
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5017463A (ja) * | 1973-06-18 | 1975-02-24 | ||
WO2008085926A1 (en) * | 2007-01-04 | 2008-07-17 | Supresta Llc | Phosphoramide ester flame retardant and resins containing same |
CN101608348A (zh) * | 2009-06-16 | 2009-12-23 | 天津工业大学 | 一种阻燃纤维素纤维及其制备方法 |
WO2014002958A1 (ja) * | 2012-06-28 | 2014-01-03 | 大八化学工業株式会社 | 難燃剤、該難燃剤を含有する難燃性水性樹脂組成物及び難燃性ウレタン樹脂組成物、並びにそれらの用途 |
Non-Patent Citations (1)
Title |
---|
JOURNAL OF CENTRAL CHINA NORMAL UNIVERSITY( NAT. SCI., vol. 38, no. 2, 2004, pages 197 - 200 * |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2019093066A1 (ja) * | 2017-11-10 | 2019-05-16 | 大八化学工業株式会社 | 難燃剤組成物および該難燃剤組成物を含む難燃性熱可塑性樹脂組成物 |
JPWO2019093066A1 (ja) * | 2017-11-10 | 2020-12-17 | 大八化学工業株式会社 | 難燃剤組成物および該難燃剤組成物を含む難燃性熱可塑性樹脂組成物 |
JP7244085B2 (ja) | 2017-11-10 | 2023-03-22 | 大八化学工業株式会社 | 難燃剤組成物および該難燃剤組成物を含む難燃性熱可塑性樹脂組成物 |
JP2020063439A (ja) * | 2018-10-16 | 2020-04-23 | 株式会社エフコンサルタント | 硬化性組成物 |
JP7421900B2 (ja) | 2018-10-24 | 2024-01-25 | 株式会社エフコンサルタント | 断熱サンドイッチパネル及びそれに用いる硬化性組成物 |
WO2021132597A1 (ja) * | 2019-12-27 | 2021-07-01 | 大八化学工業株式会社 | 難燃剤組成物および該難燃剤組成物を含む難燃性熱可塑性樹脂組成物 |
CN115010992A (zh) * | 2022-07-08 | 2022-09-06 | 威海海润新材料科技有限公司 | 一种含磷阻燃剂及其合成与应用 |
Also Published As
Publication number | Publication date |
---|---|
US20160244582A1 (en) | 2016-08-25 |
CN105683337B (zh) | 2018-07-03 |
CN105683337A (zh) | 2016-06-15 |
MX2016005544A (es) | 2016-07-21 |
KR20160079002A (ko) | 2016-07-05 |
KR102295291B1 (ko) | 2021-08-30 |
TWI631131B (zh) | 2018-08-01 |
JP6513571B2 (ja) | 2019-05-15 |
TW201527311A (zh) | 2015-07-16 |
JPWO2015064018A1 (ja) | 2017-03-09 |
US9988510B2 (en) | 2018-06-05 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP6513571B2 (ja) | 難燃剤および難燃性ポリウレタン樹脂組成物 | |
Chen et al. | Inherently flame-retardant flexible polyurethane foam with low content of phosphorus-containing cross-linking agent | |
JP6082393B2 (ja) | 新規なホスホンアミデート、並びにその合成、及びその難燃化剤への応用 | |
JP4497245B2 (ja) | アルコール可溶型ウレタン樹脂組成物の製造方法、ポリウレタン多孔体及び透湿性フィルム | |
JP5313968B2 (ja) | ホスフェート−ホスホネート結合を有する有機リン化合物、およびそれを用いた難燃性ポリエステル繊維、難燃性ポリウレタン樹脂組成物 | |
TWI242569B (en) | Description composition for flame-retardant flexible polyurethane foam | |
JP6284476B2 (ja) | 難燃剤、該難燃剤を含有する難燃性水性樹脂組成物及び難燃性ウレタン樹脂組成物、並びにそれらの用途 | |
JP4410665B2 (ja) | 軟質ポリウレタン発泡体の製造方法 | |
JP5024524B2 (ja) | 難燃性ポリウレタンフォーム | |
AU2016310087B2 (en) | Polymer-modified polyol dispersion | |
JPH0629313B2 (ja) | 難燃性軟質ウレタンフォームの製造法 | |
WO2017029337A1 (en) | Flame-resistant polymer polyol dispersion | |
JP2006526047A (ja) | 重合体物質の製造方法 | |
JP2002003713A (ja) | 難燃性軟質ポリウレタンフォーム | |
JP5042449B2 (ja) | 難燃性フィルターフォームとその製造方法 | |
JP4814600B2 (ja) | 低燃焼性ポリウレタン発泡体 | |
US20200140640A1 (en) | Flexible foam with halogen-free flame retardant | |
JP6482208B2 (ja) | ポリウレタンフォーム | |
JP2013189519A (ja) | ポリウレタン発泡シートの製造方法及びポリウレタン発泡シート並びに皮革様シート状物 | |
JP2007297442A (ja) | ポリウレタン発泡体 | |
Giacomello | Development of flexible polyurethane foams with improved reaction to fire | |
EP3608347A1 (de) | Weichschaumstoff mit halogenfreiem flammschutz |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 14858997 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 2015544776 Country of ref document: JP Kind code of ref document: A |
|
WWE | Wipo information: entry into national phase |
Ref document number: 15027672 Country of ref document: US |
|
WWE | Wipo information: entry into national phase |
Ref document number: MX/A/2016/005544 Country of ref document: MX |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
ENP | Entry into the national phase |
Ref document number: 20167013304 Country of ref document: KR Kind code of ref document: A |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 14858997 Country of ref document: EP Kind code of ref document: A1 |