JP2015160898A - Flame-retardant soft foam and method for producing the same - Google Patents

Abstract

To impart flame retardancy to a soft foam.
A flame retardant soft foam 7 is produced by impregnating or adhering an impregnating liquid 4 containing a phosphorus compound, a binder and a dispersant to a soft foam 1 and drying the impregnating liquid.
[Selection] Figure 1

Description

  The present invention relates to a flame retardant soft foam and a method for producing the same.

  Soft foams such as flexible polyurethane foam have elasticity, compression restoring force, moderate breathability, etc., so cushion materials for kitchen and commercial sponges, furniture, bedding, automobile parts, etc., and electronic equipment It is used for gaskets.

  The soft foam used for these applications is required to have high flame retardance that extinguishes when the flame goes away, and shape retention so that the porous skeleton of the foam remains even after combustion. For this reason, as described in Patent Documents 1-3, a method for imparting flame retardancy to a flexible polyurethane foam has been proposed.

  Patent Document 1 discloses a method for producing a flame-retardant flexible polyurethane foam by impregnating a flexible polyurethane foam with an impregnating liquid containing a clay mineral, a metal hydroxide, and a binder, and drying.

  Patent Document 2 discloses an ink adsorbent manufacturing method including an impregnation step of immersing a flexible polyurethane foam with an impregnation liquid containing an inorganic flame retardant, a binder, and a surfactant.

  Patent Document 3 uses an aqueous solution of a ceramic flame retardant prepared so as to dissolve and contain a boric acid compound as a main component at a high concentration of at least 20% or more when mixed and dissolved in water. A method for producing a low-flammability flexible polyurethane foam characterized by impregnating and adhering the ceramic flame retardant is disclosed.

  In the case of the above Patent Documents 1-3, it is necessary to impregnate a large amount of an organic or inorganic flame retardant in order to increase the flame retardancy. There was a problem that it could not be obtained.

JP2012-111826 JP 2009-173753 A JP-A-9-272754

  The objective of this invention is providing the flame-retardant soft foam excellent in the flame retardance, and its manufacturing method.

  The present inventors have found that a soft foam excellent in flame retardancy can be constituted by using an impregnation liquid containing a phosphorus compound, a binder, and a dispersant as an impregnation liquid for a soft foam, and the present invention is completed. It came to.

  That is, the present invention is as follows.

  Item 1. A flame retardant soft foam, which is obtained by impregnating or adhering a phosphorus compound, a binder and a dispersant to a soft foam having open cells.

  Item 2. Item 2. The flame retardant flexible foam according to item 1, wherein the phosphorus compound contains red phosphorus and phosphate.

  Item 3. Item 3. The flame retardant soft foam according to Item 1 or 2, wherein the phosphorus compound is impregnated or adhered to 5 to 50 parts by weight with respect to 100 parts by weight of the soft foam.

  Item 4. Item 1. The soft foam is further impregnated or adhered with a flame retardant selected from a phosphate ester, a bromine-containing flame retardant, a boron-containing flame retardant, an antimony-containing flame retardant, a metal hydroxide and a polyisocyanurate resin. The flame-retardant soft foam according to any one of 3.

Item 5. Impregnating or adhering an impregnating liquid containing a phosphorus compound, a binder and a dispersant to a soft foam having open cells;
And a step of obtaining a flame retardant soft foam by drying the soft foam impregnated or adhered with the impregnation liquid.

  Item 6. Item 6. The method according to Item 5, wherein the impregnating liquid further comprises a flame retardant selected from a phosphate ester, a bromine-containing flame retardant, a boron-containing flame retardant, an antimony-containing flame retardant, a metal hydroxide, and a polyisocyanurate resin.

  According to the present invention, a flexible foam excellent in flame retardancy is provided.

The schematic which shows the impregnation equipment for enforcing the manufacturing method of the flexible foam of this invention.

  The flame-retardant soft foam of the present invention is characterized by impregnating or adhering a phosphorus compound, a binder, and a dispersant to a soft foam having open cells.

  In the present specification, the “soft foam having open cells” refers to a soft foam in which bubbles in the soft foam are connected and gas or liquid can pass through the soft foam. “Impregnating” the impregnating liquid refers to impregnating the impregnating liquid into the structure of the soft foam. “Attaching” the impregnating liquid to the soft foam refers to attaching the impregnating liquid to the soft foam regardless of the outer surface or the inner surface of the soft foam.

Soft foams include soft polyurethane foam, polyethylene foam, propylene foam, polystyrene foam, polyvinyl chloride foam, EVA (ethylene vinyl acetate copolymer) cross-linked foam, PET resin foam, and melamine resin foam. The body etc. are included. The density of the flexible foam (JIS K7222) is not particularly limited, but is usually preferably 10 to 80 kg / m ³ . If it is less than 10 kg / m ³ , the strength of the urethane resin is small, and if it exceeds 80 kg / m ³ , impregnation into the cell may be difficult. Also, when the soft foam is soft polyurethane, it has good affinity with the impregnating liquid containing the polyisocyanurate resin, and when the impregnating liquid contains a foaming agent, the impregnating liquid can also be given foaming properties and flame retardant. The flexible foam is excellent not only in flame retardancy but also in flexibility.

  Impregnation or adhesion of a phosphorus compound, a binder and a dispersant to a soft foam having open cells is usually performed by impregnating or attaching a soft foam having open cells to an impregnation liquid containing a phosphorus compound, a binder and a dispersant. Done.

  Next, a phosphorus compound is demonstrated. In one embodiment, the phosphorus compound includes red phosphorus. In another embodiment, the phosphorus compound comprises red phosphorus and phosphate.

  The phosphorus compound is preferably impregnated or adhered to 5 to 50 parts by weight with respect to 100 parts by weight of the flame retardant soft foam.

  There is no limitation in red phosphorus used for this invention, A commercial item can be selected suitably and can be used.

  Moreover, it is preferable that the addition amount of red phosphorus used for the refractory urethane resin composition according to the present invention is in the range of 1.0 to 20 parts by weight in 100 parts by weight of the impregnating liquid.

  When the range of the red phosphorus is 1.0 part by weight or more, the self-extinguishing property of the flame retardant soft foam is maintained, and when it is 20 parts by weight or less, the viscosity of the impregnating liquid does not increase excessively and the impregnating property is increased. Is retained.

  The phosphate used in the present invention contains phosphoric acid. The phosphoric acid used for the phosphate is not particularly limited, and examples thereof include various phosphoric acids such as monophosphoric acid, pyrophosphoric acid, polyphosphoric acid, and combinations thereof.

  Examples of the phosphate include phosphoric acid composed of a salt of the various phosphoric acids with at least one metal or compound selected from metals of Group IA to IVB of the periodic table, ammonia, aliphatic amines, and aromatic amines. Mention may be made of salts. Examples of the metals in groups IA to IVB of the periodic table include lithium, sodium, calcium, barium, iron (II), iron (III), and aluminum.

  Examples of the aliphatic amine include methylamine, ethylamine, diethylamine, triethylamine, ethylenediamine, piperazine and the like.

  Examples of the aromatic amine include pyridine, triazine, melamine, and ammonium.

  The above-mentioned phosphate may be added with a known water resistance improving treatment such as silane coupling agent treatment or coating with a melamine resin, or may be added with a known foaming aid such as melamine or pentaerythritol. .

  Specific examples of the phosphate include monophosphate, pyrophosphate, polyphosphate, and the like.

  The monophosphate is not particularly limited, and examples thereof include ammonium salts such as ammonium phosphate, ammonium dihydrogen phosphate, and diammonium hydrogen phosphate, phosphoric acid-sodium phosphate, disodium phosphate, trisodium phosphate, and phosphorous acid. Sodium salt of acid-sodium, disodium phosphite, sodium hypophosphite, etc., monopotassium phosphate, dipotassium phosphate, tripotassium phosphate, monopotassium phosphite, dipotassium phosphite, hypophosphorous acid Potassium salts such as potassium phosphate, lithium salts such as lithium phosphate, dilithium phosphate, trilithium phosphate, lithium phosphite, dilithium phosphite, lithium hypophosphite, barium dihydrogen phosphate, Barium salts such as barium hydrogen phosphate, tribarium phosphate, barium hypophosphite, magnesium monohydrogen phosphate, phosphoric acid Magnesium salts such as elemental magnesium, trimagnesium phosphate, magnesium hypophosphite, calcium dihydrogen phosphate, calcium hydrogen phosphate, tricalcium phosphate, calcium hypophosphite, etc., zinc phosphate, zinc phosphite And zinc salts such as zinc hypophosphite.

  The polyphosphate is not particularly limited, and examples thereof include ammonium polyphosphate, piperazine polyphosphate, melamine polyphosphate, ammonium amide polyphosphate, and aluminum polyphosphate.

  Among these, since the self-extinguishing property of the phosphate is improved, it is preferable to use a monophosphate, and it is more preferable to use ammonium dihydrogen phosphate.

  The said phosphate can use 1 type, or 2 or more types.

  The amount of the phosphate used in the present invention is preferably in the range of 0.5 to 10 parts by weight in 100 parts by weight of the impregnating solution.

  When the range of the phosphate is 0.5 parts by weight or more, the self-extinguishing property of the flame-retardant soft foam is maintained, and when it is 10 parts by weight or less, the viscosity of the impregnating liquid does not increase excessively, Sex is preserved.

  As the binder, acrylic resins such as acrylic resin, polyacrylic ester resin, acrylic acid-styrene copolymer resin, acrylic acid-vinyl acetate copolymer resin, polyvinyl alcohol, polyacrylamide, urethane resin, vinyl acetate resin, Examples thereof include butadiene resin, epoxy resin, alkyd resin, melamine resin, and rubber such as natural rubber or polychloroprene rubber. Acrylic resin and urethane resin are preferable. A binder can be used by 1 type, or 2 or more types of mixtures.

  The dispersant is for stably dispersing the particles in the impregnating liquid, and is preferably a polymer dispersant having a molecular weight of 2,000 to 1,000,000, and includes an aqueous system such as a polycarboxylic acid type or a naphthalene sulfonic acid formalin condensation type. Anionic polymer dispersants for organic solvents such as polycarboxylic acid partial alkyl ester systems; Cationic polymer dispersants of organic solvent systems such as polyalkylene polyamine systems; Water systems such as polyethylene glycol, polyether systems, etc. Nonionic polymer dispersants for organic solvents are included. Examples of commercially available dispersants include Byk190 (Bic Chemie Japan Co., Ltd.), SN Dispersant 5027 (San Nopco Co., Ltd.) and the like.

  The impregnating liquid containing a phosphorus compound, a binder, and a dispersant may further contain, as a flame retardant, a phosphate ester, a bromine-containing flame retardant, a boron-containing flame retardant, an antimony-containing flame retardant, a metal hydroxide, a polyisocyanurate resin, and the like. Good.

  The amount of the flame retardant added is not particularly limited, but is usually in the range of 0.5 to 20 parts by weight in 100 parts by weight of the impregnating liquid.

  Although the phosphate ester used for this invention is not specifically limited, It is preferable to use a monophosphate ester, condensed phosphate ester, etc.

  The monophosphate ester is not particularly limited, and examples thereof include trimethyl phosphate, triethyl phosphate, tributyl phosphate, tri (2-ethylhexyl) phosphate, tributoxyethyl phosphate, triphenyl phosphate, tricresyl phosphate, and trixylyl phosphate. , Tris (isopropylphenyl) phosphate, tris (phenylphenyl) phosphate, trinaphthyl phosphate, cresyl diphenyl phosphate, xylenyl diphenyl phosphate, diphenyl (2-ethylhexyl) phosphate, di (isopropylphenyl) phenyl phosphate, monoisodecyl phosphate 2-acryloyloxyethyl acid phosphate, 2-methacryloyloxyethyl acid phosphate, di- Phenyl-2-acryloyloxyethyl phosphate, diphenyl-2-methacryloyloxyethyl phosphate, melamine phosphate, dimelamine phosphate, melamine pyrophosphate, triphenylphosphine oxide, tricresylphosphine oxide, diphenyl methanephosphonate, diethyl phenylphosphonate, Resylcinol bis (diphenyl phosphate), bisphenol A bis (diphenyl phosphate), phosphaphenanthrene, tris (β-chloropropyl) phosphate and the like.

  The condensed phosphate ester is not particularly limited, and examples thereof include trialkyl polyphosphate, resorcinol polyphenyl phosphate, resorcinol poly (di-2,6-xylyl) phosphate (trade name PX-, manufactured by Daihachi Chemical Industry Co., Ltd.). 200), hydroquinone poly (2,6-xylyl) phosphate and condensed phosphates such as condensates thereof.

  Examples of commercially available condensed phosphate esters include resorcinol polyphenyl phosphate (trade name CR-733S), bisphenol A polycresyl phosphate (trade name CR-741), aromatic condensed phosphate ester (trade name CR747), and resorcinol. Examples thereof include polyphenyl phosphate (trade name ADK STAB PFR manufactured by ADEKA), bisphenol A polycresyl phosphate (trade names FP-600, FP-700), and the like.

  Among these, it is preferable to use a monophosphate ester because the effect of reducing the viscosity in the composition before curing and the effect of reducing the initial calorific value are high, and tris (β-chloropropyl) phosphate is used. Is more preferable.

  The said phosphate ester can use 1 type, or 2 or more types.

  The amount of the phosphate ester added is preferably in the range of 1.0 to 20 parts by weight in 100 parts by weight of the impregnating solution.

  When the range of the phosphate ester is 1.0 part by weight or more, the self-extinguishing property of the flame-retardant soft foam is maintained, and when it is 20 parts by weight or less, the viscosity of the impregnating liquid does not increase excessively, Sex is preserved.

  The bromine-containing flame retardant used in the present invention is not particularly limited as long as it is a compound containing bromine in the molecular structure, and examples thereof include aromatic brominated compounds.

  Specific examples of the aromatic brominated compound include, for example, hexabromobenzene, pentabromotoluene, hexapromobiphenyl, decapromobiphenyl, hexapromocyclodecane, decapromodiphenyl ether, octabromodiphenyl ether, hexapromodiphenyl ether, bis (penta Monomeric organic bromine compounds such as bromophenoxy) ethane, ethylene-bis (tetraprophthalphthalimide), tetraprobisbisphenol A; polycarbonate oligomers produced using brominated bisphenol A as a raw material, copolycarbonate oligomer and bisphenol A Brominated polycarbonates such as polymers; diepoxy compounds produced by the reaction of brominated bisphenol A and epichlorohydrin, brominated phenols and epichloro Brominated epoxy compounds such as monoepoxy compounds obtained by reaction with hydrin; poly (brominated benzyl acrylate); brominated polyphenylene ether; condensates of brominated bisphenol A, cyanuric chloride and brominated phenol; brominated (polystyrene) And brominated polystyrene such as poly (brominated styrene) and crosslinked brominated polystyrene; and halogenated bromine compound polymers such as crosslinked or non-crosslinked brominated poly (-methylstyrene).

  From the viewpoint of controlling the calorific value at the initial stage of combustion, brominated polystyrene, hexabromobenzene and the like are preferable, and hexabromobenzene is more preferable.

  One or two or more of the bromine-containing flame retardants can be used.

  The amount of bromine-containing flame retardant added is preferably in the range of 0.5 to 10 parts by weight in 100 parts by weight of the impregnating liquid.

  When the range of the bromine-containing flame retardant is 0.5 parts by weight or more, the self-extinguishing property of the flame retardant soft foam is maintained, and when it is 10 parts by weight or less, the viscosity of the impregnation liquid does not increase too much, Impregnation is maintained.

  Examples of the boron-containing flame retardant used in the present invention include borax, boron oxide, boric acid, and borate.

  Examples of the boron oxide include diboron trioxide, boron trioxide, diboron dioxide, tetraboron trioxide, and tetraboron pentoxide.

  Examples of the borate include alkali metals, alkaline earth metals, elements of Group 4, Group 12, and Group 13 of the periodic table, and ammonium borate.

  Specifically, alkali metal borate such as lithium borate, sodium borate, potassium borate, cesium borate, alkaline earth metal borate such as magnesium borate, calcium borate, barium borate, boron Examples thereof include zirconium acid, zinc borate, aluminum borate, and ammonium borate.

  The boron-containing flame retardant is preferably a borate, and more preferably zinc borate.

  One or more boron-containing flame retardants can be used.

  The amount of boron-containing flame retardant added is preferably in the range of 1.0 to 20 parts by weight per 100 parts by weight of the impregnating liquid.

  When the range of the boric acid-containing flame retardant is 1.0 part by weight or more, the self-extinguishing property of the flame retardant soft foam is maintained, and when it is 20 parts by weight or less, the viscosity of the impregnating liquid does not increase too much. The impregnation property is maintained.

  Examples of the antimony-containing flame retardant used in the present invention include antimony oxide, antimonate, pyroantimonate, and the like.

  Examples of the antimony oxide include antimony trioxide and antimony pentoxide.

  Examples of the antimonate include sodium antimonate and potassium antimonate.

  Examples of the pyroantimonate include sodium pyroantimonate and potassium pyroantimonate.

  The antimony-containing flame retardant used in the present invention is preferably antimony oxide.

  The said antimony containing flame retardant can use 1 type, or 2 or more types.

  The amount of the antimony-containing flame retardant used in the present invention is preferably in the range of 1.0 to 20 parts by weight per 100 parts by weight of the impregnating liquid.

  When the range of the antimony-containing flame retardant is 1.0 part by weight or more, the self-extinguishing property of the flame retardant soft foam is maintained, and when it is 20 parts by weight or less, the viscosity of the impregnating liquid does not increase too much, Impregnation is maintained.

  Examples of the metal hydroxide used in the present invention include magnesium hydroxide, calcium hydroxide, aluminum hydroxide, iron hydroxide, nickel hydroxide, zirconium hydroxide, titanium hydroxide, zinc hydroxide, copper hydroxide. , Vanadium hydroxide, tin hydroxide and the like.

  The said metal hydroxide can use 1 type, or 2 or more types.

  The amount of the metal hydroxide used in the present invention is preferably in the range of 1.0 to 20 parts by weight per 100 parts by weight of the impregnating solution.

  When the range of the metal hydroxide is 1.0 part by weight or more, the self-extinguishing property of the flame retardant soft foam is maintained, and when it is 20 parts by weight or less, the viscosity of the impregnating liquid does not increase too much, Impregnation is maintained.

  The polyisocyanurate resin is usually contained in the impregnation liquid as a powder of a composition containing the polyisocyanurate resin (hereinafter referred to as “polyisocyanurate resin composition”).

  The polyisocyanurate resin is a flame retardant polyurethane resin obtained by reacting and foaming a polyisocyanate compound as a main component and a polyol compound as a curing agent with a trimerization catalyst.

  The polyisocyanurate resin composition contains a polyisocyanate compound as a main agent, a polyol compound as a curing agent, a trimerization catalyst, a foaming agent, and a foam stabilizer.

  Examples of the polyisocyanate compound that is a main component of the polyisocyanurate resin include aromatic polyisocyanates, alicyclic polyisocyanates, and aliphatic polyisocyanates.

  Examples of the aromatic polyisocyanate include phenylene diisocyanate, tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, dimethyldiphenylmethane diisocyanate, triphenylmethane triisocyanate, naphthalene diisocyanate, polymethylene polyphenyl polyisocyanate, and the like.

  Examples of the alicyclic polyisocyanate include cyclohexylene diisocyanate, methylcyclohexylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, and dimethyldicyclohexylmethane diisocyanate.

  Examples of the aliphatic polyisocyanate include methylene diisocyanate, ethylene diisocyanate, propylene diisocyanate, tetramethylene diisocyanate, and hexamethylene diisocyanate.

  One or more polyisocyanate compounds can be used. The main component of the polyisocyanurate resin is preferably diphenylmethane diisocyanate for reasons such as ease of use and availability.

   Examples of the polyol compound that is a curing agent for the polyisocyanurate resin include polylactone polyol, polycarbonate polyol, aromatic polyol, alicyclic polyol, aliphatic polyol, polyester polyol, polymer polyol, polyether polyol, and the like. .

  Examples of the polylactone polyol include polypropiolactone glycol, polycaprolactone glycol, and polyvalerolactone glycol.

  Examples of the polycarbonate polyol include a polyol obtained by a dealcoholization reaction of a hydroxyl group-containing compound such as ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, octanediol, and nonanediol with diethylene carbonate, dipropylene carbonate, and the like. Etc.

  Examples of the aromatic polyol include bisphenol A, bisphenol F, phenol novolac, and cresol novolak.

  Examples of the alicyclic polyol include cyclohexanediol, methylcyclohexanediol, isophoronediol, dicyclohexylmethanediol, dimethyldicyclohexylmethanediol, and the like.

  Examples of the aliphatic polyol include ethylene glycol, propylene glycol, butanediol, pentanediol, and hexanediol.

  Examples of the polyester polyol include a polymer obtained by dehydration condensation of a polybasic acid and a polyhydric alcohol, a polymer obtained by ring-opening polymerization of a lactone such as ε-caprolactone and α-methyl-ε-caprolactone, Examples thereof include condensates of hydroxycarboxylic acid and the above polyhydric alcohol.

  Specific examples of the polybasic acid include adipic acid, azelaic acid, sebacic acid, terephthalic acid, isophthalic acid, and succinic acid. Specific examples of the polyhydric alcohol include bisphenol A, ethylene glycol, 1,2-propylene glycol, 1,4-butanediol, diethylene glycol, 1,6-hexane glycol, and neopentyl glycol. It is done.

  Specific examples of the hydroxycarboxylic acid include castor oil, a reaction product of castor oil and ethylene glycol, and the like.

  As the polymer polyol, for example, a polymer obtained by graft polymerization of an ethylenically unsaturated compound such as acrylonitrile, styrene, methyl acrylate, methacrylate, or the like to the aromatic polyol, alicyclic polyol, aliphatic polyol, polyester polyol, or the like, Examples thereof include polybutadiene polyols, modified polyols of polyhydric alcohols, and hydrogenated products thereof.

  Examples of the modified polyol of the polyhydric alcohol include those modified by reacting a raw material polyhydric alcohol with an alkylene oxide.

  Examples of the polyhydric alcohol include trihydric alcohols such as glycerin and trimethylolpropane; pentaerythritol, sorbitol, mannitol, sorbitan, diglycerin, dipentaerythritol, etc., sucrose, glucose, mannose, fructose, methyl glucoside And tetravalent to octavalent alcohols such as derivatives thereof; phenol, phloroglucin, cresol, pyrogallol, catechol, hydroquinone, bisphenol A, bisphenol F, bisphenol S, 1-hydroxynaphthalene, 1,3,6,8-tetrahydroxy Phenolic polybutadiene polyols such as naphthalene, anthrol, 1,4,5,8-tetrahydroxyanthracene, 1-hydroxypyrene; castor oil polyol; hydroxyalkyl (meth) Polyfunctional (e.g. functionality 2 to 100) polyol such as (co) polymers and polyvinyl alcohol acrylate include condensates of phenol and formaldehyde (novolac) it is.

  The method for modifying the polyhydric alcohol is not particularly limited, but a method of adding alkylene oxide (hereinafter abbreviated as AO) is preferably used.

  Examples of the AO include AO having 2 to 6 carbon atoms such as ethylene oxide (hereinafter abbreviated as EO), 1,2-propylene oxide (hereinafter abbreviated as PO), 1,3-propyloxide, 1,2 -Butylene oxide, 1, 4- butylene oxide, etc. are mentioned.

  Among these, from the viewpoints of properties and reactivity, PO, EO, and 1,2-butylene oxide are preferable, and PO and EO are more preferable. When two or more types of AO are used (for example, PO and EO), block addition or random addition may be used, or a combination thereof may be used.

  Examples of the polyether polyol include ring-opening polymerization of at least one alkylene oxide such as ethylene oxide, propylene oxide, and tetrahydrofuran in the presence of at least one low molecular weight active hydrogen compound having two or more active hydrogens. And the resulting polymer.

  Examples of the low molecular weight active hydrogen compound having two or more active hydrogens include diols such as bisphenol A, ethylene glycol, propylene glycol, butylene glycol, and 1,6-hexanediol, and triols such as glycerin and trimethylolpropane. And amines such as ethylenediamine and butylenediamine.

  The polyol used in the present invention is preferably a polyester polyol or a polyether polyol because the effect of reducing the total calorific value upon combustion is great.

  Among them, it is more preferable to use a polyester polyol having a molecular weight of 200 to 800, and it is more preferable to use a polyester polyol having a molecular weight of 300 to 500.

  The isocyanate index is a percentage of the equivalent ratio of the isocyanate group of the polyisocyanate compound to the hydroxyl group of the polyol compound, but a value exceeding 100 means that the isocyanate group is in excess of the hydroxyl group. .

  The range of the isocyanate index of the polyisocyanurate resin used in the present invention is preferably in the range of 120 to 1000, more preferably in the range of 200 to 800, and even more preferably in the range of 300 to 600.

  The trimerization catalyst causes the isocyanate group contained in polyisocyanate, which is the main component of the polyurethane resin, to react and trimerize, thereby promoting the formation of an isocyanurate ring.

  In order to promote the formation of the isocyanurate ring, for example, as a catalyst, tris (dimethylaminomethyl) phenol, 2,4-bis (dimethylaminomethyl) phenol, 2,4,6-tris (dialkylaminoalkyl) hexahydro Nitrogen-containing aromatic compounds such as -S-triazine; carboxylic acid alkali metal salts such as potassium acetate, potassium 2-ethylhexanoate and potassium octerate; tertiary ammonium such as trimethylammonium salt, triethylammonium salt and triphenylammonium salt Salt: Quaternary ammonium salts such as tetramethylammonium salt, tetraethylammonium salt, and tetraphenylammonium salt can be used.

   The addition amount of the trimerization catalyst used in the polyisocyanurate resin composition is preferably in the range of 0.6 to 10 parts by weight with respect to 100 parts by weight of the polyisocyanurate resin. The range is more preferably 8 parts by weight, still more preferably in the range of 0.6 to 6 parts by weight, and most preferably in the range of 0.6 to 3.0 parts by weight. In the case of 0.6 parts by weight or more, there is no problem that the trimerization of isocyanate is inhibited, and in the case of 10 parts by weight or less, an appropriate foaming rate can be maintained and the handling is easy.

The foaming agent promotes foaming of the polyisocyanurate resin. Specific examples of the blowing agent include, for example, water, propane, butane, pentane, hexane, heptane, cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, and other low boiling hydrocarbons, dichloroethane, propyl chloride, isopropyl chloride, Hydrochloric compounds such as chlorinated aliphatic hydrocarbon compounds such as butyl chloride, isobutyl chloride, pentyl chloride and isopentyl chloride, fluorine compounds such as trichloromonofluoromethane and trichlorotrifluoroethane, and hydrous such as CHF ₃ , CH ₂ F ₂ and CH ₃ F Fluorocarbons, dichloromonofluoroethane (eg, HCFC141b (1,1-dichloro-1-fluoroethane), HCFC22 (chlorodifluoromethane), HCFC142b (1-chloro-1,1-difluoroethane)), Hydrochlorofluorocarbon compounds such as HFC-245fa (1,1,1,3,3-pentafluoropropane), HFC-365mfc (1,1,1,3,3-pentafluorobutane), and ether compounds such as diisopropyl ether Or organic physical foaming agents such as mixtures of these compounds, inorganic physical foaming agents such as nitrogen gas, oxygen gas, argon gas and carbon dioxide gas.

  The range of the foaming agent is preferably in the range of 0.1 to 30 parts by weight with respect to 100 parts by weight of the polyisocyanurate resin. The foaming agent is more preferably in the range of 0.1 to 18 parts by weight, and further in the range of 0.5 to 18 parts by weight with respect to 100 parts by weight of the polyisocyanurate resin. Preferably, the range is 1 to 10 parts by weight.

  When the water range is 0.1 parts by weight or more, foaming is promoted and the density of the resulting molded product can be reduced. When the water content is 30 parts by weight or less, the foam does not foam and a foam is formed. Can be prevented.

  Examples of the foam stabilizer include surfactants such as polyoxyalkylene foam stabilizers such as polyoxyalkylene alkyl ether and silicone foam stabilizers such as organopolysiloxane.

  The amount of the foam stabilizer used for the polyisocyanurate resin cured by the chemical reaction is appropriately set according to the polyisocyanurate resin cured by the chemical reaction to be used. A range of 0.1 to 10 parts by weight is preferable with respect to 100 parts by weight of the nurate resin.

  The catalyst, the foaming agent, and the foam stabilizer may be used alone or in combination of two or more.

  In a preferred embodiment, the polyisocyanurate resin composition has a trimerization catalyst in the range of 0.6 to 10 parts by weight based on 100 parts by weight of the polyisocyanurate resin composition composed of polyisocyanate and polyol, and foaming. The agent is in the range of 0.1 to 30 parts by weight, and the foam stabilizer is in the range of 0.1 to 10 parts by weight.

  When the impregnating liquid contains a phosphorus compound and the polyisocyanurate resin composition contains the components constituting the polyisocyanurate resin, a flame retardant polyisocyanurate resin composition containing a phosphorus compound is produced, and the flame retardant soft It is possible to contribute to improving the flame retardancy of the foam.

  The polyisocyanurate resin composition comprises red phosphorus and at least one selected from a phosphate ester, a phosphate-containing flame retardant, a bromine-containing flame retardant, a boric acid-containing flame retardant, an antimony-containing flame retardant, and a metal hydroxide. May contain an additive. Red phosphorus, phosphate esters, phosphate-containing flame retardants, bromine-containing flame retardants, boric acid-containing flame retardants, antimony-containing flame retardants, and metal hydroxides of the type described for these components in the impregnation liquid Things can be used.

  The amount of red phosphorus added is, for example, in the range of 3.0 to 18 parts by weight with respect to 100 parts by weight of the polyisocyanurate resin, and the amount of phosphate added is 100 parts by weight of the polyisocyanurate resin. The amount of the phosphate-containing flame retardant added is, for example, 1.5 parts by weight to 52 parts by weight with respect to 100 parts by weight of the polyisocyanurate resin. The addition amount of the bromine-containing flame retardant is, for example, in the range of 1.5 to 52 parts by weight with respect to 100 parts by weight of the polyisocyanurate resin, and the addition amount of the boron-containing flame retardant is polyisocyanate. The amount of antimony-containing flame retardant is, for example, in the range of 1.5 to 52 parts by weight with respect to 100 parts by weight of the nurate resin. The polyisocyanurate resin is in the range of 1.5 parts by weight to 52 parts by weight with respect to 100 parts by weight of the polyisocyanurate resin. Although it is advantageous for imparting flame retardancy to the composition, since the impregnating solution contains a phosphorus compound, the polyisocyanurate resin composition may not contain an additive, and the above-mentioned range. It may be contained at a lower concentration.

  The polyisocyanurate resin composition may further contain a catalyst other than the above trimerization catalyst. Examples of such a catalyst include triethylamine, N-methylmorpholine bis (2-dimethylaminoethyl) ether, N, N , N ′, N ″, N ″ -pentamethyldiethylenetriamine, N, N, N′-trimethylaminoethyl-ethanolamine, bis (2-dimethylaminoethyl) ether, N-methyl, N′-dimethylaminoethylpiperazine, And nitrogen atom-containing catalysts such as imidazole compounds in which the secondary amine functional group in the imidazole ring is substituted with a cyanoethyl group.

  The amount of the catalyst added is preferably the total amount of the trimerization catalyst and the catalyst other than the trimerization catalyst, and is in the range of 0.6 to 10 parts by weight with respect to 100 parts by weight of the polyisocyanurate resin. More preferably, it is in the range of 0.6 parts by weight to 8 parts, more preferably in the range of 0.6 parts by weight to 6 parts by weight, and in the range of 0.6 parts by weight to 3.0 parts by weight. Most preferred.

  When the amount is 0.6 parts by weight or more, there is no problem that the formation of urethane bonds is hindered. When the amount is 10 parts by weight or less, an appropriate foaming rate can be maintained and the handling is easy.

  The polyisocyanurate resin composition may further contain an inorganic filler. The inorganic filler is not particularly limited. For example, silica, diatomaceous earth, alumina, titanium oxide, calcium oxide, magnesium oxide, iron oxide, tin oxide, antimony oxide, ferrites, basic magnesium carbonate, calcium carbonate, carbonate Magnesium, zinc carbonate, barium carbonate, dosonite, hydrotalcite, calcium sulfate, barium sulfate, gypsum fiber, calcium silicate, potassium salt, talc, clay, mica, montmorillonite, bentonite, activated clay, sepiolite, imogolite, Sericite, glass fiber, glass beads, silica parun, aluminum nitride, boron nitride, silicon nitride, carbon black, graphite, carbon fiber, carbon parun, charcoal powder, various metal powders, potassium titanate, magnesium sulfate, zirconate titanate Lead, aluminum port rate, molybdenum sulfide, silicon carbide, stainless steel fiber, various magnetic powder, slag fibers, fly ash, silica alumina fiber, alumina fiber, silica fiber, zirconia fiber, and the like.

  One or more inorganic fillers can be used.

  The polyisocyanurate resin composition is a phenol-based, amine-based, sulfur-based antioxidant, heat stabilizer, metal harm-preventing agent, antistatic agent, etc., as long as the object of the present invention is not impaired. , Stabilizers, crosslinking agents, lubricants, softeners, pigments, auxiliary components such as tackifier resins, and tackifiers such as polybutene and petroleum resins.

  The flame-retardant soft foam of the present invention includes a step of impregnating or adhering an impregnating liquid containing a phosphorus compound, a binder and a dispersant to a soft foam having open cells, and a soft foam obtained by impregnating or adhering the impregnating liquid And a step of obtaining a flame retardant soft foam by drying. The impregnating solution may further contain phosphate ester, bromine-containing flame retardant, boron-containing flame retardant, antimony-containing flame retardant, metal hydroxide, polyisocyanurate resin, and the like as the above-mentioned flame retardant in the above-described ratio. .

  FIG. 1 shows an impregnation facility for continuously producing a flame-retardant soft foam. A method for producing a flame-retardant soft foam in this impregnation facility will be described. The soft foam 1 is pulled out from the supply roll 2 wound with the soft foam 1 in the form of a sheet having a predetermined thickness, and guided into the impregnation tank 3 in which the impregnating liquid 4 is accommodated. Next, the soft foam 1 is soaked in the impregnating liquid 4, and the excess foam liquid is squeezed out of the soft foam 1 by sandwiching the soft foam 1 with a pair of squeezing rolls 5, and includes a drying furnace, a heater, or the like. The soft foam is dried by the drying device 6 to remove unnecessary impregnating liquid and solvent. Thereby, the flame-retardant soft foam 7 in which the flame-retardant impregnating liquid 4 is impregnated or attached with the binder is obtained. The temperature during drying is preferably 60 to 200 ° C. The flame retardant soft foam 7 thus obtained is cut into an appropriate size according to the use or the like.

  The production of the flame-retardant soft foam is not limited to the continuous production as described above, but a discontinuous method, for example, the soft foam having a predetermined size is impregnated with the impregnation liquid. It can also be carried out by a method of dipping in an impregnation tank and impregnating, and then removing from the impregnation tank and squeezing out the excess impregnation liquid by compression or the like and drying it with a drying apparatus. The production of the flame-retardant soft foam may be performed automatically or manually.

  The obtained flame retardant soft foam can be evaluated by a combustion test such as flame retardant standard UL-94.

  Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited thereto.

As the soft foam, urethane foam manufactured by Inoac Corporation (commercial product: density 22 kg / m ³ ) was cut into 200 mm × 200 mm × 30 mm and used.

The impregnating liquids of Examples 1-3 and Comparative Examples 1 and 2 were prepared according to the composition shown in Table 1 (the ratio of each component is shown in parts by weight with respect to 100 parts by weight of the polyisocyanurate resin) and stirred for 10 minutes at 400 rpm. . The composition of the isocyanurate resin powder used in Example 3 was as shown in Table 2. The soft foam was impregnated with the impregnation liquid using a metal roll (roll clearance: 5 mm), and the excess impregnation liquid impregnated in the foam was squeezed out. Next, the impregnated foam was dried in an oven at 90 ° C. for 12 hours. The density of the soft foam after drying was measured and subjected to a combustion test.
[Combustion test] (UL94)
The foam after drying was cut into 125 mm × 13 mm × 10 mm, and a combustion test was performed in accordance with UL94 V-0 test method.
[Combustion test] (Electric furnace)
The dried foam was cut into 50 mm × 50 mm × 30 mm and subjected to a combustion test in an electric furnace at 600 ° C. × 30 minutes.

  As a result, it was shown that the soft foam of Example 1-3 was excellent in flame retardancy as compared with the soft foams of Comparative Examples 1 and 2.

  DESCRIPTION OF SYMBOLS 1 ... Soft foam, 4 ... Impregnation liquid, 7 ... Flame-retardant soft foam.

Claims (6)

  A flame retardant soft foam, which is obtained by impregnating or adhering a phosphorus compound, a binder and a dispersant to a soft foam having open cells.   The flame retardant soft foam according to claim 1, wherein the phosphorus compound contains red phosphorus and phosphate.   The flame-retardant soft foam according to claim 1 or 2, wherein the phosphorus compound is impregnated or adhered to 5 to 50 parts by weight with respect to 100 parts by weight of the soft foam.   The flame retardant selected from phosphate ester, bromine-containing flame retardant, boron-containing flame retardant, antimony-containing flame retardant, metal hydroxide and polyisocyanurate resin is further impregnated or adhered to the soft foam. The flame-retardant soft foam as described in any one of -3. Impregnating or adhering an impregnating liquid containing a phosphorus compound, a binder and a dispersant to a soft foam having open cells;
And a step of obtaining a flame retardant soft foam by drying the soft foam impregnated or adhered with the impregnation liquid. The said impregnation liquid is a manufacturing method of Claim 5 which further contains the flame retardant selected from phosphate ester, a bromine containing flame retardant, a boron containing flame retardant, an antimony containing flame retardant, a metal hydroxide, and polyisocyanurate resin.