JP2022053336A - Mixing system and method for manufacturing polyurethane foam - Google Patents

Abstract

To provide a mixing system and a method for manufacturing a polyurethane foam capable of performing good miscibility of a raw material composition to form the polyurethane foam that excels in curability and flame retardancy even when the raw material composition containing a filler is used.SOLUTION: A mixing system using a raw material composition containing a polyol compound, a filler, a foaming agent, and an isocyanate to form a polyurethane foam, comprises: two or more raw material containers 10a and 10b; a mixer 20 having communication parts 21a and 21b fluid-communicating with the raw material containers 10a and 10b, and for mixing raw materials supplied from each of the raw material containers 10a and 10b via the communication parts 21a and 21b to prepare the raw material composition; a temperature controller 30 for heating at least one of the raw materials supplied to the mixer 20; a pressure adjustment gas supply device 40 for supplying air or inert gas into the raw material containers 10a and 10b in order to pressurize inside the mixer 20; and a discharging device 50 for discharging the raw material composition prepared in the mixer 20.SELECTED DRAWING: Figure 1

Description

The present invention relates to a mixing system and a method for producing polyurethane foam.

Conventionally, polyurethane foam has been used as a heat insulating material in vehicles such as automobiles, railroad vehicles, ships, and buildings. It is also used as a repair agent to fill defects in vehicles, buildings, etc. Recently, there is an increasing need to impart flame retardancy to these heat insulating materials and repair agents.

As the polyurethane foam, a two-component polyurethane in which a polyol solution and an isocyanate solution filled in separate containers are mixed to form a foam is widely used (see, for example, Patent Document 1). In recent years, due to the growing awareness of disaster prevention, polyurethane foams used as heat insulating materials and repair agents are required to have high flame retardancy. As a method for imparting flame retardancy to polyurethane foam, attempts have been made to include a filler such as red phosphorus having a high flame retardant effect (see, for example, Patent Document 2).

Japanese Unexamined Patent Publication No. 2019-218430 Japanese Unexamined Patent Publication No. 2017-075326

However, when a filler having a high flame-retardant effect is contained in the polyol liquid, the viscosity of the polyol liquid increases, the mixing property with the isocyanate liquid deteriorates, and curing failure or deterioration of flame retardancy may occur.

Therefore, the present invention is a mixing system capable of forming a polyurethane foam having good mixing properties and excellent curability and flame retardancy even when a raw material composition containing a filler is used. An object of the present invention is to provide a method for producing a polyurethane foam.

As a result of diligent studies, the present inventors have found that the above problems can be solved by providing a temperature control device for heating raw materials, and have completed the present invention. That is, the present invention provides the following [1] to [13].
[1] A mixing system for forming a polyurethane foam using a raw material composition containing a polyol compound, a filler, a foaming agent and an isocyanate, in which two or more raw material containers and a communication portion in which the raw material container is fluidly communicated with each other A mixer for preparing a raw material composition by mixing raw materials supplied from each raw material container via the communication portion, and a temperature for heating at least one of the raw materials supplied to the mixer. A regulator, a pressure-adjusting gas supply device that supplies air or an inert gas into the raw material container to adjust the pressure in the mixer, and a discharge that discharges the raw material composition prepared by the mixer. Mixing system with equipment.
[2] The discharge device is further provided with a spray gas supply device for supplying air or an inert gas, and the spray gas supply device mixes air or an inert gas with the raw material composition in the discharge device. The mixing system according to [1], wherein the discharging device sprays and discharges the raw material composition mixed with air or an inert gas.
[3] The mixing system according to [1] or [2], wherein the temperature control device adjusts the temperature of the raw material composition to 30 ° C. or higher and 50 ° C. or lower.
[4] The mixing system according to any one of [1] to [3], wherein the temperature control device heats at least one of the raw material container and the communication portion.
[5] The mixing system according to any one of [1] to [4], wherein the temperature control device heats the raw material containing a filler.
[6] When measured using a B-type viscometer with the probe rotation speed set to 60 rpm at 25 ° C., the viscosity difference of the raw materials supplied from the raw material container to be mixed by the mixer is 10 mPa · s. The mixing system according to any one of [1] to [5], which is 2,000 mPa · s or less.
[7] The mixing system according to any one of [1] to [6], wherein the pressure adjusting gas supply device adjusts the pressure in the mixer to 0.05 MPa or more and 1.0 MPa or less.
[8] The mixing system according to any one of [1] to [7], wherein the filler is at least one selected from the group consisting of a red phosphorus flame retardant, a boron-containing flame retardant and a bromine-containing flame retardant.
[9] The mixing system according to any one of [1] to [8], wherein the filler contains an inhibitor of sedimentation.
[10] The mixing system according to any one of [1] to [9], wherein the foaming agent contains a hydrofluoroolefin.
[11] The mixing system according to any one of [1] to [10], wherein the raw material composition contains a catalyst.
[12] The raw material container includes a first container filled with the raw material composition containing a polyol compound, a filler and a foaming agent, and a second container filled with the raw material composition containing isocyanate. The mixing system according to any one of [1] to [11].
[13] A method for producing a polyurethane foam using a raw material composition containing a polyol compound, a filler, a foaming agent and an isocyanate, wherein the raw material is filled in two or more raw material containers, and the raw material container is fluidly communicated with the raw material container. A step of preparing a raw material composition by mixing raw materials supplied from each raw material container through the communication portion in a mixer having a communication portion, and at least one of the raw materials supplied to the mixer. A step of heating with a temperature control device, a step of supplying air or an inert gas into the raw material container with a pressure adjusting gas supply device in order to adjust the pressure in the mixer, and a step of preparing with the mixer. A method for producing a polyurethane foam, which comprises a step of discharging the above-mentioned raw material composition from a discharge device.

According to the present invention, even when a raw material composition containing a filler is used, a mixing system capable of forming a polyurethane foam having good mixing properties of the raw material composition and excellent curability and flame retardancy can be formed. And a method for producing polyurethane foam can be provided.

It is a schematic diagram of the mixing system which concerns on 1st Embodiment of this invention. It is a schematic diagram which shows another form of the temperature control apparatus in the mixing system which concerns on 1st Embodiment of this invention. It is a schematic diagram of the mixing system which concerns on the 2nd Embodiment of this invention.

[First Embodiment]
The mixing system according to the first embodiment of the present invention is a mixing system for forming a polyurethane foam using a raw material composition containing a polyol compound, a filler, a foaming agent and an isocyanate. Hereinafter, the raw material composition used in this system will be described first.

(Raw material composition)
The raw material composition contains a polyol compound, a filler, a catalyst, a foaming agent and an isocyanate.
<polyol compound>
The raw material composition of the present invention contains a polyol compound as a raw material for polyurethane foam.
Examples of the polyol compound used in the present invention include polylactone polyols, polycarbonate polyols, aromatic polyols, alicyclic polyols, aliphatic polyols, polyester polyols, polymer polyols, and polyether polyols.

Examples of the polylactone polyol include polypropiolactone glycol, polycaprolactone glycol, polyvalerolactone glycol and the like.
Examples of the polycarbonate polyol include a polyol obtained by a dealcohol reaction between a hydroxyl group-containing compound such as ethylene glycol, propylene glycol, butanediol, pentandiol, hexanediol, octanediol, and nonanediol and ethylene carbonate, propylene carbonate, or the like. And so on.

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

As the polyester polyol, for example, 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. , And a condensate of hydroxycarboxylic acid and the polyhydric alcohol or the like.
Examples of the polybasic acid include adipic acid, azelaic acid, sebacic acid, isophthalic acid (m-phthalic acid), terephthalic acid (p-phthalic acid), succinic acid and the like. Examples of the polyhydric alcohol include bisphenol A, ethylene glycol, 1,2-propylene glycol, 1,4-butanediol, diethylene glycol, 1,6-hexaneglycol, neopentyl glycol and the like.
Examples of the hydroxycarboxylic acid include castor oil, a reaction product of castor oil and ethylene glycol, and the like.

Examples of the polymer polyol include a polymer obtained by graft-polymerizing an ethylenically unsaturated compound such as acrylonitrile, styrene, methyl acrylate, and methacrylate with an aromatic polyol, an alicyclic polyol, an aliphatic polyol, a polyester polyol, or the like. , Polybutadiene polyols, or their hydrogenated additives and the like.

As the polyether polyol, for example, at least one kind of alkylene oxide (hereinafter, also referred to as “AO”) is ring-opened polymerized in the presence of at least one kind such as a low molecular weight active hydrogen compound having two or more active hydrogens. Examples thereof include the obtained polymer. Examples of AO include AOs having 2 to 6 carbon atoms, for example, ethylene oxide (hereinafter, also referred to as “EO”), 1,2-propylene oxide (hereinafter, also referred to as “PO”), 1,3-propyleneoxide, and the like. Examples thereof include 1,2-butylene oxide and 1,4-butylene oxide.
Among these, PO, EO and 1,2-butylene oxide are preferable, and PO and EO are more preferable, from the viewpoint of properties and reactivity. When two or more types of AO are used (for example, PO and EO), the addition method may be block addition, random addition, or a combination thereof.
Examples of the low molecular weight active hydrogen compound having two or more active hydrogens include diols such as ethylene glycol, propylene glycol, butylene glycol and 1,6-hexanediol, triols such as glycerin and trimethylolpropane, and pentaerythritol. Tetra-octavalent alcohols such as sorbitol, mannitol, sorbitan, diglycerin, dipentaerythritol, sucrose, glucose, mannose, fructose, methylglucoside and derivatives thereof, fluoroglucolcinol, cresol, pyrogallol, catechol, Aromatic polyols such as hydroquinone, bisphenol A, bisphenol F, bisphenol S, 1,3,6,8-tetrahydroxynaphthalene, and 1,4,5,8-tetrahydroxyanthracene, castor oil polyols, hydroxyalkyl (meth). Examples thereof include a (co) polymer of acrylate, a polyfunctional (for example, 2 to 100 functional groups) polyol such as polyvinyl alcohol, a condensate (novolak) of phenol and formaldehyde, and amines such as ethylenediamine and butylene diamine.

As the polyol compound used in the present invention, polyester polyols and polyether polyols are preferable. Further, a polyol having two hydroxyl groups is preferable. Of these, aromatic polyester polyols, which are polyester polyols having an aromatic ring, are preferable from the viewpoint of enhancing flame retardancy. Examples of the aromatic polyester polyol include polybasic acids having an aromatic ring such as isophthalic acid (m-phthalic acid) and terephthalic acid (p-phthalic acid), bisphenol A, ethylene glycol, 1,2-propylene glycol and the like. The one obtained by dehydration condensation with the dihydric alcohol of No. 1 is more preferable.

The hydroxyl value of the polyol compound is preferably 20 to 300 mgKOH / g, more preferably 30 to 250 mgKOH / g, and even more preferably 50 to 220 mgKOH / g. When the hydroxyl value of the polyol compound is not more than the above upper limit, the viscosity of the raw material composition tends to decrease, which is preferable from the viewpoint of handleability and the like. On the other hand, when the hydroxyl value of the polyol compound is at least the above lower limit, the crosslink density of the polyurethane foam increases and the strength increases.
The hydroxyl value of the polyol can be measured according to JIS K 1557-1: 2007.

<Filler>
The raw material composition of the present invention contains a filler as a raw material for polyurethane foam. When the raw material composition contains a filler, the flame retardancy of the obtained polyurethane foam is improved.
The filler is contained as a solid component in a liquid raw material composition, and is a component generally present as a granular or powdery component in the raw material composition.
The filler may be a component that is solid at normal temperature (23 ° C.) and normal pressure (1 atm) and does not dissolve in the liquid raw material composition.
Examples of the filler include solid flame retardants and anti-settling agents. Examples of the solid flame retardant include red phosphorus flame retardants, boron-containing flame retardants, bromine-containing flame retardants, phosphate-containing flame retardants, chlorine-containing flame retardants, antimony-containing flame retardants, metal hydroxides and needle-like fillers. It is preferable that the flame retardant is at least one selected from the group consisting of a red phosphorus flame retardant, a boron-containing flame retardant and a bromine-containing flame retardant.

《Red phosphorus flame retardant》
The red phosphorus flame retardant may be composed of red phosphorus alone, may be a red phosphorus coated with a resin, a metal hydroxide, a metal oxide, or the like, or may be a red phosphorus coated with a resin, a metal hydroxide, or a metal. It may be mixed with an oxide or the like. The resin coated with red phosphorus or mixed with red phosphorus is not particularly limited, and examples thereof include thermosetting resins such as phenol resin, epoxy resin, unsaturated polyester resin, melamine resin, urea resin, aniline resin, and silicone resin. Be done. As the film or the compound to be mixed, a metal hydroxide is preferable from the viewpoint of flame retardancy. As the metal hydroxide, those described later may be appropriately selected and used.

<< Boron-containing flame retardant >>
Examples of the boron-containing flame retardant used in the present invention include borax, boron oxide, boric acid, borate and the like. Examples of the boron oxide include diboron trioxide, boron trioxide, diboron dioxide, tetraboron trioxide, tetraboron pentoxide and the like.
Examples of the borate include alkali metals, alkaline earth metals, elements of Groups 4, 12, and 13 of the Periodic Table, and ammonium borates. Specifically, an alkali metal borate salt such as lithium borate, sodium borate, potassium borate, and cesium borate, an alkaline earth metal salt borate such as magnesium borate, calcium borate, and barium borate, boro Examples thereof include zirconium acid, zinc borate, aluminum borate, and ammonium borate.
The boron-containing flame retardant may be used alone or in combination of two or more.
The boron-containing flame retardant used in the present invention is preferably borate, more preferably zinc borate.

<< Flame retardant containing bromine >>
The bromine-containing flame retardant is not particularly limited as long as it is a compound containing bromine in its molecular structure and becomes solid at normal temperature and pressure, and examples thereof include brominated aromatic ring-containing aromatic compounds.
Examples of the brominated aromatic ring-containing aromatic compound include hexabromobenzene, pentabromotoluene, hexabromobiphenyl, decabromobiphenyl, decabromodiphenyl ether, octabromodiphenyl ether, hexabromodiphenyl ether, bis (pentabromophenoxy) ethane, and ethylenebis (pentabromophenoxy). Examples thereof include monomer-based organic bromine compounds such as pentabromophenyl), ethylene bis (tetrabromophthalimide), and tetrabromobisphenol A.

Further, the brominated aromatic ring-containing aromatic compound may be a bromine compound polymer. Specifically, a polycarbonate oligomer produced from brominated bisphenol A as a raw material, a brominated polycarbonate such as a copolymer of this polycarbonate oligomer and bisphenol A, and a diepoxy compound produced by the reaction of brominated bisphenol A with epichlorohydrin. And so on. Furthermore, brominated epoxy compounds such as monoepoxy compounds obtained by the reaction of brominated phenols with epichlorohydrin, poly (bromineed benzyl acrylate), brominated polyphenylene ether, brominated bisphenol A, and brominated phenol of cyanur chloride. Condensates, brominated (polystyrene), poly (bromineed styrene), brominated polystyrene such as crosslinked brominated polystyrene, crosslinked or non-crosslinked brominated poly (-methylstyrene) and the like.
Further, it may be a compound other than the brominated aromatic ring-containing aromatic compound such as hexabromocyclododecane.
These brominated flame retardants may be used alone or in combination of two or more. Further, among the above, a brominated aromatic ring-containing aromatic compound is preferable, and among them, a monomer-based organic bromine compound such as ethylene bis (pentabromophenyl) is preferable.

<< Phosphate-containing flame retardant >>
As the phosphate-containing flame retardant, for example, at least one selected from various phosphoric acids, metals of Group IA to IVB of the Periodic Table, ammonia, aliphatic amines, aromatic amines, and heterocyclic compounds containing nitrogen in the ring. Phosphates consisting of salts with the metal or compound of.
The phosphoric acid is not particularly limited, and examples thereof include monophosphoric acid, pyrophosphoric acid, and polyphosphoric acid.
Examples of the metals of Group IA to Group 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 aniline, o-triidin, 2,4,6-trimethylaniline, anicidin, 3- (trifluoromethyl) aniline and the like. Examples of the heterocyclic compound containing nitrogen in the ring include pyridine, triazine, melamine and the like.

Specific examples of the phosphate-containing flame retardant include monophosphates such as aluminum tertiary phosphate, pyrophosphates, polyphosphates and the like. Here, the polyphosphate is not particularly limited, and examples thereof include ammonium polyphosphate, piperazine polyphosphate, melamine polyphosphate, ammonium polyphosphate, aluminum polyphosphate, and the like.
As the phosphate-containing flame retardant, one or more of the above-mentioned ones can be used.

<< Chlorine-containing flame retardant >>
Examples of the chlorine-containing flame retardant include those commonly used in flame-retardant resin compositions, for example, polychlorinated naphthalene, chlorendic acid, and dodecachlorododecahydrodimethanodibenzocyclo sold under the trade name of "Dechloran Plus". Octene and the like can be mentioned.

<< Antimony-containing flame retardant >>
Examples of the antimony-containing flame retardant include antimony oxide, antimony acid salt, pyroantimony acid salt and the like. Examples of antimony oxide include antimony trioxide and antimony pentoxide. Examples of the antimonate include sodium antimonate, potassium antimonate and the like. Examples of the pyroantimonate include sodium pyroantimonate, potassium pyroantimonate and the like.
The antimony-containing flame retardant may be used alone or in combination of two or more. The preferred antimony-containing flame retardant used in the present invention is antimony trioxide.

《Metal hydroxide》
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, and copper hydroxide. Examples thereof include vanadium hydroxide and tin hydroxide. The metal hydroxide may be used alone or in combination of two or more.

《Needle-shaped filler》
Examples of the needle-shaped filler used in the present invention include potassium titanate whisker, aluminum borate whisker, magnesium-containing whisker, silicon-containing whisker, wollastonite, sepiolite, zonolite, elestadite, boehmite, rod-shaped hydroxyapatite, and glass fiber. Examples thereof include carbon fiber, graphite fiber, metal fiber, slag fiber, gypsum fiber, silica fiber, alumina fiber, silica alumina fiber, zirconia fiber, boron nitride fiber, boron fiber, and stainless steel fiber.
These needle-shaped fillers may be used alone or in combination of two or more.

The range of the aspect ratio (length / diameter) of the needle-shaped filler used in the present invention is preferably in the range of 5 to 50, and more preferably in the range of 10 to 40. The aspect ratio can be obtained by observing 50 needle-shaped fillers with a scanning electron microscope and measuring the length and width thereof.

The content of the solid flame retardant in the raw material composition of the present invention is preferably 10 to 100 parts by mass, more preferably 20 to 90 parts by mass, still more preferably 30 to 80 parts by mass with respect to 100 parts by mass of the polyol compound. When the content of the solid flame retardant is within the above range, it becomes easy to improve the flame retardant of the obtained polyurethane foam.

<< Anti-precipitation agent >>
The polyol composition of the present invention may contain a settling inhibitor as a filler. The anti-settling agent may be used in combination with, for example, the above-mentioned solid flame retardant. By using the precipitation inhibitor, it is possible to prevent the precipitation of the solid flame retardant and the like dispersed in the polyol composition. Further, the use of the sedimentation inhibitor facilitates uniform dispersion of the solid flame retardant. The sedimentation inhibitor generally becomes a solid at normal temperature and pressure, and usually has a solid content (insoluble content) in the polyol composition.

The sedimentation inhibitor is not particularly limited, but for example, it is preferable to use one or more selected from carbon black, powdered silica, organic clay and the like, and among these, powdered silica is more preferable. ..
As the carbon black used as the settling inhibitor, one produced by a method such as a furnace method, a channel method, or a thermal method can be used. For carbon black, a commercially available product may be appropriately selected and used.
Further, as the powdery silica, fumed silica, colloidal silica, silica gel and the like can be used. Of these, fumed silica is preferred. As fumed silica, Aerosil (registered trademark) manufactured by Aerosil Japan Co., Ltd. can be used.

The content of the anti-precipitation agent in the raw material composition of the present invention is preferably 0.5 to 10 parts by mass, more preferably 1.0 to 8 parts by mass, and 1.5 to 8 parts by mass with respect to 100 parts by mass of the polyol compound. Parts by mass are more preferred. By setting the content of the anti-settlement agent within the above range, the solid flame retardant can be prevented from settling and its dispersibility can be improved without increasing the solid content more than necessary.

In the polyol composition of the present invention, an inorganic filler other than the solid flame retardant and the sedimentation inhibitor may be used as the filler. Examples of the inorganic filler include silica, slag, alumina, titanium oxide, calcium oxide, magnesium oxide, iron oxide, tin oxide, antimony oxide, ferrites, calcium carbonate, magnesium carbonate, zinc carbonate, barium carbonate, dosonite, and hydro. Talsite, calcium sulfate, barium sulfate, gypsum fiber, calcium silicate, talc, clay, mica, wollastonite, montmorillonite, bentonite, active white clay, sepiolite, imogolite, sericite, glass fiber, glass beads, silica balloon, nitride Aluminum, boron nitride, silicon nitride, carbon black, graphite, carbon fiber, carbon balloon, charcoal powder, various metal powders, potassium titanate, magnesium sulfate, lead zirconate titanate, aluminum porate, molybdenum sulfide, silicon carbide, stainless fiber , Various magnetic powders, slag fibers, fly ash, silica-alumina fibers, alumina fibers, silica fibers, zirconia fibers and the like. These inorganic fillers may be used alone or in combination of two or more.

The content of the filler in the raw material composition of the present invention is preferably 10 to 110 parts by mass, more preferably 20 to 100 parts by mass, still more preferably 30 to 90 parts by mass with respect to 100 parts by mass of the polyol compound. By setting the content of the filler to the above lower limit value or more, it becomes easy to improve the mechanical strength, flame retardancy and the like of the obtained polyurethane foam. Further, by setting the content of the filler to the above upper limit value or less, foaming is less likely to be inhibited by the filler.

<Effervescent agent>
The raw material composition of the present invention contains a foaming agent as a raw material for polyurethane foam. The foaming agent preferably contains a hydrofluoroolefin (HFO). In the present invention, even when a hydrofluoroolefin is used as the foaming agent, the stability of the foaming agent is high and the catalytic activity is unlikely to decrease. Examples of the hydrofluoroolefin include fluoroalkenes having about 3 to 6 carbon atoms. The hydrofluoroolefin may be a hydrochlorofluoroolefin having a chlorine atom, and therefore may be a chlorofluoroalkene having about 3 to 6 carbon atoms.
More specifically, trifluoropropene, tetrafluoropropene such as HFO-1234, pentafluoropropene such as HFO-1225, chlorotrifluoropropene such as HFO-1233, chlorodifluoropropene, chlorotrifluoropropene, and chlorotetra. Fluoropropene and the like can be mentioned. More specifically, 1,3,3,3-tetrafluoropropene (HFO-1234ze), 1,1,3,3-tetrafluoropropene, 1,2,3,3,3-pentafluoropropene (HFO). -1225ye), 1,1,1-trifluoropropene, 1,1,1,3,3-pentafluoropropene (HFO-1225zc), 1,1,1,3,3,3-hexafluorobut-2 -En, 1,1,2,3,3-pentafluoropropene (HFO-1225yc), 1,1,1,2,3-pentafluoropropene (HFO-1225yez), 1-chloro-3,3,3 -Trifluoropropene (HFO-1233zd), 1,1,1,4,4,4-hexafluorobut-2-ene and the like can be mentioned. Of these, HFO-1233zd is preferred.
These hydrofluoroolefins may be used alone or in combination of two or more.

The blending amount of the hydrofluoroolefin is preferably 20 to 50 parts by mass, more preferably 22 to 47 parts by mass, still more preferably 25 to 45 parts by mass with respect to 100 parts by mass of the polyol compound. When the blending amount of the hydrofluoroolefin is at least the above lower limit value, foaming is promoted and the density of the obtained polyurethane foam can be reduced. On the other hand, when the blending amount of the hydrofluoroolefin is not more than the above upper limit value, it is possible to suppress the excessive progress of foaming.

The raw material composition of the present invention preferably contains water as a foaming agent. As the water contained, for example, ion-exchanged water, distilled water and the like can be appropriately used. Water is preferably blended from the viewpoint of adjusting the isocyanate index and from the viewpoint of ease of handling.

The blending amount of water is preferably 0.1 to 10 parts by mass, more preferably 0.2 to 5 parts by mass, still more preferably 0.3 to 3 parts by mass with respect to 100 parts by mass of the polyol compound. When the blending amount of water is within the above range, it becomes easy to appropriately foam the raw material composition.

The raw material composition of the present invention may contain a foaming agent other than hydrofluoroolefin and water. Examples of the hydrofluoroolefin and other foaming agents include low boiling hydrocarbons such as propane, butane, pentane, hexane, heptane, cyclopropane, cyclobutane, cyclopentane, cyclohexane, and cycloheptane, dichloroethane, propylchloride, isopropyl. Examples thereof include chlorinated aliphatic hydrocarbon compounds such as chloride, butyl chloride, isobutyl chloride, pentyl chloride, and isopentyl chloride, and organic physical foaming agents such as ether compounds such as diisopropyl ether.

The blending amount of the hydrofluoroolefin and the foaming agent other than water in the raw material composition is preferably 0.1 to 10 parts by mass, more preferably 0.3 to 5 parts by mass, and 0 by mass with respect to 100 parts by mass of the polyol compound. .4 to 1 part by mass is more preferable. When the blending amount of the foaming agent is at least the above lower limit value, foaming is promoted and the density of the obtained polyurethane foam can be reduced. On the other hand, when the blending amount of the foaming agent is not more than the above upper limit value, it is possible to suppress excessive progress of foaming.

<Isocyanate>
The raw material composition of the present invention contains isocyanate as a raw material for polyurethane foam. Examples of the isocyanate include aromatic polyisocyanates, alicyclic polyisocyanates, and aliphatic polyisocyanates.
Examples of the aromatic polyisocyanate include phenylenediocyanate, tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, dimethyldiphenylmethane diisocyanate, triphenylmethane triisocyanate, naphthalene diisocyanate, and polymethylene polyphenyl polyisocyanate.

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, hexamethylene diisocyanate and the like.

Among these, aromatic polyisocyanates are preferable, and diphenylmethane diisocyanates are more preferable, from the viewpoint of ease of use and availability. As the polyisocyanate, one type may be used alone, or two or more types may be mixed and used.

(Isocyanate index)
The isocyanate index of the polyurethane composition of the present invention is not particularly limited, but is preferably 150 or more. When the isocyanate index is at least the lower limit value, the amount of the polyisocyanate compound with respect to the polyol compound becomes excessive, and isocyanurate bonds are easily generated by the trimerated polyisocyanate compound, and as a result, the flame retardancy of the polyurethane foam is improved. The isocyanate index is more preferably 200 or more, further preferably 300 or more, and particularly preferably 350 or more.
The isocyanate index is preferably 1,000 or less, more preferably 800 or less, and even more preferably 500 or less. When the isocyanate index is not more than the above upper limit value, the balance between the flame retardancy of the obtained polyurethane foam and the manufacturing cost is good.

The isocyanate index can be calculated by the following method.
Isocyanate index = equivalent number of polyisocyanate compound ÷ (equivalent number of polyol compound + equivalent number of water) × 100
Here, each equivalent number can be calculated as follows.
Equivalent number of polyisocyanate compound = amount of polyisocyanate compound used (g) x NCO content (mass%) / molecular weight of NCO (mol) x 100
Equivalent number of polyol compound = OHV × amount of polyol compound used (g) ÷ molecular weight of KOH (mmol)
OHV is the hydroxyl value (mgKOH / g) of the polyol compound.
Equivalent number of water = molecular weight of water (g) / molecular weight of water (mol) x number of OH groups of water In each of the above formulas, the molecular weight of NCO is 42 (mol) and the molecular weight of KOH is 56,100 (mmol). ), The molecular weight of water is 18 (mol), and the number of OH groups in water is 2.

<Catalyst>
The raw material composition of the present invention preferably contains a catalyst. Examples of the catalyst include at least one selected from the group consisting of a trimerization catalyst and a resinification catalyst, and preferably include a trimerization catalyst. By including the trimerization catalyst, isocyanurate formation is promoted and flame retardancy is enhanced. Further, it is more preferable to contain both a trimerization catalyst and a resinification catalyst. By containing a trimerization catalyst, a resinification catalyst, or both as a catalyst, the raw material composition of the present invention can enhance the activity of the catalyst and improve the foamability.

《Triquantization catalyst》
The trimerization catalyst is a catalyst that promotes an isocyanurate-forming reaction in which an isocyanate group contained in polyisocyanate is reacted to tritrate, and promotes the formation of an isocyanurate ring. As the trimerization catalyst, nitrogen-containing aromatic compounds such as tris (dimethylaminomethyl) phenol, 2,4-bis (dimethylaminomethyl) phenol, and 2,4,6-tris (dialkylaminoalkyl) hexahydro-S-triazine. , Carboxylic acid alkali metal salts such as potassium acetate, potassium 2-ethylhexanoate, potassium octylate, tertiary ammonium salts such as trimethylammonium salt, triethylammonium salt, triphenylammonium salt, tetramethylammonium salt, tetraethylammonium, tetra. A quaternary ammonium salt such as a phenylammonium salt or a triethylmonomethylammonium salt can be used. Examples of the ammonium salt include ammonium salts of carboxylic acids such as 2,2-dimethylpropanoic acid, and more specifically, quaternary ammonium salts of carboxylic acid.
These may be used alone or in combination of two or more.
Among these, one or more selected from carboxylic acid alkali metal salt and carboxylic acid quaternary ammonium salt is preferable, and an embodiment using both of them is also preferable. Further, from the viewpoint of improving foamability when used in combination with a hydrofluoroolefin, the trimerization catalyst preferably contains at least a quaternary ammonium salt of a carboxylic acid.

The blending amount of the trimerization catalyst is preferably 1 to 30 parts by mass, more preferably 2 to 25 parts by mass, still more preferably 3 to 20 parts by mass with respect to 100 parts by mass of the polyol compound. When the blending amount of the trimerization catalyst is not less than these lower limit values, trimerization of polyisocyanate is likely to occur, and the flame retardancy of the obtained polyurethane foam is improved. On the other hand, when the blending amount of the trimerization catalyst is not more than the above upper limit value, the reaction can be easily controlled.

《Resinization catalyst》
The resinification catalyst is a catalyst that promotes the reaction between the polyol and the polyisocyanate. Examples of the resinification catalyst include amine-based catalysts such as imidazole compounds and piperazine compounds, and metal-based catalysts.
Examples of the imidazole compound include a tertiary amine in which the secondary amine at the 1-position of the imidazole ring is replaced with an alkyl group, an alkenyl group or the like. Specifically, N-methylimidazole, 1,2-dimethylimidazole, 1-ethyl-2-methylimidazole, 1-methyl-2-ethylimidazole, 1,2-diethylimidazole, and 1-isobutyl-2-methyl. Examples include imidazole. Further, an imidazole compound in which the secondary amine in the imidazole ring is substituted with a cyanoethyl group may be used.
Examples of the piperazine compound include tertiary amines such as N-methyl-N'N'-dimethylaminoethylpiperazine and trimethylaminoethylpiperazine.
In addition to the imidazole compound and piperazine compound, the resinification catalyst includes pentamethyldiethylenetriamine, triethylamine, N-methylmorpholinbis (2-dimethylaminoethyl) ether, N, N, N', N ", N"-. Pentamethyldiethylenetriamine, N, N, N'-trimethylaminoethyl-ethanolamine, bis (2-dimethylaminoethyl) ether, N, N-dimethylcyclohexylamine, diazabicycloundecene, triethylenediamine, tetramethylhexamethylenediamine , Various tertiary amines such as tripropylamine and the like.

Examples of the metal-based catalyst include catalysts containing bismuth, tin, copper, lead, zinc, cobalt, nickel and the like, and are selected from the group consisting of bismuth and tin from the viewpoint of suppressing an excessive isocyanurate-forming reaction. It is preferable to contain at least one kind. The metal catalyst is preferably a metal salt.
The metal salt is preferably an organic acid metal salt, more preferably a metal salt of a carboxylic acid having 5 or more carbon atoms. When the carboxylic acid has 5 or more carbon atoms, its stability with a foaming agent, particularly a hydrofluoroolefin, becomes good. The carbon number of the carboxylic acid is preferably 18 or less, more preferably 12 or less, from the viewpoint of catalytic activity and the like. The carboxylic acid is preferably an aliphatic carboxylic acid, more preferably a saturated aliphatic carboxylic acid. The carboxylic acid may be linear or may have a branched structure, but it is preferable that the carboxylic acid has a branched structure.
Specific examples of the carboxylic acid include octyl acid, lauryl acid, versatic acid, pentanic acid and acetic acid, and among these, octyl acid is preferable. That is, the transition metal salt is preferably a metal salt of octyl acid. These carboxylic acids may be linear as described above, but may have a branched structure. Examples of the octylic acid having a branched structure include 2-ethylhexanoic acid.
As the metal salt of carboxylic acid, a bismuth salt of carboxylic acid and a tin salt of carboxylic acid are preferable, and a bismuth salt of octyl acid is particularly preferable. Further, the metal salt of the carboxylic acid may be a carboxylate of an alkyl metal. For example, the carboxylic acid tin salt may be a dialkyltin carboxylate or the like, preferably a dioctyltin carboxylate or the like.
Specific examples of the metal salt of the carboxylic acid include bismuth trioctate, dioctyl tin versate, dibutyl tin dilaurate, dioctyl tin dilaurate, tin dioctylate, lead dioctylate and the like, and bismuth trioctate and dioctyl tin versa are preferable. Tate, more preferably bismuth trioctate.
In the present invention, a metal catalyst containing at least one selected from the group consisting of bismuth and tin is preferable as the resinification catalyst, and a metal catalyst containing bismuth is particularly preferable. By using these metal catalysts, the foamability is appropriately adjusted, elongation due to foaming is suppressed, and delamination is less likely to occur. Further, the metal catalyst may be used in combination with an amine-based catalyst, and more preferably in combination with an imidazole compound.

The blending amount of the resinification catalyst is preferably 1 to 30 parts by mass, more preferably 2 to 25 parts by mass, still more preferably 3 to 20 parts by mass with respect to 100 parts by mass of the polyol compound. When the blending amount of the resinification catalyst is at least these lower limit values, urethane bonds are likely to be formed, and the reaction proceeds rapidly. On the other hand, when it is not more than these upper limit values, it becomes easy to control the reaction rate.

The total amount of the catalyst in the raw material composition is preferably 1 to 40 parts by mass, more preferably 2 to 35 parts by mass, still more preferably 3 to 30 parts by mass with respect to 100 parts by mass of the polyol compound. When it is equal to or more than these lower limit values, the formation of urethane bonds and the quantification of urethane bonds are likely to proceed appropriately. Further, when it is not more than these upper limit values, it becomes easy to control the urethanization and triquantization reactions.

<Other ingredients>
The raw material composition may be a phenol-based, amine-based, sulfur-based or other antioxidant, inorganic filler, defoaming agent, heat stabilizer, metal damage inhibitor, as necessary, as long as the object of the present invention is not impaired. It can contain one or more additives selected from antistatic agents, stabilizers, cross-linking agents, lubricants, softeners, pigments and the like.

<Mixed system>
Next, the mixing system according to the first embodiment of the present invention will be described in more detail. As shown in FIG. 1, the mixing system according to the first embodiment of the present invention includes raw material containers 10a and 10b, a mixer 20, a temperature control device 30, a pressure adjusting gas supply device 40, and a discharge device 50. And.

(Raw material container)
The raw material containers 10a and 10b are filled with raw materials for obtaining polyurethane foam. The raw materials filled in the raw material containers 10a and 10b are mixed to form a raw material composition.
The raw material container in the present embodiment is filled with a first container 10a filled with a first raw material (polyol liquid agent) 11a containing a polyol compound and a second raw material (isocyanate liquid agent) 11b containing isocyanate. A second container 10b is provided. Further, the first raw material may contain a filler and a foaming agent, and when the raw material composition further contains a catalyst, the first raw material may further contain a catalyst. In addition, the above-mentioned other components may also be contained in the first raw material.
The raw material containers 10a and 10b are not particularly limited as long as they are materials that are resistant to pressurization by the pressure adjusting gas supply device 40 shown below, and examples thereof include stainless steel.

(Mixer)
The mixer 20 has communication portions 21a and 21b that are in fluid communication with the raw material containers 10a and 10b. A valve (not shown) is provided in the flow path of the communication portions 21a and 21b, and the introduction of the raw material into the raw material container 10a and 10b into the mixer 20 is controlled by opening and closing the valve.
The mixer 20 prepares a raw material composition by mixing the raw materials 11a and 11b supplied from the raw material containers 10a and 10b via the communication portions 21a and 21b. Examples of the mixer 20 include a static mixer called a so-called static mixer. The stationary mixer is a mixer without a drive unit, and the fluid is mixed by passing the fluid through the inside of the pipe body. Examples of the stationary mixer include a mixer element in which a mixer element is arranged inside a tube body. Examples of the mixer element include those formed in a spiral shape and those in which a plurality of baffle plates are formed. Further, the mixer 20 may be a mixer 20 in which pressurized raw materials are made to collide with each other to be mixed inside the mixer 20. The raw material composition prepared by the mixer 20 is sent to the discharge device 50.

When the polyol liquid and the isocyanate liquid are mixed as described above, the mixer 20 preferably has substantially the same volume. Specifically, the volume ratio of the isocyanate liquid to the polyol liquid is preferably 0.8 to 1.2, more preferably 0.9 to 1.1, and even more preferably 0.95 to 1.05.

From the viewpoint of improving the mixing property of each raw material in the mixer 20, the difference in viscosity of the raw materials filled in each raw material container is measured by using a B-type viscometer and setting the probe rotation speed to 60 rpm at 25 ° C. It is preferable to adjust the temperature within the range of 10 mPa · s or more and 2,000 mPa · s or less. Therefore, in the present embodiment, the viscosity difference between the first raw material (polyol solution) and the second raw material (isocyanate solution) is preferably 10 mPa · s or more and 2,000 mPa · s or less. From the above viewpoint, the viscosity difference is more preferably 30 mPa · s or more and 1,500 mPa · s or less, and further preferably 50 mPa · s or more and 800 mPa · s or less.

The viscosity of the first raw material (polypoly solution) when measured using a B-type viscometer at 25 ° C. with the probe rotation speed set to 60 rpm is preferably 200 mPa · s or more and 2,500 mPa · s or less. , 230 mPa · s or more and 1,000 mPa · s or less is more preferable.
The viscosity of the second raw material (isocyanate solution) when measured using a B-type viscometer at 25 ° C. with the probe rotation speed set to 60 rpm is preferably 100 mPa · s or more and 1,000 mPa · s or less. , 150 mPa · s or more and 500 mPa · s or less is more preferable.

(Temperature control device)
The temperature control device 30 heats at least one of the raw materials supplied to the mixer 20. The temperature control device 30 may heat a raw material containing at least a filler among the raw materials filled in each raw material container. Therefore, in this embodiment, it is advisable to heat at least the first raw material. As the viscosity of the raw material containing the filler increases, the difference in viscosity from the raw material containing no filler increases and the reactivity decreases, but the viscosity is reduced by heating with the temperature control device 30 and the filler is contained. By reducing the difference in viscosity with the raw material that does not, the mixing property can be improved, and the raw material having excellent reactivity can be prepared.

Further, the temperature control device 30 may heat all the raw materials supplied to the mixer 20. By heating all the raw materials supplied to the mixer 20 by the temperature control device 30 and adjusting the temperature to the same level, for example, the temperature difference between the first raw material 11a and the second raw material 11b is reduced. , The reactivity of the first raw material 11a and the second raw material 11b in the mixer 20 can be improved. The difference in viscosity in the mixer 20 is further reduced, and the mixing property is improved.

It is preferable that the temperature control device 30 adjusts the temperature of the raw material to 30 ° C. or higher and 50 ° C. or lower, and supplies the raw material adjusted to the temperature to the mixer 20. By adjusting the raw material to a temperature equal to or higher than the above lower limit value by the temperature control device 30, it is possible to reduce the difference in viscosity between the raw material containing the filler and the raw material not containing the filler without excessively increasing the foamability. It is possible to improve the mixing property of two or more raw materials. Further, by adjusting the temperature of the raw material to a temperature equal to or lower than the above upper limit value by the temperature control device 30, it is possible to suppress the occurrence of charring inside the formed polyurethane foam and prevent a fire.

The location where the temperature control device 30 is installed is not particularly limited as long as the raw material supplied to the mixer 20 can be heated. For example, as shown in FIG. 1, the raw material containers 10a and 10b are connected to the mixer 20. It can be installed in the communication portions 21a and 21b. Further, as shown in FIG. 2, the temperature control device 30 can be installed around the raw material containers 10a and 10b, respectively. That is, the temperature control device 20 only needs to be able to heat at least one of the raw material containers 10a and 10b and the communication portions 21a and 21b.

The temperature control device 30 is not particularly limited as long as the raw material can be adjusted to the above temperature range, and examples of the temperature control device installed in the communication portions 21a and 21b include a band heater and an electric blanket. Examples of the device for heating the raw material containers 10a and 10b include a band heater, an electric blanket, a water bath, and a throw-in heater.

(Pressure adjustment gas supply device)
The pressure adjusting gas supply device 40 includes gas supply paths 41a and 41b communicating with the raw material containers 10a and 10b, respectively, and supplies air or an inert gas into the raw material containers 10a and 10b. The inside of the raw material containers 10a and 10b is pressurized by the air or the inert gas supplied from the pressure adjusting gas supply device 40, and the raw materials 11a and 11b are sent out to the mixer 20 through the communication portions 21a and 21b by the pressure. To. That is, the pressure in the mixer 20 can be adjusted by pressurizing the raw material containers 10a and 10b by the pressure adjusting gas supply device 40.
The pressure adjusting gas supply device 40 supplies air or an inert gas so as to adjust the pressure in the mixer 20. The pressure in the mixer 20 is, for example, 0.05 MPa or more and 1.0 MPa or less, and the pressure in the mixer 20 should be higher than the atmospheric pressure, and more preferably 0.11 MPa or more and 0.9 MPa or less. It is more preferably 0.2 MPa or more and 0.85 MPa or less, and even more preferably 0.4 MPa or more and 0.85 MPa or less. In order to keep the pressure in the mixer 20 within the above range, the pressure in each of the raw material containers 10a and 10b may be within the above range.
Examples of the inert gas supplied by the pressure adjusting gas supply device 40 include nitrogen, argon, carbon dioxide and the like.
Examples of the pressure adjusting gas supply device 40 include an air compressor.

(Discharge device)
The discharge device 50 discharges the raw material composition prepared by the mixer 20 and foams it to form a polyurethane foam.

(Spray gas supply device)
The mixing system may include a spray gas supply device 60, as shown in FIG.
The spray gas supply device 60 mixes air or an inert gas into the raw material composition prepared by the mixer 20 in the discharge device 50 to obtain a raw material composition in which the air or the inert gas is mixed. The raw material composition mixed with air or the inert gas is uniformly mixed with the air or the inert gas, and the mixing property and reactivity are improved. Examples of the inert gas include nitrogen, argon, carbon dioxide and the like.
Examples of the spray gas supply device 60 include an air compressor.

The raw material composition mixed with air or the inert gas by the spray gas supply device 60 is spray-discharged from the discharge device 50 provided with the spray nozzle to the object to be coated and foamed to form a polyurethane foam. The discharge device 50 is not particularly limited as long as it can spray and discharge the raw material composition mixed with air or an inert gas, and examples thereof include a spray device.

<Manufacturing method of polyurethane foam>
Polyurethane foam can be formed by using the mixing system according to the first embodiment of the present invention. Specifically, the method for producing polyurethane foam includes the following steps (1) to (5).
(1) Step of filling two or more raw material containers with raw materials (2) In a mixer having a communication portion that is fluidly communicated with the raw material container, the raw materials supplied from each raw material container are mixed through the communication portion. Step of preparing raw material composition (3) Step of heating at least one of the raw materials supplied to the mixer with a temperature control device (4) Air in the raw material container to adjust the pressure in the mixer. Alternatively, the step of supplying the inert gas with the pressure adjusting gas supply device (5) the step of discharging the raw material composition prepared by the mixer from the discharge device.

The mixing system according to the first embodiment of the present invention is provided with a temperature control device for heating the raw material composition, so that the raw material composition can be mixed even when the raw material composition containing a filler is used. It is possible to form a polyurethane foam having good properties and excellent curability and flame retardancy.
The use of the polyurethane foam of the present invention is not particularly limited, but since it is excellent in flame retardancy and heat insulating property, a building such as a wall, ceiling, roof, or floor of a building can be suitably used as a construction target surface. Further, the polyurethane foam of the present invention can be used for repairs and the like, and can also be used as a member for filling arbitrary openings generated in a building, including joints and holes generated between structural materials of the building.

[Second Embodiment]
A second embodiment of the present invention will be described in detail. In the second embodiment, the difference from the first embodiment is that the pressure adjusting gas supply device 40 further includes a gas supply path 41c communicating with the discharge device 50, as shown in FIG. Hereinafter, the differences between the second embodiment and the first embodiment will be described. Moreover, the part where the description is omitted is the same as that of the first embodiment. Further, in the following description, the members having the same configuration as that of the first embodiment are designated by the same reference numerals.

The pressure adjusting gas supply device 40 in the present embodiment also serves as the spray gas supply device shown in FIG. 1 and supplies air or an inert gas to the discharge device 50. In this aspect, the type and pressure of the gas mixed in the raw material composition are substantially the same as the pressure adjusting gas supplied to the raw material containers 10a and 10b. This aspect is preferable from the viewpoint of cost and simple device configuration.

[Other embodiments]
The mixing system described by showing each embodiment as described above and the method for producing polyurethane foam are examples of the present invention, and the present invention is not limited to the configuration of the above embodiment and deviates from the gist of the present invention. Various improvements and changes can be made to the extent that it does not occur, and components may be added as appropriate.
For example, in the above description, the number of raw material containers is shown as two, but the number may be three or more. Specifically, when there are three raw material containers, the first raw material container is filled with a polyol, the second raw material container is filled with isocyanate, and the third raw material container is filled with a foaming agent. The first raw material container may contain a filler, and when the raw material composition further contains a catalyst, the first raw material container may further contain a catalyst. In this case, the raw material of the first raw material container may contain the above-mentioned other components. In this case, it is preferable to adjust the viscosity difference between the raw material filled in the first raw material container and the raw material filled in the second raw material container within the above range.

Further, in the above description, the discharge device is shown as a spray device, but the discharge device is not limited to the spray device. For example, the raw material composition discharged from the discharge port of the discharge device may be filled inside a building material such as a panel or a pillar member without being sprayed.

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

Each component used in Examples and Comparative Examples is shown below, and the content (part by mass) of each component is shown in Table 1.

-Polyol compound: Polyester polyol (manufactured by Kawasaki Kasei Kogyo Co., Ltd., product name: Maximol RLK-087)
-Catalyst 1: Triquantization catalyst, potassium 2-ethylhexanoate-containing catalyst (manufactured by Eponic Japan, product name: DABCO K-15), concentration 75% by mass
-Catalyst 2: Resinification catalyst, 1,2-dimethylimidazole (manufactured by Kao Corporation, product name: Kaorizer No. 390) concentration 65-75% by mass
-Effervescent agent 1: Trans-1-chloro-3,3,3-trifluoropropene (manufactured by Honeywell, product name: Solstice LBA, HFO)
・ Foaming agent 2: Water ・ Filler 1: Red phosphorus flame retardant (red phosphorus, manufactured by Phosphorus Chemical Industry Co., Ltd., product name: Nova Excel 140)
-Filler 2: Boron-containing flame retardant (zinc borate, manufactured by Hayakawa Shoji Co., Ltd., product name: Firebrake ZB)
-Filler 3: Flame retardant containing bromine (ethylene bis, manufactured by Albemarle, product name: SAYTEX 8010)
-Filler 4: Anti-settling agent (manufactured by Aerosil Japan, product name: Aerosil R976S)
-Polyisocyanate (isocyanate compound): diphenylmethane-4,4'-diisocyanate (MDI), manufactured by Bayer, product name: DESMODUR (registered trademark) 44V20L

[Example 1]
First, weighed according to the formulation shown in Table 1 and kneaded with a hand drill mixer to obtain a polyol liquid.
Next, the mixing system shown in FIG. 1 was prepared. One raw material container was filled with the obtained polyol liquid, and the other raw material container was filled with the isocyanate liquid. The polyol solution and the isocyanate solution were filled so as to have the same mass. The pressure of each raw material container filled with the polyol solution and the isocyanate solution was set to 0.6 MPa by the air supplied from the pressure adjusting gas supply device.
A band heater as a temperature control device was wound around the communication portion of the mixer and installed, and the temperature control setting temperature of the polyol liquid and the isocyanate liquid was set to 40 ° C. and left for 1 hour or more.
Then, a polyol solution and an isocyanate solution were mixed on a gypsum board with a mixer to prepare a raw material composition, and the prepared raw material composition was discharged from a discharge device to obtain a polyurethane foam. The curing time and flame retardancy of the polyurethane foam were evaluated as follows.

[Example 2]
Example 1 was carried out in the same manner as in Example 1 except that the temperature control setting temperature of the polyol liquid was set to 50 ° C. and the temperature control set temperature of the isocyanate liquid was set to 30 ° C.

[Example 3]
The same procedure as in Example 1 was carried out except that the pressure of each raw material container filled with the polyol solution and the isocyanate solution was set to 0.5 MPa and the temperature control setting temperature of the isocyanate solution was set to 50 ° C. ..

[Examples 4 and 5]
Example 1 was carried out in the same manner as in Example 1 except that the polyol liquid was changed according to the formulation shown in Table 1.

[Example 6]
The procedure was carried out in the same manner as in Example 1 except that the polyol solution was changed according to the formulation shown in Table 1 and the pressure of each raw material container filled with the polyol solution and the isocyanate solution was set to 0.8 MPa.

[Example 7]
As shown in FIG. 2, the temperature control device was carried out in the same manner as in Example 6 except that the band heater was wound around the raw material container and installed.

[Comparative Example 1]
Example 1 was carried out in the same manner as in Example 1 except that the polyol liquid was changed according to the formulation shown in Table 1.

[Comparative Example 2]
Example 1 was carried out in the same manner as in Example 1 except that the temperature control device was eliminated.

[Comparative Example 3]
First, weighed according to the formulation shown in Table 1 and kneaded with a hand drill mixer to obtain a polyol liquid.
Next, the obtained polyol solution and isocyanate solution were placed in a pail. A band heater was wrapped around the pail and installed, and the temperature control setting temperature of the polyol liquid and the isocyanate liquid was set to 40 ° C. and left for 1 hour or more. Then, the polyol liquid and the isocyanate liquid were filled in the raw material container so as to have the same mass. The pressure of each raw material container filled with the polyol solution and the isocyanate solution was set to 0.6 MPa by the air supplied from the pressure adjusting gas supply device.
Then, a polyol solution and an isocyanate solution were mixed on a gypsum board with a mixer to prepare a raw material composition, and the prepared raw material composition was discharged from a discharge device to obtain a polyurethane foam. The curing time and flame retardancy of the polyurethane foam were evaluated as follows.

[Curing time]
The raw material composition was discharged onto the gypsum board for 3 seconds, and the time from the end of the discharge until the surface of the polyurethane foam became non-adhesive (until it did not deform when touched) was measured as the curing time. When the curing time was less than 30 seconds, it was designated as "A", when it was 30 seconds or more and 90 seconds or less, it was designated as "B", and when it exceeded 90 seconds, it was designated as "C". The results are shown in Table 1.

〔Flame retardance〕
The raw material composition was discharged onto the gypsum board to form a polyurethane foam left for 12 hours. Then, a polyurethane foam was cut out so that the thickness including the gypsum board was 50 mm, and a sample was obtained. The total calorific value when the obtained sample was heated at a radiant heat intensity of 50 kW / m ² for 5 minutes according to the test method of ISO-5660 was measured by a cone calorimeter. The case where the total calorific value for 5 minutes was 8 MJ or less was designated as "A", the case where it exceeded 8 MJ and was 10 MJ or less was designated as "B", and the case where it exceeded 10 MJ was designated as "C". The results are shown in Table 1.

From the results of the above examples, even when a raw material composition containing a filler is used, it is possible to form a polyurethane foam having good mixing properties of the raw material composition and excellent curability and flame retardancy. rice field.

10a, 10b Raw material container 11a, 11b Raw material composition 20 Mixer 21a, 21b Communication part 30 Temperature control device 40 Pressure adjustment gas supply device 41a to 41c Gas supply path 50 Discharge device 60 Spray gas supply device

Claims (13)

A mixing system for forming polyurethane foams using raw material compositions containing polyol compounds, fillers, foaming agents and isocyanates.
Two or more raw material containers and
A mixer having a communication portion that is fluidly communicated with the raw material container and mixing raw materials supplied from each raw material container through the communication portion to prepare a raw material composition.
A temperature control device that heats at least one of the raw materials supplied to the mixer, and
A pressure-adjusting gas supply device that supplies air or an inert gas into the raw material container in order to adjust the pressure in the mixer.
A mixing system including a discharge device for discharging the raw material composition prepared by the mixer. A spray gas supply device for supplying air or an inert gas to the discharge device is further provided.
The spray gas supply device mixes air or an inert gas into the raw material composition in the discharge device.
The mixing system according to claim 1, wherein the discharging device sprays and discharges the raw material composition mixed with air or an inert gas. The mixing system according to claim 1 or 2, wherein the temperature control device adjusts the temperature of the raw material composition to 30 ° C. or higher and 50 ° C. or lower. The mixing system according to any one of claims 1 to 3, wherein the temperature control device heats at least one of the raw material container and the communication portion. The mixing system according to any one of claims 1 to 4, wherein the temperature control device heats the raw material containing a filler. When the probe rotation speed is set to 60 rpm at 25 ° C. using a B-type viscometer, the viscosity difference of the raw materials supplied from the raw material container to be mixed by the mixer is 10 mPa · s or more 2, The mixing system according to any one of claims 1 to 5, which is 000 mPa · s or less. The mixing system according to any one of claims 1 to 6, wherein the pressure adjusting gas supply device adjusts the pressure in the mixer to 0.05 MPa or more and 1.0 MPa or less. The mixing system according to any one of claims 1 to 7, wherein the filler is at least one selected from the group consisting of a red phosphorus flame retardant, a boron-containing flame retardant and a bromine-containing flame retardant. The mixing system according to any one of claims 1 to 8, wherein the filler contains an inhibitor of sedimentation. The mixing system according to any one of claims 1 to 9, wherein the foaming agent contains a hydrofluoroolefin. The mixing system according to any one of claims 1 to 10, wherein the raw material composition contains a catalyst. The raw material container is claimed to include a first container filled with the raw material composition containing a polyol compound, a filler and a foaming agent, and a second container filled with the raw material composition containing isocyanate. Item 12. The mixing system according to any one of Items 1 to 11. A method for producing a polyurethane foam using a raw material composition containing a polyol compound, a filler, a foaming agent and an isocyanate.
The process of filling two or more raw material containers with raw materials,
A step of preparing a raw material composition by mixing raw materials supplied from each raw material container through the communication portion in a mixer having a communication portion that is fluidly communicated with the raw material container.
A step of heating at least one of the raw materials supplied to the mixer with a temperature control device, and
A step of supplying air or an inert gas into the raw material container by a pressure adjusting gas supply device in order to adjust the pressure in the mixer, and
A method for producing a polyurethane foam, which comprises a step of discharging the raw material composition prepared by the mixer from a discharge device.

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