JP2022025989A - Method for producing polyurethane foam - Google Patents

Abstract

To produce a polyurethane foam having excellent quality by preventing the degradation of liquid, for example, during storage.SOLUTION: A method for producing a polyurethane foam includes the steps of: preparing liquid A and liquid B; mixing the liquid A and liquid B to make polyol liquid; and mixing the polyol liquid P and isocyanate liquid IP. The liquid A contains a polyol, a filler and a catalyst. The liquid B contains a foamer.SELECTED DRAWING: Figure 1

Description

The present invention relates to a method for producing a polyurethane foam containing a filler.

As a method for producing a polyurethane foam, a method of mixing an isocyanate liquid having a polyisocyanate and a polyol liquid having a polyol and foaming them is generally performed. In this method, a foaming agent and a catalyst are added to either liquid or both in order to obtain polyurethane foam.

Further, in order to impart further functions to the polyurethane foam, the liquid agent may be designed to contain components other than the polyisocyanate, the polyol, the catalyst, and the foaming agent. As one of the designs, an attempt is made to add a filler. For example, Patent Document 1 reports that a solid flame retardant is added to improve the flame retardancy.

Here, additives such as foaming agents, catalysts, and fillers are generally added to the polyol liquid because of the high reactivity of the isocyanate liquid. In addition, the polyol liquid may be stored for a long period of time before use with additives such as a foaming agent, a catalyst, and a filler added.

International Publication 2014/11394

However, some of the foaming agents used in polyurethane foam may affect the catalyst and accelerate deterioration. Therefore, if a foaming agent, a catalyst, and a filler are added to the polyol liquid and then stored for a long period of time, the polyol liquid may deteriorate and it may not be possible to produce urethane foam having good quality.
Further, in the polyol liquid containing the filler, the filler may settle during storage and hard caking may occur. When hard caking occurs, the filler may not be uniformly dispersed even if the polyol liquid in the container is stirred.

Therefore, the present invention is a method for producing a urethane foam, which can suppress deterioration of the liquid agent even when the liquid agent is stored for a long period of time, and can produce a polyurethane foam having good quality and less likely to cause hard caking. The challenge is to provide.

The gist of the present invention is as follows (1) to (6).
(1) The process of preparing the liquid agent A and the liquid agent B,
The step of mixing the liquid agent A and the liquid agent B to obtain a polyol liquid agent, and
A step of mixing the polyol liquid and the isocyanate liquid is provided.
A method for producing a polyurethane foam, wherein the liquid agent A contains a polyol, a filler, and a catalyst, and the liquid agent B contains a foaming agent.
(2) The method for producing a polyurethane foam according to (1) above, wherein the liquid agent A has a viscosity of 2000 to 60,000 mPa · s at 25 ° C. and 1 rpm.
(3) The filler contains a solid flame retardant, and the solid flame retardant is a red phosphorus flame retardant, a bromine-containing flame retardant, a phosphate-containing flame retardant, a chlorine-containing flame retardant, an antimony-containing flame retardant, and metal hydroxylation. The method for producing a polyurethane foam according to (1) or (2) above, which is at least one selected from the group consisting of a substance and a needle-shaped filler.
(4) The item according to any one of (1) to (3) above, wherein the liquid agent A and the liquid agent B are mixed so that the mass ratio of the liquid agent A is higher than that of the liquid agent B to obtain a polyol liquid agent. How to make polyurethane foam.
(5) The method for producing a polyurethane foam according to any one of (1) to (4) above, wherein the polyol liquid has a viscosity of 200 to 2500 mPa · s at 25 ° C. and 60 rpm.
(6) The method for producing a polyurethane foam according to any one of (1) to (5) above, wherein the foaming agent contains a hydrofluoroolefin compound.

According to the present invention, it is possible to produce a polyurethane foam that suppresses deterioration of the liquid agent, has good quality, and is less likely to cause hard caking even when the liquid agent is stored for a long period of time.

It is a conceptual diagram which shows the manufacturing method of the polyurethane foam which concerns on one Embodiment of this invention.

Hereinafter, the method for producing the polyurethane foam of the present invention will be described in detail using embodiments. The method for producing a polyurethane foam according to an embodiment of the present invention includes the following steps 1 to 3.
(Step 1) Step of preparing liquid agent A and liquid agent B (Step 2) Step of mixing liquid agent A and liquid agent B to obtain a polyol liquid agent (Step 3) Step of mixing the polyol liquid agent and the isocyanate liquid agent In this method, , Liquid A contains a polyol, a filler, and a catalyst, and Liquid B contains a foaming agent.

In the above method, the raw materials for forming the polyurethane foam are stored in the state of the liquids A and B, and then the polyol liquid is prepared by step 2 before use, and then the polyol liquid is prepared by step 3. A polyurethane foam is produced by mixing with an isocyanate solution and foaming the mixture.
By such a method, it is possible to prevent the foaming agent and the catalyst from being stored in a mixed state, so that deterioration of the liquid agent due to storage can be suppressed, and a polyurethane foam having good quality can be produced.

Further, the liquid agent A contains a filler. Fillers are generally effective as a method of imparting additional functions to liquids, but have the disadvantage of settling. In the present invention, since the foaming agent is contained in the liquid agent B different from the liquid agent A, the liquid agent A can suppress the decrease in viscosity due to the foaming agent. Therefore, the liquid agent A is maintained at a relatively high viscosity, and even if it is stored at room temperature and a temperature below normal temperature (for example, 30 ° C. or lower), it is possible to prevent the filler from settling and causing hard caking.
The "liquid agent" may be liquid at the time of preparation of each liquid agent, at the time of storage until it is mixed with another liquid agent, or at the time of mixing with other liquid agents, which is typical. The liquid is liquid from the time of preparation of each liquid to the time when it is mixed with other liquids, and is preferably liquid at room temperature (23 ° C.) and normal pressure (1 atm). Of course, each liquid may contain a solid content such as a filler, and thus may be in the form of a slurry.

<polyol solution>
In the present invention, as described above, the liquid agent A and the liquid agent B are mixed to obtain a polyol liquid agent. Hereinafter, the components used in each liquid as a raw material for the polyol liquid will be described in detail.

[Polyol]
The polyol is contained in the liquid agent A as described above. When the liquid agent A containing the catalyst and the filler further contains the polyol, the catalyst is easily dissolved or dispersed in the liquid agent A, and the filler is easily dispersed in the liquid agent A, so that the handleability of the liquid agent A is improved. ..

Examples of the polyol include polylactone polyols, polycarbonate polyols, aromatic polyols, alicyclic 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 polyester polyol include a polymer obtained by dehydrating and condensing a polybasic acid and a polyhydric alcohol, and a condensate of a hydroxycarboxylic acid and the polyhydric alcohol and 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 and reaction products of castor oil and ethylene glycol.

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 polymer, for example, at least one kind of alkylene oxide such as ethylene oxide, propylene oxide and tetrahydrofuran is ring-opened 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 a polymer obtained by polymerization. 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. , Ethylenediamine, amines such as butylene diamine, and the like.

The polyol used in the present invention preferably contains at least one selected from polyester polyols and polyether polyols, and preferably contains at least polyester polyols. Among them, polybasic acids having an aromatic ring such as isophthalic acid (m-phthalic acid) and terephthalic acid (p-phthalic acid), and dihydric alcohols such as bisphenol A, ethylene glycol, and 1,2-propylene glycol. It is more preferable to contain a polyester polyol obtained by dehydration condensation.
At this time, the content of at least one selected from the polyester polyol and the polyether polyol is preferably 50 to 100 parts by mass, more preferably 70 to 100 parts by mass, and 85 to 100 parts by mass with respect to 100 parts by mass of the polyol. The unit is more preferable.
Further, the polyol used in combination with at least one selected from the polyester polyol and the polyether polyol is not particularly limited and may be appropriately selected from the above, and examples thereof include the above-mentioned aliphatic polyol.

The hydroxyl value of the polyol is preferably 20 to 350 mgKOH / g, more preferably 30 to 300 mgKOH / g. When the hydroxyl value of the polyol is not more than the upper limit, the viscosity of the polyol liquid does not become excessively large, which is preferable from the viewpoint of handleability and the like. On the other hand, when the hydroxyl value of the polyol is at least the above lower limit value, the crosslink density of the polyurethane foam is increased and the strength is increased.
The hydroxyl value of the polyol can be measured according to JIS K 1557-1: 2007.

[catalyst]
In the present invention, the catalyst is contained in the liquid agent A. Examples of the catalyst include a resinification catalyst and a quantification catalyst. From the viewpoint of appropriately advancing the urethanization reaction and the trimerization reaction to obtain a polyurethane foam having excellent flame retardancy, the catalyst preferably contains both a resinification catalyst and a trimerization catalyst.

(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 a secondary amine in the imidazole ring is substituted with a cyanoethyl group can also be mentioned.
Examples of the piperazine compound include tertiary amines such as N-methyl-N', N'-dimethylaminoethylpiperazine, and trimethylaminoethylpiperazine.
In addition to imidazole compounds and piperazine compounds, amine-based catalysts include pentamethyldiethylenetriamine, triethylamine, N-methylmorpholinbis (2-dimethylaminoethyl) ether, N, N, N', N ", N" -pentamethyl. Diethylenetriamine, N, N, N'-trimethylaminoethyl-ethanolamine, bis (2-dimethylaminoethyl) ether, N, N-dimethylcyclohexylamine, diazabicycloundecene, triethylenediamine, tetramethylhexamethylenediamine, tri Examples thereof include various tertiary amines such as propylamine.
As the amine-based catalyst, an imidazole compound is preferable.

Examples of the metal-based catalyst include metal salts such as lead, tin, bismuth, copper, zinc, cobalt and nickel, and preferably organic acid metal salts such as lead, tin, bismuth, copper, zinc, cobalt and nickel. .. More preferably, organic acid tin salts such as dibutyltin dilaurate, dioctyltin dilaurate and dioctyltin versatete, and organic acid bismuth salts such as bismuth trioctate and bismuth tris (2-ethylhexanoate) are mentioned, and among them, organic acid bismuth. Salt is preferred.
The resinification catalyst may be used alone or in combination of two or more. As the resinification catalyst, at least one selected from an amine-based catalyst and a metal-based catalyst is preferable, and it is also preferable to use an amine-based catalyst and a metal-based catalyst in combination.

The content of the resinification catalyst in the polyol solution is preferably 0.1 to 20 parts by mass, more preferably 0.2 to 17 parts by mass, and further preferably 0.3 with respect to 100 parts by mass of the polyol. ~ 15 parts by mass. When the content of the resinification catalyst is in such a range, the reaction between the polyol and the isocyanate can easily proceed appropriately.

(Triquantization catalyst)
The trimerization catalyst is a catalyst that promotes the formation of an isocyanurate ring by reacting an isocyanate group contained in polyisocyanate to trimerize it. Examples of the trimerization catalyst include nitrogen-containing aromatic compounds, alkali metal salts, ammonium salts and the like.
Examples of the nitrogen-containing aromatic compound include tris (dimethylaminomethyl) phenol, 2,4-bis (dimethylaminomethyl) phenol, 2,4,6-tris (dialkylaminoalkyl) hexahydro-S-triazine and the like.
Examples of the alkali metal salt include carboxylic acid alkali metal salts typified by carboxylic acid potassium salts such as potassium acetate, potassium 2-ethylhexanoate, and potassium octylate.
Examples of the ammonium salt include tertiary ammonium salts such as trimethylammonium salt, triethylammonium salt and triphenylammonium salt, tetramethylammonium salt, tetraethylammonium salt, tetraphenylammonium salt, triethylmonomethylammonium salt, quaternary ammonium salt of carboxylic acid and the like. A quaternary ammonium salt or the like can be used.
A preferred specific example of the carboxylic acid in the ammonium carboxylic acid salt is at least one selected from the group consisting of 2-ethylhexanoic acid, 2,2-dimethylpropanoic acid, acetic acid, and formic acid.
The trimerization catalyst may be used alone or in combination of two or more, but it is preferable to use two or more in combination.
As the trimerization catalyst, at least one selected from the group consisting of a carboxylic acid alkali metal salt and a carboxylic acid quaternary ammonium salt is preferable, and it is also preferable to use a carboxylic acid metal salt and a carboxylic acid quaternary ammonium salt in combination.

The content of the trimerization catalyst in the polyol solution is preferably 0.1 to 20 parts by mass, more preferably 0.2 to 17 parts by mass, and further preferably 0.3 to 15 parts by mass with respect to 100 parts by mass of the polyol. It is a mass part. When the content of the trimerization catalyst is in such a range, the trimerization reaction can proceed appropriately, and the physical properties such as flame retardancy of the polyurethane foam are improved.

The content of the catalyst in the polyol solution is preferably 0.2 to 40 parts by mass, more preferably 0.4 to 35 parts by mass, and further preferably 0.6 to 30 parts by mass with respect to 100 parts by mass of the polyol. Is. When the content of the catalyst is in such a range, the reactivity between the polyol and the polyisocyanate becomes appropriate, and it becomes easy to obtain a polyurethane foam having flame retardancy while improving foamability.
The catalyst content is the total amount of the catalyst contained in the polyol solution. For example, when a resinification catalyst and a quantification catalyst are used as catalysts, the total amount of the resinification catalyst and the quantification catalyst is used. be.
Further, the catalyst is generally diluted with a diluent such as an organic solvent and blended in the liquid agent B, but the content of the catalyst is the amount of the active ingredient excluding the diluent. Generally, the diluent is a solvent, the active ingredient is a solute, and the amount of the active ingredient is the dissolved mass.
The organic solvent may be of any kind as long as it can dissolve the catalysts, but may be alcohols such as ethylene glycol, diethylene glycol, propylene glycol and dipropylene glycol. As for these low-short chain alcohols (chain alcohols having 6 or less carbon atoms), those having 2 or more hydroxyl groups are also referred to as organic solvents in the present specification.

Depending on the combination of catalysts, catalyst components that are diluted with a diluent may precipitate when the catalysts are mixed. Therefore, when selecting a catalyst, only basic, basic and neutral, acidic only, acidic and neutral It is preferable to use a combination of. For example, an amine-based catalyst that is a urethanization catalyst and an ammonium salt that is a trimerization catalyst, an amine-based catalyst that is a urethanization catalyst and an alkali metal salt that is a quantification catalyst, and an amine-based catalyst and a metal-based catalyst that are urethanization catalysts. A combination of an alkali metal salt as a quantification catalyst, or an amine-based catalyst as a urethanization catalyst and an ammonium salt and an alkali metal salt as a quantification catalyst is preferable.

[Effervescent agent]
The polyol liquid agent contains a foaming agent, and the foaming agent is contained in the liquid agent B. As the foaming agent, a mixture obtained by mixing a polyol liquid agent and an isocyanate liquid agent can be foamed to form a polyurethane foam.
Further, in the present invention, the foaming agent is contained in a liquid agent B different from the liquid agent A containing the catalyst, so that the foaming agent does not affect the catalyst and accelerate deterioration. Further, the liquid agent A further contains a filler, but by being contained in a liquid agent B different from the liquid agent A containing the filler, it is possible to prevent the foaming agent from affecting the filler, and the liquid agent. It may be possible to prevent the promotion of deterioration of the product more effectively.

Examples of the effervescent agent include organic effervescent agents, and examples thereof include organic fluorine-based compounds such as hydrocarbon compounds, chlorinated aliphatic hydrocarbon compounds, hydrofluorocarbon-based compounds, and hydrofluoroolefin-based compounds. The foaming agent may be used alone or in combination of two or more.
Among these, an organic fluorine-based compound is preferable from the viewpoint of foamability, a global warming potential is low, and a hydrofluoroolefin-based compound is more preferable from the viewpoint of environmental protection. The hydrofluoroolefin compound may be used alone as a foaming agent or may be used in combination with other foaming agents. It should be noted that the hydrofluoroolefin compound tends to deteriorate when coexisting with the catalyst, but in the present invention, the foaming agent and the catalyst are contained in different liquids in the step 1, so that such a compound is contained. The progress of deterioration can be effectively prevented.

Examples of the hydrocarbon compound include propane, butane, pentane, hexane, heptane, cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane and the like.
Examples of the chlorinated aliphatic hydrocarbon compound include dichloroethane, propyl chloride, isopropyl chloride, butyl chloride, isobutyl chloride, pentyl chloride, isopentyl chloride and the like.

Examples of the hydrofluorocarbon compound include hydrofluorocarbons such as CHF ₃ , CH ₂ F ₂ , and CH ₃ F, dichloromonofluoroethane, (for example, HCFC141b (1,1-dichloro-1-fluoroethane), HCFC22 (chlorodifluoromethane). ), HCFC142b (1-chloro-1,1-difluoroethane)), HFC-245fa (1,1,1,3,3-pentafluoropropane), HFC-365mfc (1,1,1,3,3-penta) Hydrochlorofluorocarbons such as fluorobutane) can be mentioned.

Examples of the hydrofluoroolefin compound include fluoroalkenes having 3 to 6 carbon atoms. Further, the hydrofluoroolefin may be a hydrochlorofluoroolefin having a chlorine atom, and therefore may be a chlorofluoroalkene having 3 to 6 carbon atoms. The hydrofluoroolefin preferably has 3 or 4 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-1225yz), (E) -1-chloro-3 , 3,3-Trifluoropropene (HFO-1233zd (E)), (Z) -1-chloro-3,3,3-trifluoropropene (HFO-1233zd (Z)) (Z) -1,1, 1,4,4,4-Hexafluorobut-2-ene (HFO-1336mzz (Z)), (E) -1,1,1,4,4,4-hexafluorobut-2-ene (HFO-) 1336mzz (E)), 2,3,3,3-tetrafluoropropene (HFO-1234yf), trifluoroethylene (HFO-1123), (E) -1-chloro-3,3,3-trifluoropropene (E) HCFO-1233zd (E)), (Z) -2,3,3,3-tetrafluoro-1-chloropropene (HCFO-1224yd (Z)) and the like can be mentioned. Of these, HFO-1233zd (E) is particularly preferred. The foaming agent may be used alone, or may be used in combination of two or more.

The content of the foaming agent in the polyol liquid is preferably 10 to 100 parts by mass, more preferably 20 to 80 parts by mass, still more preferably 25 to 70 parts by mass with respect to 100 parts by mass of the polyol. When the content of the foaming agent is at least these lower limit values, foaming is promoted and the density of the obtained polyurethane foam can be reduced. In addition, it becomes easy to exert the effect of suppressing deterioration of the polyurethane foam. On the other hand, when the content of the foaming agent is not more than the above upper limit value, it is possible to suppress excessive progress of foaming.
Further, the polyurethane foam may be foamed by an inorganic foaming agent such as nitrogen gas, oxygen gas, argon gas or carbon dioxide gas as a foaming agent in addition to the above-mentioned organic foaming agent. The inorganic foaming agent may be added to the polyol liquid separately from the liquids A and B described above, or may be added to the mixed liquid of the polyol liquid and the polyisocyanate liquid.

[water]
The polyol liquid may contain water. By containing water, the foamability when forming the polyurethane foam becomes good. Water may be contained in either liquid A or B, but is preferably contained in liquid A. By containing water in the liquid agent A, it is possible to prevent the ratio shift due to the volatilization of only the foaming agent when the liquid agents A and B are mixed.
The content of water in the polyol solution is, for example, 0.1 to 10 parts by mass, preferably 0.2 to 5 parts by mass, and more preferably 0.3 to 3 parts by mass with respect to 100 parts by mass of the polyol. By setting the water content within these ranges, it becomes easy to appropriately foam the mixed solution obtained by mixing the polyol solution and the isocyanate solution.

[Filler]
The polyol liquid contains a filler. By containing the filler in the polyol liquid, the polyurethane foam can be provided with a function according to the type of the filler. The filler preferably contains a flame retardant. By using a flame retardant as a filler, high flame retardant performance can be imparted to the polyurethane foam. The filler is contained in the liquid agent A.

(Solid flame retardant)
The flame retardant used as the filler is a solid flame retardant. In the present invention, the flame retardant can be more effectively enhanced by using the solid flame retardant. The solid flame retardant is a flame retardant that becomes solid at normal temperature (23 ° C.) and normal pressure (1 atm).
The solid flame retardant is selected from 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. At least one is mentioned. By using these solid flame retardants, flame retardancy can be effectively enhanced. These may be used alone or in combination of two or more.

<Red phosphorus flame retardant>
The red phosphorus-based flame retardant may be composed of red phosphorus alone, or may be red phosphorus coated with a resin, a metal hydroxide, a metal oxide, or the like, or red phosphorus may be 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.

The content of the red phosphorus flame retardant is preferably 5 to 130 parts by mass, more preferably 15 to 120 parts by mass, and further preferably 30 to 110 parts by mass with respect to 100 parts by mass of the polyol. By setting the content of the red phosphorus flame retardant to these lower limit values or more, the effect of containing the red phosphorus flame retardant can be easily exhibited. On the other hand, when the value is not more than the upper limit, foaming is not hindered by the red phosphorus flame retardant.

<Boron-containing flame retardant>
Examples of the boron-containing flame retardant 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 is preferably borate, more preferably zinc borate.

The content of the boron-containing flame retardant is not particularly limited, but is preferably 5 to 120 parts by mass, more preferably 15 to 110 parts by mass, and further preferably 20 to 100 parts by mass with respect to 100 parts by mass of the polyol. By setting the content of the boron-containing flame retardant to these lower limit values or more, the effect of containing the boron-containing flame retardant can be easily exerted, and the flame retardancy can be enhanced. On the other hand, when the value is not more than the upper limit, the foaming is not hindered by the boron-containing flame retardant.

<Brominated flame retardant>
The brominated 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.

The content of the bromine-containing flame retardant is preferably 5 to 120 parts by mass, more preferably 15 to 110 parts by mass, and further preferably 20 to 100 parts by mass with respect to 100 parts by mass of the polyol. By setting the content of the bromine-containing flame retardant to these lower limit values or more, the effect of containing the bromine-containing flame retardant can be easily exhibited. On the other hand, when the value is not more than the upper limit, foaming is not hindered by the brominated flame retardant.

<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.

The content of the phosphate-containing flame retardant is not particularly limited, but is 3 to 40 parts by mass, more preferably 5 to 35 parts by mass, and further preferably 10 to 30 parts by mass with respect to 100 parts by mass of the polyol. By setting the content of the phosphate-containing flame retardant to these lower limit values or more, the effect of containing the phosphate-containing flame retardant can be easily exerted. On the other hand, when the value is set to the upper limit or less, the foaming is not hindered by the phosphate-containing flame retardant.

<Chlorine-containing flame retardant>
Examples of the chlorine-containing flame retardant include those commonly used in flame-retardant resin compositions, for example, polynaphthalene chloride, chlorendic acid, and dodecachlorododecahydrodimethanodibenzocyclo sold under the trade name of "Dechloran Plus". Octene and the like can be mentioned.
The content of the chlorine-containing flame retardant is not particularly limited, but is preferably 3 to 40 parts by mass, more preferably 5 to 35 parts by mass, and further preferably 10 to 30 parts by mass with respect to 100 parts by mass of the polyol. By setting the content of the chlorine-containing flame retardant to these lower limit values or more, the effect of containing the chlorine-containing flame retardant can be easily exerted. On the other hand, when the value is not more than the upper limit, the foaming is not hindered by the chlorine-containing flame retardant.

<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.

The content of the antimony-containing flame retardant is not particularly limited, but is preferably 1 to 40 parts by mass, more preferably 2 to 35 parts by mass, and further preferably 3 to 30 parts by mass with respect to 100 parts by mass of the polyol. By setting the content of the antimony-containing flame retardant to these lower limit values or more, the effect of containing the antimony-containing flame retardant can be easily exerted, and the flame retardancy can be enhanced. On the other hand, when the value is not more than the upper limit, the foaming is not hindered by the antimony-containing flame retardant.

<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.

The content of the metal hydroxide is, for example, 0.1 to 50 parts by mass, preferably 0.2 to 30 parts by mass, more preferably 0.3 to 20 parts by mass, still more preferably, with respect to 100 parts by mass of the polyol. Is 0.5 to 15 parts by mass. By setting the content of the metal hydroxide to these lower limit values or more, the effect of containing the metal hydroxide is easily exerted, and the flame retardancy is enhanced. On the other hand, when the value is not more than the upper limit, foaming is not hindered by the metal hydroxide.

<Needle-shaped filler>
Examples of the needle-shaped filler include potassium titanate whisker, aluminum borate whisker, magnesium-containing whisker, silicon-containing whisker, wollastonite, sepiolite, zonolite, elestadite, boehmite, rod-shaped hydroxyapatite, glass fiber, carbon fiber, and graphite fiber. , Metal fiber, slag fiber, gypsum fiber, silica fiber, alumina fiber, silica alumina fiber, zirconia fiber, boron nitride fiber, boron fiber, stainless fiber and the like.
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 the needle-shaped filler with a scanning electron microscope and measuring its length and width.

The content of the needle-shaped filler is preferably 5 to 120 parts by mass, more preferably 15 to 110 parts by mass, and further preferably 20 to 100 parts by mass with respect to 100 parts by mass of the polyol. By setting the needle-shaped filler to these lower limit values or more, the shape of the polyurethane foam after combustion is easily maintained, and the flame retardancy is improved. On the other hand, when it is set to the upper limit or less, foaming is less likely to be inhibited by the needle-shaped filler.

Among the above-mentioned solid flame retardants, red phosphorus flame retardants, bromine-containing flame retardants, phosphate-containing flame retardants, chlorine-containing flame retardants, antimony-containing flame retardants, metal hydroxides, and needle-like fillers are used. It is preferably selected, and more preferably selected from a red phosphorus flame retardant, a brominated flame retardant, and a needle-like filler. These solid flame retardants do not easily deteriorate the liquid agent even if they coexist with the catalyst, and even if they are contained in the liquid agent A as a filler, the deterioration of the liquid agent A can be sufficiently suppressed.
Further, two or more kinds of solid flame retardants may be used in combination, and for example, the above solid flame retardants may be appropriately selected and two or more kinds may be used in combination. It is also preferable to use two or more kinds selected from a red phosphorus flame retardant, a bromine-containing flame retardant, and a needle-shaped filler in combination.

Since the boron-containing flame retardant tends to accelerate the deterioration of the liquid agent by coexisting with the catalyst in the liquid agent A, it is preferable not to substantially contain the boron-containing flame retardant in the liquid agent A. The fact that the liquid agent A does not substantially contain the boron-containing flame retardant means that the boron-containing flame retardant may be added to the liquid agent A to the extent that the effect is not affected. Specifically, the liquid agent A may contain the boron-containing flame retardant. The content of the boron-containing flame retardant in A is, for example, less than 2% by mass, preferably less than 1% by mass, more preferably less than 0.3% by mass, and most preferably 0% by mass, based on the total amount of the liquid agent A. Is. Since the liquid agent A does not substantially contain the boron-containing flame retardant, it is possible to more effectively prevent the liquid agent A from deteriorating during storage.

The content of the solid flame retardant is not particularly limited, but is, for example, 10 to 200 parts by mass, preferably 20 to 150 parts by mass, and more preferably 40 to 120 parts by mass with respect to 100 parts by mass of the polyol. .. By setting the content of the solid flame retardant to these lower limit values or more, appropriate flame retardancy can be imparted to the polyurethane foam. Further, by setting the content of the solid flame retardant to these upper limit values or less, it is possible to prevent the viscosity of the polyol liquid agent and the liquid agent A from becoming too high, and it can be suitably used for spraying and filling applications.

(Anti-sedimentation agent)
The polyol liquid agent of the present invention may contain a sedimentation inhibitor as a filler. That is, the liquid agent A may contain an anti-sedimenting agent. The sedimentation inhibitor may be used in combination with the above-mentioned solid flame retardant or other inorganic filler described later in the liquid agent A, but is preferably used in combination with the solid flame retardant.
By using the anti-precipitation agent, it is possible to prevent the solid flame retardant and other inorganic fillers described later from precipitating in the liquid agent A or the polyol liquid agent. In addition, the use of the sedimentation inhibitor facilitates uniform dispersion of the solid flame retardant and other inorganic fillers described below in the liquid.

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. Among these, fumed silica is preferable, and hydrophobic fumed silica is particularly preferable. As fumed silica, Aerosil (registered trademark) manufactured by Aerosil Japan Co., Ltd. can be used.

The content of the sedimentation inhibitor is not particularly limited, but is, for example, 0.5 to 20 parts by mass, preferably 0.7 to 12 parts by mass, and more preferably 1.1 to 8 parts by mass with respect to 100 parts by mass of the solid flame retardant. It is a mass part. By keeping the content of the anti-sedimentant within the above range, the solid content is not increased more than necessary, and the settling of the filler other than the anti-sedimentant such as the solid flame retardant is prevented, and the filler such as the solid flame retardant is prevented from settling. Dispersibility can be improved.

As the filler, an inorganic filler (other inorganic filler) other than the above-mentioned flame retardant or sedimentation inhibitor may be used. As inorganic fillers, alumina, titanium oxide, calcium oxide, magnesium oxide, iron oxide, tin oxide, ferrites, basic magnesium carbonate, calcium carbonate, magnesium carbonate, zinc carbonate, barium carbonate, dosonite, hydrotalcite, calcium sulfate , Barium sulfate, calcium silicate, talc, mica, montmorillonite, bentonite, active white clay, imogolite, sericite, glass beads, aluminum nitride, boron nitride, silicon nitride, various metal powders, magnesium sulfate, lead zirconate titanate, sulfide Molybdenum, silicon carbonate, various magnetic powders, fly ash and the like can be used as appropriate. These inorganic fillers may be used alone or in combination of two or more.

The content of the filler in the polyol liquid is, for example, 10 to 300 parts by mass, preferably 20 to 150 parts by mass, and more preferably 45 to 120 parts by mass with respect to 100 parts by mass of the polyol. By setting the content of the filler to these lower limit values or more, it becomes easy to impart the function according to the type of the filler to the polyurethane foam. In addition, it becomes easy to adjust the viscosity of the polyol liquid agent within a predetermined range described later.

[Liquid flame retardant]
The polyol liquid agent preferably further contains a liquid flame retardant. The liquid flame retardant is a flame retardant that becomes liquid at normal temperature (23 ° C.) and normal pressure (1 atm). Specific examples of the liquid flame retardant include phosphoric acid esters. By containing a liquid flame retardant, it becomes easier to improve the flame retardancy.

The liquid flame retardant may be contained in either the liquid agent A or the liquid agent B. At this time, the liquid flame retardant may be contained only in the liquid agent A, may be contained only in the liquid agent B, or may be contained in both the liquid agent A and the liquid agent B. It is preferable to include it in the liquid agent A.
As described above, the liquid agent A contains a catalyst, and preferably contains a filler. Therefore, when the liquid agent A contains the liquid flame retardant, the catalyst can be easily dissolved or dispersed in the liquid agent A, the filler can be easily dispersed in the liquid agent A, and the handleability of the liquid agent A becomes good.

As the phosphoric acid ester, it is preferable to use a monophosphate ester, a condensed phosphoric acid ester or the like. Examples of the monophosphate include trialkyl phosphates such as trimethyl phosphate, triethyl phosphate, tributyl phosphate and tri (2-ethylhexyl) phosphate, halogen-containing phosphate esters such as tris (β-chloropropyl) phosphate, and tributoxyethyl phosphate. Arocyclic-containing phosphates such as trialkoxy phosphate, tricresyl phosphate, trixilenyl phosphate, tris (isopropylphenyl) phosphate, cresyldiphenyl phosphate, diphenyl (2-ethylhexyl) phosphate, monoisodecyl phosphate, diisodecyl Examples thereof include acidic phosphoric acid esters such as phosphate.

Examples of the condensed phosphate ester include aromatic condensed phosphate esters such as trialkylpolyphosphate, resorcinol polyphenyl phosphate, bisphenol A polycresyl phosphate, and bisphenol A polyphenyl phosphate.
Commercially available products of condensed phosphoric acid ester include, for example, "CR-733S", "CR-741" and "CR747" manufactured by Daihachi Chemical Industry Co., Ltd., and "ADEKA STUB PFR" and "FP-600" manufactured by ADEKA. And so on.

As the liquid flame retardant, one of the above-mentioned ones may be used alone, or two or more of them may be used in combination. Among these, monophosphate ester is preferable, and tris (β-chloropropyl) phosphate is more preferable, from the viewpoint of facilitating the production of polyurethane foam and improving the flame retardancy of polyurethane foam.

When the liquid flame retardant is contained, the content of the liquid flame retardant in the polyol liquid is preferably 5 to 90 parts by mass, more preferably 15 to 80 parts by mass, and 25 to 70 parts by mass with respect to 100 parts by mass of the polyol. More preferred. By setting the content of the liquid flame retardant to these lower limit values or more, the effect of containing the liquid flame retardant can be easily exerted. Further, by setting the value to the upper limit or less, the foaming of the polyurethane foam is not hindered by the liquid flame retardant.

[Foam control agent]
The polyol liquid may contain a defoaming agent. The defoaming agent improves the foamability of the mixed liquid obtained by mixing the polyol liquid agent and the isocyanate liquid agent. The foam stabilizer may be contained in either liquid A or liquid B, but is preferably contained in liquid A. By containing the foam stabilizer in the liquid agent A, it is possible to prevent the ratio deviation from occurring due to the volatilization of only the foaming agent when the liquid agents A and B are mixed.
Examples of the defoaming agent include a polyoxyalkylene-based defoaming agent such as polyoxyalkylene alkyl ether and a surfactant such as a silicone-based defoaming agent such as organopolysiloxane. These defoaming agents may be used alone or in combination of two or more.
The content of the defoaming agent in the polyol solution is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 8 parts by mass, still more preferably 1 to 5 parts by mass with respect to 100 parts by mass of the polyol. When the content of the defoaming agent is at least these lower limit values, it becomes easy to foam the mixed liquid of the polyol liquid agent and the isocyanate liquid agent, and it becomes easy to obtain a homogeneous polyurethane foam. Further, when the content of the defoaming agent is not more than these upper limit values, the balance between the manufacturing cost and the obtained effect becomes good.

[Other ingredients]
The polyol solution may be a phenol-based, amine-based, sulfur-based or other antioxidant, heat stabilizer, metal damage inhibitor, antistatic agent, stabilizer, or cross-linking agent, if necessary, as long as the object of the present invention is not impaired. , Lubricants, softeners, pigments, additives such as tackifier resins, tackifiers such as polybutene and petroleum resins, and the like.
The other components may be contained in either the liquid agent A or the liquid agent B, but are preferably contained in the liquid agent A.

(Viscosity of polyol liquid)
The viscosity of the polyol solution at 25 ° C. and 60 rpm is preferably 200 to 2500 mPa · s. When the viscosity is within the above range, the polyol liquid can be efficiently collision-mixed with the isocyanate liquid while preventing the filler from settling in the polyol liquid. From these viewpoints, the viscosity of the polyol solution at 25 ° C. and 60 rpm is more preferably 500 to 2000 mPa · s. The viscosity of the polyol liquid is measured in detail by the method described in Examples described later.

[Liquid A, B]
The liquid agent A contains a catalyst, a filler and a polyol as described above. It is also preferable that the liquid agent A contains a liquid flame retardant. Further, the liquid agent A may contain a defoaming agent, water, the above-mentioned other components, and the like. That is, the liquid agent A preferably contains a catalyst, a filler, a polyol, and a liquid flame retardant, and the liquid agent A may contain a catalyst, a filler, a polyol, a liquid flame retardant, a defoaming agent, and water. preferable.
Since the liquid agent A contains a polyol or a polyol and a liquid flame retardant, the filler can be easily dispersed in the liquid agent A, and the handleability of the liquid agent A becomes good.

The liquid agent B contains a foaming agent as described above. The liquid agent B is preferably composed substantially of the foaming agent alone, but may appropriately contain components other than the foaming agent, for example, at least one selected from a polyol and a liquid flame retardant.

It is preferable that the liquid agent A does not substantially contain a foaming agent. Since the liquid agent does not substantially contain the foaming agent, it is possible to effectively prevent deterioration from progressing during storage of the liquid agent A due to the coexistence of the catalyst and the foaming agent in the liquid agent A. From the same viewpoint, it is preferable that the liquid agent B contains substantially no catalyst. Further, since the liquid agent A does not substantially contain the foaming agent, the viscosity of the liquid agent A can be easily increased as described later.
The fact that the liquid agent A does not substantially contain the foaming agent means that the foaming agent may be blended in the liquid agent A in a small amount so as not to impair the effect of the present invention. The content of the foaming agent in the above is, for example, less than 2% by mass, preferably less than 1% by mass, more preferably less than 0.3% by mass, and most preferably 0% by mass based on the total amount of the liquid agent A. ..
Further, the fact that the liquid agent B does not substantially contain the catalyst means that a small amount of the catalyst may be blended in the liquid agent B so as not to impair the effect of the present invention, and specifically, the catalyst in the liquid agent B. The content of the solution B is, for example, less than 1% by mass, preferably less than 0.5% by mass, more preferably less than 0.1% by mass, and most preferably 0% by mass based on the total amount of the liquid agent B.

Similarly, the liquid agent B preferably contains substantially no filler. The fact that the liquid agent B does not substantially contain the filler means that a small amount of the filler may be added to the liquid agent B to the extent that the effect is not affected, and specifically, the content of the filler in the liquid agent B. Is, for example, less than 2% by mass, preferably less than 1% by mass, more preferably less than 0.3% by mass, and most preferably 0% by mass, based on the total amount of the liquid agent B. Since the liquid agent B does not substantially contain the filler, it is possible to prevent the filler from settling in the liquid agent B during storage.

As described above, the liquid agent B is preferably composed substantially of the foaming agent alone, and such a structure can simplify the step of producing the liquid agent B. It should be noted that the fact that the liquid agent B is substantially composed of the foaming agent alone means that the liquid agent B does not have to contain any components other than the foaming agent except for the component inevitably mixed, and the liquid agent B does not contain any components other than the foaming agent. The content of the component is, for example, 1% by mass or less, preferably 0.5% by mass or less, more preferably 0.1% by mass or less, and most preferably 0% by mass.

(Viscosity of Liquid A)
The viscosity of the liquid agent A at 25 ° C. and 1 rpm is preferably 2000 to 60,000 mPa · s. By setting the viscosity of the liquid agent A to 2000 mPa · s or more, even if the liquid agent A is stored at room temperature or a temperature of room temperature or less (for example, 30 ° C. or less), it is possible to prevent the filler from settling and causing hard caking. Further, when the viscosity is set to 60,000 mPa · s or less, the viscosity of the polyol liquid can be easily kept within the above viscosity range. From these viewpoints, the viscosity of the liquid agent A at 25 ° C. and 1 rpm is more preferably 3500 to 50,000 mPa · s, further preferably 4000 to 40,000 mPa · s. The viscosity of the liquid agent A is measured in detail by the method described in Examples described later.

As described above, in step 2, a plurality of liquids (liquids A and B) are mixed to obtain a polyol liquid, but the mass ratio of the liquid A is higher than the mass ratio of the other liquids (liquid B). It is preferable that a plurality of components are mixed. The liquid agent A contains the filler as described above, but by increasing the mass ratio of the liquid agent A containing the filler, the filler is dispersed in the liquid agent A by a component other than the filler (for example, a polyol or a liquid flame retardant). When preparing the polyol liquid, it becomes easy to uniformly disperse the filler in the polyol liquid.

The mass ratio of the liquid agent A is preferably 50 to 97% by mass based on the total amount of the polyol liquid agent. When the content is 50% by mass or more, the catalyst can be easily dispersed or dissolved in the liquid agent A. Further, when the liquid agent A contains a filler, the filler can be dispersed in the liquid agent A by a component other than the filler. Further, by setting the content to 97% by mass or less, the amount of the liquid agent B can be set to a certain amount or more. From these viewpoints, the mass ratio of the liquid agent A is more preferably 60 to 95% by mass, still more preferably 65 to 90% by mass.
The mass ratio of the liquid agent B is preferably 3 to 45% by mass based on the total amount of the polyol liquid agent. By setting the content to 3% by mass or more, the amount of the foaming agent can be adjusted to an appropriate amount. Further, by setting the content to 45% by mass or less, the amount of the liquid agent A can be set to a certain amount or more. From these viewpoints, the mass ratio of the liquid agent B is more preferably 5 to 35% by mass, still more preferably 10 to 30% by mass.

In the liquid agent A, the filler content, that is, the solid content concentration is preferably 10 to 50% by mass. By setting the content to 10% by mass or more, it is effective to add various functions by the filler. Further, when the content is 50% by mass or less, the filler can be easily dispersed in the liquid agent A1. From the above viewpoint, the above range is more preferably 15 to 45% by mass, further preferably 20 to 40% by mass.

<Isocyanate solution>
The isocyanate solution contains polyisocyanate. As the polyisocyanate, known polyisocyanates used for molding polyurethane foam can be used, and examples thereof 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 diisocyanate, polymethylene polyphenyl polyisocyanate and the like 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 liquid of the present invention is preferably mixed with the polyol liquid so that the isocyanate index of the mixed liquid obtained by mixing the polyol liquid and the isocyanate liquid is preferably 250 to 600, more preferably 300 to 550. .. When the isocyanate index is at least the above lower limit value, the amount of polyisocyanate with respect to the polyol becomes excessive, and isocyanurate bonds are easily generated by the trimerated polyisocyanate, and as a result, the flame retardancy of the polyurethane foam is improved. Further, when the isocyanate index is not more than the above upper limit value, the flyability of the obtained polyurethane foam becomes good.
The isocyanate liquid agent may be composed of polyisocyanate alone, or may be appropriately blended with an additive or the like conventionally blended in the isocyanate liquid preparation.

The isocyanate index can be calculated by the following method.
Isocyanate index = equivalent number of polyisocyanate ÷ (equivalent number of polyol + equivalent number of water) × 100
Here, each equivalent number can be calculated as follows.
Equivalent number of polyisocyanate = amount of polyisocyanate used (g) x NCO content (mass%) / molecular weight of NCO (mol) x 100
Equivalent number of polyol = OHV × amount of polyol used (g) ÷ molecular weight of KOH (mmol)
OHV is the hydroxyl value (mgKOH / g) of the polyol.
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 56100 (mmol). The molecular weight of water is 18 (mol), and the number of OH groups in water is 2.

Next, each step of the method for producing a polyurethane foam of the present invention will be described in detail with reference to FIG.
[Step 1]
In this manufacturing method, liquid agent A and liquid agent B are prepared in step 1. In step 1, each of the liquids A and B may be prepared by filling a known container 11 with the component 10 constituting each liquid. Examples of the container 11 include a known container for storing the urethane raw material. Examples of the container include a drum, an itto-kan, a gallon can, a pail can, a glass container, a tank, and the like, but the container is not particularly limited.

The method for preparing each liquid preparation in step 1 is not particularly limited, but when the number of components constituting the liquid preparation is two or more, each component may be added and each component may be mixed and prepared by stirring or the like. .. Each component may be added directly to the container 11 and each component may be mixed in the container 11 to prepare each of the liquids A and B, or each component may be mixed in advance with a mixing device (not shown). The liquid preparations A and B may be prepared, and the prepared liquid preparations A and B may be filled in the container 11.
At this time, the catalyst or the like of each component may be added in a state of being diluted with a small amount of a polyol or an organic solvent.

It is preferable that each of the liquids A and B prepared in the step 1 is stored, transported, delivered, etc. in a state of being filled in the container 11. The storage time varies depending on the mode of use, but may be, for example, 1 hour or more and 2 years or less, 24 hours or more and 1 year or less, or 24 hours or more and 6 months or less. There may be. The storage temperature is not particularly limited, but is, for example, about 0 to 40 ° C, preferably about 5 to 30 ° C. The storage time is the time from the preparation of the liquids A and B to the start of mixing with the other liquids in the step 2.

[Step 2]
In step 2, the liquids A and B prepared in step 1 are mixed to obtain a polyol liquid P. Here, as shown in FIG. 1, in the mixing of the liquid agents A and B, the liquid agents A and B are sent from the container 11 to the mixer 12 and appropriately stirred inside the mixer 12 to mix the liquid agents. It is advisable to obtain the polyol liquid agent P. Further, although not shown, the liquid agent B may be added to the container 11 of the liquid agent A and mixed in the container 11 to obtain the polyol liquid agent P. Further, the liquids A and B may be transferred to another container and mixed in that container.
As a specific example of the mixing method, stirring may be performed by rotating the blades in the container or in the mixer 12, or a stirrer such as a static mixer that mixes by utilizing the momentum of the liquid feed may be used. good. Further, the liquid agent may be mixed in the mixer 12 at, for example, 5 to 30 ° C, preferably 10 to 25 ° C.
Further, the polyol liquid P obtained in step 2 may be temporarily transferred from the container 11 or the mixer 12 to a container and then sent to the mixing / discharging device 13 described later via the container, or the mixer 12 may be used. The obtained polyol liquid agent P may be directly sent to the mixing / discharging device 13 without going through a container or the like.

[Step 3]
In step 3, the polyol liquid P obtained in step 2 is mixed with the isocyanate liquid IS, and the mixed liquid obtained by the mixing is used to obtain a polyurethane foam. The mixed liquid may be discharged, for example, reacted and foamed to obtain a polyurethane foam.
Here, in step 2, the polyol solution P and the isocyanate solution IS may be mixed after being adjusted to, for example, 10 to 60 ° C, preferably 15 to 50 ° C. ..

Step 3 may be performed in a known mixing / discharging device 13, and the polyol liquid agent P and the isocyanate liquid agent IS are, for example, collision-mixed inside the mixing / discharging device 13 to discharge the mixed liquid from the discharging port of the mixing / discharging device 13. It is good. In order to mix and collide the polyol liquid P and the isocyanate liquid IS, for example, they may be transferred in a pipe in a pressurized state and collided at a mixing section (not shown), or may be mixed and discharged by another method. May be good. Examples of other mixing and discharging methods include those using a static mixer and those using an impeller.

The mixed liquid discharged from the discharge port is foamed by a foaming agent while the reaction (for example, resinification and quantification) proceeds by the catalyst, whereby a polyurethane foam is formed.
The mixing / discharging device 13 is not particularly limited as long as the polyol liquid and the isocyanate liquid can be mixed and discharged, but a spray gun or the like can be used. Further, in the above description, the mixer 12 used in step 2 and the mixing / discharging device 13 used in step 3 have been described as separate devices, but they may be integrally incorporated as one device. ..
Further, in step 3, it is not always necessary to discharge the mixture, and after mixing with a propeller, the propeller side may be moved to separate the mixture, and then the mixed solution may be foamed.

The manufacturing method of the present invention can be applied to, for example, spraying applications. Therefore, the mixed liquid discharged from the mixing / discharging device 13 can be sprayed on the construction target surface at a constant discharge pressure and foamed to form a polyurethane foam on the construction target surface. The surface to be constructed is not particularly limited, and examples thereof include a wall surface, a ceiling surface, and a floor surface of a building.
The production method of the present invention can also be applied to filling applications. Therefore, the mixed liquid discharged from the mixing / discharging device 13 is injected into the inside of the structure having a cavity inside the mold, the frame material, etc., and is cured while being foamed inside the structure to be polyurethane. The foam may be molded.

In the production method of the present invention, as described above, after preparing the polyol liquid in step 2, the polyol liquid and the isocyanate liquid are mixed in step 3 to obtain a polyurethane foam, but after preparing the polyol liquid. It is preferable to quickly mix the polyol liquid with the isocyanate liquid. By mixing the polyol liquid and the isocyanate liquid immediately after preparing the polyol liquid, deterioration of the liquid can be prevented more effectively.
Specifically, the interval time from obtaining the polyol liquid to the start of mixing the polyol liquid and the isocyanate liquid may be, for example, 10 days or less, preferably 5 days or less, and more preferably 3 days or less. .. Further, the interval time should be as short as possible, and is not particularly limited, but is, for example, 1 second or longer, and practically 1 minute or longer.
The interval time means the time from when the liquid agent A and the liquid agent B are mixed to obtain the polyol liquid agent to the start of mixing the polyol liquid agent and the isocyanate liquid agent.
Further, in the interval time, the polyol liquid may be placed at a constant temperature of, for example, 0 to 35 ° C, preferably about 5 to 25 ° C.

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

Examples 1 to 6
Each component was mixed according to Table 1 to prepare liquids A and B, which were filled in pressure-resistant drums, respectively. The liquids A and B filled in the drum can were left at room temperature (25 ° C.) for 30 minutes after preparation. Next, the liquids A and B were mixed in a metal pail according to the amount to obtain a polyol liquid. In addition, an isocyanate solution made of polyisocyanate (Sumijuru 44V20, manufactured by Sumitomo Chemical Co., Ltd.) sealed in an itto-kan was prepared.
The temperature of each container was adjusted by bathing the polyol solution and the isocyanate solution composed of polyisocyanate at 15 ° C. in ice water. Immediately after the temperature is adjusted, 100 g of the polyol solution is added to a 500 ml PP cup, then 110 g of the isocyanate solution is gently added, and after the addition, a stirrer (Homo Disper, manufactured by Primix Corporation) that immediately rotates at 8000 rpm is used for 2 seconds. Stirred. The time at which stirring was started was 0 seconds, the foam that started foaming was pecked with a thin rod, and the time at which the thread was pulled when released was defined as gel time (T1).

(Deterioration measurement)
Instead of leaving the prepared liquids A and B at room temperature for 30 minutes after preparation, they were left in an environment of 40 ° C. for 2 weeks after preparation to accelerate deterioration. Then, after re-stirring the filler with a stirrer, the same operation as above was performed, and the gel time (T2) was measured. The deterioration of the liquid agent was indirectly evaluated by the difference between the gel time (T1) before the deterioration acceleration and the gel time (T2) after the deterioration acceleration.
A: Gel time difference is less than 10 seconds B: Gel time difference is 10 seconds or more and 20 seconds or more C: Gel time difference is 20 seconds or more

(Redispersity evaluation)
The liquid agent A was left at 35 ° C. for 12 weeks after preparation, but in the re-stirring operation, the case where it could be used without residual agglomerates in the lower part of the drum container was defined as redispersibility A, and the case where the agglomerates remained was re-stirred. Dispersibility C was used.

Comparative Examples 1 and 2
Each component was mixed according to Table 1 to prepare a liquid preparation A, which was filled in a metal pressure-resistant can. The liquid agent A filled in a metal pressure-resistant can was left at room temperature (25 ° C.) for 30 minutes after preparation. Next, the liquid agent A was used as a polyol liquid, cooled together with the isocyanate liquid, and the polyol liquid and the isocyanate liquid were mixed, and the gel time (T1) was measured. Further, the deterioration of the liquid agent A was promoted in the same manner as in Example 1, the gel time (T2) after the deterioration was accelerated was also measured, and the deterioration of the liquid agent was indirectly evaluated according to the above evaluation criteria based on the difference in gel time. Furthermore, redispersibility evaluation was also performed.

<Viscosity>
The viscosity of the liquid agent A of each example and the viscosity of the polyol liquid agent of each example and the comparative example were measured as follows.
The liquid agent A was measured at a liquid temperature of 25 ° C. using a B-type viscometer under the condition of 1 rpm, and the value measured 1 minute after the start of rotation was taken as the viscosity of the liquid agent A. The polyol liquid was measured at a liquid temperature of 25 ° C. using a B-type viscometer under the condition of 60 rpm, and the value measured 1 minute after the start of rotation was taken as the viscosity of the polyol liquid.

※なお、比較例２では、攪拌による均一分散ができなかったため、ゲルタイムは測定しなかった。 The components used in Examples and Comparative Examples are as follows. The number of copies of each component shown in Table 1 indicates the number of copies of the diluted product as a diluted product (product).
(Polyol)
Polyester polyol (manufactured by Kawasaki Kasei Chemicals, product name: Maximol RLK-087, hydroxyl value = 200 mgKOH / g)
Polyester polyol (PHANTOR SV-208 manufactured by Hitachi Kasei Co., Ltd., hydroxyl value 235 mgKOH / g)
(Defoamer)
Silicone defoaming agent (SH-193, manufactured by Toray Dow Corning)
(Liquid flame retardant)
Tris (β-chloropropyl) phosphate (manufactured by Daihachi Chemical Co., Ltd., product name: TMCPP)
(catalyst)
Triquantization catalyst: Quaternary ammonium salt of carboxylic acid (diluted product with an active ingredient amount of 45 to 55% by mass) (Evonik Japan Co., Ltd., product name: DABCO TMR-7)
Resinification catalyst: Imidazole compound (manufactured by Kao Corporation, product name: Kaorizer No. 390, diluted product with an active ingredient amount of 65 to 75% by mass)
(Filler)
Red phosphorus flame retardant (manufactured by Rinkagaku Kogyo Co., Ltd., product name: Nova Excel 140, metal hydroxide coating, red phosphorus content of 94% by mass or more)
Zinc borate (manufactured by Hayakawa Shoji Co., Ltd., product name: Firebreak ZB)
Ethylene bis (pentabromophenyl) (manufactured by Albemarle, product name: SAYTEX 8010)
Wollastonite (SiO2 ・ CaO) (manufactured by Kinsei Matek Co., Ltd., product name: SH-12
50)
Fumed silica (manufactured by Aerosil Japan, product name: Aerosil R976S)
(Effervescent agent)
HFO-1233zd (E) (manufactured by Central Glass Co., Ltd., product name: Solstice LBA)

* In Comparative Example 2, the gel time was not measured because uniform dispersion by stirring was not possible.

As shown in Table 1, in Examples 1 to 6, liquid preparation A containing a catalyst and a filler and liquid preparation B containing a foaming agent were separately prepared, and a polyol liquid preparation obtained by mixing these was used. Even if the deterioration of each of the liquid agents A and B was promoted, the deterioration did not progress significantly, and a polyurethane foam having good quality could be produced. Further, in Examples 1 to 6, since the liquid agent A could have a high viscosity, hard caking during storage was suppressed, and the filler could be easily redispersed by stirring after storage.
On the other hand, in Comparative Example 1, since the liquids constituting the polyol liquid were not prepared separately, if the deterioration of the liquid was accelerated, the liquids deteriorated and it was not possible to produce a polyurethane foam having good quality. rice field. Further, in Comparative Example 2, although the composition was the same as that of Example 6, the viscosity of the liquid agent A was low, hard caking occurred during storage, and it was difficult to redisperse the filler by stirring after storage.

10 Ingredients 11 Container 12 Mixer 13 Mixing and discharging device A, B liquid agent P polyol liquid agent IS isocyanate liquid agent

Claims (6)

The process of preparing liquid agent A and liquid agent B,
The step of mixing the liquid agent A and the liquid agent B to obtain a polyol liquid agent, and
A step of mixing the polyol liquid and the isocyanate liquid is provided.
A method for producing a polyurethane foam, wherein the liquid agent A contains a polyol, a filler, and a catalyst, and the liquid agent B contains a foaming agent. The method for producing a polyurethane foam according to claim 1, wherein the liquid agent A has a viscosity of 2000 to 60,000 mPa · s at 25 ° C. and 1 rpm. The filler contains a solid flame retardant, and the solid flame retardant is a red phosphorus flame retardant, a bromine-containing flame retardant, a phosphate-containing flame retardant, a chlorine-containing flame retardant, an antimony-containing flame retardant, a metal hydroxide, and the like. The method for producing a polyurethane foam according to claim 1 or 2, which is at least one selected from the group consisting of needle-shaped fillers. The method for producing a polyurethane foam according to any one of claims 1 to 3, wherein the liquid agent A and the liquid agent B are mixed so that the mass ratio of the liquid agent A is higher than that of the liquid agent B to obtain a polyol liquid agent. .. The method for producing a polyurethane foam according to any one of claims 1 to 4, wherein the polyol liquid has a viscosity of 200 to 2500 mPa · s at 25 ° C. and 60 rpm. The method for producing a polyurethane foam according to any one of claims 1 to 5, wherein the foaming agent contains a hydrofluoroolefin compound.

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