JP7251958B2 - Liquid mixtures, polyurethane compositions, cartridge containers for caulking guns, pressure-resistant containers for spraying, and mixing systems - Google Patents

Description

The present invention relates to polyurethane compositions, cartridge containers for caulking guns, pressure containers for spraying and mixing systems.

BACKGROUND ART Conventionally, polyurethane foams have been used as heat insulating materials in vehicles such as automobiles, railroad vehicles and ships, and in buildings. It is also used as a repairing agent for filling defects in vehicles, buildings, and the like. Recently, there is an increasing need to impart flame retardancy to these heat insulating materials and repair agents.

For polyurethane foam, a two-pack type polyurethane is widely used, which is formed by mixing a polyol liquid agent and an isocyanate liquid agent filled in separate containers to form a foam. Raising the isocyanate index of the polyisocyanate can be mentioned.

For example, in Patent Document 1, an isocyanate component filled in an aerosol can containing an isocyanate and a propellant as main components, and a polyol component containing a polyol, a trimerization catalyst and a propellant as main components and filled in another aerosol can are used. , a two-part aerosol flame retardant polyisocyanurate foam reacted to give an NCO/OH of 1.5-5.0.

JP-A-11-49837

As in Patent Document 1, when using a two-liquid type polyurethane, a small device such as a caulking gun or a spray can is used. These small devices are equipped with a static mixer such as a static mixer as a mixer for promoting mixing of the two liquids.
However, when the isocyanate index is increased, a large amount of trimerization catalyst is required in order to obtain a foam having excellent flame retardancy. When a large amount of the trimerization catalyst is used, the residual liquid present in the static mixer hardens in a short time and causes clogging. As a result, there is a problem that the replacement frequency of the static mixer becomes high.

Therefore, it is conceivable to reduce the amount of the trimerization catalyst used, but in that case, the trimerization reaction becomes difficult to proceed, and the flame retardancy of the formed polyurethane foam is lowered.

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a mixed solution that prevents the residual solution from hardening in a static mixer and that can form a highly flame-retardant polyurethane foam even with a small amount of trimerization catalyst. do.

The inventors of the present invention have made intensive studies to solve the above problems. The inventors have found that it is possible to prevent the residual liquid from hardening and produce a highly flame-retardant polyurethane foam without using a large amount of a trimerization catalyst, and have completed the present invention.
That is, the present invention is as follows.

[1] contains a polyol compound, a resinification catalyst, a trimerization catalyst and a foaming agent, the content of the resinization catalyst is 0.1 to 5 parts by mass with respect to 100 parts by mass of the polyol compound, and the trimerization catalyst is 0.5 to 5 parts by mass per 100 parts by mass of the polyol compound.
[2] Content of resinification catalyst: The mixed solution according to [1], wherein the content of the trimerization catalyst is in the range of 1:1 to 1:50.
[3] Content of the resin catalyst: The polyol mixed solution according to [2], wherein the content of the trimerization catalyst is in the range of 1:1 to 1:10.
[4] The content of the resinification catalyst is 0.1 to 2 parts by mass with respect to 100 parts by mass of the polyol compound, and the content of the trimerization catalyst is 0 parts by mass with respect to 100 parts by mass of the polyol compound. .5 to 3 parts by mass of the liquid mixture according to any one of [1] to [3].
[5] further comprising a flame retardant, wherein the flame retardant is selected from the group consisting of a phosphate ester, a phosphate-containing flame retardant, red phosphorus, a bromine-containing flame retardant, a boron-containing flame retardant, an antimony-containing flame retardant, and a metal hydroxide; The liquid mixture according to any one of [1] to [4], which is at least one selected.
[6] The mixed solution according to [5], wherein the content of the flame retardant is 50 to 150 parts by mass with respect to 100 parts by mass of the polyol compound.
[7] A polyurethane composition formed from a mixture obtained by mixing the liquid mixture according to any one of [1] to [6] and an isocyanate liquid containing polyisocyanate in a static mixer.
[8] The polyurethane composition according to [7], which constitutes a polyurethane foam.
[9] The polyurethane composition according to [7] or [8], which is used as a heat insulating material for vehicles or buildings.
[10] A cartridge container for a caulking gun, filled with the liquid mixture according to any one of [1] to [6].
[11] A spray pressure container filled with the liquid mixture according to any one of [1] to [6].
[12] A first container filled with the mixed solution according to any one of [1] to [6], a second container filled with an isocyanate solution containing a polyisocyanate compound, and A mixing system comprising a static mixer for mixing the liquid mixture discharged from one container and the isocyanate liquid discharged from the second container.

According to the present invention, it is possible to provide a liquid mixture that prevents the residual liquid from hardening in a static mixer and that can form a highly flame-retardant polyurethane foam with a small amount of trimerization catalyst.

[mixed solution]
The liquid mixture of the present invention contains a polyol compound, a resinification catalyst, a trimerization catalyst and a blowing agent. The reaction rate of the resinification reaction including the foaming reaction of the mixture of the mixed solvent of the present invention and the isocyanate solution containing the polyisocyanate is faster than the reaction rate of the trimerization reaction. Therefore, by setting these amounts to specific ranges, even if the liquid mixture of the present invention and the isocyanate liquid are mixed in a static mixer, the increase in the viscosity of the mixture due to the trimerization reaction is slowed, and the mixture is trimerized. It is thought that clogging in the static mixer due to reaction is less likely to occur. Furthermore, the trimerization reaction of the mixture mainly proceeds after the mixture is discharged from a discharger such as a caulking gun or a sprayer, so even if the amount of the trimerization catalyst used is small, a highly flame-retardant polyurethane foam can be obtained. Conceivable. The liquid mixture will be described in detail below.

(Polyol compound)
The liquid mixture of the present invention contains a polyol compound.
Examples of polyol compounds used in the present invention include polylactone polyols, polycarbonate polyols, aromatic polyols, alicyclic polyols, aliphatic polyols, polyester polyols, polymer polyols, and polyether polyols.

Polylactone polyols include, for example, polypropiolactone glycol, polycaprolactone glycol, and polyvalerolactone glycol.
Examples of polycarbonate polyols include polyols obtained by dealcoholization of hydroxyl group-containing compounds such as ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, octanediol, and nonanediol with ethylene carbonate, propylene carbonate, and the like. etc.

Examples of aromatic polyols include bisphenol A, bisphenol F, phenol novolak, and cresol novolak.
Examples of alicyclic polyols include cyclohexanediol, methylcyclohexanediol, isophoronediol, dicyclohexylmethanediol, and dimethyldicyclohexylmethanediol.
Aliphatic polyols include, for example, ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, and the like.

Polyester polyols include, for example, polymers obtained by dehydration condensation of polybasic acids and polyhydric alcohols, and polymers obtained by ring-opening polymerization of lactones such as ε-caprolactone and α-methyl-ε-caprolactone. , and condensates of hydroxycarboxylic acids and the above polyhydric alcohols.
Examples of polybasic acids include adipic acid, azelaic acid, sebacic acid, isophthalic acid (m-phthalic acid), terephthalic acid (p-phthalic acid), and succinic acid. Examples of polyhydric alcohols include bisphenol A, ethylene glycol, 1,2-propylene glycol, 1,4-butanediol, diethylene glycol, 1,6-hexane glycol, and neopentyl glycol.
Examples of hydroxycarboxylic acids include castor oil, reaction products of castor oil and ethylene glycol, and the like.

Examples of polymer polyols include polymers obtained by graft-polymerizing ethylenically unsaturated compounds such as acrylonitrile, styrene, methyl acrylate, and methacrylate onto aromatic polyols, alicyclic polyols, aliphatic polyols, and polyester polyols. , polybutadiene polyol, modified polyols of polyhydric alcohols, and hydrogenated products thereof.

Modified polyols of polyhydric alcohols include, for example, polyhydric alcohols that have been modified by reacting them with alkylene oxide.
Examples of polyhydric alcohols include trihydric alcohols such as glycerin and trimethylolpropane, pentaerythritol, sorbitol, mannitol, sorbitan, diglycerin, dipentaerythritol, sucrose, glucose, mannose, fructose, methylglucoside and tetrahydric to octahydric alcohols such as derivatives thereof, phloroglucinol, cresol, pyrogallol, catechol, hydroquinone, bisphenol A, bisphenol F, bisphenol S, 1,3,6,8-tetrahydroxynaphthalene, and 1,4 , 5,8-tetrahydroxyanthracene, castor oil polyol, (co)polymers of hydroxyalkyl (meth)acrylates and polyfunctional (for example, 2 to 100 functional groups) polyols such as polyvinyl alcohol, condensation of phenol and formaldehyde. (Novolak).

The method of modifying the polyhydric alcohol is not particularly limited, but a method of adding alkylene oxide (hereinafter also referred to as "AO") is preferably used. AO includes AO having 2 to 6 carbon atoms, such as ethylene oxide (hereinafter also referred to as "EO"), 1,2-propylene oxide (hereinafter also referred to as "PO"), 1,3-propyroxide, 1,2-butylene oxide, 1,4-butylene oxide and the like.
Among these, PO, EO and 1,2-butylene oxide are preferred, and PO and EO are more preferred, 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.

As the polyether polyol, for example, in the presence of at least one low-molecular-weight active hydrogen compound having two or more active hydrogens, at least one alkylene oxide such as ethylene oxide, propylene oxide, and tetrahydrofuran is ring-opened. Examples thereof include polymers obtained by polymerization. Low-molecular-weight active hydrogen compounds having two or more active hydrogens include, for example, bisphenol A, ethylene glycol, propylene glycol, butylene glycol, diols such as 1,6-hexanediol, and triols such as glycerin and trimethylolpropane. , ethylenediamine, and butylenediamine.

Polyester polyols and polyether polyols are preferred as the polyol compound used in the present invention. Polyols having two hydroxyl groups are also preferred. Among them, polybasic acids having aromatic rings 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 Polyester polyol obtained by dehydration condensation of is more preferable.

The hydroxyl value of the polyol compound is preferably 20 to 300 mgKOH/g, more preferably 30 to 250 mgKOH/g, even more preferably 50 to 220 mgKOH/g. When the hydroxyl value of the polyol is equal to or less than the above upper limit, the viscosity of the mixed liquid agent 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 is at least the above lower limit, the cross-linking density of the polyurethane foam increases, resulting in increased strength.
The hydroxyl value of polyol can be measured according to JIS K 1557-1:2007.

The content of the polyol compound in the liquid mixture of the present invention is preferably 10 to 80% by mass, more preferably 20 to 70% by mass, still more preferably 25 to 60% by mass. When the content of the polyol compound is at least the lower limit, it becomes easier to react the polyol compound with the polyisocyanate compound. On the other hand, when the content of the polyol compound is equal to or less than the above upper limit, the viscosity of the liquid mixture does not become too high, and the handleability of the liquid mixture is improved.

(Resinification catalyst)
The liquid mixture of the present invention contains a resinification catalyst. The resinification catalyst is a catalyst that accelerates the reaction between the polyol compound and the polyisocyanate compound. In the present invention, a foaming catalyst that catalyzes the reaction between water and isocyanate is also included in the resinification catalyst. Examples of resin-forming catalysts include amine-based catalysts such as imidazole compounds and piperazine compounds, and metal-based catalysts.
Examples of imidazole compounds include tertiary amines in which the secondary amine at the 1-position of the imidazole ring is substituted 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 imidazole and the like. Also included are imidazole compounds in which the secondary amine in the imidazole ring is substituted with a cyanoethyl group.
Further, piperazine compounds include tertiary amines such as N-methyl-N'N'-dimethylaminoethylpiperazine and trimethylaminoethylpiperazine.
Examples of amine-based catalysts include imidazole compounds, piperazine compounds, pentamethyldiethylenetriamine, triethylamine, N-methylmorpholine bis(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 various tertiary amines such as propylamine;

Metal catalysts include metal salts of lead, tin, bismuth, copper, zinc, cobalt, nickel and the like, preferably organic acid metal salts of lead, tin, bismuth, copper, zinc, cobalt and nickel. . More preferred are organic acid tin salts such as dibutyltin dilaurate, dioctyltin dilaurate and dioctyltin versatate, and organic acid bismuth salts such as bismuth trioctate and bismuth tris(2-ethylhexanoate). Salt is preferred.
The resinification catalyst may be used singly or in combination of two or more. Among the above, it is preferable to use one or more selected from triethylenediamine and bismath tris(2-ethylhexanoate).

The content of the resinification catalyst (the total when two or more are contained) is 0.1 to 5 parts by mass, preferably 0.1 to 2 parts by mass, and 0.1 to 5 parts by mass, preferably 0.1 to 2 parts by mass, based on 100 parts by mass of the polyol compound. 2 to 1.5 parts by mass is more preferable. When the content of the resinification catalyst is less than the above lower limit, it becomes difficult to form urethane bonds, and the reaction does not proceed quickly. On the other hand, if it is more than the above upper limit, it becomes difficult to control the reaction rate, and the mixture of the mixed liquid agent and the isocyanate liquid agent containing the polyisocyanate compound hardens and tends to cause clogging in the static mixer.
The liquid mixture of the present invention may contain a substance containing impurities other than the resinification catalyst component that functions as the resinification catalyst together with the resinification catalyst. In this case, the mass of only the resinification catalyst component excluding impurities from the substance is the "resinification catalyst content".

(Trimerization catalyst)
The liquid mixture of the present invention contains a trimerization catalyst. The trimerization catalyst is a catalyst that reacts and trimerizes the isocyanate groups contained in the polyisocyanate to promote the formation of isocyanurate rings. Examples of trimerization catalysts include nitrogen-containing aromatic compounds such as tris(dimethylaminomethyl)phenol, 2,4-bis(dimethylaminomethyl)phenol, 2,4,6-tris(dialkylaminoalkyl)hexahydro-S-triazine, etc. , potassium acetate, potassium 2-ethylhexanoate, carboxylic acid alkali metal salts such as potassium octylate, trimethylammonium salts, triethylammonium salts, tertiary ammonium salts such as triphenylammonium salts, tetramethylammonium salts, tetraethylammonium salts, Quaternary ammonium salts such as tetraphenylammonium salts, triethylmonomethylammonium salts, carboxylic acid quaternary ammonium salts, and the like can be used. These may be used individually by 1 type, and may use 2 or more types together.

Among the above, one or more carboxylates selected from the group consisting of alkali metal carboxylates and quaternary ammonium carboxylates are preferred. These carboxylate trimerization catalysts allow the reaction to proceed immediately from the start of the trimerization reaction, and the amount of unreacted isocyanate can be reduced. As a result, the flame retardancy of the polyurethane foam can be improved.

The content of the trimerization catalyst (the total when containing two or more) is 0.5 to 5 parts by mass, preferably 0.5 to 3 parts by mass, and 1 to 3 parts by mass is more preferred. If the content of the trimerization catalyst is less than the above lower limit, trimerization of the polyisocyanate will be difficult to occur, and the resulting polyurethane foam will have reduced flame retardancy. On the other hand, if the content of the trimerization catalyst is more than the above upper limit, it becomes difficult to control the reaction, and the mixture of the mixed solution and the isocyanate solution containing polyisocyanate hardens, which tends to cause clogging in the stationary mixer. Become.
The mixed solution of the present invention may contain a substance containing impurities other than the trimerization catalyst component functioning as the trimerization catalyst together with the trimerization catalyst. In this case, the mass of only the trimerization catalyst component excluding impurities from the substance is the "content of the trimerization catalyst."

The total content of the trimerization catalyst and the resinification catalyst in the liquid mixture of the present invention is not particularly limited, but is preferably 0.5 to 10 parts by mass, more preferably 0.5 to 8 parts by mass, and still more preferably 1 to 6 parts by mass. When the total content of both catalysts in the liquid mixture of the present invention is at least these lower limits, the formation and trimerization of urethane bonds proceed appropriately, and the flame retardancy of the polyurethane foam tends to be good. Further, when the total content of both catalysts in the liquid mixture of the present invention is equal to or less than these upper limits, the urethanization and trimerization reactions can be easily controlled, and a mixture of the liquid mixture and an isocyanate liquid containing a polyisocyanate compound can be obtained. hardens and is less likely to clog in static mixers.

In the liquid mixture of the present invention, the content of the resinification catalyst: the content of the trimerization catalyst preferably ranges from 1:1 to 1:50, more preferably from 1:1 to 1:20, and still more preferably. The range is 1:1 to 1:10. When the content of the trimerization catalyst/the content of the resinification catalyst is at least the lower limit, the formation of urethane bonds and the trimerization proceed appropriately, and the flame retardancy of the polyurethane foam tends to be good. On the other hand, when the content of the trimerization catalyst/the content of the resinification catalyst is equal to or less than the upper limit, the contents of the resinification catalyst and the trimerization catalyst are reduced, and the mixture of the mixed liquid agent and the isocyanate liquid agent containing the polyisocyanate compound is obtained. hardens and is less likely to clog in static mixers.

(foaming agent)
The liquid mixture of the present invention contains a foaming agent. When a caulking gun is used as a static mixer for the mixed solution of the present invention and an isocyanate solution containing a polyisocyanate compound, specific examples of the foaming agent include hydrofluoroolefins and hydrofluorocarbons. One or more of these are used as a foaming agent.
When the dispenser is a spray, specific examples of the foaming agent are hydrocarbons having 2 to 5 carbon atoms, dimethyl ether, and the like. One or more of these are used as a foaming agent.

Hydrofluoroolefins include, for example, fluoroalkenes having about 3 to 6 carbon atoms. The hydrofluoroolefin may be a hydrochlorofluoroolefin having a chlorine atom, and thus may be a chlorofluoroalkene having about 3 to 6 carbon atoms, or the like. Preferred hydrofluoroolefins are fluoroalkenes having 3 or 4 carbon atoms, and more preferred hydrofluoroolefins are fluoroalkenes having 3 carbon atoms.
More specifically, trifluoropropene, tetrafluoropropene such as HFO-1234, pentafluoropropene such as HFO-1225, chlorotrifluoropropene such as HFO-1233, chlorodifluoropropene, chlorotrifluoropropene, and chlorotetrafluoropropene. fluoropropene and the like. 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 -ene, 1,1,2,3,3-pentafluoropropene (HFO-1225yc), 1,1,1,2,3-pentafluoropropene (HFO-1225yez), trans-1-chloro-3,3 ,3-trifluoropropene (HFO-1233zd) and 1,1,1,4,4,4-hexafluorobut-2-ene. Among these, HFO-1233zd is preferred.
These hydrofluoroolefins may be used alone or in combination of two or more.

Specific examples of hydrofluorocarbons include hydrochlorofluorocarbon compounds such as trichloromonofluoromethane, trichlorotrifluoroethane, and dichloromonofluoroethane, HFC-245fa (1,1,1,3,3-pentafluoropropane), and HFC-365mfc. (1,1,1,3,3-pentafluorobutane) and the like. Among these, HFC-245fa and HFC-365mfc are preferred.
These hydrofluorocarbons may be used alone or in combination of two or more.

Specific examples of hydrocarbons having 2 to 5 carbon atoms are propane, isobutane, normal butane and the like. Preferred specific examples of at least one blowing agent selected from the group consisting of hydrocarbons having 2 to 5 carbon atoms and dimethyl ether are dimethyl ether, a mixed solvent of dimethyl ether and propane, isobutane or normal butane, and the like.

The content of the foaming agent is preferably 10 to 60 parts by mass, more preferably 20 to 55 parts by mass, still more preferably 25 to 50 parts by mass, and even more preferably 25 to 40 parts by mass, relative to 100 parts by mass of the polyol compound. preferable. When the content of the foaming agent is at least the lower limit, foaming is promoted, and the density of the resulting polyurethane foam can be reduced. On the other hand, when the content of the foaming agent is equal to or less than the upper limit, it is possible to suppress the excessive progress of foaming.

The mixed solution of the present invention may contain water from the viewpoint of adjusting the isocyanate index and ease of handling.

(Flame retardants)
The liquid mixture of the present invention may contain a flame retardant. Polyurethane foams produced using the liquid mixture of the present invention contain isocyanurate bonds resulting from trimerization of polyisocyanate compounds, and are therefore excellent in flame retardancy. Use of a flame retardant further improves the flame retardancy of polyurethane foams. be done.
The flame retardant used in the present invention is selected from the group consisting of phosphate esters, phosphate-containing flame retardants, red phosphorus, bromine-containing flame retardants, boron-containing flame retardants, antimony-containing flame retardants, and metal hydroxides. At least one is preferred. The phosphate ester may be a liquid flame retardant that becomes liquid at normal temperature (23° C.) and normal pressure (1 atm). By including the liquid flame retardant, the flame retardancy of the polyurethane composition of the present invention can be more easily improved without substantially reducing the discharge flow rate, mixability, etc. of the mixed solution of the present invention.

As the phosphate, it is preferable to use a monophosphate, a condensed phosphate, or the like. Examples of monophosphates include trialkyl phosphates such as trimethyl phosphate, triethyl phosphate, tributyl phosphate, tri(2-ethylhexyl) phosphate, halogen-containing phosphates such as tris(β-chloropropyl) phosphate, and tributoxyethyl phosphate. Aromatic ring-containing phosphates such as trialkoxy phosphate, tricresyl phosphate, trixylenyl phosphate, tris(isopropylphenyl) phosphate, cresyl diphenyl phosphate, diphenyl(2-ethylhexyl) phosphate, monoisodecyl phosphate, diisodecyl Acidic phosphoric acid esters such as phosphate and the like are included. Among them, halogen-containing phosphate esters, particularly tris(β-chloropropyl) phosphate, are preferred.

Condensed phosphates include, for example, aromatic condensed phosphates such as trialkyl polyphosphate, resorcinol polyphenyl phosphate, bisphenol A polycresyl phosphate, and bisphenol A polyphenyl phosphate.
Commercially available condensed phosphate esters include, for example, "CR-733S", "CR-741", and "CR747" manufactured by Daihachi Chemical Industry Co., Ltd., and "ADEKA STAB PFR" and "FP-600" manufactured by ADEKA. etc.

Among these, from the viewpoint of facilitating the production of polyurethane foam by reducing the viscosity of the mixture of the mixed liquid agent of the present invention and the isocyanate liquid agent containing the polyisocyanate compound, and from the viewpoint of improving the flame retardancy of the polyurethane foam, Monophosphates are preferred and tris(β-chloropropyl)phosphate is more preferred.

As the phosphate-containing flame retardant, for example, at least one selected from various phosphoric acids and metals of Groups 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 metals or compounds of
Examples of phosphoric acid include, but are not particularly limited to, monophosphoric acid, pyrophosphoric acid, polyphosphoric acid, and the like.
Metals of Groups IA to IVB of the periodic table include lithium, sodium, calcium, barium, iron (II), iron (III), and aluminum.
Examples of the aliphatic amine include methylamine, ethylamine, diethylamine, triethylamine, ethylenediamine, piperazine and the like. Aromatic amines include aniline, o-triidine, 2,4,6-trimethylaniline, anisidine, 3-(trifluoromethyl)aniline and the like. Heterocyclic compounds containing nitrogen in the ring include pyridine, triazine, melamine and the like.

Specific examples of the phosphate-containing flame retardant include monophosphates such as trialuminum phosphate, pyrophosphates, and polyphosphates. Here, the polyphosphate is not particularly limited, but examples thereof include ammonium polyphosphate, piperazine polyphosphate, melamine polyphosphate, ammonium polyphosphate amide, and aluminum polyphosphate.
One or two or more of the above-described phosphate-containing flame retardants can be used. In the present invention, trialuminum phosphate is preferred.

Red phosphorus may be composed of red phosphorus alone, red phosphorus may be coated with resin, metal hydroxide, metal oxide, or the like, or red phosphorus may be coated with resin, metal hydroxide, metal oxide, or the like. It may be mixed with Resins coated with red phosphorus or mixed with red phosphorus are not particularly limited, but include thermosetting resins such as phenol resins, epoxy resins, unsaturated polyester resins, melamine resins, urea resins, aniline resins, and silicone resins. be done. From the viewpoint of flame retardancy, metal hydroxides are preferable as the film or compound to be mixed. It is preferable to appropriately select and use the metal hydroxide described later.

The bromine-containing flame retardant is not particularly limited as long as it contains bromine in its molecular structure and is solid at normal temperature and pressure. Examples thereof include brominated aromatic ring-containing aromatic compounds.
Brominated aromatic ring-containing aromatic compounds include hexabromobenzene, pentabromotoluene, hexabromobiphenyl, decabromobiphenyl, decabromodiphenyl ether, octabromodiphenyl ether, hexabromodiphenyl ether, bis(pentabromphenoxy)ethane, ethylenebis( pentabromophenyl), ethylenebis(tetrabromophthalimide), tetrabromobisphenol A and other monomeric organic bromine compounds.

Also, the brominated aromatic ring-containing aromatic compound may be a brominated compound polymer. Specifically, a polycarbonate oligomer produced using brominated bisphenol A as a starting material, a brominated polycarbonate such as a copolymer of this polycarbonate oligomer and bisphenol A, and a diepoxy compound produced by reacting brominated bisphenol A with epichlorohydrin. etc. Furthermore, brominated epoxy compounds such as monoepoxy compounds obtained by reacting brominated phenols with epichlorohydrin, poly(brominated benzyl acrylate), brominated phenols of brominated polyphenylene ether, brominated bisphenol A and cyanuric chloride brominated polystyrene such as brominated (polystyrene), poly(brominated styrene), crosslinked brominated polystyrene, crosslinked or non-crosslinked brominated poly(-methylstyrene), and the like.
Compounds other than the brominated aromatic ring-containing aromatic compound such as hexabromocyclododecane may also be used.
These bromine-containing flame retardants may be used singly or in combination of two or more. Among the above-described compounds, the brominated aromatic ring-containing aromatic compounds are preferred, and monomeric organic bromine compounds such as hexabromobenzene are particularly preferred.

Boron-containing flame retardants for use in the present invention include borax, boron oxide, boric acid, borates, and the like. Examples of boron oxide include diboron trioxide, boron trioxide, diboron dioxide, tetraboron trioxide, and tetraboron pentoxide.
Examples of borates include borates of alkali metals, alkaline earth metals, elements of Groups 4, 12 and 13 of the periodic table, and ammonium. Specifically, alkali metal borate salts such as lithium borate, sodium borate, potassium borate and cesium borate; alkaline earth metal borate salts such as magnesium borate, calcium borate and barium borate; Zirconium borate, zinc borate, aluminum borate, ammonium borate and the like.
A boron-containing flame retardant may be used individually by 1 type, and may use 2 or more types together.
The boron-containing flame retardant used in the present invention is preferably a borate, more preferably zinc borate.

Antimony-containing flame retardants include, for example, antimony oxide, antimonate, pyroantimonate, and the like. Examples of antimony oxide include antimony trioxide and antimony pentoxide. Examples of antimonates include sodium antimonate and potassium antimonate. Examples of pyroantimonate include sodium pyroantimonate and potassium pyroantimonate.
Antimony-containing flame retardants may be used singly or in combination of two or more. A preferred antimony-containing flame retardant for use in the present invention is antimony trioxide.

Examples of metal hydroxides used in the present invention include magnesium hydroxide, calcium hydroxide, aluminum hydroxide, iron hydroxide, nickel hydroxide, zirconium hydroxide, titanium hydroxide, zinc hydroxide, copper hydroxide, vanadium hydroxide, tin hydroxide and the like. A metal hydroxide may be used individually by 1 type, and may use 2 or more types together. A preferred metal hydroxide for use in the present invention is aluminum hydroxide.

When the mixed solution of the present invention contains a flame retardant, the content thereof is preferably 10 to 200 parts by mass, more preferably 20 to 180 parts by mass, more preferably 40 to 170 parts by mass with respect to 100 parts by mass of the polyol compound. More preferably, 50 to 150 parts by mass is even more preferable. When the content of the flame retardant is at least the above lower limit, sufficient flame retardancy can be imparted to the polyurethane foam produced using the mixed solution. On the other hand, when the content of the flame retardant is equal to or less than the above upper limit, foaming during production of polyurethane foam is not hindered.

(foam stabilizer)
The mixed liquid agent of the present invention may contain a foam stabilizer for the purpose of facilitating foaming of the mixture of the mixed liquid agent and the isocyanate liquid agent containing the polyisocyanate compound.
Examples of foam stabilizers include polyoxyalkylene-based foam stabilizers such as polyoxyalkylene alkyl ethers, surfactants such as silicone foam stabilizers such as organopolysiloxane, and the like. These foam stabilizers may be used alone or in combination of two or more.

The content of the foam stabilizer in the mixed solution of the present invention is preferably 0.1 to 10 parts by mass, more preferably 1 to 8 parts by mass, and further 1 to 5 parts by mass with respect to 100 parts by mass of the polyol compound. preferable. When the content of the foam stabilizer is at least the above lower limit, it becomes easier to foam the mixture of the mixed solution and the isocyanate solution containing the polyisocyanate compound, making it possible to obtain a homogeneous polyurethane foam. Further, when the content of the foam stabilizer is equal to or less than the above upper limit, the balance between the production cost and the effect obtained is optimal.

(Anti-settling agent)
The liquid mixture of the present invention may contain an anti-settling agent. By using an anti-settling agent, it is possible to prevent the solid flame retardant dispersed in the mixed solution from settling. Also, the use of an anti-settling agent facilitates uniform dispersion of the solid flame retardant. The anti-settling agent generally becomes solid at normal temperature and pressure, and usually forms a solid content (insoluble content) in the liquid mixture.

The anti-settling agent is not particularly limited, but it is preferable to use one or more selected from, for example, carbon black, powdered silica, hydrogenated castor oil wax, fatty acid amide wax, organic clay, and the like. Among them, powdered silica is more preferable.
Carbon black used as an anti-settling agent can be produced by a furnace method, a channel method, a thermal method, or the like. Commercially available carbon black may be appropriately selected and used.
Fumed silica, colloidal silica, silica gel and the like can be used as powdery silica. Among these, fumed silica is preferred, and hydrophobic fumed silica is particularly preferred. Aerosil (registered trademark) manufactured by Nippon Aerosil Co., Ltd. can be used as fumed silica.
Hydrogenated castor oil wax, fatty acid amide wax and the like form a swelling gel structure in a liquid. In addition, these are generally commercially available under the names of thixotropic imparting agent, thickener, anti-settling agent, anti-sagging agent, etc., and commercially available products can be appropriately selected and used.

The content of the anti-settling agent is not particularly limited, but is, for example, 0.5 to 20 parts by mass, preferably 1 to 12 parts by mass, and more preferably 2 to 8 parts by mass with respect to 100 parts by mass of the polyol compound. By setting the content of the anti-settling agent within the above range, it is possible to prevent the solid flame retardant from settling and improve its dispersibility without increasing the solid content more than necessary.

(Other ingredients)
The mixed solution of the present invention may contain components other than the polyol compound, the resinification catalyst, the trimerization catalyst, the foaming agent, the flame retardant and the anti-settling agent, and may contain, for example, an inorganic filler.
Examples of inorganic fillers include silica, diatomaceous earth, alumina, titanium oxide, calcium oxide, magnesium oxide, iron oxide, tin oxide, antimony oxide, ferrites, calcium carbonate, magnesium carbonate, zinc carbonate, barium carbonate, dawsonite, hydro Talcite, calcium sulfate, barium sulfate, gypsum fiber, calcium silicate, talc, clay, mica, wollastonite, montmorillonite, bentonite, activated clay, sepiolite, imogolite, sericite, glass fiber, glass beads, silica balloon, nitriding 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 steel fiber , various magnetic powders, slag fibers, fly ash, silica-alumina fibers, alumina fibers, silica fibers, and zirconia fibers. These inorganic fillers may be used alone or in combination of two or more.
When the mixed solution of the present invention contains an inorganic filler, the content of the inorganic filler is preferably 1 to 100 parts by mass, more preferably 10 to 80 parts by mass, more preferably 20 to 100 parts by mass with respect to 100 parts by mass of the polyol compound. 70 parts by mass is more preferable.

In addition, the mixed solution of the present invention may optionally contain antioxidants such as phenolic, amine, and sulfur antioxidants, heat stabilizers, metal damage inhibitors, antistatic agents, One or more selected from stabilizers, cross-linking agents, lubricants, softeners, pigments and the like may be included.

(Manufacturing method of mixed solution)
The method for producing the liquid mixture of the present invention is not particularly limited. For example, in the case of caulking gun applications, each component other than the foaming agent is stirred with, for example, a known stirring device, and then the foaming agent is added to the obtained raw material. It can be manufactured by stirring with and filling a cartridge container for a caulking gun. Further, in the case of spray application, after mixing each component other than the foaming agent, it can be produced by filling a pressure-resistant container for spraying together with the foaming agent.

[Polyurethane composition]
The polyurethane composition of the present invention is formed from a mixture obtained by mixing the liquid mixture of the present invention and an isocyanate liquid containing polyisocyanate in a static mixer.

(Isocyanate solution)
As the polyisocyanate used in the isocyanate solution, known polyisocyanate compounds used for forming polyurethane foams can be used. Examples of polyisocyanate compounds include aromatic polyisocyanates, alicyclic polyisocyanates, and aliphatic polyisocyanates.
Examples of aromatic polyisocyanates include phenylene diisocyanate, tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, dimethyldiphenylmethane diisocyanate, triphenylmethane triisocyanate, naphthalene diisocyanate, and polymethylene polyphenyl polyisocyanate.

Examples of alicyclic polyisocyanates include cyclohexylene diisocyanate, methylcyclohexyl diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, and dimethyldicyclohexylmethane diisocyanate.

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

Among these, aromatic polyisocyanates are preferred, and polymethylene polyphenyl polyisocyanates are more preferred, from the viewpoints of ease of use and availability. Polyisocyanate compounds may be used singly or in combination of two or more.
Further, the isocyanate liquid agent may appropriately contain known additives contained in the polyisocyanate compound before being mixed with the mixed liquid agent.

In addition, it is preferable that the mixed liquid agent and the isocyanate liquid agent have substantially the same volume. Specifically, the volume ratio of the isocyanate solution to the mixed solution is preferably 0.8 to 1.2, more preferably 0.9 to 1.1, and even more preferably 0.95 to 1.05.

(isocyanate index)
Although the isocyanate index of the polyurethane composition of the present invention is not particularly limited, it is preferably 200 or more. If the amount of the polyisocyanate compound is excessive relative to the polyol compound, a large amount of trimerization catalyst is required. can be used less. If the isocyanate index is equal to or higher than the lower limit, the amount of the polyisocyanate compound becomes excessive relative to the polyol compound, and the trimerization of the polyisocyanate compound facilitates formation of isocyanurate bonds, resulting in improved flame retardancy of the polyurethane foam. In addition, it becomes possible to impart nonflammability. Furthermore, when the amount is at least the above lower limit, it is easy to produce a polyurethane foam having an isocyanurate bond, that is, a polyurethane foam having both flame retardancy and heat insulation at high levels. From these viewpoints, the isocyanate index is more preferably 250 or more, more preferably 300 or more, and particularly preferably 350 or more.
Also, the isocyanate index is preferably 1000 or less, more preferably 800 or less, and particularly preferably 500 or less. When the isocyanate index is equal to or less than the upper limit, the resulting polyurethane foam has a good balance between flame retardancy and production cost.

In addition, the isocyanate index can be calculated by the following method.
Isocyanate index = number of equivalents of polyisocyanate compound / (number of equivalents of polyol compound + number of equivalents of water) x 100
Here, each equivalent number can be calculated as follows.
· Equivalent number of polyisocyanate compound = amount of polyisocyanate compound used (g) × NCO content (% by mass) / molecular weight of NCO (mol) × 100
Equivalent number of polyol compound = OHV x 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 = amount of water used (g) / molecular weight of water (mol) x number of OH groups of water In the above formulas, the molecular weight of NCO is 42 (mol), the molecular weight of KOH is 56100 (mmol), It is assumed that the molecular weight of water is 18 (mol) and the number of OH groups of water is two.

(Method for producing polyurethane composition)
The method for producing the polyurethane composition of the present invention is not particularly limited, but an isocyanate solution containing the mixed solution of the present invention and a polyisocyanate compound is mixed in a static mixer and discharged from a caulking gun, a sprayer or the like. formed by
A method for forming the polyurethane composition of the present invention with a caulking gun is carried out, for example, as follows. Two liquid agents discharged from a cartridge container filled with the mixed liquid agent of the present invention and an isocyanate liquid agent containing a polyisocyanate compound are mixed in a static mixer such as a static mixer, and the mixture is sprayed from a caulking gun to foam. .
A method for forming the polyurethane composition of the present invention by spraying is carried out, for example, as follows. The mixed solution of the present invention and the isocyanate solution containing a polyisocyanate compound are respectively discharged from a pressure-resistant container for spraying, and the two solutions are mixed in a static mixer such as a static mixer, and the mixture is sprayed from a nozzle. foam.

(Application of polyurethane composition)
In the present invention, the polyurethane composition can be used for various purposes, but is preferably used as a heat insulating material. Also, the polyurethane composition preferably constitutes a polyurethane foam. The polyurethane foam has a large number of air cells, thereby exhibiting a heat insulating effect.
More preferably, the polyurethane composition is used as thermal insulation, especially in vehicles or buildings. Vehicles include railroad vehicles, automobiles, ships, aircraft, and the like. The polyurethane composition of the present invention has high flame retardancy by using the above mixed solution. Therefore, from the viewpoint of disaster prevention and safety, it can be suitably used for vehicles or buildings.

The liquid mixture of the present invention can be formed into a polyurethane foam with a simple configuration using a caulking gun and a spray can as described above. Moreover, since the polyurethane composition of the present invention is formed using a caulking gun or a spray can, it is particularly suitable when the surface to be applied is relatively small. Therefore, for example, the mixed liquid agent of the present invention is preferably used for repairing by spraying the existing heat-resistant material where it has been deteriorated or damaged. Of course, it is not limited to such applications, and the mixed solution of the present invention may be used to form a new heat-resistant material.

(Cartridge containers for caulking guns, pressure-resistant containers for spraying, mixing systems)
The mixing system of the present invention comprises a first container filled with the mixed solution, a second container filled with an isocyanate solution containing a polyisocyanate compound, and the A static mixer for mixing the mixed solution and the isocyanate solution discharged from the second container is provided.
The mixing system of the present invention is not limited to any particular system. When the mixing system of the present invention is a caulking gun, the first container filled with the liquid mixture is the caulking gun cartridge container. The second caulking gun cartridge container may or may not be filled with a foaming agent other than water together with the polyisocyanate compound, but preferably is not filled with a foaming agent.
When the mixing system of the present invention is a pressure-resistant spray container, the first container filled with the liquid mixture is the pressure-resistant spray container. A second spray pressure vessel is filled with a foaming agent other than water.

EXAMPLES The present invention will be described in more detail with reference to Examples below, but the present invention is not limited to these.

Each component used in Examples and Comparative Examples is shown below, and the content (parts by mass) of each component is shown in Tables 1 and 2.

1) Polyol compound: polyester polyol (Maximol RLK-087 manufactured by Kawasaki Kasei Co., Ltd.)
2) foam stabilizer: polyoxyalkylene foam stabilizer (SH-193 manufactured by Dow Corning Toray Co., Ltd.)
3) Trimerization catalyst A-1: catalyst containing tetramethylammonium acetate salt (TOYOCAT-TRX manufactured by Tosoh Corporation, tetramethylammonium acetate salt concentration 65% by mass)
A-2: Catalyst containing potassium 2-ethylhexanoate (DABCO K-15 manufactured by Eponic Japan, potassium ethylhexanoate concentration 75% by mass)
4) Resin catalyst B-1: triethylenediamine-containing catalyst (DABCO 33LV manufactured by Eponic Japan, triethylenediamine concentration 33% by mass)
B-2: Bismuth compound-containing catalyst (U-600 manufactured by Nitto Kasei Co., Ltd., bismuth compound concentration 55% by mass)
5) Foaming agent Water trans-1-chloro-3,3,3-trifluoropropene (Solstice LBA, HFO manufactured by Honeywell)
Dimethyl ether (DME)
6) Flame retardant C-1: Red phosphorus (Nova Excel 140 manufactured by Rin Kagaku Kogyo Co., Ltd.)
C-2: tris (β-chloropropyl) phosphate (TMCPP manufactured by Daihachi Chemical Industry Co., Ltd.)
C-3: Tertiary aluminum phosphate (manufactured by Taihei Chemical Industry Co., Ltd.)
C-4: Hexabromobenzene (manufactured by Manac)
C-5: Antimony trioxide (Patox C manufactured by Nippon Seiko Co., Ltd.)
C-6: aluminum hydroxide (B-325 manufactured by Armorix)
7) Anti-settling agent: Aerosil (R756S manufactured by Nippon Aerosil Co., Ltd.)
8) Polyisocyanate (isocyanate compound): polymeric MDI (Mitsui Chemicals MR-400)

Examples 1 to 10 and Comparative Examples 1 and 2
Each operation was performed according to the formulations shown in Tables 1 and 2. First, components other than trans-1-chloro-3,3,3-trifluoropropene (hereinafter referred to as "HFO") were stirred in a 1000 ml beaker at 1500 rpm for 3 minutes with a three-one motor. Thereafter, HFO was further added and stirred for 3 minutes under the same conditions to obtain a mixed solution.

The obtained mixed solution and the polyisocyanate compound, which is an isocyanate solution, were each filled in a 100 ml cartridge (AC200-01-10-01 manufactured by Mixpack). Each of the cartridges was then placed in a gas-powered caulking gun (Mixpack DP200-70-01/SP, 100×100). A gas-driven caulking gun was equipped with a static mixer for spraying (SM616SP manufactured by Mixpack Co., Ltd.) having an inner diameter of 6 mm and 16 elements. A 7 m ³ compressed nitrogen cylinder was used to drive the caulking gun, and the working pressure on the secondary side of the cylinder was adjusted to 0.3 MPa.
Each cartridge was discharged by pressing the trigger of the caulking gun. The mixed solution and the isocyanate solution discharged from each cartridge were mixed through a static mixer and discharged onto a gypsum board having a thickness of 12 mm to obtain a polyurethane foam.
The re-discharging property of the mixture and the flame retardancy of the polyurethane foam were evaluated as follows. Results are shown in Tables 1 and 2.

(1) Re-ejectability of mixture A mixture of a mixed liquid agent and an isocyanate liquid agent was ejected for 2 seconds, and was rated as A if it could be ejected again after 60 seconds, B if it could be ejected again after 30 seconds, and C if it could not be ejected again after 30 seconds.

(2) Flame Retardancy of Polyurethane Foam Gypsum board and polyurethane foam were cut into pieces of 10 cm×10 cm. Next, the polyurethane foam was cut out together with the gypsum board so that the thickness of the polyurethane foam was 30 mm, and the obtained sample was heated for 5 minutes at a radiant heat intensity of 50 kW/m ² in accordance with the test method of ISO-5660. The total calorific value was measured with a cone calorimeter. The case where the total calorific value for 5 minutes was 8 MJ or less was evaluated as A, the case where it was over 8 MJ and 10 MJ or less was evaluated as B, and the case where it exceeded 10 MJ was evaluated as C.

Examples 11 and 12 and Comparative Examples 3 and 4
Each operation was performed according to the formulations shown in Tables 1 and 2. First, components other than DME were stirred for 3 minutes at 1500 rpm in a 1000 ml beaker with a three-one motor to obtain a liquid mixture. A 100 ml aerosol test bottle (manufactured by Tokyo Kobunshi Co., Ltd.) was filled with the mixed solution and DME. Another aerosol test bottle was filled with an isocyanate solution containing polyisocyanate and DME. Two aerosol test bottles were connected to a static mixer (ACF Helix 08-18 manufactured by Ritter), and a mixed liquid agent and polyisocyanate were simultaneously applied from a nozzle with a stem hole of 0.5 × 2 (manufactured by Maruichi Co., Ltd.) to a gypsum having a thickness of 12 mm. A polyurethane foam was obtained by spraying on a board. The re-discharging property of the mixture and the flame retardancy of the polyurethane foam were evaluated in the same manner as in Example 1. Results are shown in Tables 1 and 2.

In Tables 1 and 2 above, the unit for the content of each component is parts by mass. The mass of the trimerization catalyst component is the mass (unit: parts by mass) of only the trimerization catalyst component obtained by removing impurities from the substance contained in the mixed solution as the trimerization catalyst. The mass of the resinification catalyst component is the mass (in parts by mass) of only the resinification catalyst component obtained by removing impurities from the substance contained in the mixed solution as the resinification catalyst. The trimerization/resinification catalyst is the ratio of the weight of the trimerization catalyst component alone/the weight of the resinification catalyst component alone.

The examples were good in both the redischarge evaluation and the flame retardancy evaluation, but the flame retardancy of the polyurethane foams of Comparative Examples 1 and 3, in which the respective contents of the resinification catalyst and the trimerization catalyst were too small, was low. In addition, the mixture of the mixed solution and polyisocyanate used in Comparative Examples 2 and 4, in which the contents of the resinification catalyst and the trimerization catalyst were too high, had low re-discharging properties.

Claims (5)

It contains a polyol compound, a resinification catalyst, a trimerization catalyst, a foaming agent and a flame retardant, and the content of the resinization catalyst is 0.1 to 5 parts by mass with respect to 100 parts by mass of the polyol compound, and the trimerization catalyst is 0.5 to 5 parts by mass with respect to 100 parts by mass of the polyol compound, and the content of the flame retardant is 50 to 150 parts by mass with respect to 100 parts by mass of the polyol compound. a first spray pressure vessel filled with
a second pressure-resistant spray container filled with an isocyanate solution containing a polyisocyanate compound and a foaming agent;
a static mixer for mixing the liquid mixture discharged from the first pressure-resistant spray container and the isocyanate liquid discharged from the second pressure-resistant spray container;
Mixing system with The mixing system according to claim 1, wherein the resinification catalyst content: the trimerization catalyst content is in the range of 1:1 to 1:50. 3. The mixing system of claim 2, wherein the resinification catalyst content: the trimerization catalyst content is in the range of 1:1 to 1:10. The content of the resinification catalyst is 0.1 to 2 parts by mass with respect to 100 parts by mass of the polyol compound, and the content of the trimerization catalyst is 0.5 to 0.5 parts by mass with respect to 100 parts by mass of the polyol compound. The mixing system according to any one of claims 1 to 3, which is 3 parts by weight. wherein the flame retardant is at least one selected from the group consisting of phosphate esters, phosphate-containing flame retardants, red phosphorus, bromine-containing flame retardants, boron-containing flame retardants, antimony-containing flame retardants, and metal hydroxides. The mixing system according to any one of items 1 to 4.