JP7628491B2 - Polyol composition, polyurethane composition, and polyurethane foam - Google Patents

Description

The present invention relates to a polyol composition, a polyurethane composition comprising the polyol composition and a polyisocyanate composition, and a polyurethane foam formed from the polyurethane composition.

Conventionally, polyurethane foams have been used as heat insulating materials in vehicles such as automobiles, railway cars, and ships, buildings, etc. For polyurethane foams, two-component polyurethanes in which a polyol composition and a polyisocyanate composition filled in separate containers are mixed to form a foam are widely used.
Two-component polyurethanes are sometimes used in aerosol containers because each liquid can be discharged from a container with a relatively simple structure and mixed. When two-component polyurethanes are used in aerosol containers, one container is filled with a polyol compound and a low-boiling compound, and the other container is filled with a polyisocyanate compound and a low-boiling compound. The polyol liquid and the polyisocyanate liquid are discharged from each container by the vapor pressure of the low-boiling compound, and are mixed to form a polyurethane foam.

Low boiling point compounds used in aerosol containers include hydrofluorocarbons (HFCs), hydrochlorofluorocarbons (HCFCs), dimethyl ether, liquefied petroleum gas, etc. Furthermore, since HFCs and HCFCs have a high global warming potential, there is a demand for alternative compounds to replace them.
For example, Patent Document 1 describes a two-liquid aerosol composition for rigid polyurethane foams that contains a specific amount of a low-boiling point compound, and describes that by using liquefied petroleum gas (LPG), dimethyl ether (DME), etc. as the low-boiling point compound, there is no adverse effect on global warming.

JP 2006-169474 A

However, polyurethane foams formed from the above-mentioned conventional two-liquid aerosol compositions tend to shrink easily, and there is room for improvement in terms of shape stability. In response to this, it has been considered to incorporate a filler into the polyol composition in order to suppress the shrinkage of the foam. However, the incorporation of a filler causes problems such as an insufficient amount of polyol composition discharged from the aerosol container, a decrease in the mixing efficiency of the composition, and deterioration of workability.

Therefore, the present invention aims to provide a polyol composition that is easy to extrude when sealed in a container and can produce a polyurethane foam with a low shrinkage rate, as well as a polyurethane composition and polyurethane foam comprising the polyol composition.

As a result of extensive investigations, the present inventors have found that the above-mentioned problems can be solved by a polyol composition containing a polyol compound, a filler, a catalyst, and an organic blowing agent having a boiling point of −10° C. or less, a polyurethane composition including the polyol composition, and a polyurethane foam, and have completed the present invention as described below. That is, the present invention provides the following [1] to [11].
[1] A polyol composition comprising a polyol compound, a filler, a catalyst, and an organic blowing agent having a boiling point of −10° C. or lower.
[2] The polyol composition according to the above [1], wherein the filler ratio calculated by the following formula (1) is 5 to 80%.
Formula (1) Filler ratio (%) = (E/D) x 100
D: The weight of a discharged product obtained by sealing the polyol composition in a container and keeping the container at 35° C. for 10 seconds and then drying the discharged product at 40° C. for 30 minutes. E: The weight of an aggregate obtained by diluting the dried discharged product of D with acetone and subjecting it to suction filtration. [3] The polyol composition according to the above [1] or [2], wherein the organic blowing agent is at least one selected from the group consisting of a hydrocarbon compound represented by formula (1), an ether compound represented by formula (2), and a fluorine-containing compound having 3 or less carbon atoms.
Formula (1): C _n H _2n+2
(In formula (1), n is an integer of 1 to 4.)
Formula (2): C _n H _2n+1 -O-C _m H _2m+1
(In formula (2), n and m are each independently 1 or 2.)
[4] The polyol composition according to any one of the above [1] to [3], wherein the organic blowing agent is at least one selected from the group consisting of propane, dimethyl ether, and HFO-1234ze.
[5] The polyol composition according to any one of the above [1] to [4], wherein the catalyst comprises a resinification catalyst and a trimerization catalyst.
[6] A container enclosing the polyol composition according to any one of [1] to [5] above.
[7] The container described in [6] above, which is an aerosol container.
[8] A polyurethane composition comprising the polyol composition according to any one of [1] to [5] above and a polyisocyanate composition containing a polyisocyanate compound.
[9] The polyurethane composition according to the above [8], having an isocyanate index of 200 to 1,000.
[10] A polyurethane foam formed from the polyurethane composition described in [9] above.
[11] The polyurethane foam according to the above [10], having a shrinkage rate of less than 20%.

According to the present invention, it is possible to provide a polyol composition that is easy to extrude when sealed in a container and can produce a polyurethane foam having a low shrinkage rate, as well as a polyurethane composition and polyurethane foam comprising the polyol composition.

FIG. 1 is a schematic diagram illustrating one embodiment of a mixing system. FIG. 2 is a schematic diagram illustrating another embodiment of a mixing system.

The present invention will be described in detail below.
The present invention is a polyol composition comprising a polyol compound, a filler, a catalyst, and an organic blowing agent having a boiling point of -10°C or lower.

[Organic foaming agents with a boiling point of -10°C or less]
The polyol composition of the present invention contains an organic foaming agent (hereinafter, simply referred to as an organic foaming agent) having a boiling point of -10°C or less. The organic foaming agent expels the polyol composition by its vapor pressure, and vaporizes when expelling the polyol composition, thereby foaming the polyol composition and the polyurethane composition described below. In this specification, the boiling point means a boiling point at 1 atmospheric pressure. Here, the boiling point of the organic foaming agent means the boiling point of the organic foaming agent alone, and does not mean, for example, the boiling point of the azeotropic mixture when the organic foaming agent forms an azeotropic mixture with another compound.

If the boiling point of the organic foaming agent exceeds -10°C, it becomes difficult to eject the polyol composition containing the filler. From the viewpoint of making it easier to eject the polyol composition, the boiling point of the organic foaming agent is preferably -12°C or lower, and more preferably -15°C or lower.

The organic foaming agent in the present invention is not particularly limited as long as it has a boiling point of -10°C or less, but from the viewpoint of making the polyol composition easier to extrude, it is preferable that it is at least one selected from the group consisting of a hydrocarbon compound represented by formula (1), an ether compound represented by formula (2), and a fluorine-containing compound having 3 or less carbon atoms.

(Hydrocarbon compound represented by formula (1))
The hydrocarbon compounds represented by formula (1) are as follows:
Formula (1): C _n H _2n+2
In formula (1), n is an integer of 1 or more and 4 or less.
Specific examples of the hydrocarbon compound represented by formula (1) include various butanes such as methane, ethane, propane, isobutane, and normal butane. From the viewpoint of handling and dischargeability of the polyol composition, the hydrocarbon compound represented by formula (1) is preferably an integer of 2 to 4 inclusive for n, and specifically, various butanes such as ethane, propane, isobutane, and normal butane are preferred. The hydrocarbon compound represented by formula (1) may be used alone or in combination of two or more types, and LPG (liquefied petroleum gas) mainly composed of propane and butanes is also a preferred specific example.

(Ether compound represented by formula (2))
The ether compound represented by formula (2) is as follows.
Formula (2): C _n H _2n+1 -O-C _m H _2m+1
In formula (2), n and m are each independently 1 or 2. Among the ether compounds represented by formula (2), it is preferable that both n and m are 1. That is, it is preferable that the ether compound represented by formula (2) is dimethyl ether.

(Fluorine-containing compounds having 3 or less carbon atoms)
In the present invention, examples of fluorine-containing compounds having 3 or less carbon atoms include hydrofluorocarbons (HFCs), hydrochlorofluorocarbons (HCFCs), hydrofluoroolefins (HFOs), etc. Among these, hydrofluoroolefins (HFOs) are preferred from the viewpoint of low global warming potential and reducing environmental load.
As the hydrofluoroolefin, from the viewpoint of improving the dischargeability of the polyol composition, 1,3,3,3-tetrafluoropropene (HFO-1234ze), 1,2,3,3,3-pentafluoropropene (HFO-1225ye), 1,1,1,3,3-pentafluoropropene (HFO-1225zc), 2,3,3,3-tetrafluoropropene (HFO-1234yf), etc. are preferred. Among these, HFO-1234ze is preferred.

As described above, the organic blowing agent in the present invention is preferably at least one selected from the group consisting of hydrocarbon compounds represented by formula (1), ether compounds represented by formula (2), and fluorine-containing compounds having 3 or less carbon atoms, and is particularly preferably at least one selected from propane, dimethyl ether, and HFO-1234ze.

The content of the organic blowing agent in the polyol composition is preferably 5 to 50 parts by mass, more preferably 8 to 35 parts by mass, and even more preferably 10 to 30 parts by mass, per 100 parts by mass of the polyol compound.

The polyol composition contains an organic blowing agent having a boiling point of -10°C or less, but may contain other blowing agents other than the organic blowing agent having a boiling point of -10°C or less, as long as the effects of the present invention are not impaired. The amount of the other blowing agent is preferably 70% by mass or less, more preferably 30% by mass or less, based on the total amount of the blowing agents contained in the polyol composition.

[Filler]
The polyol composition of the present invention contains a filler. By containing a filler, shrinkage of the obtained polyurethane foam can be suppressed.
The filler ratio of the polyol composition calculated by formula (1) is preferably 5 to 80%. When the filler ratio is 5% or more, shrinkage of the resulting polyurethane foam is easily suppressed, and when the filler ratio is 80% or less, the polyol composition is easily discharged from a container.
The filler content of the polyol composition is preferably 8 to 78%, more preferably 10 to 75%.

The filler ratio is calculated by the following formula (1).
Formula (1) Filler ratio (%) = (E/D) x 100
D: The weight of the polyol composition after sealing it in a container and keeping the container at 35° C. and then discharging the polyol composition from the container for 10 seconds and drying the discharged material at 40° C. for 30 minutes. E: The weight of the aggregate obtained by diluting the dried discharged material of D with acetone and filtering it by suction.

In the above D, the polyol composition of the present invention is sealed in a container. The container is a container capable of discharging the polyol composition at the vapor pressure of the organic blowing agent of the present invention, and is typically an aerosol container described later. The operation of keeping the container at 35°C may be, for example, immersing the container in warm water at 35°C for 60 minutes. In addition, when discharging the polyol composition for 10 seconds in the above D, the polyol composition is discharged in a state in which each component constituting the polyol composition is uniformly mixed. For example, if an unused aerosol container is used that is a polyol composition that is sufficiently mixed to be uniform and is filled with a sufficient amount of polyol composition such that not all of it is discharged in 10 seconds, the amount discharged during the above 10 seconds will be constant. In order to uniformly mix each component constituting the polyol composition, it is recommended to shake the container sufficiently before discharging. Shaking the container can be performed, for example, by holding the container by hand and shaking it up and down. The method of uniformly mixing the polyol composition is not limited to the above-mentioned method.

When drying the extrudate at 40°C for 30 minutes, the extrudate is placed in a cylindrical polyethylene container with a diameter of 10 cm and a height of 12 cm, and the top of the container is left open.

In the above E, the amount of acetone used when diluting the discharged material with acetone is not particularly limited as long as suction filtration can be performed, but for example, 0.1 to 10 mL per 1 mg of discharged material may be used. The filter paper used for suction filtration is a filter paper that can filter out fillers, for example, Advantec's circular quantitative filter paper No. 3. When suction filtration is performed, aggregates (acetone insolubles) remain on the filter paper. The aggregates are dried and the acetone contained in the aggregates is removed, and then the weight is measured, and this value is the weight of the aggregates in E.

Examples of the filler include a solid flame retardant and an inorganic filler.
The use of a solid flame retardant as a filler can effectively improve the flame retardancy of the polyurethane foam. The solid flame retardant is usually in a state of being dispersed in the polyol composition as a powder component. The solid flame retardant is a flame retardant that is solid at room temperature (23° C.) and normal pressure (1 atm).
Specific examples of solid flame retardants include red phosphorus-based flame retardants, phosphate-containing flame retardants, bromine-containing flame retardants, chlorine-containing flame retardants, antimony-containing flame retardants, boron-containing flame retardants, and metal hydroxides. These may be used alone or in combination of two or more.

<Red phosphorus-based flame retardants>
The red phosphorus-based flame retardant may be made of red phosphorus alone, may be red phosphorus coated with a resin, a metal hydroxide, a metal oxide, or may be red phosphorus mixed with a resin, a metal hydroxide, a metal oxide, or the like. The resin that coats the red phosphorus or mixes with the red phosphorus is not particularly limited, but examples thereof include thermosetting resins such as phenol resin, epoxy resin, unsaturated polyester resin, melamine resin, urea resin, aniline resin, and silicone resin. From the viewpoint of flame retardancy, metal hydroxide is preferable as the compound to be coated or mixed. The metal hydroxide to be used may be appropriately selected from those described later.

<Phosphate-containing flame retardants>
Examples of the phosphate-containing flame retardant include phosphates formed from salts of various phosphoric acids and at least one metal or compound selected from metals in Groups IA to IVB of the periodic table, ammonia, aliphatic amines, aromatic amines, and heterocyclic compounds containing nitrogen in the ring.
The phosphoric acid is not particularly limited, but examples thereof include monophosphoric acid, pyrophosphoric acid, and polyphosphoric acid.
Examples of metals in Groups IA to IVB of the periodic table include lithium, sodium, calcium, barium, iron (II), iron (III), and aluminum.
Examples of the aliphatic amine include methylamine, ethylamine, diethylamine, triethylamine, ethylenediamine, piperazine, etc. Examples of the aromatic amine include aniline, o-triidine, 2,4,6-trimethylaniline, anisidine, 3-(trifluoromethyl)aniline, etc. Examples of the heterocyclic compound containing nitrogen in the ring include pyridine, triazine, melamine, etc.

Specific examples of the phosphate-containing flame retardant include monophosphate, pyrophosphate, polyphosphate, etc. Here, the polyphosphate is not particularly limited, but examples thereof include ammonium polyphosphate, piperazine polyphosphate, melamine polyphosphate, ammonium amide polyphosphate, aluminum polyphosphate, etc.
The phosphate-containing flame retardant may be used alone or in combination of two or more of the above-mentioned compounds.

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

The brominated aromatic ring-containing aromatic compound may be a bromine compound polymer.Specific examples of the brominated aromatic ring-containing aromatic compound include brominated polycarbonates such as polycarbonate oligomers produced from brominated bisphenol A as a raw material, copolymers of the polycarbonate oligomers and bisphenol A, and diepoxy compounds produced by the reaction of brominated bisphenol A and epichlorohydrin.Further examples include brominated epoxy compounds such as monoepoxy compounds obtained by the reaction of brominated phenols with epichlorohydrin, poly(brominated benzyl acrylate), brominated phenol condensates of brominated polyphenylene ether, brominated bisphenol A, and cyanuric chloride, brominated (polystyrene), poly(brominated styrene), brominated polystyrenes such as crosslinked brominated polystyrene, crosslinked or non-crosslinked brominated poly(-methylstyrene), and the like.
In addition, compounds other than brominated aromatic ring-containing aromatic compounds such as hexabromocyclododecane may be used.
These bromine-containing flame retardants may be used alone or in combination of two or more.
Among the above, brominated aromatic ring-containing aromatic compounds are preferred, and among these, monomeric organic bromine compounds such as ethylenebis(pentabromophenyl) are preferred.

Chlorine-containing flame retardants include those commonly used in flame-retardant resin compositions, such as polychlorinated naphthalenes, chlorendic acid, and dodecachlorododecahydrodimethanodibenzocyclooctene, sold under the trade name "Dechlorane Plus."

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

<Boron-containing flame retardants>
The boron-containing flame retardant used in the present invention includes borax, boron oxide, boric acid, borate, etc. 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. Specific examples include alkali metal borates such as lithium borate, sodium borate, potassium borate, and cesium borate, alkaline earth metal borates such as magnesium borate, calcium borate, and barium borate, zirconium borate, zinc borate, aluminum borate, and ammonium borate.
The boron-containing flame retardants may be used alone or in combination of two or more.
The boron-containing flame retardant used in the present invention is preferably a borate, more preferably zinc borate.

<Metal hydroxide>
Examples of the 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, etc. The metal hydroxides may be used alone or in combination of two or more kinds.

The content of the solid flame retardant in the polyol composition may be appropriately adjusted so that the filler ratio falls within the above range, but is preferably 5 to 100 parts by mass, more preferably 10 to 50 parts by mass, relative to 100 parts by mass of the polyol compound.
When the content of the solid flame retardant is equal to or more than the lower limit, the shrinkage rate of the obtained polyurethane foam can be reduced and the flame retardancy can be improved. When the content of the solid flame retardant is equal to or less than the upper limit, the dischargeability of the polyol composition can be improved.

<Inorganic filler>
Examples of inorganic fillers include silica, diatomaceous earth, alumina, titanium oxide, calcium oxide, magnesium oxide, iron oxide, tin oxide, antimony oxide, ferrites, basic magnesium carbonate, calcium carbonate, magnesium carbonate, zinc carbonate, barium carbonate, dawsonite, hydrotalcite, calcium sulfate, barium sulfate, gypsum fiber, calcium silicate, talc, clay, mica, wollastonite, montmorillonite, bentonite, activated clay, sepiolite, imogolite, sericite, glass fiber, glass beads, silica palan, aluminum nitride, boron nitride, silicon nitride, carbon black, graphite, carbon fiber, carbon palan, charcoal powder, various metal powders, potassium titanate, magnesium sulfate, lead zirconate titanate, aluminum borate, molybdenum sulfide, silicon carbide, stainless steel fiber, various magnetic powders, slag fiber, fly ash, silica alumina fiber, alumina fiber, silica fiber, and zirconia fiber. These inorganic fillers may be used alone or in combination of two or more.
The content of the inorganic filler in the polyol composition may be appropriately adjusted so that the filler ratio falls within the above range, but is preferably 5 to 150 parts by mass, and more preferably 10 to 100 parts by mass, relative to 100 parts by mass of the polyol compound.
When the content of the inorganic filler is equal to or more than the above lower limit, the shrinkage rate of the obtained polyurethane foam can be reduced.When the content of the inorganic filler is equal to or less than the above upper limit, the dischargeability of the polyol composition is improved.

[Polyol compounds]
The polyol composition of the present invention contains a polyol compound that is a raw material for polyurethane foam. Examples of the polyol compound include polylactone polyol, polycarbonate polyol, aromatic polyol, alicyclic polyol, aliphatic polyol, polyester polyol, polymer polyol, and polyether polyol. The polyol compound is usually liquid at room temperature (23° C.) and normal pressure (1 atm).

Examples of the polylactone polyol include polypropiolactone glycol, polycaprolactone glycol, and polyvalerolactone glycol.
Examples of polycarbonate polyols include polyols obtained by dealcoholization reaction 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.

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

Examples of polyester polyols include polymers obtained by dehydration condensation of polybasic acids and polyhydric alcohols, 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-mentioned 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, etc. 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, etc.
Examples of hydroxycarboxylic acids include castor oil and reaction products of castor oil and ethylene glycol.

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 polyols, and modified polyols of polyhydric alcohols or hydrogenated versions of these.

Examples of modified polyols of polyhydric alcohols include those obtained by reacting a raw material polyhydric alcohol with an alkylene oxide to modify it.
Examples of polyhydric alcohols include trihydric alcohols such as glycerin and trimethylolpropane; tetrahydric to octahydric alcohols such as pentaerythritol, sorbitol, mannitol, sorbitan, diglycerin, and dipentaerythritol; sucrose, glucose, mannose, fructose, methyl glucoside, and derivatives thereof; polyols such as phloroglucinol, cresol, pyrogallol, catechol, hydroquinone, bisphenol A, bisphenol F, bisphenol S, 1,3,6,8-tetrahydroxynaphthalene, and 1,4,5,8-tetrahydroxyanthracene; polyfunctional polyols (e.g., having 2 to 100 functional groups) such as castor oil polyol, (co)polymers of hydroxyalkyl (meth)acrylate, and polyvinyl alcohol; and condensates of phenol and formaldehyde (novolaks).

Although the method for modifying the polyhydric alcohol is not particularly limited, a method of adding an alkylene oxide (hereinafter also referred to as "AO") is preferably used. Examples of the AO include AOs 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-propylene oxide, 1,2-butylene oxide, and 1,4-butylene oxide.
Among these, from the viewpoints of properties and reactivity, PO, EO and 1,2-butylene oxide are preferred, and PO and EO are more preferred. When two or more AOs are used (for example, PO and EO), the addition method may be block addition or random addition, or a combination of these may be used.

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

As the polyol compound used in the present invention, polyester polyols and polyether polyols are preferred. Among them, aromatic polyester polyols obtained by dehydration condensation of polybasic acids having aromatic rings such as isophthalic acid (m-phthalic acid) and terephthalic acid (p-phthalic acid) with dihydric alcohols such as bisphenol A, ethylene glycol, and 1,2-propylene glycol are more preferred. Polyols having two hydroxyl groups are also preferred.

The hydroxyl value of the polyol compound is preferably 20 to 300 mgKOH/g, more preferably 30 to 250 mgKOH/g, and even more preferably 50 to 220 mgKOH/g. When the hydroxyl value of the polyol compound is equal to or less than the upper limit, the viscosity of the polyol composition is likely to decrease, which is preferable from the viewpoint of handleability, etc. On the other hand, when the hydroxyl value of the polyol compound is equal to or more than the lower limit, the crosslink density of the polyurethane foam increases, thereby increasing the strength.
The hydroxyl value of the polyol compound can be measured in accordance with JIS K 1557-1:2007.

The content of the polyol compound in the polyol composition of the present invention is preferably 10 to 80% by mass, more preferably 20 to 75% by mass, and even more preferably 25 to 70% by mass. If the content of the polyol compound is equal to or greater than the lower limit, it is preferable because it makes it easier to react the polyol with the polyisocyanate. On the other hand, if the content of the polyol compound is equal to or less than the upper limit, it is preferable from the viewpoint of handleability because the viscosity of the polyol-containing composition does not become too high.

[catalyst]
The polyol composition of the present invention contains a catalyst. As the catalyst, it is preferable to contain at least one of a trimerization catalyst and a resinification catalyst, and it is more preferable to contain both a trimerization catalyst and a resinification catalyst. A polyol foam produced using both of these catalysts is preferable because it tends to have a low shrinkage rate.

The trimerization catalyst is a catalyst that reacts isocyanate groups contained in a polyisocyanate compound to trimerize them and promote the formation of an isocyanurate ring. Examples of the trimerization catalyst include nitrogen-containing aromatic compounds such as tris(dimethylaminomethyl)phenol, 2,4-bis(dimethylaminomethyl)phenol, and 2,4,6-tris(dialkylaminoalkyl)hexahydro-S-triazine; alkali metal salts of carboxylic acids such as potassium acetate, potassium 2-ethylhexanoate, and potassium octylate; tertiary ammonium salts such as trimethylammonium salt, triethylammonium salt, and triphenylammonium salt; and quaternary ammonium salts such as tetramethylammonium salt, tetraethylammonium, tetraphenylammonium salt, and triethylmonomethylammonium salt. Examples of the ammonium salt include ammonium salts of carboxylic acids such as 2,2-dimethylpropanoic acid, and more specifically, quaternary ammonium salts of carboxylic acids.
These may be used alone or in combination of two or more.
Among these, one or more selected from alkali metal carboxylates and quaternary ammonium carboxylates are preferred, and among these, quaternary ammonium carboxylates are more preferred.

The amount of trimerization catalyst is preferably 1 to 25 parts by mass, more preferably 2 to 18 parts by mass, and even more preferably 3 to 15 parts by mass, per 100 parts by mass of polyol compound. When the amount of trimerization catalyst is equal to or greater than these lower limits, trimerization of the polyisocyanate compound occurs more easily, and the flame retardancy of the resulting polyurethane foam is improved. On the other hand, when the amount of trimerization catalyst is equal to or less than the upper limit, the reaction is easier to control.

The resinification catalyst is a catalyst that promotes the reaction between a polyol compound and a polyisocyanate compound. 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 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. Specific examples include N-methylimidazole, 1,2-dimethylimidazole, 1-ethyl-2-methylimidazole, 1-methyl-2-ethylimidazole, 1,2-diethylimidazole, and 1-isobutyl-2-methylimidazole. In addition, imidazole compounds in which the secondary amine in the imidazole ring is substituted with a cyanoethyl group may also be used.
Furthermore, 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, examples of the resinification catalyst include various tertiary amines such as pentamethyldiethylenetriamine, triethylamine, N-methylmorpholinebis(2-dimethylaminoethyl)ether, N,N,N',N",N"-pentamethyldiethylenetriamine, N,N,N'-trimethylaminoethyl-ethanolamine, bis(2-dimethylaminoethyl)ether, N,N-dimethylcyclohexylamine, diazabicycloundecene, triethylenediamine, tetramethylhexamethylenediamine, and tripropylamine.

Examples of the metal catalyst include metal salts of lead, tin, bismuth, copper, zinc, cobalt, nickel, etc., and preferably organic acid metal salts of lead, tin, bismuth, copper, zinc, cobalt, nickel, etc. More preferred are dibutyltin dilaurate, dioctyltin dilaurate, dioctyltin versatate, bismuth trioctate, bismuth tris(2-ethylhexanoate), tin dioctylate, lead dioctylate, etc., and among these, organic acid bismuth salts are even more preferred.
The resinification catalyst may be used alone or in combination of two or more. Among the above, it is preferable to use one or more selected from the group consisting of imidazole compounds and organic acid bismuth salts, and it is also preferable to use both of them.

The amount of resinification catalyst is preferably 1 to 25 parts by mass, more preferably 2 to 18 parts by mass, and even more preferably 3 to 12 parts by mass, per 100 parts by mass of polyol compound. If the amount of resinification catalyst is equal to or greater than these lower limits, urethane bonds are more easily formed and the reaction proceeds quickly. On the other hand, if the amount is equal to or less than these upper limits, the reaction rate is easier to control.

When a trimerization catalyst and a resinification catalyst are used in combination as catalysts, the amount of resinification catalyst relative to the trimerization catalyst (amount of resinification catalyst/amount of trimerization catalyst) is preferably 0.2 to 10, and more preferably 0.5 to 2, from the viewpoint of reducing the shrinkage rate of the resulting polyurethane foam.

The total amount of catalyst in the polyol composition is not particularly limited, but is preferably 2 to 40 parts by mass, more preferably 4 to 25 parts by mass, and even more preferably 5 to 20 parts by mass. If it is equal to or greater than these lower limits, the formation of urethane bonds and trimerization proceed appropriately, and flame retardancy tends to be good. If it is equal to or less than these upper limits, it becomes easier to control the urethane formation and trimerization reactions.

[Liquid flame retardant]
The polyol composition in the present invention may contain a liquid flame retardant. The liquid flame retardant is a flame retardant that is liquid at room temperature and normal pressure. A specific example of the liquid flame retardant is a phosphoric acid ester. By including the liquid flame retardant in the polyol composition, it is possible to improve the flame retardancy without substantially decreasing the discharge flow rate, the mixing property, and the like.

As the phosphate ester, monophosphate ester, condensed phosphate ester, etc. can be used. A monophosphate ester is a phosphate ester having one phosphorus atom in the molecule. There is no limitation on the monophosphate ester as long as it is liquid at room temperature and normal pressure, but examples of the monophosphate ester 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, trialkoxy phosphates such as tributoxyethyl phosphate, aromatic ring-containing phosphate esters such as tricresyl phosphate, trixylenyl phosphate, tris(isopropylphenyl)phosphate, cresyl diphenyl phosphate, and diphenyl(2-ethylhexyl)phosphate, and acidic phosphate esters such as monoisodecyl phosphate and diisodecyl phosphate.

Examples of the condensed phosphate ester include aromatic condensed phosphate esters 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 Corporation.

The liquid flame retardants may be used alone or in combination of two or more of the above. Among these, monophosphate esters are preferred from the viewpoint of making it easier to adjust the viscosity of the polyol compound to an appropriate level and from the viewpoint of improving the flame retardancy of the polyurethane foam, and halogen-containing phosphate esters such as tris(β-chloropropyl)phosphate are more preferred.

When the polyol composition contains a liquid flame retardant, the amount of the liquid flame retardant is preferably 5 to 70 parts by mass, more preferably 10 to 60 parts by mass, and even more preferably 20 to 50 parts by mass, per 100 parts by mass of the polyol compound. By making the amount of the liquid flame retardant equal to or greater than these lower limits, the effect of including the liquid flame retardant is easily achieved. Furthermore, by making the amount equal to or less than the upper limits, the foaming of the polyurethane foam is not inhibited by the liquid flame retardant.

[Foam stabilizer]
The polyol composition of the present invention may contain a foam stabilizer. The foam stabilizer improves the foamability of the polyurethane composition obtained from the polyol composition and the polyisocyanate composition.
Examples of the foam stabilizer include surfactants such as polyoxyalkylene-based foam stabilizers such as polyoxyalkylene alkyl ethers, silicone-based foam stabilizers such as organopolysiloxanes, etc. These foam stabilizers may be used alone or in combination of two or more.
The amount of the foam stabilizer is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 8 parts by mass, and even more preferably 1 to 5 parts by mass, based on 100 parts by mass of the polyol compound. When the amount of the foam stabilizer is equal to or greater than these lower limits, the polyurethane composition is easily foamed, and a homogeneous polyurethane foam is easily obtained. When the amount of the foam stabilizer is equal to or less than these upper limits, a good balance between the production cost and the obtained effect is obtained.

[water]
The polyol composition of the present invention may contain water. By containing water, the foamability when forming a polyurethane foam is improved. The blend amount of water 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, based on 100 parts by mass of the polyol compound. By setting the blend amount of water within these ranges, the polyurethane composition can be easily foamed appropriately.

[Other ingredients]
The polyol composition may contain, as necessary, additives such as phenol-based, amine-based, sulfur-based and other antioxidants, anti-settling agents, heat stabilizers, metal damage inhibitors, antistatic agents, stabilizers, crosslinking agents, lubricants, softeners, pigments, and tackifying resins, as well as tackifiers such as polybutene and petroleum resins, provided that the object of the present invention is not impaired.

[container]
The container of the present invention is a container in which the above-mentioned polyol composition is enclosed. The container is not particularly limited as long as it can discharge the polyol composition by the vapor pressure of the organic foaming agent, and is preferably an aerosol container. The aerosol container, for example, comprises a container body filled with the polyol composition and a cap part that seals the upper part of the container body, and when a button or the like provided on the cap part is pressed, a valve or the like is opened to release the internal pressure, and the polyol composition is discharged from the discharge port provided on the cap part by the vapor pressure of the organic foaming agent.
The method of sealing the polyol composition in the container is not particularly limited, but the components other than the organic foaming agent are mixed as necessary using a disper or the like, then filled into the container, the container is sealed, and then the organic foaming agent is filled in. The filling of the organic foaming agent can be performed, for example, by opening a valve provided on the cap of the container and injecting the organic foaming agent into the container.

When the polyol composition is discharged from the container, each component constituting the polyol composition is discharged in a state in which it is uniformly mixed. In order to uniformly mix each component constituting the polyol composition, it is recommended to shake the container thoroughly before discharging. The container can be shaken, for example, by holding the container by hand and shaking it up and down. The method of uniformly mixing the polyol composition is not limited to the above-mentioned method. In addition, the temperature of the container when discharging is preferably, for example, 10°C or higher and 40°C or lower. If it is 10°C or higher, the liquid temperature is high to a certain extent, so discharging is good, and if it is 40°C or lower, the container is prevented from bursting.

[Polyurethane composition]
The polyurethane composition of the present invention comprises a polyol composition and a polyisocyanate composition containing a polyisocyanate compound. That is, the above-mentioned polyol composition of the present invention is used as a polyol composition for two-component polyurethane, and is mixed with a polyisocyanate composition containing a polyisocyanate compound to be used as a polyurethane composition. The polyol composition and the polyisocyanate composition are preferably mixed in a mass ratio such that the isocyanate index falls within a predetermined range, as described below.
The polyurethane composition obtained by mixing the polyol composition and the polyisocyanate composition reacts with each other and foams due to the organic foaming agent contained in the polyol composition described above or the organic foaming agent contained in the polyisocyanate composition described below, thereby forming a polyurethane foam.

<Polyisocyanate Composition>
The polyisocyanate composition contains a polyisocyanate compound. As the polyisocyanate compound, a known polyisocyanate compound used for forming a polyurethane foam can be used. As the polyisocyanate compound, for example, an aromatic polyisocyanate, an alicyclic polyisocyanate, an aliphatic polyisocyanate, etc. can be mentioned.
Examples of aromatic polyisocyanates include phenylene diisocyanate, tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, dimethyldiphenylmethane diisocyanate, triphenylmethane triisocyanate, naphthalene diisocyanate, and polymethylene polyphenyl polyisocyanate (polymeric MDI).

Examples of the alicyclic polyisocyanate include cyclohexylene diisocyanate, methylcyclohexylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, and dimethyldicyclohexylmethane diisocyanate.
Examples of the aliphatic polyisocyanate include methylene diisocyanate, ethylene diisocyanate, propylene diisocyanate, tetramethylene diisocyanate, and hexamethylene diisocyanate.

Among these, from the viewpoints of ease of use and availability, aromatic polyisocyanates are preferred, and diphenylmethane diisocyanate, polymeric MDI, or a mixture thereof is more preferred. The polyisocyanates may be used alone or in combination of two or more kinds.

The polyisocyanate composition usually further contains an organic foaming agent. As the organic foaming agent, the above-mentioned ones can be used without any particular limitation. The organic foaming agent used in the polyisocyanate composition may be the same as or different from the organic foaming agent used in the polyol composition.
The proportion of the organic foaming agent contained in the polyisocyanate composition is preferably 5% by mass or more and less than 20% by mass, and more preferably 7% by mass or more and less than 15% by mass. By containing the organic foaming agent at 5% by mass or more, sufficient ejection force can be obtained. In addition, by containing the organic foaming agent at less than 20% by mass, the foam density obtained is not too low, and appropriate physical properties can be obtained.
Furthermore, the polyisocyanate composition may appropriately contain known additives that are blended in polyisocyanates.

<Isocyanate Index>
The isocyanate index of the polyurethane composition of the present invention is preferably 200 or more. When the isocyanate index is 200 or more, the amount of the polyisocyanate compound relative to the polyol compound becomes excessive, which makes it easier for isocyanurate bonds to be formed by the trimer of the polyisocyanate, and as a result, the flame retardancy of the polyurethane foam is improved. In order to further improve the flame retardancy, the isocyanate index is more preferably 250 or more, and even more preferably 340 or more.
The isocyanate index is preferably not more than 1000, more preferably not more than 650, and even more preferably not more than 500. When the isocyanate index is not more than these upper limit values, the resulting polyurethane foam has a good balance between flame retardancy and production costs.

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

[Mixed system]
The present invention also provides a mixing system for mixing a polyol composition and a polyisocyanate composition. As shown in Fig. 1, the mixing system 10 includes a first container 11 in which a polyol composition is enclosed, and a second container 12 in which a polyisocyanate composition is enclosed. Both of the first containers 11 and 12 are aerosol containers (spray cans).
The polyol composition sealed in the first container 11 is discharged by the vapor pressure of the organic blowing agent contained in the polyol composition. The polyisocyanate composition sealed in the second container 12 is discharged by the vapor pressure of the organic blowing agent contained in the polyisocyanate composition. In the first container 11, a part of the organic blowing agent vaporizes to form a gas phase. The same is true in the second container 12.
The polyol composition and the polyisocyanate composition discharged from the first and second containers 11, 12 are mixed while being foamed by an organic foaming agent or the like, and the polyisocyanate compound and the polyol compound react with each other to form a polyurethane foam.

The mixing system 10 may include a mixer 13. The outlets 11A and 12A of the first and second containers 11 and 12 are connected to the mixer 13 via supply lines 11B and 12B. The polyol composition and polyisocyanate composition discharged from the first and second containers 11 and 12 are supplied to the mixer 13 via supply lines 11B and 12B, respectively, and are mixed in the mixer 13. The polyol composition and polyisocyanate composition mixed in the mixer 13 may be sprayed onto the surface to be applied using a sprayer or the like.

The mixer 13 is preferably a static mixer, so-called a static mixer. A static mixer is a mixer without a driving part, and the fluids are mixed by passing through the inside of the tube. An example of a static mixer is one in which a mixer element 13B is arranged inside a tube 13A as shown in FIG. 1. The mixer element 13B may be one formed in a spiral shape or one formed with a plurality of baffles.
The static mixer may also function as an injector, in which case the mixture of the polyol composition and the polyisocyanate composition mixed inside the pipe 13A may be injected from the tip 13C of the pipe as shown in Fig. 1. Note that Fig. 1 shows an embodiment in which the polyol composition and the polyisocyanate composition discharged from the first and second containers 11 and 12 are introduced into the mixer, but a discharge gun, jig, or the like may be provided before the composition is introduced into the mixer.

As an example of an embodiment equipped with a discharge gun before being introduced into the mixer, a mixing system 20 is shown in FIG. 2. The mixing system 20 includes a two-liquid discharge device 15 having a first container 11 and a second container 12, supply lines 11B and 12B, a discharge gun 14, and a mixer 13. The first container 11 and the second container 12 are as described above, and contain a polyol composition and a polyisocyanate composition, respectively. The polyol composition and the polyisocyanate composition are sent from the first and second containers to the discharge gun 14 via supply lines 11B and 12B, respectively. The discharge gun 14 includes a lever 14A and has an ON-OFF mechanism for sending the liquid. Specifically, when the lever 14A is pulled, the polyol composition and the polyisocyanate composition are sent to the mixer 13, and when the lever 14A is released, the sending to the mixer 13 is stopped. By using the mixing system 20 equipped with the dispensing gun 14, liquid can be delivered as needed, improving workability when forming the polyurethane foam.

The polyurethane foam of the present invention is formed from the polyurethane composition described above. Since the polyurethane foam of the present invention contains the filler described above, it has a low shrinkage rate and excellent shape stability. Specifically, the shrinkage rate of the polyurethane foam is preferably less than 20%, more preferably less than 10%.
The shrinkage rate of a polyurethane foam is determined as follows. Immediately after completion of foaming (immediately after production), a polyurethane foam is cut into a 5 cm square (5 cm long, 5 cm wide, 5 cm thick) and the length of each side (length before test) is measured. Note that each side means all sides (12 sides) of the cut foam. The cut foam is then left to stand for 24 hours at a temperature of 23° C. and a relative humidity of 50%, and the length of each side (length after test) is measured. The rate of change in the length of each side [100×(length before test−length after test)/length before test] is determined, and the average rate of change in the length of each side (average rate of change of the 12 sides) is taken as the shrinkage rate.

In the present invention, the polyurethane foam formed from the polyurethane composition can be used for various purposes, but is preferably used as a thermal insulation material. The polyurethane foam has a large number of cells, which provides a thermal insulation effect.
The polyurethane foam is particularly preferably used as a thermal insulation material for vehicles or buildings, such as railroad cars, automobiles, ships, and aircraft.
In addition, in the present invention, a polyurethane foam can be formed with a simple structure using a container such as an aerosol container. In addition, since the foam can be formed using a container, it is particularly suitable for cases where the surface to be treated is relatively small. Therefore, it is preferable to use it for repair purposes, for example, by spraying it onto a portion of an existing heat-resistant material that has deteriorated or been damaged. Of course, it is not limited to such uses, and it may also be used to form a new heat-resistant material.

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

The evaluation method is as follows:

[Filler ratio]
The filler ratio in the polyol composition is calculated by the following formula (1).
Formula (1) Filler ratio (%) = (E/D) x 100
D: The weight of the aerosol container containing the polyol composition after keeping the container at 35° C. and then discharging the polyol composition from the container for 10 seconds and drying the discharged product at 40° C. for 30 minutes. E: The weight of the aggregate obtained by diluting the dried discharged product of D with acetone and subjecting it to suction filtration.

[Shrinkage rate]
The shrinkage rate of the polyurethane foam was calculated by the following method. Immediately after completion of foaming (immediately after production), the polyurethane foam was cut into a 5 cm square (5 cm long, 5 cm wide, 5 cm thick) and the length of each side (length before test) was measured. The cut foam was then left to stand for 24 hours at a temperature of 23°C and a relative humidity of 50%, and the length of each side (length after test) was measured. The rate of change in the length of each side [100 x (length before test - length after test) / length before test] was calculated, and the average of the rate of change in the length of each side was taken as the shrinkage rate. A: shrinkage rate less than 10% B: shrinkage rate 10% or more but less than 20% C: shrinkage rate 20% or more

[Discharge volume]
The aerosol container containing the polyol composition was immersed in warm water at 35° C. for 60 minutes, and then discharged for 5 seconds. The amount of discharged was calculated based on the following formula and evaluated based on the following criteria.
Discharge amount (g) = weight of aerosol container before discharge - weight of aerosol container after discharge A: Discharge amount is 15g or more B: Discharge amount is 10g or more but less than 15g C: Discharge amount is less than 10g

The components used in the examples and comparative examples are as follows. Note that the number of parts of each component shown in Table 1 indicates the number of parts as diluted product.

Polyol compound: Phthalic acid polyester polyol (manufactured by Kawasaki Chemical Industries, Ltd., product name: Maximol RLK-087, hydroxyl value = 200 mg KOH/g)

Resinification catalyst: Imidazole compound (active ingredient amount 65 to 75 mass%, diluted with ethylene glycol, manufactured by Tosoh Corporation, product name: TOYOCAT-DM70)
Trimerization catalyst: quaternary ammonium carboxylate (active ingredient amount 45 to 55 mass%, diluted with ethylene glycol) (Evonik Japan Co., Ltd., product name: DABCO TMR-7)

Filler 1: Wollastonite (Kinsei Matec Co., Ltd. Product name: SH1250)
Filler 2: Red phosphorus-based flame retardant (manufactured by Rinkagaku Kogyo Co., Ltd., product name: Nova Excel 140, metal hydroxide coating, red phosphorus content 94% by mass or more)
Filler 3: Bromine-containing flame retardant, ethylene bis(pentabromophenyl) (manufactured by Albemarle Corporation, product name: SAYTEX 8010)
Filler 4: Boron-containing flame retardant (Hayakawa Shoji "FIREBREAK ZB")
Foam stabilizer: Polyoxyalkylene foam stabilizer (manufactured by Toray Dow Corning Co., Ltd., product name SH-193)
Organic foaming agent 1: DME (dimethyl ether) Boiling point: -24°C
Organic foaming agent 2: LPG (Koike Chemical's liquefied petroleum gas)
Boiling point of propane that makes up LPG: -42°C
Boiling point of isobutane that constitutes LPG: -11.7°C
Boiling point of normal butane that constitutes LPG: -0.5°C
Boiling point of isopentane that constitutes LPG: 27.8°C
Boiling point of normal pentane that constitutes LPG: 36.1°C
The amount of each component in LPG is 30 to 40 mass % for propane, 60 to 70 mass % in total for isobutane and normal butane, and less than 1.7 mass % in total for normal pentane and isopentane.
Organic foaming agent 3: HFO-1234ze (manufactured by Honeywell, product name: Soltis GBA)
Boiling point: -19℃
Organic blowing agent 4: HFO-1233zd (manufactured by Honeywell, product name: Soltis LBA)
Boiling point: 18°C
Organic foaming agent 5: Pentane Boiling point: 36°C
Other foaming agents: Nitrogen, boiling point -195.8℃

Polyisocyanate compound: 4,4'-diphenylmethane diisocyanate (4,4'-MDI) (manufactured by Manka Chemical Japan Co., Ltd., product name: PM200)

Example 1
According to the formulation in Table 1, the components other than the foaming agent were weighed into a 1000 ml polypropylene beaker, mixed for 5 minutes at 1500 rpm using a disper, transferred to an aerosol container, sealed using a vacuum crimper, and then further filled with the foaming agent to obtain a first aerosol container with the polyol composition sealed inside. The amount of the polyol composition filled was 460 g of the polyol composition other than the foaming agent, and the foaming agent was filled so as to have the blending ratio in Table 1. Using the first aerosol container, the above-mentioned filler ratio and discharge amount were measured.
In another aerosol container, 4,4'-diphenylmethane diisocyanate (4,4'-MDI, manufactured by Manka Chemical Japan Co., Ltd., product name: PM200) was charged as a polyisocyanate compound, and then an organic blowing agent (DME) was further added to obtain a second aerosol container containing a polyisocyanate composition. In the polyisocyanate composition, the amount of the organic blowing agent was 65 g relative to 420 g of the polyisocyanate compound.
The polyol composition and the polyisocyanate composition were discharged from the first aerosol container and the second aerosol container, respectively, and mixed in a static mixer to obtain a polyurethane composition, which was then sprayed from the tip of the container onto a gypsum board to obtain a polyurethane foam. The evaluation results are shown in Table 1.

Examples 2 to 14, Comparative Examples 1 to 5
A first aerosol container and a second aerosol container were produced, and polyurethane foams were obtained, in the same manner as in Example 1, except that the composition of the polyol composition was changed as shown in Table 1. The evaluation results are shown in Table 1.

The above examples are examples in which the polyol composition of the present invention containing an organic blowing agent having a boiling point of -10°C or less was used, and it was found that the discharge amount was excellent and the shrinkage rate of the obtained polyurethane foam was small.
In contrast, Comparative Example 1 is an example in which a polyol composition containing no filler was used, and the shrinkage rate of the obtained polyurethane foam was large. Comparative Examples 2 to 4 are examples in which a polyol composition containing no organic blowing agent having a boiling point of -10°C or less was used, and the discharge amount was small. Comparative Example 5 is an example in which a polyol composition containing no catalyst was used, and no polyurethane foam was formed, making it impossible to evaluate the shrinkage rate.

REFERENCE SIGNS LIST 10 Mixing system 11 First container 12 Second container 11A, 12A Discharge port 11B, 12B Supply line 13 Mixer 13A Tube 13B Mixer element 13C Tip 14 Discharge gun 14A Lever 20 Mixing system

Claims (5)

a polyol composition comprising a polyol compound, a filler, a catalyst, and an organic blowing agent having a boiling point of −10° C. or less ;
A polyisocyanate composition comprising a polyisocyanate compound and an organic blowing agent having a boiling point of −10° C. or less,
the polyol composition is contained in a first aerosol container;
the polyisocyanate composition is contained in a second aerosol container;
A polyurethane composition having a filler ratio calculated by the following formula (1) of 5 to 80%:
Formula (1) Filler ratio (%) = (E/D) x 100
D: The weight of the polyol composition after sealing it in an aerosol container and keeping the container at 35° C. and then ejecting the polyol composition from the container for 10 seconds in a homogeneously mixed state and drying the ejected product at 40° C. for 30 minutes.
E: The weight of the aggregate obtained by diluting the dried discharged material of D with acetone and filtering the diluted material by suction. 2. The polyurethane composition according to claim 1, wherein the organic blowing agent is at least one selected from the group consisting of a hydrocarbon compound represented by formula (1), an ether compound represented by formula (2), and a fluorine-containing compound having 3 or less carbon atoms.
Formula (1): C _n H _2n+2
(In formula (1), n is an integer of 1 to 4.)
Formula (2): C _n H _2n+1 -O-C _m H _2m+1
(In formula (2), n and m are each independently 1 or 2.) 3. The polyurethane composition according to claim 1, wherein the organic blowing agent is at least one selected from the group consisting of propane, dimethyl ether, and HFO-1234ze. The polyurethane composition according to any one of claims 1 to 3 , wherein the catalyst comprises a resinification catalyst and a trimerization catalyst. 5. The polyurethane composition according to claim 1, having an isocyanate index of 200 to 1,000.

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