JP2022042289A - Spray heat insulation material for building - Google Patents

Abstract

To provide a spray heat insulation material for a building having a heat insulation property that is stable for a long time.SOLUTION: A spray heat insulation material for a building has, inside it, one or more laminar local high-density region having higher density than that of other regions.SELECTED DRAWING: None

Description

The present invention relates to a building spray insulation material.

Insulation is provided on the surface of each building member such as the ceiling, roof, and wall surface of apartment buildings such as condominiums, detached houses, and commercial buildings from the viewpoint of heat retention and prevention of dew condensation. As the heat insulating material, a foam such as a polyurethane foam is preferably used. The polyurethane foam is formed, for example, by spraying, foaming and curing a urethane resin composition containing a polyol compound and a polyisocyanate compound on the surface of each building member.

Regarding the polyurethane foam having excellent heat insulating properties, for example, Patent Document 1 describes that an active hydrogen component (A) having a total amine value of 150 to 250 mgKOH / g and a specific viscosity and an organic polyisocyanate (B) are foamed. An invention relating to a method for producing a rigid polyurethane foam to be reacted in the presence of an agent (C), a urethanization catalyst (D) and a foaming agent (E) is disclosed. It is described that the rigid polyurethane foam obtained by the production method can reduce the thermal conductivity of the foam and can provide a heat insulating material for buildings having good heat insulating performance.

Japanese Patent Application Laid-Open No. 2015-52042

However, it has been confirmed that even if the conventional heat insulating material has good heat insulating properties at the beginning of production, the heat insulating properties decrease with the passage of time. Therefore, a heat insulating material having stable heat insulating performance for a long period of time is desired.
Therefore, it is an object of the present invention to provide a sprayed heat insulating material for buildings having stable heat insulating performance for a long period of time.

As a result of diligent studies, the present inventor has found that the above-mentioned problems can be solved by a building spray insulation material having one or more local high-density regions inside, and has completed the present invention. That is, the present invention provides the following [1] to [11].
[1] A building spray insulation material having one or more layered local high-density regions having a higher density than other regions inside.
[2] The building spray heat insulating material according to the above [1], wherein at least one of the local high-density regions is formed within a range of 3 to 50 mm in the thickness direction from the surface of the heat insulating material.
[3] The ratio of the density of the local high-density region to the density of the non-local high-density region, which is another region (density of the local high-density region / density of the non-local high-density region) is 1.2 or more. The building spray insulation material according to the above [1] or [2].
[4] The building spray heat insulating material according to any one of the above [1] to [3], which is formed of a polyurethane foam.
[5] The building spray according to the above [4], wherein the polyurethane foam is formed of a urethane resin composition containing a polyol compound, a polyisocyanate compound, a flame retardant, a catalyst, and a foaming agent. Insulation material.
[6] The building spray heat insulating material according to the above [5], wherein the foaming agent contains a hydrofluoroolefin.
[7] The architectural spray heat insulating material according to the above [5] or [6], wherein the polyol compound contains a polyol having an aromatic ring.
[8] The building spray heat insulating material according to any one of [5] to [7] above, wherein the polyisocyanate compound contains a polyisocyanate having an aromatic ring.
[9] The building spray heat insulating material according to any one of [5] to [8] above, wherein the catalyst contains a quantification catalyst.
[10] The building spray heat insulating material according to any one of [5] to [9] above, wherein the catalyst contains a urethanization catalyst.
[11] The building spray heat insulating material according to any one of [5] to [10] above, wherein the urethane resin composition contains a filler.

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a building spray heat insulating material having stable heat insulating performance for a long period of time.

It is sectional drawing which shows typically one Embodiment of the heat insulating material of this invention. It is sectional drawing which shows the other embodiment of the heat insulating material of this invention schematically. It is sectional drawing which shows the other embodiment of the heat insulating material of this invention schematically.

The building spray insulation of the present invention has one or more layered locally high-density regions having a higher density than other regions inside. The sprayed heat insulating material for construction means a heat insulating material formed on the surface of a building member by using a spraying device or the like.

[Building spray insulation]
Hereinafter, the building spray insulation material of the present invention will be described with reference to the drawings. The present invention is not limited to the contents of the drawings.

FIG. 1 is a cross-sectional view schematically showing the building spray heat insulating material 10 of the present invention (hereinafter, also simply referred to as heat insulating material 10). The heat insulating material 10 is a heat insulating material having a thickness T formed on the surface 11s of the building member 11. The heat insulating material 10 is a foam having a plurality of foam cells (not shown) inside, and a heat insulating gas derived from a foaming agent is contained in the foam cells, whereby the thermal conductivity is lowered and the heat insulating performance is reduced. Can be demonstrated.

The heat insulating material 10 includes a locally high-density region 10b and a non-local high-density region 10a (another region 10a) on the front surface side and the back surface side of the local high-density region 10b, respectively.
That is, the heat insulating material 10 shown in FIG. 1 is provided with a locally high-density region 10b inside, and is formed by a non-local high-density region 10a other than that. In other words, the heat insulating material 10 is a heat insulating material having a form in which the non-local high-density region 10a, the local high-density region 10b, and the non-local high-density region 10a are arranged in layers so as to be laminated in this order.
A locally dense region is a region that is denser than the other regions. Here, the other region is a region near the thickness direction of the local high-density region, and in FIG. 1, the non-local high-density region 10a (10a1 and 10a1 and) existing on the front surface side and the back surface side of the local high-density region 10b. 10a2).

The local high-density region 10b is formed in a layered manner in a region having a thickness t inside the heat insulating material 10, and more specifically, from a distance d from the surface 10s of the heat insulating material 10 in the thickness direction to the inner side. It is formed in the entire region of t.
The presence of the local high-density region 10b can prevent the heat insulating gas in the foam cell from escaping and diffusing. In the present specification, the function of preventing the adiabatic gas from escaping and diffusing may be referred to as a gas barrier property.
Further, since the heat insulating material 10 is provided with the local high-density region 10b, the heat insulating material 10 is less likely to be deformed by an external force, and the shape stability is improved. Therefore, the heat insulating material can be used stably for a long period of time.
Since the local high-density region 10b is provided so as to cover the portion of the non-local high-density region 10a2 inside (the side closer to the building member 11), the portion of the non-local high-density region 10a2 is used. It is possible to effectively prevent the heat insulating gas from coming out. In other words, when the local high-density region 10b does not exist, the heat insulating material does not have a gas barrier property, so that the heat insulating gas in the foam cell escapes with the passage of time, and the heat conductivity of air or the like becomes higher. It is replaced by a high gas, resulting in poor insulation performance.
Further, even in the conventional manufacturing method, a locally high-density region may be formed only on the surface of the heat insulating material, but since the heat insulating material of the present invention also has a locally high-density region formed inside. The gas barrier property is improved. Further, the surface of the heat insulating material is often removed by cutting or the like, and in this case, the conventional heat insulating material loses the local high-density region on the surface. On the other hand, since the heat insulating material of the present invention has a locally high-density region inside, the gas barrier property is maintained even if the surface is cut, and the long-term heat insulating property is good.

The ratio of the density of the local high density region 10b to the density of the nonlocal high density region 10a (density of the local high density region 10b / density of the nonlocal high density region 10a) may be 1.2 or more. It is preferably 1.3 or more, and more preferably 1.3 or more. With such a density ratio, it is possible to more effectively prevent deterioration of the heat insulating performance over time.
The density of the local high-density region 10b is preferably 25 to 80 kg / m ³ , more preferably 35 to 70 kg / m ³ , and even more preferably 45 to 60 kg / m ³ .
The density of the nonlocal high density region 10a is preferably 20 to 60 kg / m ³ , more preferably 25 to 50 kg / m ³ , and even more preferably 30 to 46 kg / m ³ .

It is preferable that at least one local high-density region 10b is formed within a range of 3 to 50 mm in the thickness direction from the surface of the heat insulating material 10, and at least one is formed within a range of 5 to 45 mm. Is more preferable. In other words, in FIG. 1, d is preferably 3 to 50 mm, more preferably 5 to 45 mm. This makes it easier to maintain the heat insulating performance of the heat insulating material 10 for a long period of time.
The thickness t of the local high-density region 10b is not particularly limited, but is preferably 0.5 to 10 mm, more preferably 1 to 7 mm. When the thickness of the local high-density region 10b is at least these lower limit values, it becomes easy to maintain the heat insulating performance of the heat insulating material for a long period of time. When the thickness of the local high-density region 10b is not more than these upper limit values, the heat insulating material can be reduced in weight and can maintain flexibility.
The total thickness T of the heat insulating material 10 is not particularly limited, but is, for example, 10 to 100 mm, preferably 15 to 80 mm.

In FIG. 1, only one local high-density region 10b is formed, but the heat insulating material of the present invention is not limited to this embodiment, and a plurality of local high-density regions 10b may be formed.
For example, as shown in FIG. 2, a heat insulating material may be used in which one local high-density region 10b is formed inside and one is formed on the surface, and the other is a non-local high-density region 10a. In other words, the non-local high-density region 10a (10a2), the local high-density region 10b, the non-local high-density region 10a (10a1), and the local high-density region 10b are laminated in this order from the surface 11s side of the building member. It may be a heat insulating material having a form arranged in layers as described above.
Further, as shown in FIG. 3, two local high-density regions 10b may be formed inside the heat insulating material 10, and local high-density regions 10b may be formed on the surface thereof. Among these, the heat insulating material 10 shown in FIG. 2 or 3 is preferable in consideration of the ease of maintaining the heat insulating performance of the heat insulating material for a long period of time and the ease of manufacturing. In this case, since the local high-density region exists not only inside the heat insulating material but also on the surface, it is possible to effectively prevent the heat insulating gas in the foam cell existing in the vicinity of the surface of the heat insulating material from escaping. It is possible to prevent the deterioration of the heat insulating performance more effectively.
When a plurality of local high-density regions 10b exist, the densities of the plurality of 10b may be the same or different. Further, the densities of the plurality of nonlocal high-density regions 10a may be the same or different, but are preferably the same from the viewpoint of ease of manufacturing the heat insulating material.

The method for obtaining the heat insulating material 10 having the locally high-density region 10b is not particularly limited, and layers having different densities may be sequentially formed on the surface 11s of the building member 11. For example, a method of preparing a plurality of compositions having different foaming agent concentrations and sequentially forming layers having different densities using the plurality of compositions may be used, or a single composition (one type of composition having the same composition) may be used. A method of forming a heat insulating material on the surface 11s of the building member 11 in a plurality of times using a product) may be used, but a method of using a single composition is preferable from the viewpoint of ease of production.
For example, first, a urethane resin composition described later is prepared, and the urethane resin composition is sprayed onto the surface 11s of a building member to be foamed and cured. At that time, although it depends on the composition, the surface on which heat is easily taken away by contact with the outside air tends to be less likely to foam as compared with the inside, so that a local high-density region 10b is likely to be formed on the surface. That is, it includes a non-local high-density region 10a (10a2 in FIG. 1) formed on the surface 11s of the building member by the first spraying, and a local high-density region 10b formed on the region 10a. A polyurethane foam (first polyurethane foam) is formed. Then, the urethane resin composition is sprayed again on the surface of the first polyurethane foam to foam and cure the non-local high-density region 10a (10a1 in FIG. 1) on the local high-density region 10b. ) Is formed, and the heat insulating material 10 having a local high-density region 10b inside can be obtained. When spraying again, a local high-density layer formed on the surface of the first polyurethane foam is formed by leaving a certain time interval (for example, 1 minute or more) after forming the first polyurethane foam. Is easy to generate and is preferable.

<Polyurethane foam>
The sprayed heat insulating material for construction of the present invention is not particularly limited, but is preferably formed of a polyurethane foam from the viewpoint of excellent heat insulating properties.
The polyurethane foam is preferably formed from a urethane resin composition containing a polyol compound, a polyisocyanate compound, a flame retardant, a catalyst, and a foaming agent.

≪Polyform compound≫
The polyol compound is not particularly limited, but for example, a polyester polyol, a polyether polyol, or the like is preferably used. Above all, it is preferable to use a polyester polyol from the viewpoint of enhancing the gas barrier property and improving the flame retardancy by densifying the locally high-density region formed inside the heat insulating material.
From such a viewpoint, out of 100 parts by mass of the polyol compound, the polyester polyol is preferably 20 parts by mass or more, more preferably 50 parts by mass or more, further preferably 60 parts by mass or more, and 80 parts by mass. It is particularly preferable to use parts by mass.

(Polyester polyol)
Examples of the polyester polyol include aromatic polyester polyols and aliphatic polyester polyols which are polyester polyols having an aromatic ring. However, considering the gas barrier property and flame retardancy of the heat insulating material, the aromatic polyester polyol may be used. preferable. The aromatic polyester polyol is a condensate of an aromatic dicarboxylic acid such as o-phthalic acid (phthalic acid), m-phthalic acid (isophthalic acid), p-phthalic acid (terephthalic acid), and naphthalenedicarboxylic acid and glycol. Is preferable. Above all, from the viewpoint of enhancing the flame retardancy of the polyurethane foam, the polyester polyol is preferably a phthalic acid-based polyester polyol which is a condensate of phthalic acid and glycol, and is a condensate of p-phthalic acid and glycol. It is more preferable to contain some p-phthalic acid-based polyester polyols.
The glycol is not particularly limited, but it is preferable to use known low molecular weight aliphatic glycols as constituents of polyester polyols such as ethylene glycol, propylene glycol and diethylene glycol.

The hydroxyl value of the polyester polyol is preferably 100 to 500 mgKOH / g, more preferably 150 to 450 mgKOH / g.

(Polyether polyol)
The polyether polyol is a polyoxyalkylene polyol obtained by ring-opening addition polymerization of an alkylene oxide to an initiator having two or more active hydrogen atoms. Specific examples of the initiator include aliphatic polyhydric alcohols (eg, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 1,4-butanediol, 1,3-butanediol, 1,6-hexane). Glycols such as diols, neopentyl glycols, cyclohexylene glycols and cyclohexanedimethanol, triols such as trimethylolpropane and glycerin, tetrafunctional alcohols such as pentaerythritol, sugars such as sucroses and sorbitols), aliphatics Amines (eg, alkylenediamines such as ethylenediamine, propylenediamine, butylenediamine, hexamethylenediamine, neopentyldiamine, alkanolamines such as monoethanolamine, diethanolamine), aromatic amines (eg, aniline, tolylene diamine, xylylene diamine). , Diphenylmethanediamine, Mannig condensate, etc.).
Among these, the polyether polyol produced by using the initiator having an aromatic ring is a polyether polyol having an aromatic ring, and for example, the polyether polyol produced by using an aromatic amine as an initiator has an aromatic ring. It is a polyether polyol having. Among the polyether polyols having an aromatic ring, tolylene diamine-based polyether polyols, Mannig-based polyether polyols and the like can be preferably used.

The tolylene diamine-based polyether polyol is a tolylene diamine-based polyether polyol produced by using tolylene diamine as an initiator.
The Mannich-based polyether polyol is obtained by utilizing the Mannich reaction, and is obtained by adding an alkylene oxide to a Mannich condensate having two or more hydroxyl groups in the molecule, or such a Mannich condensate. It is a polyether polyol. More specifically, at least one of phenol and an alkyl substituted derivative thereof, a Mannich condensation obtained by a Mannich reaction of formaldehyde and alkanolamine, or at least one of ethylene oxide and propylene oxide in this compound is ring-opened addition polymerization. It is a polyether polyol obtained by making it.

The hydroxyl value of the polyether polyol is preferably 200 to 2000 mgKOH / g, more preferably 300 to 1000 mgKOH / g. The hydroxyl value is a value measured according to JIS K1557-1: 2007.

From the viewpoint of densifying the locally high-density region formed inside the heat insulating material of the present invention and enhancing the gas barrier property, the polyol compound preferably contains a polyol having an aromatic ring.
Examples of the polyol having an aromatic ring include the above-mentioned polyether polyol having an aromatic ring, a polyester polyol having an aromatic ring, and the like. A polyester polyol having an aromatic ring is preferable from the viewpoint of improving the above.
In 100 parts by mass of the polyol compound, the content of the polyol having an aromatic ring is preferably 50 parts by mass or more, more preferably 60 parts by mass or more, further preferably 70 parts by mass or more, and 80 parts by mass. It is particularly preferable that the amount is more than one part.

≪Liquid flame retardant≫
The urethane resin composition in the present invention preferably contains a flame retardant, and more preferably contains a liquid flame retardant. By containing the liquid flame retardant, the flame retardancy of the heat insulating material composed of the polyurethane foam is improved, and the viscosity of the polyol composition can be appropriately controlled even when the filler described later is used. Here, the liquid flame retardant is a flame retardant that is liquid at 23 ° C.
Examples of the liquid flame retardant include phosphoric acid ester-based flame retardants such as monophosphate ester and condensed phosphoric acid ester.
The monophosphate ester is not particularly limited, and examples thereof include trimethyl phosphate, triethyl phosphate, tricresyl phosphate, cresyldiphenyl phosphate, and tris (β-chloropropyl) phosphate.
The condensed phosphoric acid ester is not particularly limited, and is, for example, resorcinol polyphenyl phosphate (trade name CR-733S), bisphenol A polycredyl phosphate (trade name CR-741), and aromatic condensed phosphoric acid ester (trade name CR747). ) And so on.
The content of the liquid flame retardant is preferably 10 to 100 parts by mass, more preferably 20 to 80 parts by mass, and further preferably 30 to 70 parts by mass with respect to 100 parts by mass of the polyol compound. When the content of the liquid flame retardant is at least these lower limit values, the flame retardancy of the heat insulating material made of polyurethane foam is likely to be improved. When the content of the liquid flame retardant is not more than these upper limit values, foaming is not hindered, and thus it becomes easy to manufacture a heat insulating material made of polyurethane foam.

≪Filler≫
The urethane resin composition of the present invention preferably contains a filler. The filler is contained as a solid component in the urethane resin composition, and is a component generally present as a granular or powdery component in the urethane resin composition. By containing the filler, various physical properties of the heat insulating material such as mechanical strength and flame retardancy can be improved depending on the type of the filler. In general, when the urethane resin composition contains a filler, the heat insulating property of the heat insulating material tends to decrease with time. However, since the heat insulating material of the present invention has a local high-density region, the filler is used. Even in some cases, the heat insulating property is likely to be maintained for a long period of time.
The filler may be a component that is solid at room temperature (23 ° C.) and normal pressure (1 atm) and does not dissolve in the urethane resin composition.
As the filler, it is preferable to use a solid flame retardant. Examples of solid flame retardants include boron-based flame retardants, brominated flame retardants, phosphate-containing flame retardants, antimony-containing flame retardants, phosphinic acid-based flame retardants, metal hydroxide-based flame retardants, red phosphorus, and needle-like fillers. Is preferable.

(Boron flame retardant)
Specific examples of the boron-based flame retardant include alkali metal borate salts such as lithium borate, sodium borate, potassium borate, and cesium borate, and boric acid such as magnesium borate, calcium borate, and barium borate. Examples thereof include alkaline earth metal salts, zirconium borate, zinc borate, aluminum borate, and ammonium borate. Of these, zinc borate is preferable.

(Brominated flame retardant)
The brominated flame retardant is not particularly limited as long as it is a compound containing bromine in its molecular structure, and examples thereof include aromatic brominated compounds.
Specific examples of the aromatic brominated compound include, for example, hexabromobenzene, pentabromotoluene, hexabromobiphenyl, decabromobiphenyl, hexabromocyclodecane, decabromodiphenyl ether, octabromodiphenyl ether, hexabromodiphenyl ether, and bis. (Pentabromophenoxy) Monomer-based organic bromine compounds such as ethane, ethylenebis (pentabromophenyl), ethylenebis (tetrabromophthalimide), tetrabromobisphenol A, polycarbonate oligomers produced from brominated bisphenol A, the above. Bromine such as brominated polycarbonate such as a copolymer of polycarbonate oligomer and bisphenol A, diepoxy compound produced by reaction between brominated bisphenol A and epichlorohydrin, and bromine such as monoepoxy compound obtained by reaction between brominated phenols and epichlorohydrin. Epoxy compounds, poly (brominated benzyl acrylate), brominated polyphenylene ether, brominated bisphenol A, condensates of cyanur chloride and brominated phenol, brominated (polystyrene), poly (brominated styrene), crosslinked brominated polystyrene, etc. Examples thereof include halogenated bromine compound polymers such as brominated polystyrene, cross-linked or non-cross-linked brominated poly (α-methylstyrene).
Among these, ethylene bis (pentabromophenyl), ethylene bis (tetrabromophthalimide), hexabromobenzene and the like are preferable.

(Phosphate-containing flame retardant)
Examples of the phosphate-containing flame retardant include phosphoric acid and metals of the Group IA to Group IVB of the Periodic Table.
Phosphates consisting of salts with at least one metal or compound selected from ammonia, aliphatic amines and aromatic amines can be mentioned.
The phosphoric acid is not particularly limited, and examples thereof include various phosphoric acids such as monophosphoric acid, pyrophosphoric acid, and polyphosphoric acid.
Examples of the metals of Group IA to Group IVB of the Periodic Table include lithium, sodium, calcium, barium, iron (II), iron (III), and aluminum. Examples of the aliphatic amine include methylamine, ethylamine, diethylamine, triethylamine, ethylenediamine, piperazine and the like. Further, examples of the aromatic amine include pyridine, triazine, melamine and the like.
The above-mentioned phosphate-containing flame retardant may be subjected to a known water resistance improving treatment such as a silane coupling agent treatment or a coating with a melamine resin.

Specific examples of the phosphate-containing flame retardant include monophosphate, pyrophosphate, polyphosphate and the like.
The monophosphate is not particularly limited, and for example, ammonium salts such as ammonium phosphate, ammonium dihydrogen phosphate, and diammonium hydrogen phosphate, monosodium phosphate, and the like.
Sodium salts such as disodium phosphate, trisodium phosphate, monosodium phosphite, dissodium phosphite, sodium hypophosphite, monopotassium phosphate, dipotassium phosphate, tripotassium phosphate, phosphite Potassium salts such as monopotassium, dipotassium phosphite, potassium hypophosphite, monolithium phosphate, dilithium phosphate, trilithium phosphate, monolithium phosphite, dilithium phosphite, hypophosphite Lithium salt such as lithium, barium dihydrogen phosphate,
Barium salts such as barium hydrogen phosphate, tribarium phosphate, barium hypophosphite, magnesium monohydrogen phosphate, magnesium hydrogen phosphate, trimagnesium phosphate, magnesium salts such as magnesium hypophosphite, dihydrogen phosphate Examples thereof include calcium salts such as calcium, calcium hydrogen phosphate, tricalcium phosphate and calcium hypophosphite, and zinc salts such as zinc phosphate, zinc phosphite and zinc hypophosphite.

The polyphosphate is not particularly limited, and examples thereof include ammonium polyphosphate, piperazine polyphosphate, melamine polyphosphate, ammonium polyphosphate amide, and aluminum polyphosphate.
The phosphate-containing flame retardant may be used alone or in combination of two or more.

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

(Phosphinic acid flame retardant)
Examples of the phosphinic acid-based flame retardant include phosphinic acid, dimethylphosphinic acid, methylethylphosphinic acid, methylpropylphosphinic acid, diethylphosphinic acid, dioctylphosphinic acid, phenylphosphinic acid, diethylphenylphosphinic acid, diphenylphosphinic acid, and bis ( 4-methoxyphenyl) phosphinic acid and the like can be mentioned.

(Metal hydroxide flame retardant)
Examples of the metal hydroxide-based flame retardant include magnesium hydroxide, calcium hydroxide, aluminum hydroxide, iron hydroxide, nickel hydroxide, zirconium hydroxide, titanium hydroxide, zinc hydroxide, copper hydroxide, and hydroxide. Examples include vanadium and tin hydroxide. The metal hydroxide-based flame retardant may be used alone or in combination of two or more.

(Red phosphorus)
The red phosphorus may be composed of a simple substance of red phosphorus, or may be a mixture or a coating of red phosphorus with a resin, a metal hydroxide, a metal oxide or the like.

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

Further, as the filler, an inorganic filler other than the above-mentioned flame retardant may be blended. As inorganic fillers, alumina, titanium oxide, calcium oxide, magnesium oxide, iron oxide, tin oxide, ferrites, basic magnesium carbonate, calcium carbonate, magnesium carbonate, zinc carbonate, barium carbonate, dosonite, hydrotalcite, calcium sulfate , Barium sulfate, calcium silicate, talc, clay, mica, montmorillonite, bentonite,
Active white clay, imogolite, sericite, glass beads, silica balun, aluminum nitride, boron nitride, silicon nitride, graphite, carbon balun, charcoal powder, various metal powders, magnesium sulfate, lead zirconate titanate, molybdenum sulfide, silicon carbide, various Magnetic powder, fly ash, etc. can be used as appropriate. The inorganic filler may be used alone or in combination of two or more.

The content of the filler in the urethane resin composition is preferably 5 to 100 parts by mass, more preferably 10 to 90 parts by mass, and 15 to 80 parts by mass with respect to 100 parts by mass of the polyol compound. Is more preferable.

The urethane resin composition may not contain the above-mentioned filler. When the filler is not contained, a precipitate is unlikely to be generated during storage, the handling property is excellent, and the wear of the equipment used at the time of use can be suppressed.

≪Catalyst≫
Examples of the catalyst include a urethanization catalyst and a trimerization catalyst. Above all, from the viewpoint of densifying the local high-density region and improving the gas barrier property, it is preferable that the catalyst contains a trimerization catalyst. A quantification catalyst is a catalyst that promotes quantification to form an isocyanate bond.

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

The content of the trimerization catalyst is preferably 1 to 30 parts by mass, and more preferably 3 to 20 parts by mass with respect to 100 parts by mass of the polyol compound.

Further, in the present invention, the catalyst preferably contains a urethanization catalyst, and more preferably contains both the above-mentioned trimerization catalyst and urethanization catalyst.
The urethanization catalyst is a catalyst that promotes the reaction between the polyol compound and the polyisocyanate compound. Specific examples thereof include amino compounds, tin compounds, bismuth compounds, and acetylacetone metal salts.

Examples of the amino compound include pentamethyldiethylenetriamine, triethylamine, N-methylmorpholinbis (2-dimethylaminoethyl) ether, bis (2-dimethylaminoethyl) ether, N, N, N', N ", N". -Pentamethyldiethylenetriamine, N, N, N'-trimethylaminoethyl-ethanolamine, bis (2-dimethylaminoethyl) ether, N-methyl-N', N'-dimethylaminoethylpiperazine, second in the imidazole ring An imidazole compound in which a primary amine functional group is substituted with a cyanoethyl group, N, N-dimethylcyclohexylamine, diazabicycloundecene, triethylenediamine, tetramethylethylenediamine, tetramethylhexamethylenediamine, 1-methylimidazole, 1,2-dimethyl. Examples thereof include imidazole, 1-isobutyl-2-methylimidazole, trimethylaminoethylpiperazine, tripropylamine and the like. Further, acid blocked products of these amino compounds can also be used. Here, examples of the acid-blocked compound of the amino compound include those obtained by blocking the amino compound with a carboxylic acid such as formic acid, acetic acid, propionic acid, oxalic acid, succinic acid, adipic acid, sebacic acid, and azelaic acid. Be done.

Examples of the tin compound include stannous octylate, dibutyl tin diacetate, and dibutyl tin dilaurate. Examples of the bismuth compound include bismuth neodecanoate and bismuth octylate.
Examples of the acetylacetone metal salt include acetylacetone aluminum, acetylacetone iron, acetylacetone copper, acetylacetone zinc, acetylacetone beryllium, acetylacetone chromium, acetylacetone indium, acetylacetone manganese, acetylacetone molybdenum, acetylacetone titanium, acetylacetone cobalt, acetylacetone vanadium, acetylacetone zirconium and the like. ..
The urethane resin curing catalyst may be used alone or in combination of two or more.

The content of the urethanization catalyst in the urethane resin composition is not particularly limited, but is preferably in the range of 1 to 30 parts by mass, preferably in the range of 3 to 20 parts by mass with respect to 100 parts by mass of the polyol compound. Is more preferable.

The total amount of the catalyst is preferably 2 to 60 parts by mass, more preferably 6 to 40 parts by mass with respect to 100 parts by mass of the polyol compound.

≪Polyisocyanate compound≫
The polyisocyanate compound is a compound having two or more isocyanate groups. The polyisocyanate compound may be a polyisocyanate having an aromatic ring or a polyisocyanate having no aromatic ring, but from the viewpoint of further densifying the local high-density region and enhancing the gas barrier property. , It is preferable to contain a polyisocyanate having an aromatic ring. Among polyisocyanates having an aromatic ring, liquid diphenylmethane diisocyanate (MDI) is used because of its ease of handling, quick reaction, excellent physical characteristics of the obtained polyurethane foam, and low cost. Is preferable. Examples of the liquid MDI include Crude MDI (also referred to as Polymeric MDI). Specific commercial products of liquid MDI include "44V-10", "44V-20" (manufactured by Sumika Cobestrourethane Co., Ltd.), "Millionate MR-200" (Nippon Polyurethane Industry Co., Ltd.) and the like. Further, MDI containing ureton imine (for example, "Millionate MTL" as a commercially available product: manufactured by Nippon Polyurethane Industry Co., Ltd.) may be used. Further, a compound in which a part of the isocyanate active group in the isopolycyanate compound is reacted with the hydroxyl group-containing compound to enhance the affinity with the polyol in advance may be used. In addition to the liquid MDI, another polyisocyanate compound may be used in combination, and as the polyisocyanate compound to be used in combination, a polyisocyanate compound known in the technical field of polyurethane can be used without limitation.

The isocyanate index of the urethane resin composition is preferably 150 or more, more preferably 200 or more, still more preferably 250 or more, from the viewpoint of densifying the local high-density region.
The isocyanate index of the urethane resin composition is preferably 700 or less, more preferably 600 or less, from the viewpoint of appropriately maintaining the reactivity between the polyol compound and the polyisocyanate compound.
The isocyanate index (INDEX) is calculated by the following method.

INDEX = equivalent of isocyanate ÷ (equivalent of polyol + equivalent of water) x 100
here,
Equivalent number of isocyanate = number of copies of polyisocyanate used x NCO content (%) x 100 / NCO molecular weight Equivalent number of polyol = OHV x number of copies of polyol ÷ molecular weight of KOH, OHV is the hydroxyl value of the polyol (mgKOH / g),
Equivalent number of water = number of copies of water used x number of OH groups of water / molecular weight of water. In the above formula, the unit of the number of copies used is the weight (g), the molecular weight of the NCO group is 42, and the NCO content is the ratio of the NCO group in the polyisocyanate compound expressed in mass%. For convenience of unit conversion, the molecular weight of KOH is 56100, the molecular weight of water is 18, and the number of OH groups of water is 2.

≪Blowing agent≫
Specific examples of the foaming agent include water, low boiling hydrocarbons, chlorinated aliphatic hydrocarbon compounds, fluorine compounds, hydrochlorofluorocarbon compounds, hydrofluorocarbons, ether compounds, hydrofluoroolefins and the like. Further, examples of the foaming agent include organic physical foaming agents such as a mixture of these compounds, and inorganic physical foaming agents such as nitrogen gas, oxygen gas, argon gas and carbon dioxide gas.
Examples of the low boiling point hydrocarbon include propane, butane, pentane, hexane, heptane, cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane and the like.
Examples of the chlorinated aliphatic hydrocarbon compound include dichloroethane, propyl chloride, isopropyl chloride, butyl chloride, isobutyl chloride, pentyl chloride, isopentyl chloride and the like.
Examples of the fluorine compound include CHF ₃ , CH ₂ F ₂ , CH ₃ F and the like.
Examples of the hydrochlorofluorocarbon compound include trichlormonofluoromethane, trichlorotrifluoroethane, dichloromonofluoroethane (for example, HCFC141b (1,1-dichloro-1-fluoroethane), HCFC22 (chlorodifluoromethane), HCFC142b (). 1-chloro-1,1-difluoroethane)) and the like can be mentioned.
Examples of the hydrofluorocarbon include HFC-245fa (1,1,1,3,3-pentafluoropropane) and HFC-365mfc (1,1,1,3,3-pentafluorobutane).
Examples of the ether compound include diisopropyl ether and the like.
Examples of the hydrofluoroolefin include HFO-1233zd (E) (trans-1-chloro-3,3,3-trifluoropropene) and HFO-1234yf (2,3,3,3-tetrafluoro-1-. Propene), HFO-1336mzz (Z) (cis-1,1,1,4,4,4-hexafluorobut-2-en), HFO-1224yd (Z) and the like.

Among the above, the foaming agent preferably contains a hydrofluoroolefin. By using a hydrofluoroolefin, it becomes easy to obtain a foam having good heat insulating properties. Further, it is preferable to use water or the like as the foaming agent, and it is more preferable to use hydrofluoroolefin and water in combination.
The content of the foaming agent is preferably 5 to 70 parts by mass, and more preferably 10 to 60 parts by mass with respect to 100 parts by mass of the polyol compound from the viewpoint of adjusting the density of the foam to a desired range. , More preferably 20 to 50 parts by mass.

The amount of the hydrofluoroolefin used as the foaming agent is preferably 5 to 60 parts by mass, more preferably 5 to 60 parts by mass, based on 100 parts by mass of the polyol compound from the viewpoint of heat insulating properties of the polyurethane foam constituting the heat insulating material. It is 10 to 55 parts by mass, more preferably 20 to 50 parts by mass.
As the water used as the foaming agent, for example, ion-exchanged water, distilled water and the like can be appropriately used. The amount of water with respect to 100 parts by mass of the polyol compound is preferably 0.1 to 10 parts by mass, more preferably 0.2 to 5 parts by mass, from the viewpoint of adjusting the density of the polyurethane foam to a desired range. , More preferably 0.3 to 3 parts by mass.

≪Defoaming agent≫
The urethane resin composition may contain a defoaming agent. As the defoaming agent, a compound having a polar portion and a non-polar portion in the molecule and having a surface-active effect can be preferably used. Examples of the defoaming agent include silicone defoaming agents such as organopolysiloxane. Further, the silicone foam stabilizer may contain a graft copolymer of polydimethylsiloxane and polyethylene glycol.
The content of the foam stabilizer is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 8 parts by mass, and 0.5 to 5 parts by mass with respect to 100 parts by mass of the polyol compound. It is more preferably a part. The foam stabilizer may be used alone or in combination of two or more.

In addition to the above-mentioned components, the urethane resin composition may contain, for example, phenol-based, amine-based, sulfur-based antioxidants, heat stabilizers, and other additives, as long as the effects of the present invention are not impaired. It can contain light stabilizers, metal damage inhibitors, antistatic agents, cross-linking agents, lubricants, softeners, pigments, dyes, tackifier resins and the like.

The urethane resin composition of the present invention may be a one-component type, but its viscosity changes with time because the polyol compound and the polyisocyanate compound react and cure. Therefore, before using the composition, the composition is divided into two or more to prevent the composition from reacting and curing. Then, when using the composition, it is preferable to mix the composition divided into two or more.
When the urethane resin composition is divided into two or more, the curing does not start with each component of the urethane resin composition divided into two or more alone, and the curing reaction occurs after each component of the urethane resin composition is mixed. The components may be divided so that they start. Usually, the urethane resin composition is divided into a polyol composition containing a polyol compound and a polyisocyanate composition containing a polyisocyanate compound.

The above-mentioned foaming agent, catalyst, liquid flame retardant, and if necessary, a filler and a foam stabilizer may be contained in the polyol composition or may be contained in the polyisocyanate composition. , The polyol composition and the polyisocyanate composition may be provided separately, but are preferably contained in the polyol composition.

[Manufacturing method of spray insulation for construction]
The method for producing the sprayed heat insulating material for construction of the present invention is not particularly limited as long as it can form a locally high-density region inside the heat insulating material, but the above-mentioned urethane resin composition is used on the surface of a building member. On the other hand, it is preferable to apply the method of spraying in a plurality of times. Further, in consideration of ease of manufacture and the like, it is more preferable to apply a method of spraying the urethane resin composition having the same composition on the surface of the building member in 2 to 5 times except for the bottom spray. For example, as a method of spraying in two steps, specifically, first, the urethane resin composition is sprayed on the surface of the building member, and foamed and cured to form a first polyurethane foam. When the first polyurethane foam is formed, the surface side is deprived of the heat of reaction from the outside air, so that foaming is less likely to proceed than the inside. Therefore, a local high-density region is formed on the surface of the polyurethane foam. Is formed. Then, after a certain period of time is allowed to cure the surface, the urethane resin composition is sprayed again on the surface of the first polyurethane foam having a local high-density region on the surface, and the surface is foamed and cured. 2 Polyurethane foams are laminated. Similarly, a local high-density region is formed on the surface of the second polyurethane foam. In this way, the heat insulating material of the present invention having a locally high-density region inside can be manufactured.

Further, as described above, when the polyol compound or polyisocyanate compound in the urethane resin composition has an aromatic ring, or when a trimerization catalyst is used as a catalyst, the local high-density region is further densified. The gas barrier property can be improved, and the heat insulating property can be kept good for a long period of time.
The method for forming the heat insulating material of the present invention is not limited to the above method, and for example, compositions having different compositions using a plurality of urethane resin compositions in which the types and contents of the foaming agent and the catalyst are changed are used. May be adopted, in which polyurethane foams having different densities are sequentially laminated to form a heat insulating material by sequentially spraying and foaming and curing. Further, the local high-density layer is not limited to polyurethane and may be formed with a coating agent such as an inorganic paint.

The urethane resin composition can be sprayed using a spraying device (for example, GRACO: A-25) and a spray gun (for example, GRACO: AP gun). The spraying can be carried out by adjusting the temperature of the polyol composition and the polyisocyanate composition in separate containers in a spraying device, colliding and mixing the two with the tip of a spray gun, and mistizing the mixed solution by air pressure. Spraying devices and spray guns are known, and commercially available products can be used. In addition, general urethane foam spraying conditions can be applied to the undiluted solution temperature setting, pressure, etc.

As described above, the heat insulating material of the present invention can be formed on the surface of the building member. Examples of building members include walls, roofing boards, pillars, floors, deck plates, skeletons such as pipes, and various cables used in buildings. Examples of materials constituting building members such as skeletons include concrete, metal, wood, reinforced fiber concrete, lightweight bubble concrete, mortar, precast concrete, gypsum board, calcium silicate, calcium carbonate, and ceramics.

The present invention will be described in more detail by way of examples, but the present invention is not limited to these examples.

The details of each component used in each Example and Comparative Example are as follows.
<polyol compound>
(I) Polyester polyol having an aromatic ring / p-phthalic acid-based polyester polyol (Maximole RLK-087 manufactured by Kawasaki Kasei Chemicals, hydroxyl value 200 mgKOH / g)
(Ii) Polyether polyol having an aromatic ring-Mannich-based polyether polyol (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., product name: DK3776, hydroxyl value = 350 mgKOH / g)
(Iii) Polyether polyol having no aromatic ring / ethylenediamine-based polyether polyol (manufactured by AGC Inc., product name: Exenol 750ED, hydroxyl value = 760 mgKOH / g)

<Catalyst>
(I) Trimerization catalyst: Carboxylic acid quaternary ammonium salt (DABCO TMR-7 manufactured by Evonik Japan Co., Ltd.), concentration 45-55% by mass
(Ii) Triquantization catalyst: 2-ethylhexanoic acid potassium salt (manufactured by Air Products and Chemicals, product name: DABCO K-15), concentration 70 to 80% by mass
(Iii) Urethane catalyst: 1,2-dimethylimidazole (manufactured by Kao Corporation, product name: Kaorizer No. 390) Concentration 65-75% by mass
(Iv) Urethane catalyst: Bismuth 2-ethylhexanoate (manufactured by Nitto Kasei Co., Ltd., product name: Bi28), concentration 81-90% by mass

<Foam control agent>
-Silicone-based defoaming agent (manufactured by Toray Dow Corning, product name: SH-193)

<Flame retardant>
-Liquid flame retardant Phosphoric acid ester flame retardant Tris (β-chloropropyl) phosphate (manufactured by Daihachi Chemical Co., Ltd., product name: TMCPP)
-Filler-Wollastonite (SiO2-CaO) (manufactured by Kinsei Matek, product name: SH-1250)

<Effervescent agent>
-Water-HFO-1233zd <hydrofluoroolefin> (manufactured by Honeywell, product name: Solstice LBA)

<Polyisocyanate compound>
・ MDI (manufactured by Sumika Cobestro Urethane Co., Ltd., product name: 44V-20)

[Thermal conductivity]
For the heat insulating materials produced in each Example / Comparative Example, the thermal conductivity immediately after production (initial thermal conductivity) and the thermal conductivity after a certain period of time has passed after production (thermal conductivity over time) are determined by JIS A 9526. Measured according to. However, as shown below, the layer thickness (thickness of the heat insulating material) at the time of preparing the test piece was less than 60 mm.
The initial thermal conductivity was applied to a heat insulating material (length 200 mm, width 200 mm, thickness 25 mm) cut out from gypsum board.
The thermal conductivity over time was measured after the sample for which the initial thermal conductivity was measured was stored at 23 ° C. for 7 days by protecting 5 surfaces other than the surface with aluminum tape.
The thermal conductivity was measured by the heat flow meter method using "HC-074" manufactured by Hidehiro in the thickness direction of the sample.

(Stability of heat insulation performance)
When the difference between the thermal conductivity over time and the initial thermal conductivity (heat conductivity over time-initial thermal conductivity) is 0.003 W / m · K or less, "○", 0.003 W / m · K The case of exceeding was evaluated as "x".

[density]
For the density of the local high-density region and the density of the non-local high-density region, cut out the heat insulating material into a size of 100 mm in length × 100 mm in width, and observe the cross section of the heat insulating material to determine the thickness of the portion of the local high-density region. And the part of the non-local high density region was cut out and measured.
When cutting out a locally high-density region, a part of the non-local high-density region is inevitably included. Therefore, strictly speaking, the density of the local high-density region is slightly higher than the value shown in the table.

[Shape stability]
The shape stability of the heat insulating materials produced in each Example / Comparative Example was evaluated as follows.
When the heat insulating material (length 200 mm, width 100 mm, thickness 25 mm) cut out from gypsum board has an initial length L1 in the width direction and a length L2 in the width direction after storage at room temperature (23 ° C.) for 14 days. When L2 / L1 was more than 0.95, it was evaluated as “◯”, and when it was 0.95 or less, it was evaluated as “x”. As for the length L2 in the width direction, if the length in the width direction is not uniform, the minimum length in the width direction is L2.

[Examples 1 to 4]
According to the formulation shown in Table 1, the compounding amounts were adjusted so that the polyol composition consisting of the polyol compound, the trimerization catalyst, the urethanization catalyst, the foam stabilizer, the flame retardant, and the foaming agent, and the isocyanate index had the values shown in Table 1. A polyisocyanate composition composed of MDI was prepared, and each composition was introduced into a spraying device (manufactured by GRACO: A-25). The temperature is adjusted in the device, and a urethane resin composition consisting of a mixed solution of the polyol composition and the polyisocyanate composition is placed on a plaster board having a thickness of 12.5 mm using a spray gun (GRACO: AP gun). A first polyurethane foam having a thickness of 17 mm was formed by spraying on. Then, the urethane resin composition composed of the mixed solution of the polyol composition and the polyisocyanate composition of the formulation shown in Table 1 is sprayed on the surface of the first polyurethane foam again in the same manner to obtain the second polyurethane foam having a thickness of 20 mm. Was formed to form a heat insulating material on the plasterboard. The heat insulating material had a total thickness of 37 mm, and a position 20 mm in the thickness direction from the surface and a local high-density region were formed on the surface. The thickness of each of the local high-density regions was about 2 mm.

[Comparative Examples 1 and 2]
According to the formulation shown in Table 1, the compounding amounts were adjusted so that the polyol composition consisting of the polyol compound, the trimerization catalyst, the urethanization catalyst, the foam stabilizer, the flame retardant, and the foaming agent, and the isocyanate index had the values shown in Table 1. A polyisocyanate composition composed of MDI was prepared, and each composition was introduced into a spraying device (manufactured by GRACO: A-25). The temperature is adjusted in the device, and a urethane resin composition consisting of a mixed solution of the polyol composition and the polyisocyanate composition is placed on a plaster board having a thickness of 12.5 mm using a spray gun (GRACO: AP gun). By spraying on, a heat insulating material made of polyurethane foam having a thickness of 33 mm was formed. No local high density region was found inside the insulation.

なお、各触媒の質量部は製品としての質量部である。

The mass part of each catalyst is the mass part as a product.

It was found that the heat insulating material of each example in which a locally high-density region was formed had a small change in thermal conductivity with time, and the heat insulating performance could be maintained for a long period of time.
On the other hand, it was found that the heat insulating material of each comparative example in which the local high-density region was not formed inside had a large change in thermal conductivity with time, and the heat insulating performance could not be maintained for a long period of time.
For this reason, even in the actual sprayed heat insulating material, the gas barrier layer of the heat insulating material can be increased by providing a local high-density region inside, and the thermal conductivity performance can be maintained for a long period of time, and the surface layer can be maintained by cutting or the like. It is considered possible to maintain the thermal conductivity performance even when the local high-density region is removed.

10 Spray insulation for construction 10s Surface of insulation 10a Non-local high density area 10b Local high density area 11 Building member 11s Surface of building member

Claims (11)

Architectural spray insulation with one or more layered, locally dense areas that are denser than the other areas inside. The architectural spray heat insulating material according to claim 1, wherein at least one of the local high-density regions is formed within a range of 3 to 50 mm in the thickness direction from the surface of the heat insulating material. The ratio of the density of the local high density region to the density of the nonlocal high density region (density of the local high density region / density of the nonlocal high density region) of the other region is 1.2 or more. The building spray insulation material according to claim 1 or 2. The architectural spray insulation material according to any one of claims 1 to 3, which is formed of a polyurethane foam. The building spray heat insulating material according to claim 4, wherein the polyurethane foam is formed of a urethane resin composition containing a polyol compound, a polyisocyanate compound, a flame retardant, a catalyst, and a foaming agent. The building spray insulation material according to claim 5, wherein the foaming agent contains a hydrofluoroolefin. The architectural spray insulation material according to claim 5 or 6, wherein the polyol compound contains a polyol having an aromatic ring. The building spray insulation material according to any one of claims 5 to 7, wherein the polyisocyanate compound contains a polyisocyanate having an aromatic ring. The architectural spray insulation material according to any one of claims 5 to 8, wherein the catalyst contains a trimerization catalyst. The architectural spray insulation material according to any one of claims 5 to 9, wherein the catalyst contains a urethanization catalyst. The architectural spray insulation material according to any one of claims 5 to 10, wherein the urethane resin composition contains a filler.

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