JP2010270877A - Spray heat insulating material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a spray heat insulation material which reduces loads on the environment, has a low density and comprises a hard polyurethane foam having excellent flame retardancy and dimensional stability. <P>SOLUTION: The spray heat insulation material comprises a hard polyurethane foam obtained by foaming a blended solution containing (A) a polyisocyanate component, (B) a polyol component, (C) water, (D) a catalyst, (E) a foam stabilizer, (F) a flame retardant and (G) a powder, wherein the polyol component contains 20 mass% or more of polyester polyol, the water contained in the blended solution is 10 pts.mass or more and 13 pts.mass or less with respect to 100 pts.mass of the polyol component, the powder has a number average particle diameter of 0.5 μm or more and 50 μm or less and is contained in the blended solution as much as 5 pts.mass or more and 60 pts.mass or less based on 100 pts.mass of the polyol component. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention is obtained by mixing a blending solution containing a polyisocyanate component, a polyol component, water, a catalyst, a foam stabilizer and a flame retardant, and foaming carbon dioxide generated by the reaction between the polyisocyanate and water as a foaming agent. The present invention relates to a spray insulation material made of rigid polyurethane foam.

Rigid polyurethane foams with excellent heat insulation and self-adhesive properties are widely used as spray insulation for houses, refrigerators, and the like.
Spray insulation made of rigid polyurethane foam is generally applied by airless spray foaming, in which a mixture of a polyisocyanate component, a polyol component, a foaming agent, a catalyst, and a foam stabilizer is mixed with a mixing head and foamed. . If it is this method, the heat insulation layer of a favorable rigid polyurethane foam can be formed by the simple operation | work of spraying construction directly to a construction target object.

In the rigid polyurethane foam, dichloromonofluoroethane (HCFC-141b), which has been used as a main foaming agent so far, has a problem of ozone layer destruction. Hydrofluorocarbons (HFCs) that do not destroy the ozone layer are listed as candidates for next-generation foaming agents that can replace this, but strong global warming action is a problem for these materials.
For this reason, development of technology for foaming without using these fluorocarbon foaming agents is considered as one issue, and complete water foaming using carbon dioxide gas generated by the reaction of water and polyisocyanate as the foaming agent. Has been proposed (see, for example, Patent Document 1).

  However, rigid polyurethane foam by water foaming has a problem in terms of weight reduction compared to polyurethane foam obtained by using chlorofluorocarbon as a foaming agent. Therefore, it has been practiced to increase the expansion ratio to obtain a low-density polyurethane foam. To that end, it is necessary to use a large amount of water. On the other hand, when a large amount of water is used, since the compatibility between the polyol compound and water is generally not so high, water is not sufficiently dispersed in the polyol compound, and the reaction between water and the polyisocyanate compound does not proceed sufficiently. As a result, the manufactured rigid polyurethane foam has a high density.

On the other hand, a method for producing a rigid polyurethane foam by reacting a specific polyol compound having a hydroxyl value of 100 to 700 mgKOH / g with a polyisocyanate compound in the presence of a foaming agent and a catalyst has been proposed ( For example, see Patent Document 2).
However, even in the rigid polyurethane foam disclosed in the above document, the water content that has been demonstrated is around 5 parts by mass with respect to 100 parts by mass of the polyol component, and the expansion ratio was insufficient.
In addition, when a large amount of water is used, the foam tends to shrink, so that it is also required to suppress dimensional change (hereinafter referred to as “dimensional stability”).

By the way, flame retardance is mentioned as one of the important performance calculated | required by the rigid polyurethane foam used for the urethane heat insulating material for apartment houses. Conventionally, in order to increase the flame retardancy of rigid polyurethane foam and to obtain flame retardancy of flame retardant grade 3 or higher by the surface test method shown in JIS A1321 “Interior material of building and flame retardancy test method of construction method” As the polyol component, a phthalic acid-based polyester polyol obtained by esterifying phthalic acid or a phthalic acid derivative has been used.
When such flame retardancy is imparted and the above dimensional stability is taken into consideration, the density is limited to about 34 to 35 kg / m ^3, and it is difficult to achieve both low density and dimensional stability. there were.

JP 2000-256434 A JP 2004-137493 A

  As a method of suppressing dimensional change while further reducing the density by the method of water foaming, outgassing using a polymer polyol for soft or semi-rigid in the foaming liquid (controlling the closed cell ratio to an appropriate range) It is effective to ensure However, when the soft or semi-rigid polymer polyol is used, there is a problem that the flame retardancy is lowered.

  The present invention has been made in view of such circumstances, and an object of the present invention is to provide a spray insulating material made of a rigid polyurethane foam that reduces environmental burden, has low density, and is excellent in flame retardancy and dimensional stability. And

The above problems are solved by the present invention described below. That is, the present invention
<1> A blending solution containing (A) a polyisocyanate component, (B) a polyol component, (C) water, (D) a catalyst, (E) a foam stabilizer, (F) a flame retardant, and (G) a powder. Made of rigid polyurethane foam obtained by foaming,
The polyol component contains 20% by mass or more of polyester polyol, the content of water in the mixed solution is 10 parts by mass or more and 13 parts by mass or less with respect to 100 parts by mass of the polyol component, and the number average particle size of the powder It is a spraying heat insulating material having a diameter of 0.5 μm or more and 50 μm or less, and the content of the powder in the blended liquid is 1 part by mass or more and 60 parts by mass or less with respect to 100 parts by mass of the polyol component.

<2> The spray insulating material according to <1>, wherein the core density of the rigid polyurethane foam is 22 kg / m ³ or more and 30 kg / m ³ or less.

  ADVANTAGE OF THE INVENTION According to this invention, the thermal insulation which consists of a rigid polyurethane foam which reduces the load to an environment, is low density, and is excellent in a flame retardance and dimensional stability can be provided.

Hereinafter, the present invention will be described with reference to embodiments.
The spray insulation material of this embodiment includes (A) polyisocyanate component, (B) polyol component, (C) water, (D) catalyst, (E) foam stabilizer, (F) flame retardant, and (G) powder. It comprises a rigid polyurethane foam obtained by foaming a compounded liquid containing a body, the polyol component contains 20% by mass or more of a polyester polyol, and the water content in the compounded liquid is 100 parts by mass of the polyol component. 10 parts by mass or more and 13 parts by mass or less, the number average particle size of the powder is 0.5 μm or more and 50 μm or less, and the content of the powder in the blended liquid is 1 part by mass with respect to 100 parts by mass of the polyol component. The amount is 60 parts by mass or less.
Here, the rigid polyurethane foam means a polyurethane foam having a large resistance to deformation, and generally means that once the deformation occurs, it does not return to the original state even if the external force is removed.

As described above, when polyester polyol is used as the polyol component in order to ensure the flame retardancy of the polyurethane foam, dimensional stability (particularly when trying to further reduce the density (core density of about 30 kg / m ³ or less)) Dimensional change under high temperature and high quality environment) becomes a problem. On the other hand, it is effective to cause a certain amount of outgassing during the polyurethane foaming reaction.
However, conventionally, there has been no effective means other than using a soft or semi-rigid polymer polyol that reduces the flame retardancy in order to cause the above-mentioned gas escape.

  In order to solve the above problems, the present inventors have examined a material that is effective for outgassing instead of a polymer polyol. As a result, even when a polyester polyol having flame retardancy is included as a polyol component to a certain extent, by including it in a certain amount in the compounding liquid for foaming a powder having a specific particle size range. It has been found that dimensional stability can be ensured without reducing flame retardancy.

  The rigid polyurethane foam constituting the spray heat insulating material of the present embodiment includes (A) polyisocyanate component, (B) polyol component, (C) water, (D) catalyst, (E) foam stabilizer, (F) difficult It is obtained by foaming a compounded liquid containing a flame retardant and (G) powder. Hereinafter, each component will be described in detail.

<(A) Polyisocyanate component>
As the polyisocyanate component, various known polyfunctional aliphatic, alicyclic and aromatic isocyanates can be used. For example, tolylene diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, triphenyl diisocyanate, xylene diisocyanate, polymethylene polyphenylene polyisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, orthotoluidine diisocyanate, naphthylene diisocyanate, xylylene diisocyanate, lysine diisocyanate, etc. These may be used alone or in combination of two or more.
Among these, in the present embodiment, it is preferable that diphenylmethane diisocyanate (MDI) is included from the viewpoints of reactivity, physical properties, and safety.

  Here, although the compounding quantity of (A) component is not restrict | limited in particular, It is preferable that it is the range of 90-120 mass parts with respect to 100 mass parts of all the polyol components. When the blending amount of the component (A) is 90 parts by mass or more, there is no problem of insufficient strength or poor foaming, and dimensional stability is also improved. On the other hand, when it is 120 parts by mass or less, a low-density polyurethane foam is obtained, the brittleness at low temperatures is good, and it is advantageous for workability at low temperatures in winter. From the above viewpoint, the blending amount of the component (A) is more preferably in the range of 100 to 115 parts by mass with respect to 100 parts by mass of all polyol components.

  In addition, the proportion of the component (A) in the blended liquid (when two or more isocyanates are used in combination, the ratio of the total amount in the blended liquid) is the isocyanate equivalent (active hydrogen in the blended liquid) The range of 25 to 250 is preferable as the molar ratio of the isocyanate groups in the blended liquid when the amount (mole) is 100. When the isocyanate equivalent is 25 or more, foaming and curing are performed, and when it is 250 or less, the density can be reduced. From the above viewpoint, the isocyanate equivalent is more preferably in the range of 50 to 120.

<(B) polyol component>
Examples of the polyol component include polyester polyol, polyether polyol, and polymer polyol. In this embodiment, in order to ensure the flame retardance of the obtained rigid polyurethane foam, it is necessary to contain 20 mass% or more of a polyester polyol component as a polyol component. Moreover, it is preferable that 30 mass% or more of polyester polyol components are included, and it is more preferable that 40 mass% or more is included.
The required flame retardancy will be described later.

Examples of the polyester polyol include aliphatic dicarboxylic acids having 4 to 20 carbon atoms such as adipic acid, suberic acid, sebacic acid, and brassic acid, terephthalic acid, and isophthalic acid as acid components, and 1 to 1 carbon atoms such as ethylene glycol. Polyester polyols having a polyol component (alcohol component) such as 6 aliphatic diols, ether glycols such as diethylene glycol and dipropylene glycol can be mentioned. These polyester polyols may be used alone or in combination of two or more.
In particular, phthalic acid-based polyesters mainly composed of phthalic acid other than phthalic anhydride (o-phthalic acid), that is, m-phthalic acid (isophthalic acid) and / or p-phthalic acid (terephthalic acid) and derivatives thereof Use of a polyol is preferable from the viewpoint that flame retardancy can be improved. This is because a foam obtained from a polyol using phthalic acid (m, p-phthalic acid) having higher cohesive energy is difficult to burn.

  The hydroxyl value of such a phthalic acid-based polyester polyol, preferably m, p-phthalic acid-based polyester polyol, is in the range of 100 to 400 mgKOH / g, and the viscosity is in the range of 500 to 1500 mPa · s. The phthalic polyester polyol preferably has a p-phthalic acid content of 40 to 80% by mass. When the p-phthalic acid content in the phthalic polyester polyol is 40% by mass or more, sufficient flame retardancy is obtained, and when it is 80% by mass or less, sufficient pot life is obtained.

Next, the polyether polyol is not particularly limited, but a polyether polyol obtained by ring-opening polymerization of alkylene oxide is preferable from the viewpoint of reactivity. Examples of such alkylene oxides include propylene oxide (PO) and ethylene oxide (EO). These may be used alone or in combination of two or more.
As the polyether polyol, the PO homopolymer, the EO homopolymer, and the polyether polyol obtained by copolymerization of PO and EO can be used. The copolymerization may be random copolymerization or block copolymerization.

  As the polyether polyol, a polyether polyol obtained by Mannich modification of phenol and / or a derivative thereof (hereinafter referred to as “Mannich modified polyol”), that is, phenol or a phenol derivative such as nonylphenol or alkylphenol, It is preferable to use a polyether polyol obtained by subjecting Mannich modification with formaldehyde and secondary amine such as diethanolamine, ammonia or primary amine, and ring-opening addition polymerization of alkylene oxide such as ethylene oxide or propylene oxide. it can. Such a Mannich-modified polyol has a high self-reactive activity and a relatively high flame retardancy. Therefore, by using a Mannich-modified polyol, for example, in an airless spray foam type rigid polyurethane foam, flame retardancy performance is exerted at the time of blowing foam. The reaction can proceed promptly without significant loss.

Furthermore, in addition to the Mannich-modified polyol, a polyol compound of an initiator different from the Mannich-modified polyol such as ethylenediamine, tolylenediamine, sucrose, amino alcohol, and diethylene glycol may be used in combination.
In particular, in the present embodiment, the polyol component used together with the powder described later is 30 to 60% by mass of phthalic polyester polyol, 10 to 40% by mass of Mannich modified polyether polyol and / or other than the Mannich modified polyether polyol. It is preferable that 5-20 mass% of polyether polyols are included.
When the polyol component contains the above phthalic polyester polyol and Mannich-modified polyether polyol and / or polyether polyol other than Mannich-modified polyether polyol in the above composition ratio range, particularly flame retardancy and dimensional stability. And workability are realized at the same time.

  Polyether polyols other than the Mannich-modified polyether polyol include ethylenediamine-based polyether polyols obtained by ring-opening addition polymerization of propylene oxide or ethylene oxide to ethylenediamine, and ring-opening addition polymerization of propylene oxide or ethylene oxide to glycerin. The resulting glycerin-based polyether polyol, sorbitol-based polyether polyol obtained by ring-opening addition polymerization of propylene oxide or ethylene oxide to sorbitol, and tri-amine obtained by ring-opening addition polymerization of propylene oxide or ethylene oxide to tolylenediamine. Obtained by aminomethylation of range amine polyether polyol and piperazine and ring-opening addition polymerization of propylene oxide and ethylene oxide One or more selected from the group consisting of piperazines polyether polyols and the like.

  As the polyol component in the present embodiment, the hydroxyl value in the total polyol component is in the range of 84 to 1000, preferably in the range of 100 to 700, from the viewpoint of coexistence of the reaction rate of urethane foaming and the mechanical properties of the foam. And it is suitable to contain the polyol whose number average molecular weight in all the polyol components is the range of 200-2000, Preferably it is the range of 200-1000. The number average molecular weight is a value calculated as a polystyrene equivalent value by the GPC method, and the hydroxyl value is a value measured according to JIS K1557.

<(C) Water>
In this embodiment, it is essential that the content of water in the blended liquid is 10 parts by mass or more and 13 parts by mass or less with respect to 100 parts by mass of the polyol component. By setting the water content in the above range, it is possible to obtain a sufficient foaming ratio and dimensional stability as a polyurethane foam. A low boiling point compound such as methylene chloride or monofluorinated trichloromethane can be used in combination with water.
The ratio of the water is preferably 10 parts by mass or more and 12 parts by mass or less, and more preferably 10.5 parts by mass or more and 11.5 parts by mass or less.

<(D) Catalyst>
In the present embodiment, an organic acid bismuth salt and / or an amine compound is preferably used as the catalyst. In the present embodiment, it is preferable not to use lead as a catalyst. By not using lead, hydrolysis of the polyester polyol can be prevented and the storage stability of the blended liquid can be improved.
As other catalysts that can be used in combination with the organic acid bismuth salt and / or the amine compound, a potassium salt catalyst, a piperazine catalyst, or the like can be used. These catalyst components that can be used in combination can be used alone or in combination of two or more.

Examples of the organic acid bismuth salt include bismuth salts of alicyclic organic acids such as abietic acid, neoabietic acid, d-pimalic acid, iso-d-pimalic acid, podocarpic acid; benzoic acid, cinnamic acid, p -Bismuth salts of aromatic organic acids such as oxycinnamic acid; fatty acid bismuth salts of 8 to 20 carbon atoms such as octylic acid, 2-ethylhexylic acid, neodecanoic acid, neododecanoic acid, and the like. Of these, octylic acid, 2-ethylhexylic acid, and neodecanoic acid are preferably used from the viewpoint of maintaining reactivity. In addition, these organic acid bismuth salts may be used alone or in combination of two or more.
The amount of the organic acid bismuth salt is not particularly limited, but is preferably in the range of 0.1 to 5 parts by mass with respect to 100 parts by mass of the total polyol component. When the amount is 0.1 parts by mass or more, there is sufficient reaction activity, foaming is sufficiently performed, and spray foaming can be performed smoothly. On the other hand, when the amount is 5 parts by mass or less, there is no case where spray foaming cannot be performed due to the reaction being too early. From the above points, the blending amount of the organic acid bismuth salt with respect to 100 parts by mass of the total polyol is more preferably in the range of 0.5 to 3 parts by mass.

Next, examples of the amine compound include bis (3-dimethylaminopropyl) -N, N-dimethylpropanamine, tetramethylhexamethylenediamine, pentamethyldiethylenetriamine, dimethylcyclohexylamine, and bis- (dimethylaminoethyl) ether. , Tetramethylpropylenediamine, trimethylaminoethylpiperazine, tetramethylethylenediamine, dimethylbenzylamine, methylmorpholine, ethylmorpholine, triethylenediamine, 1-methylimidazole, 1-isobutyl-2-methylimidazole, 1,2-dimethylimidazole , N, N, N′-trimethylaminoethylethanolamine, and the like. Of these, tetramethylhexamethylenediamine, pentamethyldiethylenetriamine, bis (3-dimethylaminopropyl) -N, N-dimethylpropanamine and the like are preferably used from the viewpoint of reaction activity (balance between resinification and foaming). These amine compounds may be used alone or in combination of two or more.
As a compounding quantity of an amine compound, it is preferable that it is the range of 0.5-5 mass parts with respect to 100 mass parts of all the polyol components. When the amount is 0.5 parts by mass or more, a sufficient reaction rate is obtained, foaming is sufficiently performed, and spray foaming can be performed smoothly. On the other hand, when the amount is 5 parts by mass or less, there is no case where spray foaming cannot be performed due to the reaction being too early. From the above points, the compounding amount of the amine compound with respect to 100 parts by mass of the total polyol component is more preferably in the range of 1 to 4 parts by mass, and still more preferably in the range of 3 to 4 parts by mass.

  Next, as the piperazine-based catalyst, piperazine, N, N, N-trimethylaminoethylpiperazine (TOYOCAT-NP, Caorizer No. 8) or the like can be used. As the potassium salt catalyst, potassium octylate, potassium acetate or the like can be used. These catalysts may be used individually by 1 type, and may mix and use 2 or more types.

<(E) Foam stabilizer>
As the foam stabilizer used as the blending liquid in the present embodiment, all those used in the production of ordinary polyurethane foams can be used. Examples include dimethylsiloxane foam stabilizers, polyether-modified dimethylsiloxane foam stabilizers, and the like. Silicone foam stabilizers.

  In this embodiment, it is preferable to use a branched polyether-modified silicone represented by the following general formula (I) as a foam stabilizer, and further this branched polyether-modified silicone and a pendant represented by the following general formula (II). It is more preferable to use in combination with a type polyether-modified silicone.

  Here, m1 + m2 is an integer of 10-50, preferably an integer of 20-40. N1, n2, and n3 are each an integer of 1 to 10, and (a1 + a2 + a3) / (b1 + b2 + b3) is 50/50 to 90/10. Furthermore, R at the end of the polyether chain is hydrogen or a methyl group. A plurality of R may be the same or different. In the formula, “EO” is an abbreviation for ethylene oxide, and “PO” is an abbreviation for propylene oxide.

Here, m is an integer of 1-20, preferably an integer of 5-15. N is an integer of 1 to 10, preferably an integer of 2 to 5. The ratio of m to n (m / n) is in the range of 1-10, preferably in the range of 2-6. a is an integer of 10 to 50, preferably an integer of 20 to 40. In the formula, “EO” is an abbreviation for ethylene oxide. In the pendant polyether-modified silicone represented by the general formula (II), the terminal EO composition is 100% by mass and the primary OH amount is 90 to 100%. Is preferred.
The amount of the foam stabilizer used is preferably 4 parts by mass or less, more preferably in the range of 0.2 to 3 parts by mass, particularly preferably 0.5 to 2 parts by mass with respect to 100 parts by mass of the polyol component. It is a range.

<(F) Flame retardant>
The compounded liquid in this embodiment contains a flame retardant as the component (F).
As the flame retardant, a general-purpose flame retardant can be used, and examples thereof include non-halogen phosphates, halogen-containing phosphates, non-halogen condensed phosphates, and halogen-containing condensed phosphates. Of these, the use of flame retardants mainly composed of non-halogen phosphate esters keeps the viscosity of the blended solution low, improves stirring efficiency, improves the homogeneity of the resulting molded product, and is applied to the spray method Is preferable from the standpoint of performing the process more easily.

Examples of non-halogen phosphates include trimethyl phosphate, triethyl phosphate, tributyl phosphate, triisobutyl phosphate, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate. , Cresyl di-2,6-xylenyl phosphate and the like. Examples of the halogen-containing phosphate ester include tris (chloropropyl) phosphate, tris (dichloropropyl) phosphate, tris (tribromoneopentyl) phosphate, and the like. These may be used alone or in combination of two or more.
Moreover, as a compounding quantity of a flame retardant, the range of 5-50 mass parts is preferable with respect to 100 mass parts of all the polyol components, More preferably, it is the range of 10-40 mass parts.

<(G) Powder>
As the powder added to the blending liquid in the present embodiment, one having a number average particle diameter of 0.5 μm or more and 50 μm or less is used. This not only provides a sufficient gas outgassing effect during foaming, but also prevents machine filter clogging when used for spray foaming, which will be described later, and slows the sedimentation of powder particles. Can increase the sex.

The number average particle size of the powder is preferably 0.5 μm or more and 40 μm or less, and more preferably 0.5 μm or more and 20 μm or less.
The number average particle diameter of the powder is a 50% particle diameter measured by a laser diffraction / scattering particle size distribution analyzer.

In addition, the content of the powder having the average particle diameter is 5 parts by mass or more and 60 parts by mass or less with respect to 100 parts by mass of the polyol component. As a result, it is possible to prevent a decrease in dispersibility and thickening when mixed with a polyol component, and not only provide a sufficient degassing effect at the time of foaming, but also avoid a substantial increase in the density of the polyurethane foam. Can do.
The content is preferably 8 parts by mass or more and 50 parts by mass or less, and more preferably 10 parts by mass or more and 30 parts by mass or less.

  The material of the powder that can be used in the present embodiment is not particularly limited as long as it has the above-described average particle diameter and the property is maintained by mixing with the polyol component. For example, calcium carbonate, aluminum hydroxide, Inorganic compounds such as magnesium hydroxide and bentonite; metals such as iron and aluminum; and organic substances such as polyamide, polyvinyl chloride, melamine resin, and styrene resin. These may be used alone or in combination of two or more. Can be used.

The powder in the present embodiment may be subjected to a surface treatment for the purpose of improving dispersibility in the polyol component.
Surface treatment agents used for the surface treatment include various silicone oils such as methyl hydrogen polysiloxane, dimethyl polysiloxane, and methylphenyl polysiloxane, methyltrimethoxysilane, ethyltrimethoxysilane, hexyltrimethoxysilane, and octyltrimethoxysilane. , Various alkyl silanes such as decyltrimethoxysilane, octadecyltrimethoxysilane, dimethyldimethoxysilane, octyltriethoxysilane, n-octadecyldimethyl (3- (trimethoxysilyl) propyl) ammonium chloride; trifluoromethylethyltrimethoxysilane , Various fluoroalkylsilanes such as heptadecafluorodecyltrimethoxysilane; in particular vinyltrimethoxysilane, γ-aminopropyltrimethoxy Representing silane coupling agents such as silane, silane-based, titanium-based, aluminum-based, alumina-zirconia-based metal-based coupling agents, fatty acids such as isostearic acid and stearic acid, and metal salts thereof Any treatment agent such as a surfactant can be used, and these can be used alone or in admixture of two or more.

The surface treatment can be performed by either a dry process using a ball mill or the like, or a wet process using a spray dryer or the like.
The surface treatment amount is preferably in the range of 0.1 to 50 parts by mass, more preferably in the range of 1 to 30 parts by mass with respect to 100 parts by mass of the powder.

  The dispersion of the powder into the blended liquid is preferably performed by adding and mixing in advance with the polyol component, and mixing and stirring can be performed with a propeller-type stirrer, a homogenizer, or the like. Moreover, you may heat as needed at the time of the said mixing and stirring.

<Other ingredients>
In addition, the compounding liquid in the present embodiment appropriately contains a cross-linking agent, a colorant, a filler, an antioxidant, an ultraviolet absorber, a light stabilizer, a conductive material such as carbon black, an antibacterial agent, and the like as necessary. Can be blended.

Although it does not specifically limit as a compounding method of the compounding liquid in this embodiment, The polyol composition which consists of each component other than the said (A) polyisocyanate component is prepared, and is mixed with (A) component after that. In this case, from the viewpoint of improving the dispersibility of the powder as described above, it is preferable to first add (G) the powder to (B) polyol and mix.
The polyol composition is prepared by blending the catalyst (D) with the mixture of the polyol component (G) and the powder (G) from the viewpoint that water and the catalyst are not brought into contact with each other as much as possible. It is preferable to blend (E) a foam stabilizer, (F) a flame retardant, and other components, and finally blend the (C) water, which is a foaming component.

  In the present embodiment, the solution viscosity of the polyol composition is preferably in the range of 100 to 500 mPa · s, more preferably 150 to 450 mPa · s, as the viscosity (liquid temperature 25 ° C.) measured according to JIS K1557. It is a range. If the solution viscosity deviates from the above range, the apparatus used when using the conventional polyurethane compounding liquid in the spray method may not be used as it is. On the other hand, an excessively high viscosity is not preferable because it tends to lead to deterioration in workability, deterioration in stirring efficiency, and consequently reduction in homogeneity of the obtained foamed molded article.

  When a rigid polyurethane foam is produced by airless spray foaming using a mixing head using the blended liquid in the present embodiment, the above (A) polyisocyanate component, (B) polyol component, and (C) water , (D) a catalyst, (E) a foam stabilizer, (F) a flame retardant, (G) a polyol composition mixed with powder and other auxiliaries at 30 to 50 ° C. using a mixing head. And it can manufacture by spraying on a construction object surface by discharge pressure 3.9-7.8MPa, and making it foam repeatedly by repeating spraying until it becomes a predetermined thickness.

  In addition, although it can set suitably as hardening conditions at the time of foam hardening, it is preferable to set it as the range of 10-50 degreeC as foaming liquid temperature, and it is preferable to set it as the range of 0-35 degreeC as foaming atmosphere temperature. .

In the spray insulation comprising the rigid polyurethane foam of the present embodiment thus obtained, the core density of the rigid polyurethane foam to be formed is 22 kg / m ³ or more and 30 kg / m ³ or less in the method defined in JIS A9526. It is preferable. When the core density (heart density) is 22 kg / m ³ or more, the strength is not significantly reduced and shrinkage is also suppressed. On the other hand, when the core density (core density) is 30 kg / m ³ or less, desired performance can be obtained with a small amount of material. Therefore, the core density is more preferably 24 kg / m ³ or more and 30 kg / m ³ or less, and further preferably 26 kg / m ³ or more and 28 kg / m ³ or less.

  The spray insulation comprising the rigid urethane foam of the present embodiment preferably has a flame retardance performance of 3 or more flame retardant as defined in JIS A1321, and / or the Building Standard Law Enforcement Ordinance Article 6 No. 6. Is a flame retardant material

Moreover, the spraying heat insulating material made of the rigid polyurethane foam of the present embodiment is a method in which the self-adhesive strength of the spraying heat insulating material molded at an ambient temperature and a temperature of the casing surface of 0 to 10 ° C. is defined in JIS A9526. It is preferably 10 N / cm ² or more.
The rigid polyurethane foam preferably has a closed cell ratio in the range of 10 to 50% by volume. When the closed cell ratio is 10% by volume or more, sufficient foam strength can be obtained, and the standard value shown in JIS A9526 can be satisfied. On the other hand, when it is 50% by volume or less, the dimensional stability of the foam is not impaired, and shrinkage is suppressed.

  The spray heat insulating material of this embodiment is very suitable as a substitute for glass wool or styrene board that has been conventionally used as a heat insulating material for detached houses.

EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by these examples.
<Evaluation method>
Regarding the rigid polyurethane foam (spraying heat insulating material) manufactured in each Example and Comparative Example, the workability at the time of manufacturing and the characteristics of the foam were evaluated by the following methods.
(1) Machine workability Spray construction was performed under the following conditions, and the spray pattern and filter clogging were evaluated.
-Spray foaming machine: “H-2000” “FF-1600” (mixing volume ratio 100: 100) manufactured by Gasmer (mixing head: D gun)
・ Hose heater set temperature: 30 ~ 45 ℃
・ Main heater set temperature: 30 ~ 45 ℃

(Spray pattern)
The spread of the circular liquid when sprayed with a gun from a point 1 m away from the housing was evaluated according to the following criteria.
○: The diameter of the circular spread is 25 cm or more.
Δ: The diameter of the circular spread is 15 cm or more and less than 25 cm.
X: The diameter of the circular spread is less than 15 cm.

(Filter clogging)
Filter clogging when spray foaming was continuously performed for 480 minutes was evaluated according to the following criteria.
○: The increase in the pressure gauge display of the polyol component of the machine body is less than 50 mmHg / cm ² compared to the start time.
△: pressure gauge displays increase of polyol component machine body, at the start versus 50 mmHg / cm ² or more 100 mm Hg / cm less than ^2.
X: An increase in the pressure gauge display of the polyol component of the machine body is 100 mmHg / cm ² or more compared to the start time.

(2) Dimensional change rate (%)
Samples obtained by cutting the core part into a size of 100 mm × 100 mm × 30 mm are put in a high humidity environment (temperature: 50 ° C., humidity: 95% RH) for 24 hours in accordance with JIS A9526. The rate of change was measured for length, width, and thickness, respectively. In addition, if all the dimensional change rates are ± 5% or less, it is considered acceptable.
(3) Core density (kg / m ³ )
A sample cut into a size of 50 mm × 50 mm × 30 mm and collected was measured according to JIS A9526.
(4) Closed cell ratio (%)
Measured according to ASTM D2856.
(5) Flame retardance According to the surface test method shown in JIS A1321 “Interior material of building and flame retardancy test method of construction method”, a surface test was conducted by a combustibility tester manufactured by Toyo Seiki Seisakusho. In addition, the flame retardant third grade standard by the surface test method shown in JIS A1321 “Interior material of building and flame retardant test method of construction method” is as follows.
・ Exhaust temperature time ≧ 180sec
・ Smoke emission coefficient ≦ 120
・ Temperature time area ≤350 (℃ ・ min)
・ Afterflame time ≤ 30 sec
-The specimen should not have significant melting, cracking or deformation.

<Examples 1-15 and Comparative Examples 1-12>
In accordance with the formulation shown in Tables 1 to 4, a formulation solution was prepared. In the preparation, a polyol composition comprising each component other than the (A) polyisocyanate component was prepared, and a predetermined amount of the (A) polyisocyanate component was separately prepared. In the polyol composition, (D) a catalyst is mixed, (E) a foam stabilizer, then (F) a flame retardant is blended, (C) water is further mixed and stirred once, and then (G) It was prepared by adding and mixing powder (when included).
Using the obtained polyol composition and the polyisocyanate component (A), airless spray foaming was performed under the spraying conditions (mixing volume ratio 100: 100) to obtain a rigid polyurethane foam. The obtained foam was evaluated by the above method. The evaluation results are shown in Tables 1 to 4. Note that Comparative Examples 5, 6, 10, and 11 were not evaluated for flame retardancy because there was a problem in machine workability and a good rigid polyurethane foam could not be obtained.

* 1 Polyol A: Mannich modified polymer polyol ("XR7202" manufactured by Asahi Glass Polyurethane Co., Ltd., hydroxyl value 380 mgKOH / g, viscosity 1400 mPa · s (25 ° C), powder component obtained by copolymerizing acrylonitrile and vinyl acetate Is 1.4% by weight, and the composition ratio of acrylonitrile and vinyl acetate is 1: 3)
* 2 Polyol B; p-phthalic acid-based polyester polyol (“SV165” manufactured by Hitachi Chemical Co., Ltd., hydroxyl value 200 mg KOH / g, viscosity 820 mPa · s (25 ° C.), p-phthalic acid content: 62.5% by mass )
* 3 Polyol C: Polyether polyol (“GR-11” manufactured by Mitsui Chemicals, Inc., EO / PO = 100/0, hydroxyl value 450 mgKOH / g, viscosity 1200 mPa · s (25 ° C.))
* 4 Polyol D: Ethylenediamine-based polyether polyol (“600ED” manufactured by Asahi Glass Polyurethane Co., Ltd., hydroxyl value 650 mgKOH / g, viscosity 7000 mPa · s (25 ° C.))
* 5 Polyol E: Melamine polymer polyol ("M950" manufactured by Asahi Glass Polyurethane Co., Ltd., solid content concentration: 25 mass%, solid content average particle size: 0.3 to 0.5 μm, base polyether polyol: average functionality Number of groups = 3, weight average molecular weight: 5000, hydroxyl value 26 mgKOH / g)
* 6 Polyol F: Polyether polyol (“NF-04” manufactured by Mitsui Chemicals, Ltd., hydroxyl value 360 mgKOH / g, viscosity 540 mPa · s (25 ° C.))

* 7 Powder A: Calcium carbonate (Number average particle size: 3 μm)
* 8 Powder B: Melamine resin particles (Mitsubishi Chemical Corporation, product name “melamine”, number average particle size: 1.2 μm)
* 9 Powder C: Styrenic resin particles (manufactured by Sanyo Chemical Industries, Ltd., product name “styrene”, number average particle size: 0.8 μm)
* 10 Powder D: Bentonite (Organized surface treatment, number average particle size: 10 μm)
* 11 Powder E; bentonite (no surface treatment, number average particle size: 10 μm)
* 12 Powder F: Magnesium hydroxide (number average particle size: 10 μm)
* 13 Powder G: Calcium carbonate (Number average particle diameter: 10 μm)
* 14 Powder H: Calcium carbonate (Number average particle diameter: 50 μm)
* 15 Powder I: Calcium carbonate (Number average particle diameter: 100 μm)
* 16 Powder J: Calcium carbonate (Number average particle diameter: 300 μm)

* 17 Flame retardant A; Tris monochloropropyl phosphate (“TMCPP” manufactured by Daihachi Chemical Co., Ltd.)
* 18 Flame retardant B; Triethyl phosphate (“TEP” manufactured by Daihachi Chemical Co., Ltd.)
* 19 Catalyst A; N, N, N ′, N′-tetramethylhexamethylenediamine (“Kaorizer No. 1” manufactured by Kao Corporation)
* 20 Catalyst B; N, N, N ′, N ″, N ″ -pentamethyldiethylenetriamine (“Kao Riser No. 3” manufactured by Kao Corporation)
* 21 Catalyst C: “Pucat 25” (mixture of bismuth 2-ethylhexylate (25% by mass as bismuth) and bismuth octylate (20% by mass as bismuth)) manufactured by Nippon Chemical Industry Co., Ltd.
* 22 Catalyst D: “Pucat 15G” manufactured by Nippon Chemical Industry Co., Ltd. (diethylene glycol solution of potassium octylate, potassium concentration: 15% by mass)

* 23 Foam stabilizer A: pendant type polyether-modified silicone represented by formula (II) (“SH193” manufactured by Toray Dow Corning Co., Ltd., block copolymer of dimethylsiloxane and polyether, m = 11, n = 3, a = 29, weight average molecular weight by GPC method (polystyrene conversion: 5100, HLB: 19)
* 24 Foam stabilizer B: Branched polyether-modified silicone represented by formula (I) (“SF2937” manufactured by Toray Dow Corning Co., Ltd.), block copolymer of dimethylsiloxane and polyether, m1 + m2 = 30, n1 = n2 = n3 = 1, (a1 + a2 + a3) / (b1 + b2 + b3) = 75/25, weight average molecular weight by GPC method (polystyrene conversion): 8900, HLB: 13)
* 25 MDI: Diphenylmethane diisocyanate (Sumitomo Bayer Urethane Co., Ltd. “44V20”)

As is clear from the results shown in Tables 1 to 4, the spray insulation material made of the rigid polyurethane foam of the example has no problem in machine workability during production, and maintains a low density and flame retardancy while maintaining a high temperature. Dimensional change at high humidity could be suppressed.
On the other hand, in the comparative example using no blending powder having a specific particle size range or having a water or polyester polyol content outside the specific range, a problem occurred in any of the above characteristics / performances.

Claims (2)

(A) A polyisocyanate component, (B) a polyol component, (C) water, (D) a catalyst, (E) a foam stabilizer, (F) a flame retardant, and (G) a blended liquid containing powder is foamed. Made of rigid polyurethane foam obtained,
The polyol component contains 20% by mass or more of polyester polyol, the content of water in the mixed solution is 10 parts by mass or more and 13 parts by mass or less with respect to 100 parts by mass of the polyol component, and the number average particle size of the powder A spraying heat insulating material having a diameter of 0.5 μm or more and 50 μm or less, and the content of the powder in the blended solution is 5 parts by mass or more and 60 parts by mass or less with respect to 100 parts by mass of the polyol component. The spray insulation according to claim 1, wherein the core density of the rigid polyurethane foam is 22 kg / m ³ or more and 30 kg / m ³ or less.