JP2020172650A - Urethane resin composition and thermal insulation method of architectural structure - Google Patents

Abstract

To provide an urethane resin composition having at least semi-flame retardancy and having suitable properties for forming a thermal insulation layer of an architectural structure without addition of a foam stabilizer.SOLUTION: There is provided an urethane resin composition for forming a foam body constituting a thermal insulation material of an architectural structure, in which the foam body has at least semi-flame retardancy in a pyrogenicity test according to ISO-5660, contains at least a polyisocyanate compound, an ester-based polyol compound, a trimerization catalyst, additive, and a non-silicon-based surface control agent, and no foam stabilizer, and the additive contains red phosphorus as an essential component and is by combination of at least one of a phosphate-containing fire retardant and a chlorine-containing fire retardant.SELECTED DRAWING: Figure 1

Description

The present invention relates to a urethane resin composition or the like used as a heat insulating material for a building, and more particularly to a urethane resin composition or the like capable of forming a foam having at least quasi-incombustibility in a heat generation test based on ISO-5660. ..

In RC and S houses, sprayed hard urethane foam heat insulating material is often used for the purpose of preventing dew condensation, heat insulation, and energy saving.
In recent years, a fire has rarely occurred due to ignition of the heat insulating material due to inadequate construction management. In addition, when a general fire occurs, the fire may burn to the heat insulating material and cause the fire to spread.
For the purpose of preventing such combustion of urethane foam, a fireproof coat (inorganic spray material such as cement) may be applied, but it takes time to apply, and the adhesion with urethane foam is not sufficient after installation. Problems such as dropping out remain.

Therefore, in order to impart flame retardancy to urethane foam, a urethane resin composition obtained by adding a flame retardant containing red phosphorus as an essential component is disclosed in Patent Document 1 below.

Japanese Patent No. 6200435

The urethane resin composition described in Patent Document 1 has at least one of the following problems.
(1) Since the self-adhesive force of urethane is weakened by the defoaming agent that is indispensable for blending, there is a possibility that the foam may fall off from the sprayed surface. In particular, when the heat insulating layer provided in the building is formed, the foam is blown repeatedly, so that the risk of the foam falling off is further increased.
(2) In the silicon-based defoaming agent, cyclic siloxane or the like may diffuse into the air and adversely affect the malfunction or the like due to poor contact of electric or electronic devices. In Canada and Europe, these cyclic siloxanes are regulated substances that have an adverse effect on water quality, and cannot be said to be environmentally friendly.
(3) Since the storage stability of the undiluted solution is poor, the raw material settles during on-site construction, which adversely affects productivity and durability of the construction machine.
(4) When HFO-1233zd is used as the foaming agent, when the polyol component is stored for a long period of time after preparation, the foaming agent decomposes due to the influence of the amine catalyst or the like to generate HF and decompose the silicon-based foam stabilizer or the like. There is a high possibility that it will not foam.

Therefore, the present invention is suitable for forming a heat insulating layer of a building without adding a defoaming agent in the urethane resin composition having flame retardancy in order to avoid problems caused by the addition of the defoaming agent. At least one of the purposes is to provide a urethane resin composition having various properties.

The present invention made to solve the above problems is a urethane resin composition for forming a foam constituting a heat insulating material of a building, and the foam is at least in a heat generating test based on ISO-5660. A quasi-nonflammable urethane resin composition containing at least a polyisocyanate compound, an ester-based polyol compound, a trimerization catalyst, an additive, and a non-silicone-based surface conditioner, and no foam stabilizer. The additive is characterized in that red phosphorus is an essential component and at least one of a phosphate-containing flame retardant and a chlorine-containing flame retardant is combined.
Further, in the present invention, at least one of ammonium phosphate and aluminum phosphite can be selected as the phosphate-containing flame retardant.
Further, in the present invention, a chlorine-based phosphoric acid ester can be used as the chlorine-containing flame retardant.
Further, in the present invention, an acrylic surface conditioner can be used as the non-silicon type surface conditioner.
Further, in the above invention, a foaming agent having HFO (hydrofluoroolefin) can be further included.
Further, in the above invention, an ether-based polyol compound can be further included.
Further, in the above invention, an adhesion promoter can be further included.
Further, in the above invention, at least one of a urethane foaming catalyst and a urethane metal catalyst can be further included.
Moreover, in the said invention, a dispersant can be further included.
The present invention can also provide a heat insulating method for a building in which the urethane resin composition is used as an in-situ foaming type heat insulating material for spraying.

According to the present invention, it has at least one of the effects described below.
(1) In the present invention, the adhesiveness of the foam is improved by not including the foam stabilizer in the formulation of the urethane resin composition. More specifically, it is possible to avoid the possibility that the adhesion at the time of repeated blowing is deteriorated due to the improvement of the slipperiness of the skin layer surface due to the use of the silicon-based defoaming agent used as the raw material of the urethane foam. On the other hand, in the present invention, since it does not contain a defoaming agent, it is particularly suitable for use in forming a heat insulating layer of a building by spraying on-site.
(2) In the present invention, in particular, by not including a silicon-based defoaming agent, the cyclic siloxane is not diffused, and malfunctions due to poor contact of electric / electronic devices and adverse effects such as water pollution are eliminated.
(3) In the present invention, by including a phosphate-containing flame retardant or a chlorine-containing flame retardant in addition to red phosphorus, dehydration condensation, hydrolysis, dehydration charcoal action (intmesent effect), and foaming layer during combustion Higher flame retardancy can be obtained by formation.
(4) In the present invention, since the foaming agent is not included in the formulation of the urethane resin composition, the foaming agent is particularly foamed by the decomposition of the silicon foaming agent or the like by hydrogen fluoride generated by the decomposition of the HFO foaming agent such as HFO1233zd by the amine catalyst or the like. There is no problem of defoaming or slowing down the chemical reaction. As a result, there is no problem in using the HFO foaming agent, and the effect of using the HFO foaming agent (improvement of long-term storage stability of raw materials, improvement of workability in the field) can be obtained.

Comparison table of test results with and without defoamer. Comparison table of test results due to different types of surface conditioners. Comparison table of test results with and without ether-based polyol compound. Comparison table of test results with and without adhesion accelerator. Comparison table of test results with and without urethanization catalyst or metal resinification catalyst. Comparison table of test results with and without dispersant. Comparison table of test results with and without phosphate-containing flame retardant or chlorine-containing flame retardant.

<1> Overall Composition The urethane resin composition according to the present invention is for forming a foam constituting a heat insulating material of a building, and is a polyisocyanate compound, an ester-based polyol compound, a quantification catalyst, an additive, and the like. And shall contain at least a non-silicone surface conditioner and no defoaming agent.
Further, the foam obtained by the above composition is characterized by having at least quasi-incombustible in a heat generation test based on ISO-5660.
A method in which the above composition is divided into a polyisocyanate compound (first liquid) and other components (second liquid), and both are sprayed while being mixed and sprayed, or a method in which both are mixed and sprayed. A heat insulating layer can be formed on the building by the above.

各材料の最適な配合比は、実験によって適宜導けば良い。
以下、各材料の詳細について説明する。 <2> Non-combustible performance As described above, the urethane resin composition according to the present invention has at least quasi-non-combustible property in the heat generation test based on ISO-5660, that is, in Table 1 below, the non-combustible material and the forward non-combustible material. Determine the composition of each material so that it belongs to the material.
[Table 1]

The optimum compounding ratio of each material may be appropriately derived by experiment.
The details of each material will be described below.

<3> Polyisocyanate compound The polyisocyanate compound is a material used as a main agent in the urethane resin composition according to the present invention.
Examples of the polyisocyanate compound include aromatic polyisocyanates, alicyclic polyisocyanates, and aliphatic polyisocyanates.

Examples of the aromatic polyisocyanate include phenylenediocyanate, tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, dimethyldiphenylmethane diisocyanate, triphenylmethane triisocyanate, naphthalene diisocyanate, and polymethylene polyphenyl polyisocyanate.
Examples of the alicyclic polyisocyanate include cyclohexylene diisocyanate, methylcyclohexylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, and dimethyldicyclohexylmethane diisocyanate.

Examples of the aliphatic polyisocyanate include methylene diisocyanate, ethylene diisocyanate, propylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate and the like.
As the polyisocyanate compound, one kind or two or more kinds can be used.
The main agent of the urethane resin composition is preferably diphenylmethane diisocyanate because it is easy to use and easily available.

The content (% by weight) of the isocyanate compound in the urethane resin composition is preferably 20 to 80%. If it is less than 20%, the flame retardancy deteriorates, and if it exceeds 80%, the adhesiveness to the skeleton or the like deteriorates. To do.

<4> Polyurethane compound The polyurethane compound is a material used as a curing agent for the urethane resin composition according to the present invention.
The polyol compound consists of an ester-based polyol compound or an ether-based polyol compound and a combination thereof.

<4.1> Ester-based polyol compound As the ester-based polyol compound, for example, a polymer obtained by dehydration condensation of a polybasic acid and a polyhydric alcohol, a lactone such as ε-caprolactone and α-methyl-ε-caprolactone. Examples thereof include a polymer obtained by ring-opening polymerization, and a condensate of hydroxycarboxylic acid and the above-mentioned polyhydric alcohol.
Here, specific examples of the polybasic acid include adipic acid, azelaic acid, sebacic acid, terephthalic acid, isophthalic acid, succinic acid and the like. Terephthalic acid modification is preferable in terms of flame retardancy, and fatty acid modification is preferable in terms of adhesiveness.

The content (% by weight) of the ester compound in the urethane resin composition is preferably 20 to 80%. If it is less than 20%, the adhesiveness to the skeleton or the like deteriorates, and if it exceeds 80%, the resin strength is low. Problems such as bending and shrinkage may occur.

<4.2> Other polyol compounds Examples of other polyol compounds include polylactone polyols, polycarbonate polyols, aromatic polyols, alicyclic polyols, aliphatic polyols, polymer polyols, and polyether polyols.
Examples of the polylactone polyol include polypropiolactone glycol, polycaprolactone glycol, polyvalerolactone glycol and the like.
The polycarbonate polyol can be obtained, for example, by a dealcohol reaction between a hydroxyl group-containing compound such as ethylene glycol, propylene glycol, butanediol, pentandiol, hexanediol, octanediol or nonanediol and diethylene carbonate, dipropylene carbonate or the like. Examples include polyols.
Examples of the aromatic polyol include bisphenol A, bisphenol F, phenol novolac, cresol novolac and the like.
Examples of the alicyclic polyol include cyclohexanediol, methylcyclohexanediol, isophoronediol, dicyclohexylmethanediol, and dimethyldicyclohexylmethanediol.
Examples of the aliphatic polyol include ethylene glycol, propylene glycol, butanediol, pentanediol, and hexanediol.
Specific examples of the polyhydric alcohol include bisphenol A, ethylene glycol, 1,2-propylene glycol, 1,4-butanediol, diethylene glycol, 1,6-hexane glycol, neopentyl glycol and the like. ..
Specific examples of the hydroxycarboxylic acid include castor oil, a reaction product of castor oil and ethylene glycol, and the like.
Aromatic polyols are desirable in terms of flame retardancy.

<5> Triadization catalyst The triadization catalyst is a material for reacting an isocyanate group contained in a polyisocyanate compound to tritrate it and promote the formation of an isocyanurate ring.
Examples of the trimerization catalyst include tris (dimethylaminomethyl) phenol, 2,4-bis (dimethylaminomethyl) phenol, 2,4,6-tris (dialkylaminoalkyl) hexahydro-S-triazine and the like as catalysts. Nitrogen-containing aromatic compounds, alkali metal carboxylates such as potassium acetate, potassium 2-ethylhexanate, potassium octylate, tertiary ammonium salts such as trimethylammonium salt, triethylammonium salt, triphenylammonium salt, tetramethylammonium salt , Quaternary ammonium salts such as tetraethylammonium and tetraphenylammonium salts can be used.
A combination of an alkyl carboxylic acid metal salt and a quaternary ammonium salt is desirable from the viewpoint of adhesiveness and flame retardancy at low temperatures.

The urethane resin content (% by weight) of the quantification catalyst in the urethane resin composition is preferably 1 to 20%, and if it is less than 1%, the flame retardancy deteriorates, and if it exceeds 20%, the reaction is too fast. This may cause problems such as clogging of the mixing part of the spray gun.

<6> Additives Additives are elements used to impart flame retardancy to the urethane resin composition according to the present invention.
The additive contains red phosphorus as an essential component, and is composed of a combination of at least one of a phosphate-containing flame retardant and a chlorine-containing flame retardant in addition to red phosphorus.

<6.1> Red phosphorus Red phosphorus is an element for suppressing the total calorific value during combustion.
The red phosphorus used in the present invention is not limited, and a commercially available product can be appropriately selected and used. However, when considering the production of a polyol liquid, red phosphorus, which is a dangerous substance of the second class of the Fire Service Act, is thermoplastic. It is desirable to use a surface-treated product such as plastic that is resistant to oxidation and has improved safety and stability.

The content (% by weight) of the urethane resin of red phosphorus in the urethane resin composition is preferably 0.3 to 25%, if it is less than 0.3%, the flame retardancy deteriorates, and if it exceeds 25%, it is sprayed. Problems such as clogging of the mixing part of the gun may occur.

<6.2> Phosphate-containing flame retardant The phosphate-containing flame retardant is an element for further suppressing the total calorific value in combination with red phosphorus.
The phosphate-containing flame retardant used in the present invention contains phosphoric acid.

The phosphate-containing flame retardant is, for example, from a salt of the various phosphoric acids and at least one metal or compound selected from the metals of Groups IA to IVB of the Periodic Table, ammonia, aliphatic amines, and aromatic amines. Phosphate can be mentioned.
Examples of the metals of Groups IA to IVB of the Periodic Table include lithium, sodium, calcium, barium, iron (II), iron (III), and aluminum.
Examples of the aliphatic amine include methylamine, ethylamine, diethylamine, triethylamine, ethylenediamine, piperazine and the like.
Further, examples of the aromatic amine include pyridine, triazine, melamine, ammonium 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 coating with a melamine resin, or a known foaming aid such as melamine or pentaerythritol may be added. You may.

Further, specific examples of the phosphate-containing flame retardant include monophosphate, pyrophosphate, polyphosphate and the like.

The monophosphate is not particularly limited, but for example, ammonium salts such as ammonium phosphate, ammonium dihydrogen phosphate, and diammonium hydrogen phosphate, monosodium phosphate, disodium phosphate, trisodium phosphate, and phosphite. Sodium acid monosodium, disodium phosphite, sodium salts such as sodium hypophosphite, monopotassium phosphate, dipotassium phosphate, tripotassium phosphate, monopotassium phosphite, dipotassium phosphite, hypophosphite Potassium salts such as potassium acid, monolithium phosphate, dilithium phosphate, trilithium phosphate, monolithium phosphite, dilithium phosphite, lithium salts such as lithium hypophosphite, 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, aluminum polyphosphate, and the like.

Among these, polyphosphate is preferably used because the self-extinguishing property of the phosphate-containing flame retardant is improved, and ammonium polyphosphate or aluminum phosphite that forms a foam layer when heated may be used. More preferred.

The phosphate-containing flame retardant may be used alone or in combination of two or more.

The urethane resin content (% by weight) of the phosphate-containing flame retardant in the urethane resin composition is preferably 0.3 to 25%, and if it is less than 0.3%, the flame retardancy deteriorates and exceeds 25%. In this case, problems such as clogging of the mixing part of the spray gun and powder settling of the stirred raw material in a short period of time may occur.

<6.3> Chlorine-containing flame retardant The chlorine-containing flame retardant is an element for suppressing the maximum heat generation rate at the initial stage of combustion.
The following five types of flame retardants are widely used as chlorine-containing flame retardants.
(A) Tris (chloroethyl) phosphate (TCEP) CAS Registry Number 115-96-8
(B) Tris (β-chloropropyl) phosphate (TCPP) CAS Registry Number 13674-84-5
(C) Tris (dichloropropyl) phosphate (TDCP) CAS Registry Number 13674-87-8
(D) Tetrakis (2 chloroethyl) dichloroisopentyl diphosphate (V6) CAS No. 38051-10-4
(E) Polyoxyalkylene bis (dichloroalkyl) phosphate (CR-504L) CAS No. 184530-92-5

The urethane resin content (% by weight) of the chlorine-containing flame retardant in the urethane resin composition is preferably 2 to 30%, and if it is less than 2%, the flame retardancy deteriorates, and if it exceeds 30%, the resin strength is high. It may become smaller and problems such as shrinkage may occur.

<7> Non-silicon-based surface conditioner Examples of the non-silicon-based surface conditioner include an acrylic surface conditioner.
The acrylic surface conditioner is a solvent-free surface conditioner containing an acrylic polymer as a main component, and has a function of increasing the surface free energy of the cured resin.
By incorporating a highly polar part in the molecule, the acrylic surface conditioner increases the surface free energy of the added coating film, and is effective in improving the wettability and adhesion to the topcoat and imparting hydrophilicity. ..
In addition, since the acrylic surface conditioner is a solvent-free liquid product, it is easy to add, and it can be applied not only to solvent-based paints but also to solvent-free paints.
In the present invention, the surface conditioner is non-silicone in order to prevent deterioration of adhesiveness during lamination and prevent falling off and curling.

The content of the non-silicone surface conditioner in the urethane resin composition is preferably 0.2 to 10%, and if it is less than 0.2%, the predetermined expansion ratio cannot be obtained, and if it exceeds 10%, the resin strength May become smaller and problems such as shrinkage may occur.

<8> Defoamer (reason for not including it in the formulation)
The defoaming agent has the role of adjusting the surface tension when making a foam by confining the foaming agent by surface tension, and when the foaming agent is removed, the foam does not become a foam and is a lump of resin. Therefore, it is considered as an essential component in the technical field according to the present invention.
On the other hand, the use of the foam stabilizer also has disadvantages such as a decrease in the self-adhesive strength of urethane, generation of cyclic siloxane, and an adverse effect on foamability due to the combination with the HFO foaming agent.
Therefore, in the urethane resin composition according to the present invention, a foam that does not hinder the heat insulating material of the building is formed by selecting the compounding conditions of other materials even if the foam stabilizer is not included.

<9> Others In addition, the following materials may be included in the urethane resin composition according to the present invention.

<9.1> Foaming agent The foaming agent is for improving the foaming action when the polyisocyanate compound (first liquid) and the other components (second liquid) are mixed to form a foam. It is a material.
The foaming agent promotes the foaming of the urethane resin. Effervescent agents include, for example, water; low boiling hydrocarbons such as propane, butane, pentane, hexane, heptane, cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptan; dichloroethane, propyl chloride, isopropyl chloride, butyl chloride, etc. Chlorinated aliphatic hydrocarbon compounds such as isobutyl chloride, pentyl chloride, and isopentyl chloride; fluorine compounds such as CHF3, CH2F2, and CH3F; trichloromonofluoromethane, trichlorotrifluoroethane, dichloromonofluoroethane, etc. (for example, HCFC141b (1) , 1-dichloro-1-fluoroethane), HCFC22 (chlorodifluoromethane), HCFC142b (1-chloro-1,1-difluoroethane)) and other hydrocarbon compounds; HFC-245fa (1,1,1,3,3) Hydrofluorocarbons such as 3-pentafluoropropane), HFC-365mfc (1,1,1,3,3-pentafluorobutane); HFO-1233zd ((E) -1-chloro-3,3,3-trifluoro) Hydrofluoroolefins such as Propen); organic physical foaming agents such as ether compounds such as diisopropyl ether or mixtures of these compounds, inorganic physical foaming agents such as nitrogen gas, oxygen gas, argon gas, carbon dioxide gas, etc. Can be mentioned.

It is preferable to contain hydrofluoroolefin (HFO) as a foaming agent from the viewpoint of environmental impact and excellent heat insulating performance.

The content of the foaming agent is not particularly limited, but is preferably 0.3 parts by weight to 112 parts by weight, more preferably in the range of 0.3 parts by weight to 67 parts, still more preferably, with respect to 100 parts by weight of the polyol. Is in the range of 1.8 parts by weight to 67 parts by weight, most preferably in the range of 3.7 parts by weight to 37 parts by weight. In the foamable polyurethane composition, it can be in the range of 0.1 parts by weight to 30 parts by weight, and more preferably in the range of 0.1 parts by weight to 18 parts by weight with respect to 100 parts by weight of the urethane resin. It is more preferably in the range of 0.5 parts by weight to 18 parts by weight, and most preferably in the range of 1 part by weight to 10 parts by weight.

When the range of the foaming agent is not less than the above lower limit value, foaming is promoted and the density of the obtained molded product can be reduced, and when it is not more than the above upper limit value, the foam does not foam and the foam is not formed. Can be prevented.

Further, in the present invention, one or more of the above-mentioned foaming agents may be used.

<9.2> Urethane foaming catalyst The urethanization foam catalyst is a material that particularly promotes the reaction between an isocyanate compound and water. Specifically, the carbon dioxide gas generated by the reaction between isocyanate and water promotes the foaming of the stock solution.
Specifically, as the foaming catalyst, a chain tertiary amine such as bis (2-dimethylaminoethyl) ether, N, N-dimethylalkylamine, or a tertiary amine resin composition is neutralized with a carboxylic acid. An acid block type foaming catalyst can be mentioned.
From the viewpoint of not causing decomposition of HFCs and HFOs, it is preferable to use an acid block type foaming catalyst.

The content (% by weight) of the urethane resin of the urethane foaming catalyst in the urethane resin composition is preferably 0.1 to 10%, and if it is less than 0.1%, the predetermined foaming ratio cannot be obtained and 10%. If it is too high, the reaction may become too fast and problems such as clogging of the mixing part of the spray gun may occur.

<9.3> Urethaneated metal catalyst The urethanized metal catalyst is a material for accelerating the reaction between an isocyanate compound and a polyol compound.
Examples of the urethanized metal catalyst include metal salts composed of lead, tin, bismuth, copper, zinc, cobalt, nickel and the like, and preferably an organic acid metal composed of lead, tin, bismuth, copper, zinc, cobalt, nickel and the like. It is a salt and has the effect of not causing decomposition of HFC and HFO foaming agent by an amine-based urethane catalyst.

The urethane resin content (% by weight) of the urethanized metal catalyst is preferably 0.1 to 10%. If it is less than 0.1%, the predetermined expansion ratio cannot be obtained, and if it exceeds 10%, the reaction occurs. It may become too fast and problems such as clogging of the mixing part of the spray gun may occur.

<9.4> Adhesive Accelerator The adhesive accelerator is a material for improving the adhesiveness of the urethane resin composition according to the present invention.
Examples of the adhesion accelerator include cyclic esters and the like.
Adhesion promoters promote polymerization of foam surfaces to reduce surface flyability, which tends to occur with high index and / or high water content, and also provide proper foam adhesion even when spray foam is applied in low temperature environments. Sex can be realized.

<9.5> Dispersant The dispersant is a material for improving the dispersibility of the flame retardant.
Examples of the dispersant include an alkylammonium salt of an acidic copolymer having a hydroxyl group.
By including the dispersant, the wet dispersion rate of the red phosphorus at the time of dispersion and the phosphate-containing flame retardant filler is improved, and the viscosity is lowered, so that the blending amount of the filler can be increased.
The higher the blending amount of the filler, the better the flame retardancy.
Further, it is possible to obtain the effect of significantly delaying the time for the filler to settle on the bottom of the container after stirring and mixing the filler with a stirring blade or the like.

The content weight of the urethane resin of the dispersant in the urethane resin composition is preferably 0.1 to 10%. If it is less than 0.1%, the dispersibility of the filler is not improved, and if it exceeds 10%, the dispersibility of the filler is not improved. The resin strength may decrease and problems such as shrinkage may occur.

Hereinafter, the present invention will be described in detail with reference to Examples. The present invention is not limited to the following examples.

<1> Experimental conditions Various tests were carried out on examples using a foam using the urethane resin composition according to the present invention and comparative examples using the prior art.
Details of each component used in Examples and Comparative Examples are as follows.
In addition, the numerical value of each component is indicated by the weight part.

(1) Polyester compound ・ A-1: Polyester polyol terephthalate (manufactured by Kawasaki Kasei Chemicals, product name: Maximol RFK-505, hydroxyl value = 250 mgKOH / g)
-A-2: Polyester polyol terephthalate (manufactured by Kawasaki Kasei Chemicals, product name: Maximol RFK-509, hydroxyl value = 200 mgKOH / g)
-A-3: Aliphatic modified terephthalic acid-based polyol (manufactured by Kawasaki Kasei Chemicals, product name: Maximol RLK-087, hydroxyl value = 200 mgKOH / g)
-A-4: Mannich-based polyol (manufactured by Asahi Glass Co., Ltd., product name: Excelol NB-615, hydroxyl value = 579 mgKOH / g)

(2) Triquantification catalyst ・ B-1: Potassium octylate (manufactured by Evonik Industries, product name: DABCO K-15)
-B-2: Quaternary ammonium salt (manufactured by Evonik, product name: TMR-7)

(3) Urethane foaming catalyst ・ C: Tertiary amine salt (manufactured by Evonik, product name: POLYCAT 201)

(4) Metal resinification catalyst ・ D: Bismuth octylate (manufactured by Shepherd Chemical Co., Ltd., product name: Bicat 8210)

(5) Foaming agent-E-1: Water-E-2: HFO-1233zd (Manufactured by Honeywell, product name: Solstice LBA)
-E-3: HFO-1336mzz (manufactured by The Chemours Company, product name: OPTEN1100)

(6) Silicone antifoaming agent F: Silicone (manufactured by Toray Dow Corning Co., Ltd., product name: SH-193)

(7) Additives ・ G-1: Red phosphorus (manufactured by Phosphorus Chemical Industry Co., Ltd., product name: Nova Excel 140)
-G-2: Ammonium polyphosphate (manufactured by Taihei Chemical Industry Co., Ltd., product name: Taien CII)
-G-3: Aluminum unimu phosphate (manufactured by Taihei Chemical Industry Co., Ltd., product name: APA100)
-G-4: Chlorine-based phosphate ester Tris (β-chloropropyl) phosphate (manufactured by Daihachi Chemical Industry Co., Ltd., product name: TMCPP)

(8) Adhesion accelerator ・ H: Cyclic ester (manufactured by Momentive, product name: AP)

(9) Dispersant ・ I: Wet dispersant Alkylation ammonium salt of acidic copolymer (manufactured by Big Chemie Japan Co., Ltd., product name: BYK-W969)

(10) Surface conditioner ・ J-1: Acrylic polymer (manufactured by Kusumoto Kasei Co., Ltd., product name: SEI-W01)
-J-2: Acrylic polymer (manufactured by Kusumoto Kasei Co., Ltd., product name: SEI-1501)
-J-3: Anionic polymer (manufactured by Kusumoto Kasei Co., Ltd., product name: AQ-360)
-J-4: Vinyl-based polymer (manufactured by Kusumoto Kasei Co., Ltd., product name: UVX-190)

(11) Polyisocyanate ・ K: Polymeric MDI (manufactured by Tosoh Corporation, product name: Millionate MR-200)

<2> Adhesiveness Evaluation Method In the evaluation of adhesiveness, "○" was considered appropriate and "x" was considered unsuitable based on the adhesive strength of 80 kPa or more according to the method of measuring the adhesive strength of JIS A9526.

<3> Flame-retardant evaluation method For flame-retardant evaluation, a sample for a cone calorimeter test was prepared for each of the foams according to each example, and a heat-generating test based on the ISO-5660 test method was performed. The total calorific value, maximum heat generation rate, quasi-nonflammability and nonflammability were evaluated.

<4> Outline of the test The outline of the exothermic test is as follows.
The foam is cut into 10 cm in length, 10 cm in width and 5 cm in thickness to prepare a sample for a cone calorimeter test.
[hand]
The polyol solution and isocyanate solution mixed in advance according to the composition table were weighed in a 1 liter disc cup, and after the liquid temperature reached 15 ° C., the raw materials were stirred and mixed for 3 to 8 seconds with a 2800 rpm stirring drill equipped with a cage mixer. A test piece was prepared by injecting a liquid into a 200 × 200 × height-free box.
The injection was carried out twice or more in order to confirm the adhesiveness at the time of laminating.
[spray]
A polyol solution and an isocyanate solution mixed in advance according to the composition table were prepared in a 200-liter drum, and a test piece was prepared under the following conditions.
Spray equipment: GRACO A-25 type spray gun: GRACO AP AR4242
Raw material temperature: 60 ° C
Specimen preparation method: Compliant with JIS A9526

Using the corn calorimeter test sample, the total calorific value and maximum calorific value measured by the corn calorimeter test when heated for 20 minutes at a radiant heat intensity of 50 kW / m2 in accordance with the ISO-5660 test method. And confirmed the residual state.

<5> Test Results The test results for each Example and Comparative Example are shown in Tables 2 and 3, and the comparison table in which the test results are extracted for each of the following items is shown in FIGS. 1 to 7.
[Table 2]

＜５．１＞整泡剤の有無（比較例１，２と、実施例１）
図１に、整泡剤の有無による実験結果の対比を示す。
比較例１，２に示す、整泡剤（シリコン系整泡剤）を含んだウレタン樹脂組成物の場合、何れも接着性は不適であった。
実施例１は、比較例２に示す配合から整泡剤を除き、新たに表面調整剤を加えたものであるところ、接着性に問題は無かった。
よって、本発明においては、整泡剤を含めないことが接着性の確保に重要な要因であるものと推測される。 [Table 3]

<5.1> Presence or absence of antifoaming agent (Comparative Examples 1 and 2 and Example 1)
FIG. 1 shows a comparison of experimental results with and without a defoaming agent.
In the case of the urethane resin composition containing the defoaming agent (silicone-based defoaming agent) shown in Comparative Examples 1 and 2, the adhesiveness was unsuitable.
In Example 1, when the foam stabilizer was removed from the formulation shown in Comparative Example 2 and a surface conditioner was newly added, there was no problem in adhesiveness.
Therefore, in the present invention, it is presumed that not including the defoaming agent is an important factor for ensuring the adhesiveness.

<5.2> Differences in types of surface conditioners (Example 3 and Comparative Examples 3 and 4)
FIG. 2 shows a comparison of experimental results depending on the type of surface material.
In Example 3, a surface conditioner of a non-silicone acrylic polymer was used, and there was no problem in evaluating the adhesiveness and nonflammability.
On the other hand, when a surface conditioner such as an anionic surfactant or a surface conditioner of a vinyl polymer was used as in Comparative Examples 3 and 4, the cell state of the foam was not preferable. ..
Therefore, when a surface conditioner is included in the present invention, it is presumed that a non-silicone acrylic polymer surface conditioner is preferable.

<5.3> Presence or absence of ether-based polyol compound (Examples 10 and 11)
FIG. 3 shows a comparison of the experimental results with and without the ether-based polyol compound.
When Example 10 in which the ester-based polyol compound is selected as the polyol compound and Example 11 in which the ether-based polyol compound is further added to Example 10 are compared, all of the examples are adhesive, nonflammable, and quasi. There was no problem in the evaluation of nonflammability, and there was no big difference between the two.
Therefore, in the present invention, it is presumed that there is no problem in using the ester-based polyol compound and the ether-based polyol compound together as the polyol compound.

<5.4> Presence or absence of adhesion accelerator (Examples 8 and 10)
FIG. 4 shows a comparison of the experimental results with and without the adhesion accelerator.
Although the formulation was different between Example 8 and Example 10 only in the presence or absence of the adhesion promoter, there was no problem in the evaluation of adhesiveness, nonflammability and quasi-nonflammability in any of the examples.
Therefore, in the present invention, it is presumed that there is no problem in newly adding the adhesion accelerator.

<5.5> Presence or absence of urethanization catalyst or metal resinification catalyst (Examples 14 to 16)
FIG. 5 shows a comparison of the experimental results with and without the urethanization catalyst or the metal resinification catalyst.
Between Examples 14 to 16, the formulations differed only in the presence or absence of the urethanization catalyst and the metal resinification catalyst, and there was no problem in the evaluation of adhesiveness, nonflammability, and quasi-nonflammability in any of the examples.
Therefore, in the present invention, it is presumed that there is no problem in newly adding the urethanization catalyst or the metal resinification catalyst.

<5.6> Presence or absence of dispersant (Examples 12 and 17)
FIG. 6 shows a comparison of the experimental results with and without the dispersant.
The formulation was different between Example 12 and Example 17 only in the presence or absence of the dispersant, and there was no problem in the evaluation of adhesiveness, nonflammability and quasi-nonflammability in any of the examples.
Therefore, in the present invention, it is presumed that there is no problem in newly adding the urethanization catalyst or the metal resinification catalyst.

<5.7> Presence or absence of phosphate-containing flame retardant or chlorine-containing flame retardant (Examples 18 and 19 and Comparative Example 5)
FIG. 7 shows a comparison of the experimental results with and without the phosphate-containing flame retardant or the chlorine-containing flame retardant.
In Example 18 containing the chlorine-containing flame retardant (G-4) chlorine-based phosphoric acid ester, and in Example 19 containing the phosphate-containing flame retardant (G-2) ammonium polyphosphate, whichever In the example, there was no problem in evaluating the adhesiveness, nonflammability and semi-nonflammability.
On the other hand, in the example shown in Comparative Example 5 in which neither the phosphate-containing flame retardant nor the chlorine-containing flame retardant was included, the total calorific value and the maximum calorific value in the nonflammability evaluation were higher than those of Examples 18 and 19 described above. Also deteriorated, and the residual condition became unsuitable.
Therefore, in the present invention, it is presumed that improvement of flame retardancy can be expected by newly adding a phosphate-containing flame retardant or a chlorine-containing flame retardant.

Claims (10)

A urethane resin composition for forming a foam constituting a heat insulating material of a building, wherein the foam has at least semi-incombustible in a heat generation test based on ISO-5660. And
It shall contain at least a polyisocyanate compound, an ester-based polyol compound, a quantification catalyst, an additive, and a non-silicone-based surface conditioner, and shall not contain a defoaming agent.
The additive
It is characterized in that red phosphorus is an essential component and at least one of a phosphate-containing flame retardant and a chlorine-containing flame retardant is combined.
Urethane resin composition. The urethane resin composition according to claim 1, wherein the phosphate-containing flame retardant comprises at least one of ammonium phosphate and aluminum phosphite. The urethane resin composition according to claim 1 or 2, wherein the chlorine-containing flame retardant is a chlorine-based phosphoric acid ester. The urethane resin composition according to any one of claims 1 to 3, wherein the non-silicone-based surface conditioner is an acrylic surface conditioner. The urethane resin composition according to any one of claims 1 to 4, further comprising a foaming agent having an HFO (hydrofluoroolefin). The urethane resin composition according to any one of claims 1 to 5, further comprising an ether-based polyol compound. The urethane resin composition according to any one of claims 1 to 6, further comprising an adhesion accelerator. The urethane resin composition according to any one of claims 1 to 7, further comprising at least one of a urethane foaming catalyst and a urethane metal catalyst. The urethane resin composition according to any one of claims 1 to 8, further comprising a dispersant. A method for heat insulating a building, which comprises using the urethane resin composition according to any one of claims 1 to 9 as a heat insulating material for spraying on-site foam.

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