JP2018062659A - Foamable polyurethane composition for on-site spraying - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a foamable heat-insulation material for on-site spraying that has low corrosiveness and high flame retardancy.SOLUTION: A polyol composition is mixed with a polyisocyanate compound to obtain a foamable polyurethane composition for on-site spraying. The polyol composition contains a polyol compound, a flame retardant, and a catalyst. The flame retardant has a chlorine content of 100 ppm or less.SELECTED DRAWING: None

Description

  The present invention relates to a polyol composition for obtaining a foamable polyurethane composition for in-situ spraying, a foamable polyurethane premix composition for in-situ spraying, a foamable polyurethane composition for in-situ spraying, a flame retardant structure, and a method for producing the same. .

  A urethane resin composition is used as a heat insulating material for buildings such as apartment houses such as apartment buildings, detached houses, various facilities of schools, commercial buildings, and the like because of its excellent heat insulating properties and adhesive properties. Among them, it is useful as an in-situ foaming urethane.

JP 2014-193995 International Publication WO2016 / 047767 JP2014-524954

  In general, urethane used for in-situ foaming has a composition using a halogen-containing flame retardant in order to enhance the flame retardant effect. However, for example, steels (especially iron plates and stainless steel plates) that are often used in building materials because of their low cost may be corroded by halogen-containing flame retardants. On the other hand, a formulation capable of exhibiting a sufficient flame retardant effect without using a halogen-containing flame retardant is not known, and a formulation having low corrosivity and high flame retardancy is desired.

  The inventors of the present application have made various studies in order to achieve the above object, and found that the above problems can be solved by using at least one flame retardant having a chlorine content of 100 ppm or less as the flame retardant. It came to be completed.

That is, the present invention is as follows.
[1] A polyol composition for mixing with a polyisocyanate compound to obtain a foamable polyurethane composition for in-situ spraying,
Contains a polyol compound, a flame retardant, and a catalyst,
As the flame retardant, containing one or more selected from the group consisting of red phosphorus, needle filler and boron-containing flame retardant,
A polyol composition, wherein the flame retardant has a chlorine content of 100 ppm or less.
[2] The polyol composition as described in [1], wherein the flame retardant contains at least red phosphorus.
[3] A trimerization catalyst is contained as the catalyst, and the trimerization catalyst is contained in an amount of 0.3 to 38 parts by weight with respect to a total of 100 parts by weight of the isocyanate compound and the polyol compound. ] The polyol composition as described in.
[4] A urethanization catalyst is contained as the catalyst, and the urethanization catalyst is contained in an amount of 0.1 to 10 parts by weight with respect to a total of 100 parts by weight of the isocyanate compound and the polyol compound. ] The polyol composition of any one of.
[5] The polyol composition according to any one of [1] to [4], wherein a chlorine content in the polyol composition is 100 ppm or less.
[6] A foamable polyurethane premix composition for on-site spraying, comprising the polyol composition according to any one of [1] to [5] and an isocyanate compound separately.
[7] A foamable urethane resin composition for on-site spraying, which is a mixture of the polyol composition according to any one of [1] to [6] and an isocyanate compound.
[8] The foamable urethane resin composition for on-site spraying according to [7] for spraying on a steel substrate.
[9] The foamable urethane resin composition for on-site spraying according to [7], for spraying on a concrete base material.
[10] A method for producing a flame-retardant structure, comprising a step of spraying a foamable urethane resin composition for on-site spraying according to any one of [7] to [9] onto a substrate.
[11] The method for producing a flame-retardant structure according to [10], wherein the base material is steel or concrete.
[12] The method according to [10] or [11], including a step of mixing the foamable urethane resin composition for in-situ spraying according to any one of [7] to [9] on-site. Method for manufacturing a flame retardant structure.
[13] A flame-retardant structure in which urethane foam obtained by curing the foamable urethane resin composition for on-site spraying according to any one of [7] to [9] is laminated on a base material that is steel or concrete.

  Polyol composition, foamable polyurethane premix composition, foamable urethane resin composition for forming a foamed heat insulating material having low corrosivity and high flame retardancy by spraying the substrate on site in accordance with the present invention Also provided are a flame retardant structure having a foamed heat insulating material having low corrosivity and high flame retardancy, and a method for producing the same.

The present invention includes the following embodiments (i) to (v):
(I) A polyol composition for reacting with a polyisocyanate compound to obtain a foamable polyurethane composition for in-situ spraying, comprising a polyol compound, a flame retardant, and a catalyst, and as the flame retardant, red phosphorus A polyol composition comprising one or more selected from the group consisting of needle fillers and boron-containing flame retardants, and containing one or more flame retardants having a chlorine content of 100 ppm or less,
(Ii) For the above case, we will request that the submission period be extended by 2 months. A foamable polyurethane premix composition for in-situ spraying comprising the polyol composition and the polyisocyanate compound separately;
(Iii) a foamable polyurethane composition for in-situ spraying, which is a mixture of the polyol composition and a polyisocyanate compound;
(Iv) a method for producing a flame-retardant structure, comprising the step of spraying the foamable urethane resin composition for in-situ spraying on a base material, and (v) foaming for on-site spraying on a base material that is steel or concrete. Flame retardant structure in which foamed urethane with cured urethane resin composition is laminated.

  The polyol composition of the present invention contains a polyol, a polyol compound, a flame retardant, a catalyst, and optionally other components. Examples of other components include, but are not limited to, a foam stabilizer and a foaming agent.

  The polyisocyanate as the main component of the urethane resin and the polyol as the curing agent of the urethane resin are cured by a chemical reaction to form a urethane resin.

  Hereinafter, each component will be described.

1. Polyols Examples of polyols that are curing agents for urethane resins include polylactone polyols, polycarbonate polyols, aromatic polyols, alicyclic polyols, aliphatic polyols, polyester polyols, polymer polyols, and polyether polyols.

  Examples of the polylactone polyol include polypropiolactone glycol, polycaprolactone glycol, and polyvalerolactone glycol.

  Examples of the polycarbonate polyol include a polyol obtained by a dealcoholization reaction of a hydroxyl group-containing compound such as ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, octanediol, and nonanediol with diethylene carbonate, dipropylene carbonate, and the like. Etc.

  Examples of the aromatic polyol include bisphenol A, bisphenol F, phenol novolac, and cresol novolak.

  Examples of the alicyclic polyol include cyclohexanediol, methylcyclohexanediol, isophoronediol, dicyclohexylmethanediol, dimethyldicyclohexylmethanediol, and the like.

  Examples of the aliphatic polyol include ethylene glycol, propylene glycol, butanediol, pentanediol, and hexanediol.

  Examples of the polyester polyol include a polymer obtained by dehydration condensation of a polybasic acid and a polyhydric alcohol, a polymer obtained by ring-opening polymerization of a lactone such as ε-caprolactone and α-methyl-ε-caprolactone, Examples thereof include condensates of hydroxycarboxylic acid and the above polyhydric alcohol.

  Specific examples of the polybasic acid include adipic acid, azelaic acid, sebacic acid, terephthalic acid, isophthalic acid, and succinic acid. 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.

  Examples of the polymer polyol include a polymer obtained by graft polymerization of an ethylenically unsaturated compound such as acrylonitrile, styrene, methyl acrylate, and methacrylate on an aromatic polyol, alicyclic polyol, aliphatic polyol, polyester polyol, or the like, polybutadiene Examples thereof include polyols, modified polyols of polyhydric alcohols, and hydrogenated products thereof.

  Examples of the modified polyol of the polyhydric alcohol include those modified by reacting the raw material polyhydric alcohol with an alkylene oxide.

Examples of the polyhydric alcohol include trihydric alcohols such as glycerin and trimethylolpropane;
Pentaerythritol, sorbitol, mannitol, sorbitan, diglycerin, dipentaerythritol, etc.
Tetra- to octavalent alcohols such as sucrose, glucose, mannose, fructose, methyl glucoside and derivatives thereof;
Phenol, phloroglucin, cresol, pyrogallol, catechol, hydroquinone, bisphenol A, bisphenol F, bisphenol S, 1-hydroxynaphthalene, 1,3,6,8-tetrahydroxynaphthalene, anthrol, 1,4,5,8 -Phenol polybutadiene polyols such as tetrahydroxyanthracene, 1-hydroxypyrene;
Castor oil polyol;
(Co) polymer of hydroxyalkyl (meth) acrylate, polyfunctional polyol (eg 2 to 100 functional groups) such as polyvinyl alcohol, condensate of phenol and formaldehyde (novolak)
Is mentioned.

  The method for modifying the polyhydric alcohol is not particularly limited, and a method of adding alkylene oxide (hereinafter abbreviated as AO) is preferably used.

  As AO, C2-C6 AO, for example, ethylene oxide (hereinafter abbreviated as EO), 1,2-propylene oxide (hereinafter abbreviated as PO), 1,3-propyloxide, 1,2- Examples include butylene oxide and 1,4-butylene oxide.

  Among these, from the viewpoints of properties and reactivity, PO, EO, and 1,2-butylene oxide are preferable, and PO and EO are more preferable. When two or more types of AO are used (for example, PO and EO), block addition or random addition may be used, or a combination thereof may be used.

As the polyether polyol, for example, in the presence of at least one low molecular weight active hydrogen compound having two or more active hydrogens, at least one alkylene oxide such as ethylene oxide, propylene oxide or tetrahydrofuran is subjected to ring-opening polymerization. The polymer obtained by making it contain is mentioned.

  Examples of the low molecular weight active hydrogen compound having two or more active hydrogens include diols such as bisphenol A, ethylene glycol, propylene glycol, butylene glycol, and 1,6-hexanediol, and triols such as glycerol and trimethylolpropane. And amines such as ethylenediamine and butylenediamine.

  The polyol used in the present invention is preferably a polyester polyol or a polyether polyol because the effect of reducing the total calorific value upon combustion is great.

  Among them, it is more preferable to use a polyester polyol having a molecular weight of 200 to 800, and it is more preferable to use a polyester polyol having a molecular weight of 300 to 500.

2. Polyisocyanate compound Examples of the polyisocyanate compound that is a main component of the urethane resin include aromatic polyisocyanates, alicyclic polyisocyanates, and aliphatic polyisocyanates.

  Examples of the aromatic polyisocyanate include phenylene diisocyanate, tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, dimethyldiphenylmethane diisocyanate, triphenylmethane triisocyanate, naphthalene diisocyanate, polymethylene polyphenyl polyisocyanate, and the like.

  Examples of the alicyclic polyisocyanate include cyclohexylene diisocyanate, methylcyclohexylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, and dimethyldicyclohexylmethane diisocyanate.

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

  One or more polyisocyanate compounds can be used. The main component of the urethane resin is preferably an aromatic polyisocyanate such as diphenylmethane diisocyanate because it is easy to use and easily available.

  In the composition of the present invention, the isocyanate index is preferably 150 or more and 1000 or less, more preferably 200 or more and 800 or less, further preferably 250 or more and 700 or less, and most preferably 300 or more and 600 or less.

  The isocyanate index (INDEX) is calculated by the following method: INDEX = number of isocyanate equivalents ÷ (number of equivalents of polyol + number of water equivalents) × 100.

here,
Equivalent number of isocyanate = number of polyisocyanate used × NCO content (%) ÷ 100 / NCO molecular weight,
Equivalent number of polyol = OHV × number of used parts of polyol ÷ molecular weight of KOH, OHV is hydroxyl value of polyol (mg KOH / g),
Equivalent number of water = number of used parts of water × number of OH groups of water / molecular weight of water. In the above formula, the unit of the number of parts used is weight (g), the molecular weight of the NCO group is 42, and the NCO content is the percentage of the NCO group in the polyisocyanate compound expressed by 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 in water is 2.

3. Catalyst Examples of the catalyst include a trimerization catalyst. A trimerization catalyst makes the isocyanate group contained in the polyisocyanate which is the main ingredient of a polyurethane resin react and trimerize, and further promotes the production | generation of an isocyanurate ring.

As a trimerization catalyst, for example,
Nitrogen-containing aromatic compounds such as tris (dimethylaminomethyl) phenol, 2,4-bis (dimethylaminomethyl) phenol, 2,4,6-tris (dialkylaminoalkyl) hexahydro-S-triazine;
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;
Quaternary ammonium salts such as tetramethylammonium salt, tetraethylammonium salt and tetraphenylammonium salt can be used.

  The content of the trimerization catalyst is preferably in the range of 0.3 to 38 parts by weight, more preferably in the range of 0.3 to 30 parts by weight with respect to 100 parts by weight of the polyol. The range is more preferably in the range of 0.3 to 23 parts by weight, and most preferably in the range of 3 to 23 parts by weight. In the foamable polyurethane composition, it can be in the range of 0.1 to 10 parts by weight and more preferably in the range of 0.1 to 8 parts by weight with respect to 100 parts by weight of the urethane resin. The range is preferably from 0.1 parts by weight to 8 parts by weight, and more preferably from 1 part by weight to 8 parts by weight. When the amount is not less than the above lower limit value, the formation of an isocyanurate ring is sufficiently promoted, and when it is not more than the above upper limit value, an appropriate foaming rate can be maintained and the handling is easy.

  Moreover, a urethanization catalyst can also be used as a catalyst. The urethanization catalyst is a catalyst that causes a polymerization reaction simultaneously with the curing and urethanization reaction.

As urethanization catalyst,
Tertiary amine catalysts such as alkylated polyalkylene polyamines, triethylamine, triethylenediamine, N-ethylmorpholine, diethylethanolamine, N ″, N ″ -pentamethyldiethylenetriamine, N, N, N′-trimethylaminoethyl-ethanolamine, N, N, N ′, N′-tetramethylhexamethylenediamine, N, N, N ′, N ″, N ″ -pentamethyldiethylenetriamine, diaminobicyclooctane, 1,2-dimethylimidazole, 1-methylimidazole 1-isobutyl-2-methylimidazole, bis (dimethylaminoethyl) ether, 1,8-diazabicyclo- [5,4,0] -undecene-7;
Metal catalysts such as stannous octylate, dibutylstannic dilaurate, lead octylate;
And combinations thereof.

  The content of the urethanization catalyst is preferably in the range of 0 to 38 parts by weight, more preferably in the range of 0.3 to 38 parts by weight, with respect to 100 parts by weight of the polyol. More preferably, it is in the range of parts by weight to 27 parts by weight, and most preferably in the range of 3 to 15 parts by weight. In the foamable polyurethane composition, it can be in the range of 0 to 10 parts by weight with respect to 100 parts by weight of the urethane resin, more preferably in the range of 0.1 to 7 parts by weight, More preferably, it is in the range of 4 parts by weight. One type or two or more types of catalysts can be used.

4). Examples of the foam stabilizer include surfactants such as a polyoxyalkylene foam stabilizer such as polyoxyalkylene alkyl ether, and a silicone foam stabilizer such as organopolysiloxane.

  If an example shows content of a foam stabilizer, if it is the range of 0.3 weight part-38 weight part with respect to 100 weight part of polyol, for example, it is preferable. In a foaming polyurethane composition, it sets suitably according to a urethane resin. If it shows an example of content of a foam stabilizer, it can be set as the range of 0.1 weight part-10 weight part with respect to 100 weight part of urethane resins, for example. One or more foam stabilizers can be used.

5. Foaming agent Foaming agent promotes foaming of urethane resin. As a foaming agent, for example,
water;
Low boiling point hydrocarbons such as propane, butane, pentane, hexane, heptane, cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane;
Chlorinated aliphatic hydrocarbon compounds such as propyl chloride, isopropyl chloride, butyl chloride, isobutyl chloride, pentyl chloride, isopentyl chloride;
Fluorine compounds such as CHF ₃ , CH ₂ F ₂ and CH ₃ F;
Hydrofluorocarbons such as HFC-245fa (1,1,1,3,3-pentafluoropropane), HFC-365mfc (1,1,1,3,3-pentafluorobutane);
Hydrofluoroolefins such as 2,3,3,3-tetrafluoro-1-propene;
Ether compounds such as diisopropyl ether;
Or organic physical foaming agents such as mixtures of these compounds;
Examples thereof include inorganic physical foaming agents such as nitrogen gas, oxygen gas, argon gas, and carbon dioxide gas.

  The content of the foaming agent is not particularly limited, and is preferably 0.3 to 112 parts by weight, more preferably 1.6 to 68 parts by weight, and still more preferably 100 parts by weight of polyol. Is in the range of 1.8 to 68 parts by weight, most preferably in the range of 3 to 38 parts by weight. In the foamable polyurethane composition, it can be in the range of 0.1 to 30 parts by weight and more preferably in the range of 0.1 to 18 parts by weight with respect to 100 parts by weight of the urethane resin. Preferably, it is in the range of 0.5 to 18 parts by weight, more preferably in the range of 1 to 10 parts by weight.

  When the water range is not less than the above lower limit, foaming is promoted, and the density of the resulting molded product can be reduced. When the range is not more than the above upper limit, the foam does not foam and no foam is formed. Can be prevented. One or two or more foaming agents can be used.

6). Flame retardant The present invention contains one or more selected from the group consisting of red phosphorus, acicular filler, and boron-containing flame retardant as a flame retardant. Among them, it is more preferable that at least red phosphorus is contained because the flame retardancy effect by itself is high. As the flame retardant, commercially available products can be appropriately selected and used.

  There is no limitation in red phosphorus used for this invention, A commercial item can be selected suitably and can be used. The content of red phosphorus used in the present invention is preferably in the range of 4.6 to 194 parts by weight, preferably in the range of 4.6 to 75 parts by weight, with respect to 100 parts by weight of the polyol. More preferably, it is in the range of 6.2 to 56 parts by weight, and most preferably in the range of 7.4 to 38 parts by weight. In the foamable polyurethane composition, it can be in the range of 1.5 to 52 parts by weight and more preferably in the range of 1.5 to 20 parts by weight with respect to 100 parts by weight of the urethane resin. The range is preferably 2.0 parts by weight to 15 parts by weight, and more preferably 2.0 parts by weight to 10 parts by weight.

  When the range of the red phosphorus is not less than the above lower limit, the self-extinguishing property of the foam is maintained, and when it is not more than the above upper limit, foaming of the foamable urethane composition is not inhibited.

  Examples of the boron-containing flame retardant include borax, boron oxide, boric acid, and borate.

  Examples of boron oxide include diboron trioxide, boron trioxide, diboron dioxide, tetraboron trioxide, and tetraboron pentoxide.

  Examples of borates include alkali metals, alkaline earth metals, Group 4 elements, Group 12 elements, Group 13 elements, and ammonium borates.

  Specifically, alkali metal borate such as lithium borate, sodium borate, potassium borate, cesium borate, alkaline earth metal borate such as magnesium borate, calcium borate, barium borate, boron Examples thereof include zirconium acid, aluminum borate, and ammonium borate.

  The boron-containing flame retardant used in the present invention is preferably a borate. One or two or more boron-containing flame retardants can be used.

  The content of the boron-containing flame retardant used in the present invention is preferably in the range of 3 to 94 parts by weight, more preferably in the range of 3 to 56 parts by weight, based on 100 parts by weight of the polyol. More preferably, it is in the range of 4 to 56 parts by weight, and most preferably in the range of 3 to 38 parts by weight. In a foaming polyurethane composition, it can be set as the range of 1-25 weight part with respect to 100 weight part of urethane resins, It is more preferable that it is the range of 1-15 weight part, 1 weight part-10 weights More preferably, it is in the range of 2.0 parts by weight to 10 parts by weight.

  The acicular filler may be an organic filler or an inorganic filler, and is preferably an inorganic filler. The aspect ratio of the acicular filler is 5 to 50, preferably 8 to 40, more preferably 10 to 40, still more preferably 10 to 35, and most preferably 8 to 25. Here, the aspect ratio of the filler in the present specification is the minimum thickness of the maximum length of the filler that is confirmed by an image obtained by observing the acicular filler with a scanning electron microscope (relative to the maximum length). (The vertical direction) (also referred to as the diameter / thickness ratio), a sufficient number of fillers, an average of 250 or more.

  The average particle diameter of the acicular filler is 0.1 μm or more and less than 15 μm, preferably 0.1 μm or more and 14 μm or less, more preferably 0.3 to 10 μm. The average particle size is determined by an X-ray transmission type sedimentation method particle size distribution analyzer. The melting point of the acicular filler is 750 ° C. or higher, preferably 800 ° C. or higher, more preferably 1,000 ° C. or higher.

  As the needle-like inorganic filler, basic magnesium sulfate, aluminum borate, wollastonite, zonolite, dosonite, elastadite, boehmite, rod-like hydroxyapatite, potassium titanate whisker, aluminum borate whisker, magnesium-based whisker, Silicon-based whisker, acicular alumina, acicular ceramic, asbestos, acicular calcium carbonate, gypsum fiber, glass fiber, asbestos fiber, silica fiber, alumina fiber, silica / alumina fiber, zirconia fiber, carbon fiber (fiber such as carbon nanotube) , Needle-like or spherical new carbon such as fullerene), graphite fiber, boron nitride fiber, boron fiber, metal fiber and the like.

  The acicular filler prevents at least one of shrinkage and deformation. In this specification, “shrinkage” refers to changes in length including length in the length direction, length in the width direction, and length in the thickness direction, and “deformation” refers to a shape such as warpage. It refers to a change, particularly a change in shape in the thickness direction. The needle shape means that the major axis is three times or more the minor axis, and includes not only a so-called needle shape but also a spindle shape, a cylindrical shape, and the like.

  In one embodiment, the acicular filler is an acicular inorganic filler having an aspect ratio of 5 to 50 and an average particle diameter of 0.1 μm or more and less than 15 μm. Preferred acicular fillers are wollastonite or potassium titanate whiskers.

  The content of the acicular filler is preferably in the range of 3 to 94 parts by weight, more preferably in the range of 3 to 56 parts by weight, with respect to 100 parts by weight of the polyol, and 3 to 38 parts by weight. More preferably, it is in the range of parts by weight. In the foamable urethane resin composition, the amount is preferably 1 to 25 parts by weight, more preferably 1 to 15 parts by weight, and more preferably 1 to 10 parts by weight with respect to 100 parts by weight of the urethane resin. More preferably.

  Furthermore, as a flame retardant, at least one selected from a phosphoric ester, a bromine-containing flame retardant, an antimony-containing flame retardant, and a metal hydroxide can also be used.

  The phosphate ester used for this invention is not specifically limited, It is preferable to use a monophosphate ester, condensed phosphate ester, etc.

There is no limitation in particular as monophosphate ester. As monophosphate esters, for example,
Trimethyl phosphate, triethyl phosphate, tributyl phosphate, tri (2-ethylhexyl) phosphate, tributoxyethyl phosphate, triphenyl phosphate, tricresyl phosphate, trixylyl phosphate, tris (isopropylphenyl) phosphate, tris (phenylphenyl) phosphate, Trinaphthyl phosphate, cresyl diphenyl phosphate, xylenyl diphenyl phosphate, diphenyl (2-ethylhexyl) phosphate, di (isopropylphenyl) phenyl phosphate, monoisodecyl phosphate, 2-acryloyloxyethyl acid phosphate, 2-methacryloyloxyethyl acid Phosphate, diphenyl-2-acryloyloxyethyl phosphate Fate, diphenyl-2-methacryloyloxyethyl phosphate, melamine phosphate, dimelamine phosphate, melamine pyrophosphate, triphenylphosphine oxide, tricresylphosphine oxide, methanephosphonic acid diphenyl, phenylphosphonic acid diethyl, relucinol bis (diphenylphosphate) Bisphenol A bis (diphenyl phosphate), phosphaphenanthrene, and the like.

  There is no limitation in particular as condensed phosphate ester. Examples of the condensed phosphate ester include trialkyl polyphosphate, resorcinol polyphenyl phosphate, resorcinol poly (di-2,6-xylyl) phosphate (manufactured by Daihachi Chemical Industry Co., Ltd., trade name PX-200), hydroquinone poly (2, 6-xylyl) phosphate and condensed phosphate esters such as condensates thereof.

  Examples of commercially available condensed phosphate esters include resorcinol polyphenyl phosphate (trade name CR-733S), bisphenol A polycresyl phosphate (trade name CR-741), aromatic condensed phosphate ester (trade name CR747), and resorcinol. Examples thereof include polyphenyl phosphate (manufactured by ADEKA, trade name ADK STAB PFR), bisphenol A polycresyl phosphate (trade names FP-600, FP-700), and the like.

  Among these, it is preferable to use a monophosphate because the effect of reducing the viscosity in the composition before curing and the effect of reducing the initial calorific value are high.

  Phosphoric acid ester can use 1 type, or 2 or more types.

  The content of the phosphate ester is preferably in the range of 5.5 to 193 parts by weight, more preferably in the range of 5.5 to 75 parts by weight with respect to 100 parts by weight of the polyol. Is more preferably in the range of 7.4 to 56 parts by weight, and most preferably in the range of 7.4 to 38 parts by weight. In the foamable polyurethane composition, it can be in the range of 1.5 to 52 parts by weight and more preferably in the range of 1.5 to 20 parts by weight with respect to 100 parts by weight of the urethane resin. The range is preferably 2.0 parts by weight to 15 parts by weight, and more preferably 2.0 parts by weight to 10 parts by weight.

  When the range of the phosphoric acid ester is not less than the above lower limit, the molded product made of the foamable polyurethane composition can be prevented from cracking the dense residue formed by the maturity of the fire, and when the range is not more than the above upper limit, Foaming of the polyurethane composition is not inhibited.

  The phosphate-containing flame retardant used in the present invention contains phosphoric acid. The phosphoric acid used for the phosphate-containing flame retardant is not particularly limited, and examples thereof include various phosphoric acids such as monophosphoric acid, pyrophosphoric acid, polyphosphoric acid, and combinations thereof.

  Examples of the phosphate-containing flame retardant include phosphoric acid comprising salts of various phosphoric acids and at least one metal or compound selected from metals of Group IA to IVB of the periodic table, ammonia, aliphatic amines, and aromatic amines. Mention may be made of salts. Examples of metals of Group IA to IVB of the periodic table include lithium, sodium, calcium, barium, iron (II), iron (III), and aluminum.

  Examples of the aliphatic amine include methylamine, ethylamine, diethylamine, triethylamine, ethylenediamine, piperazine and the like.

  Aromatic amines include pyridine, triazine, melamine, ammonium and the like.

  The phosphate-containing flame retardant may be subjected to a known water resistance improving treatment such as silane coupling agent treatment or coating with a melamine resin, and a known foaming aid such as melamine or pentaerythritol may be added. May be.

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

The monophosphate is not particularly limited. As monophosphates, for example,
Ammonium salts such as ammonium phosphate, ammonium dihydrogen phosphate, diammonium hydrogen phosphate,
Sodium salts such as phosphoric acid-sodium phosphate, disodium phosphate, trisodium phosphate, phosphorous acid-sodium, disodium phosphite, sodium hypophosphite,
Potassium salts such as monopotassium phosphate, dipotassium phosphate, tripotassium phosphate, monopotassium phosphite, dipotassium phosphite, potassium hypophosphite,
Lithium salts such as phosphoric acid-lithium, dilithium phosphate, trilithium phosphate, phosphorous acid-lithium, dilithium phosphite, lithium hypophosphite,
Barium salts such as barium dihydrogen phosphate, barium hydrogen phosphate, tribarium phosphate, barium hypophosphite,
Magnesium salts such as magnesium monohydrogen phosphate, magnesium hydrogen phosphate, trimagnesium phosphate, magnesium hypophosphite,
Examples thereof include calcium salts such as calcium dihydrogen phosphate, calcium hydrogen phosphate, tricalcium phosphate, and calcium hypophosphite.

  Moreover, it does not specifically limit as a polyphosphate. Examples of polyphosphate include ammonium polyphosphate, piperazine polyphosphate, melamine polyphosphate, ammonium amide polyphosphate, aluminum polyphosphate, and the like.

  Among these, since the self-extinguishing property of the phosphate-containing flame retardant is improved, it is preferable to use a monophosphate, and it is more preferable to use ammonium dihydrogen phosphate.

  One or two or more phosphate-containing flame retardants can be used.

  The content of the phosphate-containing flame retardant used in the present invention is preferably in the range of 5.5 parts by weight to 193 parts by weight with respect to 100 parts by weight of the polyol, and 5.5 parts by weight to 75 parts by weight. Is more preferably in the range of 7.4 to 56 parts by weight, and most preferably in the range of 7.4 to 38 parts by weight. In the foamable polyurethane composition, it can be in the range of 1.5 to 52 parts by weight and more preferably in the range of 1.5 to 20 parts by weight with respect to 100 parts by weight of the urethane resin. The range is preferably 2.0 parts by weight to 15 parts by weight, and more preferably 2.0 parts by weight to 10 parts by weight.

  The bromine-containing flame retardant used in the present invention is not particularly limited as long as it is a compound containing bromine in the molecular structure. Examples of bromine-containing flame retardants include aromatic brominated compounds.

Specific examples of aromatic brominated compounds include, for example, hexabromobenzene, pentabromotoluene, hexabromobiphenyl, decabromobiphenyl, hexabromocyclodecane, decabromodiphenyl ether, octabromodiphenyl ether, hexabromodiphenyl ether, bis (pentabromo Monomeric organic bromine compounds such as phenoxy) ethane, ethylene-bis (tetrabromophthalimide), tetrabromobisphenol A;
Brominated polycarbonates such as polycarbonate oligomers produced from brominated bisphenol A as raw materials, copolymers of polycarbonate oligomers and bisphenol A;
Brominated epoxy compounds such as diepoxy compounds produced by reaction of brominated bisphenol A with epichlorohydrin, monoepoxy compounds obtained by reaction of brominated phenols with epichlorohydrin;
Poly (brominated benzyl acrylate);
Brominated polyphenylene ether;
Condensates of brominated bisphenol A, cyanuric chloride and brominated phenol;
Brominated polystyrene such as brominated (polystyrene), poly (brominated styrene), cross-linked brominated polystyrene;
Halogenated bromine compound polymers such as crosslinked or non-crosslinked brominated poly (-methylstyrene).

  From the viewpoint of controlling the calorific value at the initial stage of combustion, brominated polystyrene, hexabromobenzene and the like are preferable, and hexabromobenzene is more preferable.

  One or more bromine-containing flame retardants can be used.

  The content of the bromine-containing flame retardant used in the present invention is preferably in the range of 5.5 to 193 parts by weight with respect to 100 parts by weight of polyol, and in the range of 5.5 to 75 parts by weight. More preferably, it is more preferably in the range of 7.4 to 56 parts by weight, and most preferably in the range of 7.4 to 38 parts by weight. In the foamable polyurethane composition, it can be in the range of 1.5 to 52 parts by weight and more preferably in the range of 1.5 to 20 parts by weight with respect to 100 parts by weight of the urethane resin. The range is preferably 2.0 parts by weight to 15 parts by weight, and more preferably 2.0 parts by weight to 10 parts by weight.

  Examples of the antimony-containing flame retardant used in the present invention include antimony oxide, antimonate, pyroantimonate and the like.

  Examples of the antimony oxide include antimony trioxide and antimony pentoxide.

  Examples of the antimonate include sodium antimonate and potassium antimonate.

  Examples of pyroantimonate include sodium pyroantimonate and potassium pyroantimonate.

  The antimony-containing flame retardant used in the present invention is preferably antimony oxide. One or more antimony-containing flame retardants can be used.

  The content of the antimony-containing flame retardant is preferably in the range of 5.5 parts by weight to 193 parts by weight with respect to 100 parts by weight of the polyol, and more preferably in the range of 5.5 parts by weight to 75 parts by weight. The range is preferably 7.4 to 56 parts by weight, and most preferably 7.4 to 38 parts by weight. In the foamable polyurethane composition, it can be in the range of 1.5 to 52 parts by weight and more preferably in the range of 1.5 to 20 parts by weight with respect to 100 parts by weight of the urethane resin. The range is preferably 2.0 parts by weight to 15 parts by weight, and more preferably 2.0 parts by weight to 10 parts by weight.

  Examples of the metal hydroxide used in the present invention include magnesium hydroxide, calcium hydroxide, aluminum hydroxide, iron hydroxide, nickel hydroxide, zirconium hydroxide, titanium hydroxide, copper hydroxide, and vanadium hydroxide. And tin hydroxide.

  One or two or more metal hydroxides can be used.

  The content of the metal hydroxide is preferably in the range of 5.5 parts by weight to 193 parts by weight with respect to 100 parts by weight of the polyol, and more preferably in the range of 5.5 parts by weight to 75 parts by weight. The range is preferably 7.4 to 56 parts by weight, and most preferably 7.4 to 38 parts by weight. In the foamable polyurethane composition, it can be in the range of 1.5 to 52 parts by weight and more preferably in the range of 1.5 to 20 parts by weight with respect to 100 parts by weight of the urethane resin. The range is preferably 2.0 parts by weight to 15 parts by weight, and more preferably 2.0 parts by weight to 10 parts by weight.

  The total content of the flame retardant used in the present invention is preferably in the range of 16 parts by weight to 260 parts by weight and more preferably in the range of 16 parts by weight to 149 parts by weight with respect to 100 parts by weight of the polyol. Preferably, the range is from 16 parts by weight to 112 parts by weight. In the foamable polyurethane composition, it can be in the range of 4.5 to 70 parts by weight, more preferably in the range of 4.5 to 40 parts by weight with respect to 100 parts by weight of the urethane resin. More preferably, it is in the range of 4.5 to 30 parts by weight.

  When the range of the flame retardant is not less than the above lower limit, the molded product made of the foamable polyurethane composition can be prevented from cracking the dense residue formed by the heat of fire, and when the range is not more than the above upper limit, the foamable polyurethane The foaming of the composition is not inhibited.

  In the present invention, one or more flame retardants having a chlorine content of 100 ppm or less are contained. The chlorine content of the flame retardant is preferably 70 ppm or less, more preferably 50 ppm or less, and even more preferably the measurement limit value or less.

  The chlorine content can be measured by a known measuring method such as fluorescent X-ray analysis or ion chromatography. A flame retardant having a chlorine content of 100 ppm or less can be appropriately selected by those skilled in the art.

7). Other Components The composition of the present invention may further contain an inorganic filler. There is no limitation in particular as an inorganic filler. Examples of inorganic fillers include silica, diatomaceous earth, alumina, titanium oxide, calcium oxide, magnesium oxide, iron oxide, tin oxide, antimony oxide, ferrites, basic magnesium carbonate, calcium carbonate, magnesium carbonate, barium carbonate, and dawsonite. Hydrotalcite, calcium sulfate, barium sulfate, gypsum fiber, potassium salt of calcium silicate, talc, clay, mica, montmorillonite, bentonite, activated clay, sepiolite, imogolite, sericite, glass fiber, glass beads, silica parun, nitriding Aluminum, boron nitride, silicon nitride, carbon black, graphite, carbon fiber, carbon parun, charcoal powder, various metal powders, potassium titanate, magnesium sulfate, lead zirconate titanate, aluminum porate, Molybdenum, silicon carbide, stainless steel fiber, various magnetic powder, slag fibers, fly ash, silica-alumina fiber, alumina fiber, silica fiber, zirconia fiber, and the like.

  One or more inorganic fillers can be used.

  The composition of the present invention is within a range that does not impair the object of the present invention, as necessary, phenolic, amine-based, sulfur-based antioxidants, heat stabilizers, metal harm-preventing agents, antistatic agents, A stabilizer, a crosslinking agent, a lubricant, a softening agent, a pigment, an auxiliary component such as a tackifier resin, and a tackifier such as a polybutene and a petroleum resin can be included.

  Above 1. ~ 7. These components are mixed and the foamable polyurethane composition reacts and cures, so that its viscosity changes over time. Therefore, before using the foamable polyurethane composition, the foamable polyurethane composition is divided into two or more to prevent the foamable polyurethane composition from reacting and curing (foamable polyurethane premix composition). And when using a foamable polyurethane composition, a foamable polyurethane composition is obtained by mixing the foamable polyurethane composition divided | segmented into two or more, and putting them together.

  When the foamable polyurethane composition is divided into two or more, each component of the foamable polyurethane composition divided into two or more does not start to cure, and after mixing each component of the foamable polyurethane composition Each component may be divided so that the curing reaction starts.

  The foamable polyurethane composition may be cured and mixed at room temperature, or each component may be heated in advance.

  Said flame retardant and catalyst, and optionally included foam stabilizers, foaming agents, etc. may be mixed with either polyols or polyisocyanates. Alternatively, the flame retardant and catalyst, and optionally included foam stabilizers, blowing agents, etc. may be provided separately from the polyol and polyisocyanate. Preferably, the polyol, flame retardant and catalyst are provided as a polyol premix containing these components (polyol composition for reacting with a polyisocyanate compound to obtain a polyurethane foam). In addition, foam stabilizers, foaming agents and the above-mentioned 7. These other components may also be mixed with either the polyol or polyisocyanate, or may be provided separately from the polyol and polyisocyanate, and are preferably included in the polyol premix.

  Polyols, polyisocyanates, foam stabilizers, catalysts, foaming agents, and flame retardants, preferably polyisocyanates mixed with polyol premixes containing polyols, foam stabilizers, catalysts, foaming agents, and flame retardants The foamable polyurethane composition is foamed and cured to form a polyurethane foam.

  The polyol composition of the present invention preferably has a chlorine content of 200 ppm or less, more preferably 140 ppm or less, still more preferably 100 ppm or less, and particularly preferably a measurement limit value or less.

The fire resistance of the urethane foam composition and polyurethane foam of the present invention can be evaluated by a cone calorimeter test based on the test method of ISO-5660. Specifically, in this fire resistance test, a polyurethane foam made of a foamable polyurethane composition is cut into a length of 10 cm, a width of 10 cm and a thickness of 5 cm to prepare a sample for a corn calorimeter test. Next, the total calorific value when heated at a radiant heat intensity of 50 kW / m ^{2 for} 20 minutes is measured with a corn calorimeter using a sample for corn calorimeter test according to the test method of ISO-5660.

In the present specification, “nonflammable” refers to a material that has all of the following conditions (1) to (3).
(1) The total calorific value for 20 minutes after starting heating at a radiant heat intensity of 50 kW / m ² is 8 MJ / m ² or less.
(2) The heat generation rate exceeding 200 kW / m ² does not continue for more than 10 seconds in 20 minutes after the start of heating, and (3) deformation such as cracks or holes harmful to fire prevention does not occur in 20 minutes after the start of heating.

Moreover, in this specification, "flame retardance" means what comprises all the following conditions (1)-(3).
(1) The total calorific value for 5 minutes after the start of heating at a radiant heat intensity of 50 kW / m ² is 8 MJ / m ² or less.
(2) The heat generation rate exceeding 200 kW / m ² does not continue for more than 10 seconds in 5 minutes after the start of heating, and (3) deformation such as cracks or holes harmful to fire prevention does not occur in 5 minutes after the start of heating.

  The foamable polyurethane composition of the present invention is used for repairing foams used in vehicles or building insulation, or used to fill openings or gaps in buildings. Here, “building” includes any structure constituting the building, and includes not only structural materials of the building such as walls, ceilings, roofs, floors, but also windows (drawing windows, open windows, raising and lowering windows, etc.). ), Shoji screens, doors (ie doors), doors, bran, and balustrades. In addition, the “opening” refers to an arbitrary opening generated in the building including joints generated between the structural materials of the building and holes generated in one structural material. “Gap” is an opening, such as between a structural material, a structural material, between a structural material and a joinery, between a joinery and a joinery, between a structural material or joinery and furniture (such as a kitchen sink), It refers to an opening that occurs between two opposing members or parts.

  Polyurethane foams obtained by foaming and curing foamable polyurethane compositions are excellent in waterproofness, airtightness, and flame retardancy, so water, smoke, flames, or combustion from openings or gaps in buildings It is possible to effectively block the intrusion of the generated gas or the like.

  The foamable polyurethane composition of the present invention forms a foam by spraying the substrate on site in order to repair, for example, a slight opening or gap in the field without using a large apparatus such as an aerosol type. Used for field spray applications.

  Among them, it is preferable to use the building heat insulating material in the field for spraying in the present invention, and the site is preferably used for the ceiling because repair is difficult when corrosion occurs.

  On-site spraying can be performed using a known cartridge gun, a discharge device or the like. For on-site spraying, both a two-liquid mixing container in which the first liquid and the second liquid are contained in separate containers and a two-liquid mixing container in which the first liquid and the second liquid are accommodated in one container can be used. . The mixing vessel can be used in combination with the above-described device together with a stirring device as necessary.

On-site spraying can be performed on any base material (structural material). Examples of the substrate include metals (for example, steel), cement boards, concrete, gypsum and the like. The excellent characteristics of the foam of the present invention are suitably exhibited when using steel or concrete, which has high thermal conductivity and is difficult to exhibit the effect of flame retardancy, as a base material. What is steel?
Structural steel materials exemplified by JIS G 3101, JIS G 3106, JIS G 3114, JIS G 3136,
Deck plates exemplified in JIS G 3352, steel materials for piping exemplified in JIS G 3452, JIS G 3455, JIS G 3456, JIS G 3457,
Galvanized steel sheet exemplified by JIS G 3302, JIS G 3313, JIS G 3317, JIS G 3321, etc.,
Examples include stainless steel plates exemplified by JIS G 4304, JIS G 4305, and the like. As the base material in the present invention, it is preferable to use steel that has been difficult to use because it is easily corroded among the base materials, and particularly because there is a merit that the plating process can be reduced, steel that is not plated is more preferable. More preferably, it is used for a stainless steel material or an iron plate.

  The thickness (spraying thickness) at which the foamable urethane resin composition is sprayed onto the substrate is not particularly limited. The spraying thickness can be, for example, 10 to 200 mm, preferably 20 to 100 mm, and particularly preferably 20 to 50 mm.

  This invention also provides the manufacturing method of a flame-retardant structure characterized by including the step which sprays said foamable urethane resin composition for on-site spraying to a base material (structural material). The method for producing a flame-retardant structure according to the present invention preferably includes a step of mixing the polyol composition and the isocyanate compound on-site.

  The flame-retardant structure is produced by foaming and curing the foamable urethane resin composition sprayed on the base material, and adhering to the base material.

  The present invention also includes a flame retardant structure that is a laminate obtained by the above-described production method. In the flame-retardant structure (laminate) of the present invention, a foam obtained by curing the foamable urethane resin composition for in-situ spraying of the present invention is laminated on a base material.

  Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited thereto.

1. Production of in-situ foamable polyurethane composition According to the formulation shown in Table 1, in-situ foamable polyurethane compositions according to Examples and Comparative Examples were prepared by using A liquid and polyol compound comprising an isocyanate compound, a foam stabilizer, a catalyst, a foaming agent, It prepared by dividing into two of B liquid which consists of an additive which is a flame retardant. The details of each component in the table are as follows.
Isocyanate compound (A-1) 4,4′-diphenylmethane diisocyanate (4,4′-MDI) (manufactured by Wanhua Chemical Japan, product name: PM200).
Polyol compound (B-1) p-phthalic acid polyester polyol (manufactured by Kawasaki Chemical Industry Co., Ltd., product name: Maximol RLK-087, hydroxyl value = 200 mgKOH / g).
-Foam stabilizer (C-1) Polyalkylene glycol foam stabilizer (manufactured by Dow Corning Toray, product name: SH-193).
Catalyst (D-1) Trimerization catalyst (manufactured by Tosoh Corporation, product name: TOYOCAT (registered trademark) -TR20)
(D-2) Trimerization catalyst (manufactured by San Apro Co., Ltd., product name: U-CAT 18X)
(D-3) Urethane catalyst (manufactured by San Apro, product name: U-CAT 202)
(D-4) Urethane catalyst (product name: TOYOCAT (registered trademark) -RX5, manufactured by Tosoh Corporation).
-Foaming agent (E-1) Water (E-2) HFC HFC-365mfc (1,1,1,3,3-pentafluorobutane, manufactured by Solvay Japan) and HFC-245fa (1,1,1,3) , 3-pentafluoropropane, manufactured by Central Glass Co., Ltd.), mixing ratio HFC-365mfc: HFC-245fa = 3: 7, hereinafter referred to as “HFC”).
・ Flame retardant (F-1) Red phosphorus (Rin Chemical Industries, product name: Nova Excel 140)
(F-2) Wollastonite (SiO ₂ · CaO; acicular filler) (manufactured by Kinsei Matec, product name: SH-1250)
(F-3) Zinc borate (manufactured by Hayakawa Shoji, product name: FIREbrake ZB)
(F-4) Tris (β-chloropropyl) phosphate (manufactured by Daihachi Chemical Industry Co., Ltd., product name: TMCPP, “TMCPP”).

  After spraying on the adherend (steel plate) with the following machine setting at a lower spray of 5 mm or less, two layers were sprayed at a thickness of 20 mm.

[Spraying conditions]
Spray machine "H-VR" (manufactured by Graco)
Isocyanate / polyol temperature: 35 ° C setting Hose temperature: 33 ° C
Discharge pressure: 30 bar
Spray gun: “D gun” (made by Gasmer).

2. Evaluation Exothermicity and halogen content were evaluated according to the following criteria.

[Exothermic test conditions]
Based on the test method of ISO-5660, the total calorific value when heated for 5 minutes at a radiant heat intensity of 50 kW / m ² was measured by a cone calorimeter test.

[Measurement of halogen content]
The intensity of the halogen content was measured by fluorescent X-ray analysis (XRF) (HORIBA, Ltd., “XGT-5000”).

[Measurement of corrosivity]
A 100 mm × 100 mm × 0.3 mm adherend (non-plated iron plate) was sprayed at a lower spray of 5 mm or less with the following machine settings, and then two layers were sprayed at a thickness of 20 mm.

[Spraying conditions]
Spray machine "H-VR" (manufactured by Graco)
Isocyanate / polyol temperature: 35 ° C setting Hose temperature: 33 ° C
Discharge pressure: 30 bar
Spray gun: “D gun” (made by Gasmer).

  The urethane resin composition after spraying was allowed to stand in a humidified oven at 50 ° C. and 80% for one week. After taking out from the humidifying oven, the urethane was peeled off, and the corrosion of the iron plate on the peeled surface was judged visually.

  The results are shown in Table 1.

Claims (13)

A polyol composition for mixing with a polyisocyanate compound to obtain a foamable polyurethane composition for in-situ spraying,
Contains a polyol compound, a flame retardant, and a catalyst,
As the flame retardant, containing one or more selected from the group consisting of red phosphorus, needle filler and boron-containing flame retardant,
A polyol composition, wherein the flame retardant has a chlorine content of 100 ppm or less.   The polyol composition according to claim 1, wherein the flame retardant contains at least red phosphorus.   The polyol according to claim 1 or 2, comprising a trimerization catalyst as the catalyst, and containing 0.3 to 38 parts by weight of the trimerization catalyst with respect to 100 parts by weight of a total of an isocyanate compound and a polyol compound. Composition.   The urethanization catalyst is contained as the catalyst, and the urethanization catalyst is contained in an amount of 0.1 to 10 parts by weight with respect to a total of 100 parts by weight of the isocyanate compound and the polyol compound. The polyol composition according to item.   The polyol composition according to any one of claims 1 to 4, wherein a chlorine content in the polyol composition is 100 ppm or less.   A foamable polyurethane premix composition for in-situ spraying, comprising the polyol composition according to any one of claims 1 to 5 and an isocyanate compound separately.   A foamable urethane resin composition for on-site spraying, which is a mixture of the polyol composition according to any one of claims 1 to 6 and an isocyanate compound.   The foamable urethane resin composition for in-situ spraying according to claim 7, for spraying on a steel substrate.   The foamable urethane resin composition for in-situ spraying according to claim 7 for spraying on a concrete base material.   A method for producing a flame-retardant structure, comprising the step of spraying a foamable urethane resin composition for in-situ spraying according to any one of claims 7 to 9 onto a substrate.   The method for manufacturing a flame-retardant structure according to claim 10, wherein the base material is steel or concrete.   The method for producing a flame-retardant structure according to claim 10 or 11, comprising a step of mixing the foamable urethane resin composition for in-situ spraying according to any one of claims 7 to 9 on-site. .   A flame-retardant structure in which urethane foam obtained by curing the foamable urethane resin composition for on-site spraying according to any one of claims 7 to 9 is laminated on a base material that is steel or concrete.