JP2022142718A - Urethane resin composition, urethane resin foam, raw material composition of urethane resin composition, and raw material kit of urethane resin composition - Google Patents

Abstract

To provide an urethane resin composition which enables production of an urethane resin foam that prevents spread of fire and melting and has excellent adhesion to an object regardless of whether or not red phosphorus is used.SOLUTION: There is provided an urethane resin composition. The urethane resin composition contains a polyisocyanate compound, a polyalkylene glycol adduct of primary alcohol, and phenol and/or a phenol derivative.SELECTED DRAWING: None

Description

TECHNICAL FIELD The present invention relates to a urethane resin composition, a raw material composition and raw material kit thereof, and a urethane resin foam.

2. Description of the Related Art Concrete reinforced with reinforcing bars and the like is used for outer walls and the like of collective housing such as condominiums, detached houses, public facilities, commercial buildings, and the like. In order to prevent dew condensation and improve thermal insulation, such concrete structures are formed with a spray-on rigid polyurethane foam.

However, if the hard urethane resin foam is simply sprayed, the urethane foam may burn in the event of a fire or the like occurring inside the building. Accordingly, various techniques have been proposed for imparting flame retardancy to this urethane resin foam.

For example, Patent Document 1 discloses that a urethane resin composition contains red phosphorus as a flame retardant, a phosphate ester, a phosphate-containing flame retardant, a bromine-containing flame retardant, a boron-containing flame retardant, an antimony-containing flame retardant, or a metal hydroxide. It is disclosed that a urethane foam having excellent flame retardancy can be produced by combining these materials.

WO2014/112394

However, when the urethane resin composition of Patent Document 1 contains red phosphorus, which is used as a flame retardant, the adhesion of the urethane resin foam formed by spraying or the like to an object decreases.

In view of the above circumstances, the present invention provides a urethane resin composition that can be used to produce a urethane resin foam that is resistant to the spread of fire and melts and has excellent adhesion to an object regardless of whether red phosphorus is used. It was decided to.

According to one aspect of the present invention, a urethane resin composition is provided. This urethane resin composition contains a polyisocyanate compound, a polyalkylene glycol adduct of a primary alcohol, and phenol and/or a phenol derivative.

It may be provided in each aspect described below.
The urethane resin composition, wherein the number of carbon atoms in the primary alcohol is 3 or more and 8 or less.
A urethane resin composition containing 0.5% by mass or more and 30% by mass or less of the polyalkylene glycol adduct of the primary alcohol in the urethane resin composition, based on 100% by mass of the urethane resin composition.
In the urethane resin composition, as the phenol and/or the phenol derivative, one or more selected from the group consisting of natural cashew nut shell liquid, industrial cashew nut shell liquid, and cashew nut shell liquid derivatives is used. .
A urethane resin composition, wherein the urethane resin composition further contains a thickening agent.
A urethane resin composition containing 0.1% by mass or more and 10% by mass or less of the thickener with respect to 100% by mass of the urethane resin composition.
A urethane resin composition, wherein the urethane resin composition further contains a flame retardant, and the thickening action of the thickener prevents the flame retardant from settling.
A urethane resin composition containing 1% by mass or more and 30% by mass or less of the phenol and/or the phenol derivative relative to 100% by mass of the urethane resin composition.
The urethane resin composition does not contain a polyol compound or contains 1% by mass or less of a polyol compound with respect to 100% by mass of the urethane resin composition.
The urethane resin composition, wherein the foam piece formed from the urethane resin composition has an oxygen index of 30 or more as measured according to JIS K 7201-2:2007.
In the urethane resin composition, when the urethane resin composition is sprayed onto a gypsum board by a spray foaming method to form a foam piece, a gap of 2 mm or more is partially formed at the interface between the foam piece and the gypsum board. A urethane resin composition in which there is no
A urethane resin foam comprising a polymer formed by binding a polyalkylene glycol adduct of a primary alcohol and a polyisocyanate compound, and a polymer formed by binding a phenol and/or a phenol derivative and a polyisocyanate compound. Resin foam.
A raw material composition for a urethane resin composition that is used by mixing with a polyisocyanate compound, the raw material composition for the urethane resin composition comprising a polyalkylene glycol adduct of a primary alcohol and a phenol and/or a phenol derivative.
A raw material kit for a urethane resin composition, comprising a first raw material containing a polyalkylene glycol adduct of a primary alcohol, a phenol and/or a phenol derivative, and a second raw material containing a polyisocyanate compound. A raw material kit for a urethane resin composition.
Of course, this is not the only case.

ADVANTAGE OF THE INVENTION According to this invention, the urethane-resin foam which can manufacture a urethane-resin foam which is hard to spread or melt, and has the excellent adhesiveness with respect to a target object regardless of whether red phosphorus is used is obtained.

Hereinafter, the urethane resin composition, the raw material composition and raw material kit thereof, and the urethane resin foam according to the present embodiment will be described by showing specific examples. It is not limited to the examples at all, and can be carried out with appropriate modifications as long as the effect is not impaired. Also, each component shown below can be implemented in combination with each other.
Further, in this specification, "X containing A as a main component" means that the content of "A" is preferably 80% by mass or more, 85% by mass or more, 90% by mass with respect to 100% by mass of "X" % or more, 95 mass % or more, 97 mass % or more, 99 mass % or more, and may be 100 mass %.

<Urethane resin composition>
The urethane resin composition according to the present embodiment contains a polyisocyanate compound, a primary alcohol polyalkylene glycol adduct, and phenol and/or a phenol derivative.

According to such a urethane resin composition, regardless of whether red phosphorus is used or not, the urethane resin foam can produce a urethane resin foam that is resistant to the spread of fire and melts and has excellent adhesion to an object. you can get a body

[Polyisocyanate compound]
Examples of polyisocyanate compounds include, but are not limited to, aromatic polyisocyanates, alicyclic polyisocyanates, aliphatic polyisocyanates, modified products thereof (e.g., urethane groups, carbodiimide groups, allophanate groups, urea groups, biuret groups, isocyanurate group- or xazolidone group-containing modified products, etc.) may be used singly or in combination of two or more.

Examples of the aromatic polyisocyanate include, but are not limited to, phenylene diisocyanate, tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, dimethyldiphenylmethane diisocyanate, triphenylmethane triisocyanate, naphthalene diisocyanate, polymethylene polyphenyl polyisocyanate, polyarylpoly Isocyanate and the like can be used.

Although the alicyclic polyisocyanate is not particularly limited, for example, cyclohexyl diisocyanate, methylcyclohexyl diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, dimethyldicyclohexylmethane diisocyanate, and the like can be used.

Examples of the aliphatic polyisocyanate include, but are not limited to, methylene diisocyanate, ethylene diisocyanate, propylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, and the like.

The number average molecular weight of the polyisocyanate compound is not particularly limited. mol or more is particularly preferred. The number average molecular weight of the polyisocyanate compound is, for example, 3000 g/mol or less, 2500 g/mol or less, 2000 g/mol or less, 1500 g/mol or less, 1000 g/mol or less, 900 g/mol or less, 800 g/mol or less, and 700 g/mol or less. , 600 g/mol or less, 500 g/mol or less, 400 g/mol or less, 300 g/mol or less, 200 g/mol or less.

The isocyanate index originally represents the equivalent ratio of the isocyanate group of the polyisocyanate compound to the hydroxyl group of the polyol compound as a percentage, but here, the polyalkylene glycol adduct of primary alcohol, phenol and / or phenol derivative, and The equivalent ratio of the isocyanate groups of the polyisocyanate compound to the hydroxyl groups (both alcoholic hydroxyl groups and phenolic hydroxyl groups) of the polyol compound (when containing a polyol compound) is expressed in percentage. The isocyanate index is not particularly limited, and may be, for example, 120 or more. 260 or more, 270 or more, 280 or more, 290 or more, 300 or more, 320 or more, 340 or more, 360 or more, 380 or more, 400 or more, 420 or more, 440 or more, 460 or more, 480 or more, 500 or more, 520 or more, It is preferably 540 or more, 560 or more, 580 or more, 600 or more, 620 or more, 640 or more, 660 or more, 680 or more, 700 or more, 720 or more. The isocyanate index is preferably 1000 or less, 900 or less, 800 or less, 700 or less and 600 or less.

Although the content of the polyisocyanate compound is not particularly limited, it is preferably, for example, 20% by mass or more, more preferably 25% by mass or more, and 30% by mass or more with respect to 100% by mass of the urethane resin composition. more preferably, 35% by mass or more is particularly preferable, and 40% by mass or more is most preferable. On the other hand, the content of the polyisocyanate compound may be 80% by mass or less, 75% by mass or less, 70% by mass or less, 65% by mass or less, 60% by mass or less, 55% by mass or less, and 50% by mass or less.

[Polyalkylene glycol adduct of primary alcohol]
Polyalkylene glycol adducts of primary alcohols (hereinafter also referred to as “monools”) are obtained by addition polymerization of alkylene glycol to hydroxyl groups of primary alcohols. By including monools in the polyurethane resin composition, the adhesiveness of the urethane resin foam formed by spraying or the like to an object can be improved.

Specifically, primary alcohols include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 1-pentanol, 2-pentanol, 3-pentanol, 1-hexanol, 2 -hexanol, 3-hexanol, 1-heptanol, 2-heptanol, 3-heptanol, 4-heptanol, 1-octanol, 2-octanol, 3-octanol, 4-octanol, 1-nonanol, 2-nonanol, 3-nonanol , 4-nonanol, 5-nonanol, 1-decanol, 2-decanol, 3-decanol, 4-decanol, 5-decanol, 1-undecanol, 2-undecanol, 3-undecanol, 4-undecanol, 5-undecanol, 6 - undecanol, 1-dodecanol, 2-dodecanol, 3-dodecanol, 4-dodecanol, 5-dodecanol, 6-dodecanol, 1-tridecanol, 2-tridecanol, 3-tridecanol, 4-tridecanol, 5-tridecanol, 6-tridecanol , 7-tridecanol, 1-tetradecanol, 2-tetradecanol, 3-tetradecanol, 4-tetradecanol, 5-tetradecanol, 6-tetradecanol, 7-tetradecanol, 1-pentadecanol decanol, 2-pentadecanol, 3-pentadecanol, 4-pentadecanol, 5-pentadecanol, 6-pentadecanol, 7-pentadecanol, 8-pentadecanol, 1-hexadecanol , 2-hexadecanol, 3-hexadecanol, 4-hexadecanol, 5-hexadecanol, 6-hexadecanol, 7-hexadecanol, 8-hexadecanol, etc. Linear alcohols, 2-methyl-1-propanol, 2-methyl-2-propanol, 2-methyl-1-butanol, 2-methyl-2-butanol, 2-methyl-3-butanol, 2-methyl-4 Branched chain alcohols having 1 to 30 carbon atoms such as -butanol and 2,2-dimethyl-1-propanol can be used. The number of carbon atoms in the primary alcohol is preferably 2 or more, more preferably 3 or more, regardless of whether it is linear or branched. On the other hand, as the number of carbon atoms of the primary alcohol, It is preferably 16 or less, 15 or less, 14 or less, 13 or less, 12 or less, 11 or less, 10 or less, 9 or less, 8 or less, 7 or less, and 6 or less. In one embodiment, 1-propanol, 1-butanol, 1-pentanol, and 1-hexanol are preferably used as the primary alcohol, and 1-butanol is more preferably used.

As polyalkylene glycol, a polymer chain of alkylene oxide (ethylene oxide, propylene oxide, butylene oxide, hexylene oxide, etc.) can be used.

Although the content of monools is not particularly limited, it is preferably, for example, 0.5% by mass or more, more preferably 1% by mass or more, and 2% by mass with respect to 100% by mass of the urethane resin composition. % or more, and particularly preferably 2.5 mass % or more. When the content of the monools is at least the required amount, the adhesion of the urethane resin foam formed by spraying or the like to the target object can be further improved. On the other hand, the content of monools is preferably 30% by mass or less, more preferably 25% by mass or less, and preferably 20% by mass or less with respect to 100% by mass of the urethane resin composition. It is more preferably 15% by mass or less, particularly preferably 10% by mass or less, and most preferably 10% by mass or less.

[Phenol, phenol derivative]
A urethane resin foam produced from a urethane resin composition containing phenol and/or phenol derivatives (hereinafter also collectively referred to as "phenols") forms a carbonized layer upon contact with a flame. This carbonized layer can prevent the urethane resin composition from further spreading or melting. As a result, it is possible to suppress an increase in the heat generation rate of the urethane resin foam and to suppress the spread of fire in the urethane resin foam even in a state of excess oxygen.

Phenol is one in which a hydroxyl group (phenolic hydroxyl group) is bonded to one of the carbon atoms constituting benzene. Here, the “phenol derivative” is a phenol in which at least one hydrogen atom at the o-position, m-position, or p-position is substituted with a functional group. Specifically, functional groups that can be used include, for example, a hydroxyl group, a carbonyl group, a carboxyl group, an amino group, a cyano group, an ether group, a formyl group, a halogen atom, an alkyl group, an alkenyl group, and an alkynyl group. As the alkyl group, alkenyl group, and alkynyl group, one or more substituents of hydroxyl group, carbonyl group, carboxyl group, amino group, cyano group, ether group, formyl group, and halogen atom can be used.

In one embodiment, as the phenol derivative, at least one hydrogen atom at the o-position, m-position, or p-position of phenol is substituted with an alkyl group, an alkenyl group, an alkynyl group, or the above-described substituents thereof. It is preferable to use the The total number of carbon atoms in the alkyl group, alkenyl group, alkynyl group, and the above-described substituents thereof is not particularly limited, but is 1 or more, 2 or more, 3 or more, 4 or more, 5 or more, 6 or more, 7 or more, and 8 or more. , 9 or more, 10 or more, 11 or more, 12 or more, 13 or more, or 14 or more. The total number of carbon atoms in the alkyl group, alkenyl group, alkynyl group, and the above-described substituents thereof is 40 or less, 39 or less, 38 or less, 37 or less, 36 or less, 35 or less, 34 or less, 33 or less, 32 or less, 31 Below, 30 or less, 29 or less, 28 or less, 27 or less, 26 or less, 25 or less, 24 or less, 23 or less, 22 or less, 21 or less, 20 or less, 19 or less, 18 or less, 17 or less, 16 or less preferable. In the case of using a substituent of any one of an alkyl group, an alkenyl group, and an alkynyl group, the total number of carbon atoms includes the number of carbon atoms derived from the chain of the alkyl group, the alkenyl group, and the alkynyl group, in addition to the number of carbon atoms derived from the chain of the alkyl group, the alkenyl group, and the alkynyl group. group).

Specifically, phenol derivatives include cresol, salicylic acid, picric acid, naphthol, catechol, resorcinol, hydroquinone, pyrogallol, phloroglucinol, hexahydroxybenzenehydroquinone, hydroquinone monomethyl ether, dibutylhydroquinone, dibutylhydroquinone monomethyl ether, t-butyl. Catechol 2-t-butyl-4,6-dimethylphenol, 2,6-di-t-butylphenol, 3,5-di-t-butyl-4-hydroxytoluene, cardol, methyl cardol, cardanol, urushiol, etc. can be used. In addition, a phenol derivative is not limited to these.

In one embodiment, cashew nut shell liquid can be used as phenols. As cashew nut shell liquid, natural cashew nut shell liquid and industrial cashew nut shell liquid are commercially available. Either can be used, a derivative of cashew nut shell liquid can be used, or a combination of two or more of these can be used. Natural cashew nut shell liquid contains anacardic acid as a main component, as well as cardol, methyl cardol and cardanol. Industrial cashew nut shell liquid is obtained by heat-treating natural cashew nut shell liquid. Due to this heat treatment, the o-position carboxyl group of anacardic acid is decarboxylated and converted to cardanol, so industrial cashew nut shell liquid contains cardanol as a main component and also cardol and methyl cardol. Cardanol is a phenol in which the hydrogen atom at the m-position is substituted with a linear alkyl or alkenyl group having 15 carbon atoms and having 0, 1, 2 or 3 double bonds. Anacardic acid is a cardanol in which the hydrogen atom at the o-position is substituted with a carboxyl group. Most of them are phenol derivatives. Derivatives of cashew nut shell liquid include adducts such as alkylene oxide.

The content of phenols is not particularly limited, but is preferably, for example, 1% by mass or more, more preferably 2% by mass or more, and 3% by mass or more with respect to 100% by mass of the urethane resin composition. It is more preferable that the content is 4% by mass or more, and it is particularly preferable that the content is 4% by mass or more. When the content of phenols is at least the required amount, the ability to form a carbonized layer can be further enhanced. As a result, it is possible to further suppress an increase in the heat generation rate of the urethane resin foam, and to further suppress the spread of fire in the urethane resin foam even in a state of excess oxygen. On the other hand, the content of phenols is preferably 30% by mass or less, more preferably 25% by mass or less, and further preferably 20% by mass or less with respect to 100% by mass of the urethane resin composition. It is preferably 15% by mass or less, particularly preferably 12% by mass or less, and most preferably 12% by mass or less. By keeping the content of phenols below the required amount, the mechanical strength of the formed urethane resin foam can be further enhanced.

The content of phenols is not particularly limited, but the mass ratio (content of phenols/content of monools) to the content of monools described above is preferably 0.2 or more. It is preferably 0.5 or more, more preferably 0.7 or more, and particularly preferably 0.8 or more. On the other hand, the mass ratio (phenol content/monool content) is 15 or less, 12 or less, 10 or less, 9 or less, 8 or less, 7 or less, 6 or less, 5 or less, 4.5 or less, It is preferably 4 or less.

[Polyol]
The urethane resin composition of the present embodiment may or may not contain a polyol compound, but preferably does not contain a polyol compound. Moreover, even if a polyol compound is contained, the content thereof is preferably as low as possible, specifically, for example, 1% by mass or less with respect to 100% by mass of the urethane resin composition. In this specification, the term "polyol compound" refers to alcohols different from the monools and phenols described above, and refers to compounds containing two or more hydroxyl groups in the molecule. If such a compound is used, for example, other uses (flame retardants, etc.) are the same as described above.

When the urethane resin composition contains a polyol compound, the content of the polyol compound is not particularly limited. 0.2% by mass or less, 0.1% by mass or less, 0.07% by mass or less, 0.05% by mass or less, 0.02% by mass or less, 0.01% by mass or less, 0.007% by mass or less; 005% by mass or less, 0.002% by mass or less, 0.001% by mass or less, 0.0007% by mass or less, 0.0005% by mass or less, 0.0002% by mass or less, 0.0001% by mass or less, 0.00007 % by mass or less, 0.00005 mass % or less, 0.00002 mass % or less, or 0.00001 mass % or less.

Examples of polyol compounds include polylactone polyols, polycarbonate polyols, aromatic polyols, alicyclic polyols, aliphatic polyols, polyester polyols, polymer polyols, and polyether polyols.

(polylactone polyol)
Examples of polylactone polyols among polyol compounds include polypropiolactone glycol, polycaprolactone glycol, and polyvalerolactone glycol.

(polycarbonate polyol)
Among polyol compounds, polycarbonate polyols are obtained by dealcoholization reaction of hydroxyl group-containing compounds such as ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, octanediol, and nonanediol with diethylene carbonate, dipropylene carbonate, and the like. obtained polyols, etc.

(aromatic polyol)
Examples of aromatic polyols among polyol compounds include bisphenol A, bisphenol F, phenol novolak, cresol novolak and the like.

(Alicyclic polyol)
Alicyclic polyols among polyol compounds include, for example, cyclohexanediol, methylcyclohexanediol, isophoronediol, dicyclohexylmethanediol, and dimethyldicyclohexylmethanediol.

(aliphatic polyol)
Examples of aliphatic polyols among polyol compounds include ethylene glycol, propylene glycol, butanediol, pentanediol, and hexanediol.

(polyester polyol)
Among polyol compounds, polyester polyols include, for example, polymers obtained by dehydration condensation of polybasic acids and polyhydric alcohols, and ring-opening polymerization of lactones such as ε-caprolactone and α-methyl-ε-caprolactone. Polymers, condensates of hydroxycarboxylic acids and polyhydric alcohols, and the like can be mentioned.

Polybasic acids constituting polyester polyols include, for example, adipic acid, azelaic acid, sebacic acid, terephthalic acid, isophthalic acid, and succinic acid.

Examples of polyhydric alcohols constituting polyester polyols include bisphenol A, ethylene glycol, 1,2-propylene glycol, 1,4-butanediol, diethylene glycol, 1,6-hexane glycol, and neopentyl glycol.

Examples of hydroxycarboxylic acids constituting polyester polyols include castor oil and reaction products of castor oil and ethylene glycol.

(polymer polyol)
Examples of polymer polyols include polymers obtained by graft-polymerizing ethylenically unsaturated compounds such as acrylonitrile, styrene, methyl acrylate, and methacrylate to aromatic polyols, alicyclic polyols, aliphatic polyols, polyester polyols, and polybutadiene. Examples include polyols, modified polyols of polyhydric alcohols, and hydrogenated products thereof.

Examples of modified polyols of polyhydric alcohol among polymer polyols include those obtained by reacting polyhydric alcohol as a raw material with alkylene oxide to modify it.

Examples of polyhydric alcohols constituting the polymer polyol include trihydric alcohols such as glycerin and trimethylolpropane, pentaerythritol, sorbitol, mannitol, sorbitan, diglycerin, dipentaerythritol, etc., sucrose, glucose, mannose, fructose, methyl Tetra- to octahydric alcohols such as glucoside and its derivatives, phenol, phloroglucin, cresol, pyrogallol, catechol, hydroquinone, bisphenol A, bisphenol F, bisphenol S, 1-hydroxynaphthalene, 1,3,6,8-tetrahydroxynaphthalene , anthrol, 1,4,5,8-tetrahydroxyanthracene, phenol polybutadiene polyol such as 1-hydroxypyrene, castor oil polyol, hydroxyalkyl (meth)acrylate (co)polymer and polyfunctional such as polyvinyl alcohol (for example Polyols having a functional group number of 2 to 100), condensates of phenol and formaldehyde (novolak), and the like can be mentioned.

(polyether polyol)
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, and tetrahydrofuran is subjected to ring-opening polymerization. The polymer obtained is mentioned.

Low-molecular-weight active hydrogen compounds having two or more active hydrogens, which constitute the polyether polyol, include, for example, bisphenol A, ethylene glycol, propylene glycol, butylene glycol, diols such as 1,6-hexanediol, glycerin, and trimethylol. Examples include triols such as propane, amines such as ethylenediamine and butylenediamine, and the like.

[Foam stabilizer]
The urethane resin composition according to the present embodiment preferably further contains a foam stabilizer.

By including a foam stabilizer in the urethane resin composition, the dispersibility of cells in the urethane resin composition can be enhanced, and the cell structure of the urethane resin foam formed therefrom can be adjusted.

Although the foam stabilizer is not particularly limited, for example, polyoxyalkylene foam stabilizers such as polyoxyalkylene alkyl ethers and surfactants such as silicone foam stabilizers such as organopolysiloxane can be used.

The content of the foam stabilizer is not particularly limited. It is more preferably 0.2% by mass or more, and particularly preferably 0.5% by mass or more. When the content of the foam stabilizer is at least the required amount, the dispersibility of cells in the urethane resin composition can be enhanced, and the cell structure of the urethane resin foam formed therefrom can be adjusted. On the other hand, the content of the foam stabilizer is preferably 10% by mass or less, more preferably 5% by mass or less, and 3% by mass or less with respect to 100% by mass of the urethane resin composition. is more preferable, 2% by mass or less is particularly preferable, and 1% by mass or less is most preferable. By keeping the content of the foam stabilizer below the required amount, the dimensional stability of the urethane resin foam formed from the urethane resin composition can be enhanced.

[Amine catalyst]
The urethane resin composition according to the present embodiment preferably further contains an amine catalyst.

By including an amine-based catalyst in the urethane resin composition, the reaction between the polyisocyanate compound and water can be promoted.

The amine-based catalyst is not particularly limited, and may be used singly or in combination of two or more of aliphatic amines, aromatic amines, and heterocyclic amines.

Specifically, examples of amine-based catalysts include triethylamine, N-methylmorpholinebis(2-dimethylaminoethyl)ether, N,N,N',N'',N''-pentamethyldiethylenetriamine, N,N, N'-trimethylaminoethyl-ethanolamine, bis(2-dimethylaminoethyl)ether, N-methyl,N'-dimethylaminoethylpiperazine, imidazole, imidazole derivative (1,2-dimethylimidazole), hexamethyltriethylenetetramine , tris(dimethylaminopropyl)hexahydro-1,3,5-triazine, dimethylaminoethoxyethanol and the like can be used.

The content of the amine-based catalyst is not particularly limited, but is, for example, 0.1% by mass or more, 0.2% by mass or more, 0.3% by mass or more, and 0.4% by mass with respect to 100% by mass of the urethane resin composition. % or more, 0.5 mass % or more, 0.6 mass % or more, 0.7 mass % or more, 0.8 mass % or more, 0.9 mass % or more, 1.0 mass % or more, 1.1 mass % 1.2% by mass or more, 1.3% by mass or more, 1.4% by mass or more, 1.5% by mass or more, 1.6% by mass or more, 1.7% by mass or more, 1.8% by mass or more is preferably When the content of the amine-based catalyst is at least the required amount, the reaction between the polyisocyanate compound and water can be promoted more appropriately. On the other hand, the content of the amine-based catalyst is 20% by mass or less, 15% by mass or less, 10% by mass or less, 9% by mass or less, 8% by mass or less, and 7% by mass with respect to 100% by mass of the urethane resin composition. Below, it is preferable that it is 6 mass % or less, 5 mass % or less, 4 mass % or less, and 3 mass % or less. By keeping the content of the amine-based catalyst below the required amount, the foaming speed in the urethane resin composition can be appropriately maintained.

[Trimerization catalyst]
The urethane resin composition according to the present embodiment preferably further contains a trimerization catalyst.

By including a trimerization catalyst in the urethane resin composition, the isocyanate groups contained in the polyisocyanate compound can be reacted and trimerized to promote the formation of isocyanurate rings.

Examples of trimerization catalysts include nitrogen-containing aromatic compounds such as tris(dimethylaminomethyl)phenol, 2,4-bis(dimethylaminomethyl)phenol and 2,4,6-tris(dialkylaminoalkyl)hexahydro-S-triazine. compounds, potassium acetate, potassium 2-ethylhexanoate, carboxylic acid alkali metal salts such as potassium octylate, trimethylammonium salts, triethylammonium salts, tertiary ammonium salts such as triphenylammonium salts, tetramethylammonium salts, tetraethylammonium, Quaternary ammonium salts such as tetraphenylammonium salts and (2-hydroxypropyl)(2-hydroxyethyl)dimethylammonium salts can be used.

Although the content of the trimerization catalyst is not particularly limited, it is preferably, for example, 0.05% by mass or more, 0.1% by mass or more, and 0.2% by mass or more with respect to 100% by mass of the urethane resin composition. , 0.3% by mass or more, 0.4% by mass or more, 0.5% by mass or more, 0.6% by mass or more, 0.7% by mass or more, 0.8% by mass or more, 0.9% by mass or more, 1.0% by mass or more, 1.1% by mass or more, 1.2% by mass or more, 1.3% by mass or more, 1.4% by mass or more, 1.5% by mass or more, 1.6% by mass or more, 1 0.7 mass % or more is preferable. When the content of the trimerization catalyst is at least the required amount, the formation of isocyanurate rings can be promoted and flame retardancy can be enhanced. On the other hand, the content of the trimerization catalyst is preferably 10% by mass or less, 7% by mass or less, 6% by mass or less, 5% by mass or less, and 4% by mass with respect to 100% by mass of the urethane resin composition. Below, it is preferable that it is 3 mass % or less, 2.5 mass % or less, and 2 mass % or less. By keeping the content of the trimerization catalyst below the required amount, clogging of the mixing section of the spray gun due to sudden formation of isocyanurate rings can be prevented.

[Urethane metal catalyst]
The urethane resin composition according to the present embodiment preferably further contains a urethanized metal catalyst.

By including a urethanized metal catalyst in the urethane resin composition, the reaction between the polyisocyanate compound and the above-described monools, phenols and various polyol compounds can be promoted.

The urethanized metal catalyst is not particularly limited, but for example, metal salts and metal complexes of lead, tin, bismuth, copper, zinc, cobalt, nickel and the like can be used. Specifically, bismath tris(2-ethylhexanoate), di-n-butyltin dilaurate, lead 2-ethylhexanoate and the like can be used as the urethanized metal catalyst.

The content of the urethanized metal catalyst is not particularly limited, but is, for example, 0.05% by mass or more, 0.07% by mass or more, 0.09% by mass or more, or 0.10% by mass with respect to 100% by mass of the urethane resin composition. It is preferably at least 0.11% by mass, at least 0.12% by mass, at least 0.13% by mass, at least 0.14% by mass, and at least 0.15% by mass. When the content of the urethanized metal catalyst is at least the required amount, the formation of isocyanurate rings can be promoted and the flame retardancy can be enhanced. On the other hand, the content of the urethanized metal catalyst is 10% by mass or less, 7% by mass or less, 5% by mass or less, 3% by mass or less, 2% by mass or less, 1. 5% by mass or less, 1% by mass or less, 0.9% by mass or less, 0.8% by mass or less, 0.7% by mass or less, 0.6% by mass or less, 0.5% by mass or less, 0.4% by mass Below, it is preferable that it is 0.3 mass % or less, 0.25 mass % or less, 0.2 mass % or less, and 0.18 mass % or less. By keeping the content of the urethanized metal catalyst below the required amount, clogging of the mixing section of the spray gun due to sudden formation of isocyanurate rings can be prevented.

〔Flame retardants〕
The urethane resin according to the present embodiment preferably further contains a flame retardant.

Examples of flame retardants include phosphate esters, phosphate-containing flame retardants, red phosphorus, bromine-containing flame retardants, boron-containing flame retardants, antimony-containing flame retardants, metal hydroxides, graphite, phosphorus-boron compounds, vinyl One or more of the polymers can be used. These will be described below with specific examples.

(phosphate ester)
Phosphate esters are not particularly limited, but monophosphate esters, condensed phosphate esters, and the like can be used, for example.

Specifically, the monophosphate is not particularly limited, but examples include trimethyl phosphate, triethyl phosphate, tributyl phosphate, tri(2-ethylhexyl) phosphate, tributoxyethyl phosphate, triphenyl phosphate, tricresyl phosphate, trixylenyl 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, diphenyl-2-methacryloyloxyethyl phosphate, melamine phosphate, dimelamine phosphate, melamine pyrophosphate, triphenylphosphine oxide, tricresylphosphine oxide, diphenyl methanephosphonate, diethyl phenylphosphonate, resircinol bis(diphenyl phosphate), bisphenol A bis(diphenyl phosphate), phosphaphenanthrene, tris(β-chloropropyl) phosphate, etc. can be used.

Examples of the condensed phosphate include, but are not limited to, trialkyl polyphosphate, resorcinol polyphenyl phosphate, resorcinol poly(di-2,6-xylyl) phosphate (manufactured by Daihachi Chemical Industry Co., Ltd., trade name PX-200), Condensed phosphoric acid esters such as hydroquinone poly(2,6-xylyl) phosphate and condensates thereof can be used.

(Phosphate-containing flame retardant)
A phosphate-containing flame retardant contains a phosphate.

The phosphate is not particularly limited, but one or more of monophosphate, pyrophosphate, polyphosphate and the like can be used.

Specifically, the phosphates include, for example, salts of various phosphoric acids with one or more metals or compounds selected from metals of Groups IA to IVB of the periodic table, ammonia, aliphatic amines, and aromatic amines. A phosphate consisting of can be used.

Among these, the metals of Groups IA to IVB of the periodic table are not particularly limited, but lithium, sodium, calcium, barium, iron (II), iron (III), aluminum and the like can be used.

Examples of the aliphatic amine include, but are not limited to, methylamine, ethylamine, diethylamine, triethylamine, ethylenediamine, piperazine, and the like.

The aromatic amine is not particularly limited, but pyridine, triazine, melamine, ammonium and the like can be used, for example.

More specifically, the monophosphate is not particularly limited, but for example, ammonium salts such as ammonium phosphate, ammonium dihydrogen phosphate, and diammonium hydrogen phosphate; Sodium salts such as sodium, monosodium phosphite, disodium phosphite, sodium hypophosphite; monopotassium phosphate, dipotassium phosphate, tripotassium phosphate, monopotassium phosphite, dipotassium phosphite , potassium salts such as potassium hypophosphite; lithium salts such as monolithium phosphate, dilithium phosphate, trilithium phosphate, monolithium phosphite, dilithium phosphite, lithium hypophosphite; phosphoric acid barium salts such as barium dihydrogen, barium hydrogen phosphate, tribarium phosphate, and barium hypophosphite; magnesium salts such as magnesium monohydrogen phosphate, magnesium hydrogen phosphate, trimagnesium phosphate, and magnesium hypophosphite; Calcium salts such as calcium dihydrogen phosphate, calcium hydrogen phosphate, tricalcium phosphate and calcium hypophosphite; zinc salts such as zinc phosphate, zinc phosphite and zinc hypophosphite;

The polyphosphate is not particularly limited, but for example, ammonium polyphosphate, piperazine polyphosphate, melamine polyphosphate, ammonium polyphosphate, aluminum polyphosphate, and the like can be used.

The phosphate may be subjected to various water resistance improving treatments such as silane coupling agent treatment and coating treatment with melamine resin, and may be added with known foaming aids such as melamine and pentaerythritol.

(red phosphorus)
Red phosphorus is one of the allotropes of phosphorus and is an amorphous polymeric form composed of phosphorus.

(bromine-containing flame retardant)
Bromine-containing flame retardants are flame retardants that contain compounds containing bromine in their molecular structure.

The bromine-containing flame retardant is not particularly limited, but for example, an aromatic brominated compound can be used.

Specific examples of aromatic brominated compounds include hexabromobenzene, pentabromotoluene, hexabromobiphenyl, decabromobiphenyl, hexabromocyclodecane, decabromodiphenyl ether, octabromodiphenyl ether, hexabromodiphenyl ether, bis(pentabromo phenoxy)ethane, ethylene-bis(tetrabromophthalimide), tetrabromobisphenol A, ethylenebispentabromophenyl and other monomeric organic bromine compounds; polycarbonate oligomers produced from brominated bisphenol A as a raw material; brominated polycarbonates such as copolymers; diepoxy compounds produced by the reaction of brominated bisphenol A and epichlorohydrin; brominated epoxy compounds such as monoepoxy compounds obtained by the reaction of brominated phenols and epichlorohydrin; brominated benzyl acrylate); brominated polyphenylene ethers; condensates of brominated bisphenol A, cyanuric chloride and brominated phenol; Halogenated bromine compound polymers such as non-crosslinked brominated poly(-methylstyrene) and the like can be used.

(Boron-containing flame retardant)
Boron-containing flame retardants are flame retardants that contain compounds containing boron in their molecular structure.

Boron-containing flame retardants are not particularly limited, but for example, borax, boron oxide, boric acid, borates, and the like can be used.

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

Examples of borates that can be used include borates of alkali metals, alkaline earth metals, elements of Groups 4, 12 and 13 of the periodic table, and ammonium. More specifically, borate salts include alkali metal borate salts such as lithium borate, sodium borate, potassium borate, and cesium borate; and boric acids such as magnesium borate, calcium borate, and barium borate. Alkaline earth metal salts, zirconium borate, zinc borate, aluminum borate, ammonium borate and the like can be used.

(Antimony-containing flame retardant)
An antimony-containing flame retardant is a flame retardant containing a compound containing antimony in its molecular structure.

The antimony-containing flame retardant is not particularly limited, but for example, antimony oxide, antimonate, pyroantimonate and the like can be used.

As antimony oxide, for example, antimony trioxide, antimony pentoxide, or the like can be used.

As the antimonate, for example, sodium antimonate, potassium antimonate, or the like can be used.

Examples of pyroantimonate include sodium pyroantimonate and potassium pyroantimonate.

(metal hydroxide)
The metal hydroxide is not particularly limited, but magnesium hydroxide, calcium hydroxide, aluminum hydroxide, iron hydroxide, titanium hydroxide, zinc hydroxide, copper hydroxide and the like can be used.

(graphite)
Graphite is not particularly limited, but can be used in a scale-like, scale-like, plate-like, spherical shape, or the like. As the graphite, expanded graphite, expanded graphite, or the like may be used.

The average particle size of graphite is not particularly limited, but for example, it is preferably 0.5 μm or more, more preferably 1 μm or more, further preferably 2 μm or more, and particularly preferably 5 μm or more. preferable. On the other hand, the average particle size of graphite is preferably 200 μm or less, more preferably 100 μm or less, even more preferably 50 μm or less, and particularly preferably 20 μm or less. The average particle size of graphite is obtained by observing 200 particles with a scanning electron microscope, measuring the longest line segment from the contour to the contour of each particle, and calculating the arithmetic mean of the average particle size of graphite. and

(Phosphorus-boron compound)
Phosphorus-boron compounds are compounds containing phosphorus and boron.

(vinyl polymer)
As the vinyl polymer, a polymer formed by a polymerization reaction of a monomer having a vinyl group can be used.

The content (total amount) of the flame retardant is not particularly limited. % or more, particularly preferably 15% by mass or more or 17% by mass or more, and most preferably 20% by mass or more, 22% by mass or more, 24% by mass or more, or 25% by mass or more. . When the content of the flame retardant is at least the required amount, the flame retardancy of the formed urethane resin foam can be enhanced. On the other hand, the content of the flame retardant is preferably 50% by mass or less, more preferably 45% by mass or less, and 40% by mass or less with respect to 100% by mass of the urethane resin composition. It is more preferably 35% by mass or less, particularly preferably 32% by mass or less, or most preferably 30% by mass or less. When the content of the flame retardant is equal to or less than the required amount, the urethane resin composition can be foamed more appropriately.

[Blowing agent]
The urethane resin composition according to this embodiment preferably contains a foaming agent.

By including a foaming agent in the urethane resin composition, foaming of the urethane resin foam formed from the urethane resin composition can be promoted.

Specific examples of foaming agents include water; low-boiling hydrocarbons such as propane, butane, pentane, hexane, heptane, cyclopropane, cyclobutane, cyclopentane, cyclohexane, and cycloheptane; dichloroethane, propyl chloride, and isopropyl chloride. Chlorinated aliphatic hydrocarbon compounds such as , butyl chloride, isobutyl chloride, pentyl chloride and isopentyl chloride; fluorine compounds such as trichloromonofluoromethane and trichlorotrifluoroethane; CHF ₃ , CH ₂ F ₂ , CH ₃ F, HFO -1336mzz(Z) ((Z)-1,1,1,4,4,4-hexafluorobutene), HFO-1223zd(E) (trans-1-chloro-3,3,3-trifluoropropene) , hydrofluorocarbons such as HFO-1224yd(Z) ((Z)-1-chloro-2,3,3,3-tetrafluoropropene); dichloromonofluoroethanes (e.g., HCFC141b (1,1-dichloro-1- fluoroethane), HCFC22 (chlorodifluoromethane), HCFC142b (1-chloro-1,1-difluoroethane)), HFC-245fa (1,1,1,3,3-pentafluoropropane), HFC-365mfc (1, 1,1,3,3-pentafluorobutane) and other hydrochlorofluorocarbon compounds; ether compounds such as diisopropyl ether, organic physical foaming agents such as mixtures of these compounds, nitrogen gas, oxygen gas, argon gas, carbon dioxide Inorganic physical foaming agents such as gases can be used.

The content of the foaming agent is not particularly limited, but is preferably, for example, 1% by mass or more, more preferably 2% by mass or more, and 3% by mass or more with respect to 100% by mass of the urethane resin composition. More preferably, it is 4% by mass or more, 5% by mass or more, 6% by mass or more, 7% by mass or more, or 8% by mass or more. When the content of the foaming agent is equal to or greater than the required amount, it is possible to impart more appropriate foamability to the urethane resin foam. On the other hand, the content of the foaming agent is 30% by mass or less, 25% by mass or less, 20% by mass or less, 15% by mass or less, 10% by mass or less, 9% by mass or less, based on 100% by mass of the urethane resin composition. It is preferably 8% by mass or less, 7% by mass or less, and 6% by mass or less. By keeping the content of the foaming agent below the required amount, the mechanical strength of the formed urethane resin foam can be further enhanced.

[Other additives]
The urethane resin composition according to this embodiment may contain an inorganic filler.

Examples of inorganic fillers include, but are not limited to, silica, diatomaceous earth, alumina, titanium oxide, calcium oxide, magnesium oxide, iron oxide, tin oxide, antimony oxide, ferrites, basic magnesium carbonate, calcium carbonate, magnesium carbonate, Zinc carbonate, barium carbonate, dawsonite, hydrotalcite, calcium sulfate, barium sulfate, gypsum fiber, potassium salts such as calcium silicate, talc, clay, mica, montmorillonite, bentonite, activated clay, seviolite, imogolite, sericite, glass Fiber, glass beads, silica balloon, aluminum nitride, boron nitride, silicon nitride, carbon black, graphite, carbon fiber, carbon balloon, charcoal powder, various metal powders, potassium titanate, magnesium sulfate, lead zirconate titanate, aluminum borate, Molybdenum sulfide, silicon carbide, stainless steel fibers, various magnetic powders, slag fibers, fly ash, silica-alumina fibers, alumina fibers, silica fibers, zirconia fibers, etc. may be used singly or in combination of two.

In the urethane resin composition according to the present embodiment, if necessary, antioxidants such as phenolic, amine, and sulfur antioxidants, heat stabilizers, metal damage inhibitors, antistatic agents, stabilizers, cross-linking agents, Additives such as lubricants, softeners, pigments and tackifying resins, tackifiers such as polybutene and petroleum resins, and bifenthrin-based termite inhibitors can be used.

In addition, as the phenols, one or more selected from the group consisting of natural cashew nut shell liquid, industrial cashew nut shell liquid, and derivatives of cashew nut shell liquid, especially when using industrial cashew nut shell liquid, these viscosities are low. Therefore, depending on the content and the like, the viscosity of the urethane resin composition as a whole tends to decrease.
In this case, the urethane resin composition according to this embodiment preferably further contains a thickener. By including a flame retardant in the urethane resin composition, it is possible to adjust the viscosity to an appropriate one depending on the method of applying the urethane resin composition to the object (for example, spraying). In addition, due to the thickening action of the thickener, the effect of preventing sedimentation (aggregation) of the solid content of the flame retardant or the like in the urethane resin composition (especially the raw material composition or the first raw material described later). is also obtained. As a result, various properties (flame retardancy, dimensional stability, etc.) of the formed urethane resin foam can be further improved.

Although the thickening agent is not particularly limited, for example, hydrophobic fumed silica can be preferably used, and among the above inorganic fillers, clay, bentonite, talc, etc. may be used in combination. The use of these thickeners is preferable because the viscosity of the urethane resin composition can be adjusted with a small amount.

When the thickener is granular, its specific surface area according to the BET method is, for example, preferably 20 m ² /g or more, more preferably 30 m ² /g or more, and more preferably 40 m ² /g or more. More preferably, it is particularly preferably 50 m ² /g or more. On the other hand, the specific surface area of the thickener measured by the BET method is preferably 130 m ² /g or less, more preferably 120 m ² /g or less, even more preferably 110 m ² /g or less, and 100 m ² . / g or less is particularly preferred. In this case, it becomes easier to adjust the viscosity of the urethane resin composition.

In this case, the average particle diameter of the thickening agent is not particularly limited, but is preferably 20 nm or more, more preferably 30 nm or more, further preferably 40 nm or more, further preferably 50 nm or more. It is particularly preferred to have On the other hand, the average particle size of the thickener is preferably 800 nm or less, more preferably 700 nm or less, even more preferably 600 nm or less, and particularly preferably 500 nm or less. Also in this case, it becomes easier to adjust the viscosity of the urethane resin composition. The average particle size of the thickener can be measured in the same manner as the average particle size of graphite.

Although the content of the thickening agent is not particularly limited, it is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, based on 100% by mass of the urethane resin composition. It is more preferably 0.4% by mass or more, particularly preferably 0.6% by mass or more, and most preferably 0.8% by mass. On the other hand, the content of the thickener is preferably 10% by mass or less, more preferably 8% by mass or less, and 6% by mass or less with respect to 100% by mass of the urethane resin composition. is more preferable, 4% by mass or less is particularly preferable, and 2% by mass or less or 1% by mass or less is most preferable. When the content of the flame retardant is within the above range, the viscosity of the urethane resin composition can be accurately adjusted to a desired value.

The viscosity of the urethane resin composition (the raw material composition or the first raw material described later) immediately after being prepared by mixing the components is not particularly limited, but is preferably 600 mPa s or more, such as 800 mPa s. s or more, more preferably 1000 mPa·s or more, particularly preferably 1200 mPa·s or more, and most preferably 1400 mPa·s or more. On the other hand, the viscosity of the urethane resin composition is preferably 2600 mPa s or less, more preferably 2400 mPa s or less, even more preferably 2200 mPa s or less, and 2000 mPa s or less. is particularly preferable, and 1800 mPa·s or less is most preferable. In this case, the viscosity of the urethane resin composition becomes a value particularly suitable for spraying. As a result, various properties (flame retardancy, dimensional stability, etc.) of the formed urethane resin foam can be further improved.

[Physical properties of urethane resin]
The core density of the foam piece composed of the urethane resin composition according to the present embodiment is not particularly limited, but is, for example, 50 kg/m ³ or more, 51 kg/m ³ or more, 52 kg/m ³ or more, 53 kg/m ³ or more. 54 kg/m ³ or more, 55 kg/m ³ or more, 56 kg/m ³ or more, 57 kg/m ³ or more, 58 kg/m ³ or more, 59 kg/m ³ or more, 60 kg/m ³ or more, 61 kg/m ³ or more, 62 kg/m3 or more ^, 63 kg/m3 or more ^, 64 kg/m3 or more ^, 65 kg/m3 or more ^, 66 kg/m3 or more ^, 67 kg/m3 or more ^, 68 kg/m3 or more ^, 69 kg/m3 or more ^, 70 kg/m3 or more More preferably, it is 71 kg/m ³ or more ^{, or 72 kg/m 3 or} more. On the other hand, the core density of the foam pieces is 90 kg/m ³ or less, 89 kg/m ³ or less, 88 kg/m ³ or less, 87 kg/m ³ or less, 86 kg/m ³ or less, 85 kg/m ³ or less, 84 kg/m 3 or less. ³ or less, 83 kg/m ³ or less, 82 kg/m ³ or less, 81 kg/m ³ or less, 80 kg/m ³ or less, 79 kg/m ³ or less, 78 kg/m ³ or less, 77 kg/m ³ or less, 76 kg/m ³ or less , 75 kg/m ³ or less, 74 kg/m ³ or less, 73 kg/m ³ or less, 72 kg/m ³ or less, 71 kg/m ³ or less, 70 kg/m ³ or less, 69 kg/m ³ or less, 68 kg/m ³ or less, 67 kg /m ³ or less, 66 kg/m ³ or less, 65 kg/m ³ or less, 64 kg/m ³ or less, 63 kg/m ³ or less, 62 kg/m ³ or less, 61 kg/m ³ or less, 60 kg/m ³ or less, 59 kg/m It is preferably ³ or less. A specific method for measuring the core density will be described later.

The total calorific value measured by heating for 10 minutes according to ISO 5660-1:2002 of the foam piece formed from the urethane resin composition according to the present embodiment is not particularly limited, but for example 9 MJ. /m ² , 8.5 MJ/m ² or less, 8 MJ/m ² or less, 7.5 MJ/m ² or less, or 7 MJ/m ² or less. On the other hand, the total calorific value measured by heating for 10 minutes according to ISO 5660-1:2002 of the foam pieces formed from the urethane resin composition is 1 MJ/m ² or more, 1.5 MJ/ ^m2 or more, ² MJ/ ^m2 or more, 2.5 MJ/m2 or more, 3 MJ/ ^m2 or more, 3.5 MJ/ ^m2 or more, 4 MJ/ ^m2 or more, 4.5 MJ/ ^m2 or more, 5 MJ/ ^m2 Above, it may be 5.5 MJ/m ² or more. A specific method for measuring the total calorific value will be described later.

The maximum heat release rate measured by heating for 10 minutes according to ISO 5660-1:2002 of the foam piece formed from the urethane resin composition according to the present embodiment is not particularly limited, but is, for example, 117 kW. /m ² or less, 116.7 W/m ² or less, 116.5 W/m ² or less, 116 W/m ² or less, 115.5 W/m ² or less, 115 W/m ² or less, 114.5 W/m ² or less, 114 W /m ² or less, 113.5 W/m ² or less, 113 W/m ² or less, 112.5 W/m ² or less, 112 W/m ² or less, 111.5 W/m ² or less, 111 W/m ² or less, 110.5 W /m ² or less, 110 W/m ² or less, 109 W/m ² or less, 109.5 W/m ² or less, 109 W/m ² or less, 108.5 W/m ² or less, or 108 W/m ² or less. On the other hand, the maximum heat release rate measured by heating for 10 minutes according to ISO 5660-1:2002 of the foam piece formed from the urethane resin composition is 90 W/m ² or more, 91 W/m ² 92 W/m ² or more, 93 W/m ² or more, 95 W/m ² or more, 96 W/m ² or more, 97 W/m ² or more, 98 W/m ² or more, 99 W/m ² or more, 100 W/m ² or more, It may be 101 W/m ² or more. A specific method for measuring the maximum heat release rate will be described later.

The mass reduction rate measured by heating for 10 minutes according to ISO 5660-1:2002 of the foam piece composed of the urethane resin composition according to the present embodiment is not particularly limited, but for example 60 % by mass or less, 55% by mass or less, 50% by mass or less, 49% by mass or less, 48% by mass or less, 47% by mass or less, 46% by mass or less, 45% by mass or less, 44% by mass or less, 43% by mass or less, 42 % by mass or less, 41% by mass or less, 40% by mass or less, 39% by mass or less, 38% by mass or less, 37% by mass or less, 36% by mass or less, 35% by mass or less, 34% by mass or less, 33% by mass or less, 32 % by mass or less, 31% by mass or less, 30% by mass or less, 29% by mass or less, 28% by mass or less, 27% by mass or less, 26% by mass or less, 25% by mass or less, 24% by mass or less, 23% by mass or less, 22 % by mass or less, 21% by mass or less, 20% by mass or less, 19% by mass or less, 18% by mass or less, 17% by mass or less, 16% by mass or less, 15% by mass or less, 14% by mass or less, 13% by mass or less, 12 % by mass or less, preferably 11 mass % or less, or 10 mass % or less. On the other hand, the mass reduction rate may be 1% by mass or more, 2% by mass or more, 3% by mass or more, 4% by mass or more, 5% by mass or more, 6% by mass or more, or 7% by mass or more.

The oxygen index measured according to JIS K 7201-2:2007 of the foam pieces formed from the urethane resin composition according to the present embodiment is not particularly limited, but is preferably 30 or more, for example. It is more preferably 31 or more, and even more preferably 32 or more. A urethane resin foam formed from a urethane resin composition having such an oxygen index can be evaluated as having sufficiently high flame retardancy.

Further, when the urethane resin composition according to the present embodiment is sprayed onto a gypsum board by a spray foaming method to form a foam piece, there is no gap over the entire interface between the foam piece and the gypsum board. Even if there is a gap partially in the gap, it is preferable that the size of the gap is less than a predetermined value. That is, it is preferable that there is no partial gap of a predetermined value or more at the interface between the foam piece and the gypsum board. Although the predetermined value is not particularly limited, for example, it is preferably 2 mm, more preferably 1.5 mm, and even more preferably 1 mm. A urethane resin foam formed from such a urethane resin composition can be evaluated as having excellent adhesiveness.

The urethane resin composition according to the present embodiment is used by spraying onto structures such as buildings, furniture, automobiles, trains, and ships. Thus, a urethane resin foam layer can be formed on the surface of a structure or the like.

Specifically, the urethane resin composition may be divided into a polyisocyanate compound and other components, and the two may be mixed while being sprayed and sprayed onto the surface of a structure or the like, or the polyisocyanate compound and , may be mixed with other components and then sprayed onto the surface of a structure or the like.

Since the urethane resin composition according to the present embodiment reacts and cures, its viscosity changes over time. Therefore, before using the urethane resin composition according to the present invention, the urethane resin composition is divided into two or more parts to prevent the urethane resin composition from reacting and hardening. When using the urethane resin composition, the urethane resin composition according to the present embodiment is obtained by mixing raw materials or raw material compositions of the urethane resin composition divided into two or more.

In addition, when the urethane resin composition is divided into two or more raw materials or raw material compositions, each component of the urethane resin composition divided into two or more raw materials or raw material compositions does not start curing alone, and the urethane resin Each component of the composition may be divided such that the curing reaction begins after each component of the composition is mixed. Most typically, the polyisocyanate compound and other components may be divided into two. The latter raw material composition will be described below.

<Raw material composition>
The raw material composition according to the present embodiment is a raw material composition for a urethane resin composition that is used by mixing with a polyisocyanate compound. Specifically, this raw material composition contains monools and phenols.

In one embodiment, the raw material composition may further contain a foam stabilizer, an amine catalyst, a trimerization catalyst, a urethanized metal catalyst, a flame retardant, a foaming agent, and a thickener. The specific types and the like of each component are the same as those described in the section on the urethane resin composition, so detailed description thereof will be omitted here. The content of each component in the raw material composition will be described below.

In this raw material composition, the content of monools is not particularly limited, but is preferably 0.25% by mass or more, for example, 0.5% by mass or more, relative to 100% by mass of the raw material composition. is more preferably 1% by mass or more, and particularly preferably 1.25% by mass or more. On the other hand, the content of monools is preferably 15% by mass or less, more preferably 12.5% by mass or less, and 10% by mass or less with respect to 100% by mass of the raw material composition. is more preferable, 7.5% by mass or less is particularly preferable, and 5% by mass or less is most preferable.

In this raw material composition, the content of phenols is not particularly limited, but is preferably, for example, 0.5% by mass or more, more preferably 1% by mass or more, relative to 100% by mass of the raw material composition. It is preferably 1.5% by mass or more, and particularly preferably 2% by mass or more. On the other hand, the content of phenols is preferably 15% by mass or less, more preferably 12.5% by mass or less, and 10% by mass or less relative to 100% by mass of the raw material composition. It is more preferably 7.5% by mass or less, particularly preferably 6% by mass or less, and most preferably 6% by mass or less.

This raw material composition may or may not contain a polyol compound, but when it contains a polyol compound, the content of the polyol compound is not particularly limited, but for example, 0.35% with respect to 100% by mass of the raw material composition. % by mass or less, 0.25% by mass or less, 0.1% by mass or less, 0.05% by mass or less, 0.035% by mass or less, 0.025% by mass or less, 0.01% by mass or less, 0.005% by mass % or less, 0.0035 mass % or less, 0.0025 mass % or less, 0.001 mass % or less, 0.0005 mass % or less, 0.00035 mass % or less, 0.00025 mass % or less, 0.0001 mass % 0.00005% by mass or less, 0.000035% by mass or less, 0.000025% by mass or less, 0.00001% by mass or less, or 0.000005% by mass or less.

In this raw material composition, the content of the foam stabilizer is not particularly limited, but is preferably 0.025% by mass or more, for example, 0.05% by mass or more, relative to 100% by mass of the raw material composition. is more preferably 0.1% by mass or more, and particularly preferably 0.25% by mass or more. On the other hand, the content of the foam stabilizer is preferably 5% by mass or less, more preferably 2.5% by mass or less, and 1.5% by mass or less with respect to 100% by mass of the raw material composition. More preferably, it is 1% by mass or less, and most preferably 0.5% by mass or less.

In this raw material composition, the content of the amine-based catalyst is not particularly limited. , 0.2% by mass or more, 0.25% by mass or more, 0.3% by mass or more, 0.35% by mass or more, 0.4% by mass or more, 0.45% by mass or more, 0.5% by mass or more, 0.55% by mass or more, 0.6% by mass or more, 0.65% by mass or more, 0.7% by mass or more, 0.75% by mass or more, 0.8% by mass or more, 0.85% by mass or more, 0 .9% by mass or more is preferable. On the other hand, the content of the amine-based catalyst is 10% by mass or less, 7.5% by mass or less, 5% by mass or less, 4.5% by mass or less, 4% by mass or less, relative to 100% by mass of the raw material composition. It is preferably 3.5% by mass or less, 3% by mass or less, 2.5% by mass or less, 2% by mass or less, and 1.5% by mass or less.

In this raw material composition, the content of the trimerization catalyst is not particularly limited, but is preferably, for example, 0.025% by mass or more, 0.5% by mass or more, and 0.5% by mass or more, based on 100% by mass of the raw material composition. 0.1% by mass or more, 0.15% by mass or more, 0.2% by mass or more, 0.25% by mass or more, 0.3% by mass or more, 0.35% by mass or more, 0.4% by mass or more; 45% by mass or more, 0.5% by mass or more, 0.55% by mass or more, 0.6% by mass or more, 0.65% by mass or more, 0.7% by mass or more, 0.75% by mass or more, 0.8 % by mass or more, preferably 0.85% by mass or more. On the other hand, the content of the trimerization catalyst is preferably 5% by mass or less, 3.5% by mass or less, 3% by mass or less, and 2.5% by mass or less with respect to 100% by mass of the raw material composition. more preferably 2% by mass or less, 1.5% by mass or less, 1.25% by mass or less, or 1% by mass or less.

In this raw material composition, the content of the urethanized metal catalyst is not particularly limited, but is, for example, 0.025% by mass or more, 0.035% by mass or more, or 0.045% by mass with respect to 100% by mass of the raw material composition. 0.05% by mass or more, 0.055% by mass or more, 0.06% by mass or more, 0.065% by mass or more, 0.07% by mass or more, and 0.075% by mass or more. On the other hand, the content of the urethanized metal catalyst is 5% by mass or less, 3.5% by mass or less, 2.5% by mass or less, 1.5% by mass or less, and 1% by mass with respect to 100% by mass of the raw material composition. % or less, 0.75 mass % or less, 0.5 mass % or less, 0.45 mass % or less, 0.4 mass % or less, 0.35 mass % or less, 0.3 mass % or less, 0.25 mass % Below, it is preferable that it is 0.2 mass % or less, 0.15 mass % or less, 0.125 mass % or less, 0.1 mass % or less, and 0.09 mass % or less.

In this raw material composition, the content of the flame retardant is not particularly limited, but for example, it is preferably 2.5% by mass or more, more preferably 5% by mass or more, relative to 100% by mass of the raw material composition. preferably 6% by mass or more, particularly preferably 7.5% by mass or more, or 8.5% by mass or more, and 10% by mass or more, 11% by mass or more, 12% by mass or more, or 12. Most preferably, it is at least 5% by mass. On the other hand, the content of the flame retardant is preferably 25% by mass or less, more preferably 22.5% by mass or less, and 20% by mass or less with respect to 100% by mass of the raw material composition. is more preferable, 17.5% by mass or less is particularly preferable, and 16% by mass or less or 15% by mass or less is most preferable.

In this raw material composition, the content of the foaming agent is not particularly limited, but is preferably 0.5% by mass or more, more preferably 1% by mass or more, relative to 100% by mass of the raw material composition. It is preferably 1.5% by mass or more, and particularly preferably 2% by mass or more. On the other hand, the content of the foaming agent is 15% by mass or less, 12.5% by mass or less, 10% by mass or less, 7.5% by mass or less, 5% by mass or less with respect to 100% by mass of the raw material composition. It is preferably 5% by mass or less, 4% by mass or less, 3.5% by mass or less, and 3% by mass or less.

In this raw material composition, the content of the thickening agent is not particularly limited, but is preferably 0.2% by mass or more, for example, 0.4% by mass or more, relative to 100% by mass of the raw material composition. is more preferably 0.6% by mass or more, and particularly preferably 0.8% by mass or more. On the other hand, the content of the foaming agent is preferably 20% by mass or less, 16% by mass or less, 12% by mass or less, 8% by mass or less, and 4% by mass or less with respect to 100% by mass of the raw material composition.

Such a raw material composition can be mixed with a polyisocyanate to form a urethane resin composition. The ratio of the content of the raw material composition and the polyisocyanate (raw material composition: polyisocyanate) is not particularly limited, but is, for example, 80:20 to 20:80, 75:25 to 25:75, 70:30 to 30. : 70, 65:35-35:65, 60:40-40:60, 55:45-45:55, 55:45-50:50, 50:50-45:55.

<raw material kit>
A raw material kit according to the present embodiment is a raw material kit for a urethane resin composition. Specifically, this raw material kit comprises a first raw material containing monools and phenols, and a second raw material containing a polyisocyanate compound.

In this raw material kit, the first raw material corresponds to the raw material composition of the preceding paragraph.

Regarding the content of each component in the raw material kit, the content of the urethane resin composition described above is changed from "with respect to 100% by mass of the urethane resin composition" to "100% by mass of the first raw material and the second raw material. shall be applied by replacing it with "against".

<Urethane resin foam>
The urethane resin foam according to the present embodiment contains a polymer formed by combining monools and a polyisocyanate compound, and a polymer formed by combining a phenols and a polyisocyanate compound.

<Method for producing urethane resin composition>
The method for producing the urethane resin composition is not particularly limited, but examples include a method of mixing each component of the urethane resin composition, a method of suspending the urethane resin composition in an organic solvent, or a method of melting by heating. A method of preparing a slurry by dispersing in a solvent, or the like can be used. In addition, when the reaction-curable resin component contained in the urethane resin composition contains a component that is solid at room temperature, the urethane resin composition can be produced by a method such as melting the urethane resin composition under heating. can be used.

More specifically, for kneading the urethane resin composition, each component of the urethane resin composition is mixed with a known kneading machine such as a single-screw extruder, a twin-screw extruder, a Banbury mixer, a kneader mixer, a kneading roll, a Raikai machine, and a planetary stirrer. device can be used. The kneading can also be carried out by separately kneading the main agent of the urethane resin and the curing agent together with the filler and the like, and then using a static mixer, dynamic mixer, or the like immediately before the injection. Furthermore, the kneading can also be carried out in the same manner immediately before injecting the components of the urethane resin composition, excluding the catalyst, and the catalyst. The same applies to the method for producing the raw material composition and the raw material kit.

The urethane resin composition, the raw material composition, the raw material kit, and the urethane resin foam according to the present embodiment are not limited to the specific embodiments described above, and within the scope that does not impair the effects of the present invention, It can be implemented with appropriate modifications.

Hereinafter, the urethane resin composition, the raw material composition, the raw material kit, and the urethane resin foam according to the present embodiment will be described more specifically by showing Examples, but the present invention is not limited to the following Examples. not something.

<Sample preparation>
〔reagent〕
The following reagents were prepared as raw materials for urethane resin composition samples.

(1) Polypropylene glycol adduct of butanol: LB-65 (manufactured by Sanyo Chemical Industries, Ltd.)
(2A) Adduct of alkylene oxide of industrial cashew nut shell liquid (2B) Industrial cashew nut shell liquid 1 (cardanol content: 87% by mass or more)
(2C) Industrial cashew nut shell liquid 2 (cardanol content: 95% by mass or more)
(3) sucrose-based polyol: HS209 (manufactured by Sanyo Chemical Industries, Ltd.)
(4) Ester-based polyol 1: RFK505 (manufactured by Kawasaki Chemical Industry Co., Ltd.)
(5) Ester-based polyol 2: RDK142 (manufactured by Kawasaki Chemical Industry Co., Ltd.)
(6) Silicone foam stabilizer: L6100 (manufactured by Momentive PMJ LLC)
(7) Amine-based catalyst 1: TOYOCAT TT (manufactured by Tosoh Corporation)
(8) Amine-based catalyst 2: Luplagen N-600 (manufactured by BASF)
(9) Amine-based catalyst 3: Luplagen N-107 (manufactured by BASF)
(10) Quaternary ammonium salt 1: Kaorizer KL410 (manufactured by Kao Corporation)
(11) quaternary ammonium salt 2: U-CAT18X (manufactured by Evonik)
(12) Potassium octylate (potassium 2-ethylhexylate): PC9540 (manufactured by Ele Corporation)
(13) urethanized metal catalyst: BI-28 (manufactured by Nitto Kasei Co., Ltd.)
(14) Phosphate ester chloride: Tris (β-chloropropyl) phosphate (15) Aluminum hydroxide: B103 (manufactured by Nippon Light Metal Co., Ltd.)
(16) Red phosphorus: ST-400 (45-49% by mass, manufactured by Rin Kagaku Kogyo Co., Ltd.)
(17) Flaky graphite: MF-10E (manufactured by Fuji Graphite Industry Co., Ltd.)
(18) Phosphorus-boron flame retardant (19) Bromine-containing flame retardant: SAYTEX8010 (82.3% by mass, manufactured by Albemarle Japan Co., Ltd.)
(20) Vinyl polymer (21) Hydrophobic fumed silica: Aerosil RY200S (manufactured by Nippon Aerosil Co., Ltd.)
(22) Foaming agent: OP-1100 (manufactured by Mitsui Chemours Fluoro Products Co., Ltd.)
(23) Polyisocyanate: Millionate MR-200 (manufactured by Tosoh Corporation)

[Spray foaming method: preparation of spray foam sample]
The above components (1), (2A), (2B), (2C) to (22) were weighed into a spray tank and mixed and stirred at room temperature using a hand mixer (first raw material). The above-described component (23) was weighed into a spray tank and mixed and stirred at room temperature using a hand mixer (second raw material). The first raw material and the second raw material are combined using a reactor A-25 (manufactured by Graco Co., Ltd.) with a D gun (manufactured by Graco Co., Ltd.) attached to the tip of the hose (hose length 30 m). While heating to ° C., it was sprayed on each object described later to prepare a spray foam sample.

<Sample evaluation>
[Isocyanate index]
The isocyanate index is the equivalent ratio of the isocyanate groups of the polyisocyanate compound to the hydroxyl groups of the monools, phenols and polyol compounds, and is expressed as a percentage in Tables 1 and 2 below.

[Apparent core density]
Spray foam sample sprayed on acrylic plywood for physical properties (lower blow + 1 layer with a thickness of about 50 mm (for Example A3, Examples B1 to B7 and Comparative Examples B1 to B3, 2 layers with a thickness of about 25 mm)) was measured for apparent core density in accordance with JIS K 7222:2005.

〔Adhesiveness〕
By the spray foaming method, the bottom blowing and the 1-2 layer urethane resin composition sample were sprayed on the gypsum board under the conditions of 20±5° C., laminated, and kept at 40° C. for 30 minutes. After that, from the surface of the gypsum board, a foam piece obtained by cutting a spray foam sample formed by spraying the urethane resin composition sample into a size of about 100×100 mm was peeled off. Then, it was confirmed whether or not there was a gap at the interface between the foam piece and the gypsum board.
◎: There is no gap (interfacial peeling) over the entire interface between the foam piece and the gypsum board, or even if there is a gap partially at the interface, the size is less than 0.5 mm ○: Foam piece There is no gap (interfacial peeling) over the entire interface with the gypsum board, but there is a gap partially at the interface with a size of 0.5 mm or more and less than 2 mm. △: Foam piece with gypsum board There is no gap (interfacial delamination) over the entire interface, but there is a gap partially in the interface with a size of 2 mm or more ×: A gap (interfacial delamination) over the entire interface between the foam piece and the gypsum board exists

[Total calorific value, maximum heat release rate and mass reduction]
Cut out a test piece of 10 cm × 10 cm × 5 cm (including gypsum board) from the spray foam sample (downward blowing + thickness of about 50 mm) sprayed on the gypsum board, ISO 5660-1: In accordance with 2002, radiation The total heat value and maximum heat release rate were measured when heated for 10 minutes or 20 minutes at a heat intensity of 50 kW/m ² . Also, the mass loss of the spray foam sample with gypsum board upon heating was measured.

[Oxygen index]
A test piece of 10 mm×10 mm×150 mm was cut out from a spray foam sample (two layers with a thickness of about 25 mm) sprayed on an acrylic plywood board for physical properties. The oxygen index of this test piece was measured according to JIS K 7201-2:2007.

〔viscosity〕
The above components (1), (2B), (2C) to (22) were weighed into a cup and mixed and stirred at room temperature using a hand mixer to prepare the first raw material. After that, the viscosity of this first raw material was measured according to JIS K 7117-1:1999.

[Sedimentation]
The above components (1), (2B), (2C) to (22) were weighed into a cup and mixed and stirred at room temperature using a hand mixer to prepare the first raw material. After that, this first raw material was placed in a 500 mL plastic bottle, and it was visually confirmed whether or not the solid content settled.
◎: Sedimentation of solid content was confirmed from 24 hours to 48 hours ○: Sedimentation of solid content was confirmed from 1 hour to 24 hours △: Sedimentation of solid content was confirmed by 1 hour, Easily redispersible ×: Solid content is confirmed to settle by 1 hour, and redispersion takes some time and effort

Claims (14)

A urethane resin composition,
a polyisocyanate compound;
a polyalkylene glycol adduct of a primary alcohol;
A urethane resin composition comprising phenol and/or a phenol derivative. In the urethane resin composition according to claim 1,
The urethane resin composition, wherein the number of carbon atoms in the primary alcohol is 3 or more and 8 or less. In the urethane resin composition according to claim 1 or 2,
A urethane resin composition containing 0.5% by mass or more and 30% by mass or less of the polyalkylene glycol adduct of the primary alcohol with respect to 100% by mass of the urethane resin composition. In the urethane resin composition according to any one of claims 1 to 3,
As the phenol and/or the phenol derivative, at least one selected from the group consisting of natural cashew nut shell liquid, industrial cashew nut shell liquid, and derivatives of cashew nut shell liquid is used. In the urethane resin composition according to claim 4,
Furthermore, a urethane resin composition containing a thickener. In the urethane resin composition according to claim 5,
A urethane resin composition containing 0.1% by mass or more and 10% by mass or less of the thickener with respect to 100% by mass of the urethane resin composition. In the urethane resin composition according to claim 5 or 6,
In addition, it contains a flame retardant,
A urethane resin composition in which the flame retardant is prevented from settling due to the thickening effect of the thickener. In the urethane resin composition according to any one of claims 1 to 7,
A urethane resin composition containing 1% by mass or more and 30% by mass or less of the phenol and/or the phenol derivative relative to 100% by mass of the urethane resin composition. In the urethane resin composition according to any one of claims 1 to 8,
A urethane resin composition that does not contain a polyol compound or contains 1% by mass or less of a polyol compound with respect to 100% by mass of the urethane resin composition. In the urethane resin composition according to any one of claims 1 to 9,
A urethane resin composition, wherein the foam piece formed from the urethane resin composition has an oxygen index of 30 or more as measured according to JIS K 7201-2:2007. In the urethane resin composition according to any one of claims 1 to 10,
When the foam piece is formed by spraying the urethane resin composition onto the gypsum board by a spray foaming method, there is no partial gap of 2 mm or more at the interface between the foam piece and the gypsum board. . A urethane resin foam,
a polymer obtained by binding a polyalkylene glycol adduct of a primary alcohol and a polyisocyanate compound;
A urethane resin foam containing a polymer formed by bonding phenol and/or a phenol derivative and a polyisocyanate compound. A raw material composition for a urethane resin composition used by mixing with a polyisocyanate compound,
a polyalkylene glycol adduct of a primary alcohol;
A raw material composition for a urethane resin composition, comprising phenol and/or a phenol derivative. A raw material kit for a urethane resin composition,
a first raw material comprising a polyalkylene glycol adduct of a primary alcohol and a phenol and/or a phenol derivative;
A raw material kit for a urethane resin composition, comprising: a second raw material containing a polyisocyanate compound.