JP7127372B2 - Urethane-forming composition - Google Patents

Description

The present disclosure relates to urethane-forming compositions.

A polyalkylene oxide containing a large amount of a by-product monool having an unsaturated group at one end (hereinafter referred to as an unsaturated monool) is used as a raw material for polyurethane. However, when an attempt is made to obtain a polyurethane using this polyalkylene oxide, there arises a problem that the curing (solidification) associated with the reaction with the isocyanate compound takes a long time, impairing the productivity.
Furthermore, polyurethanes obtained from polyalkylene oxides containing a large amount of unsaturated monools are unlikely to have high molecular weights. On the other hand, a high-molecular-weight polyurethane can be obtained by reacting a polyalkylene oxide containing a large amount of unsaturated monool with an isocyanate compound having a large average number of isocyanate functional groups. However, in this case, the polyurethane does not have a linearly high molecular weight, but becomes a crosslinked body having a densely crosslinked structure, so that the resulting polyurethane has a small tensile elongation at break.

On the other hand, since unsaturated monools have relatively low molecular weights, compositions containing conventional polyalkylene oxides containing large amounts of unsaturated monools have low viscosities, and coating machines are used to obtain polyurethanes from these compositions. etc., there is an advantage that it is easy to apply.

Here, Patent Document 1 discloses that a polyalkylene oxide with less unsaturated monools can be obtained by using an iminophosphazenium salt and a Lewis acid as catalysts. The use of these polyalkylene oxides solves the productivity problem associated with polyalkylene oxides containing a large amount of unsaturated monools, and improves the tensile elongation at break. However, since polyalkylene oxides containing less unsaturated monools have high viscosities, it has been desired to further improve the coatability of compositions containing such polyalkylene oxides.

JP 2017-25274 A

One aspect of the present invention is a urethane-forming composition that has excellent coatability and high productivity and contributes to the formation of a polyurethane having a large tensile elongation at break, and a urethane-forming composition containing the urethane-forming composition. It is directed to provide a sexual composition solution.
Other aspects of the present invention are directed to providing urethane prepolymers that are reactants of the urethane-forming composition, and urethane prepolymer solutions containing the urethane prepolymers.
Yet another aspect of the present invention is directed to providing polyurethanes that are reactants of the urethane-forming compositions.
Yet another aspect of the present invention is directed to providing a polyurethane sheet comprising the polyurethane.

Each aspect of the present invention is [1] to [7] shown below.
[1] a polyalkylene oxide (A) having an alkylene oxide residue having 3 or more carbon atoms in one molecule and two or more hydroxyl groups;
A polyalkylene oxide (B) containing one hydroxyl group and an ethylene oxide residue in one molecule;
and an isocyanate compound (C) having an average functional number of isocyanate groups of 2.0 or more,
The polyalkylene oxide (A) is
The degree of unsaturation is 0.010 meq/g or less,
The number average molecular weight is 800 or more.
[2] A urethane prepolymer (E) that is a reaction product of the urethane-forming composition (D),
The urethane prepolymer (E) has at least one hydroxyl group in one molecule,
In the urethane-forming composition (D), the amount of isocyanate groups derived from the isocyanate compound (C) relative to the amount (M _OH ) of hydroxyl groups derived from the polyalkylene oxide (A) and the polyalkylene oxide (B) Urethane prepolymer (E), wherein the ratio (M _NCO /M _OH ) of (M _NCO ) is less than 1 in molar ratio.
[3] A urethane-forming composition (G) containing the urethane prepolymer (E) and an isocyanate compound (F).
[4] the urethane-forming composition (D), the urethane prepolymer (E), and/or the urethane-forming composition (G);
A urethane-forming composition solution (H) containing an organic solvent,
A urethane-forming composition solution (H) in which the concentration of the urethane-forming composition (D) or the urethane prepolymer (E) in the urethane prepolymer solution (I) is 10% by mass or more and 90% by mass or less. .
[5] the urethane-forming composition (D), the urethane prepolymer (E), and/or the urethane-forming composition (G);
A urethane prepolymer solution (I) containing an organic solvent,
A urethane prepolymer solution (I) in which the concentration of the urethane-forming composition (D) or the urethane prepolymer (E) in the prepolymer solution (I) is 10% by mass or more and 90% by mass or less.
[6] Polyurethane (J) which is a reaction product of the urethane-forming composition (D) or the urethane-forming composition in the urethane-forming composition solution.
[7] A polyurethane sheet comprising the above polyurethane (J).

One aspect of the present invention is a urethane-forming composition that has excellent coatability and high productivity and contributes to the formation of a polyurethane having a large tensile elongation at break, and a urethane-forming composition containing the urethane-forming composition. A sexual composition solution can be provided.
Another aspect of the invention can provide a urethane prepolymer that is a reactant of the urethane-forming composition, and a urethane prepolymer solution that includes the urethane prepolymer.
Yet another aspect of the invention can provide a polyurethane that is a reactant of the urethane-forming composition.
Yet another aspect of the present invention can provide a polyurethane sheet comprising the polyurethane.

DETAILED DESCRIPTION OF SPECIFIC EMBODIMENTS Illustrative modes for carrying out the invention are set forth in detail below.

<Polyalkylene oxide (A)>
The urethane-forming composition (D) according to one aspect of the present invention is
A polyalkylene oxide (A) having an alkylene oxide residue having 3 or more carbon atoms in one molecule and two or more hydroxyl groups;
A polyalkylene oxide (B) containing one hydroxyl group and an ethylene oxide residue in one molecule;
and an isocyanate compound (C) having an average functional number of isocyanate groups of 2.0 or more,
The polyalkylene oxide (A) is
The degree of unsaturation is 0.010 meq/g or less,
The number average molecular weight is 800 or more.

The degree of unsaturation of the polyalkylene oxide (A) is 0.010 meq/g or less, preferably 0.007 meq/g or less, more preferably 0.004 meq/g or less.
When the degree of unsaturation of the polyalkylene oxide (A) exceeds 0.010 meq/g, the urethane-forming composition (D) containing the polyalkylene oxide (A) cures due to the reaction with the isocyanate compound (C). (Solidification) takes a long time, resulting in poor productivity, and the resulting polyurethane does not have a high molecular weight and is poor in mechanical properties. Even with a polyalkylene oxide (A) having a degree of unsaturation exceeding 0.010 meq/g, a high-molecular-weight polyurethane can be obtained by reacting it with an isocyanate compound having a large average number of isocyanate functional groups. becomes a crosslinked body having a dense crosslinked structure, and the tensile elongation at break becomes small. When the degree of unsaturation of the polyalkylene oxide (A) is 0.010 meq/g or less, the curing (hardening) accompanying the reaction with the polyalkylene oxide (B) and the isocyanate compound (C) is rapid, and the resulting polyurethane is straight. The molecular weight increases in chain form, and the tensile elongation at break increases. The lower the degree of unsaturation of the polyalkylene oxide (A), the higher the tensile elongation at break of the resulting polyurethane, and the lower the amount of low-molecular-weight substances that cause staining, the better the stain resistance, which is preferable.

Here, the "unsaturation degree (meq/g)" of the polyalkylene oxide (A) is the amount of unsaturated groups contained per 1 g of the polyalkylene oxide, and the unsaturated monool contained in the polyalkylene oxide. corresponds to the number. That is, the higher the degree of unsaturation, the more unsaturated monools, and the lower the degree of unsaturation, the less unsaturated monools.

In this embodiment, the degree of unsaturation of the polyalkylene oxide was measured according to the NMR method described in Kobunshi Ronbunshu 1993, 50, 2, 121-126. In this embodiment, since polyalkylene oxide with a small amount of unsaturated monool is to be measured, the number of scans in NMR measurement is set to 500 or more in order to improve the measurement accuracy.

The polyalkylene oxide (A) has a number average molecular weight of 800 or more, preferably 1000 or more and 30000 or less, more preferably 3000 or more and 13000 or less. When the polyalkylene oxide (A) has a number-average molecular weight of less than 800, the polyalkylene oxide (A) has a low molecular weight, so the polyurethane obtained by reaction with the polyalkylene oxide (B) or the isocyanate compound (C) forms a dense crosslinked structure, resulting in a small tensile elongation at break. When the polyalkylene oxide (A) has a number average molecular weight of 800 or more, the polyurethane obtained by reaction with the polyalkylene oxide (B) or the isocyanate compound (C) has a large tensile elongation at break. The higher the number average molecular weight of the polyalkylene oxide (A), the higher the tensile elongation at break of the polyurethane, which is preferable. However, when the number average molecular weight of the polyalkylene oxide (A) exceeds 30,000, the resulting polyurethane may become sticky.
The number average molecular weight of the polyalkylene oxide (A) is the hydroxyl value of the polyalkylene oxide (A) calculated by the method described in JIS K-1557-1, and the number of hydroxyl groups in one molecule of the polyalkylene oxide (A). and can be calculated from

The polyalkylene oxide (A) preferably has a molecular weight distribution (mass average molecular weight (Mw)/number average molecular weight (Mn); Mw/Mn) of 1.1 or less. When Mw/Mn is 1.1 or less, the mechanical properties of the polyurethane obtained from the urethane-forming composition (D) containing the polyalkylene oxide (A) are further improved. Further, when the Mw/Mn is 1.029 or less, the mechanical properties of the obtained polyurethane are further improved, and the amount of low-molecular-weight substances that cause contamination is reduced, resulting in excellent contamination resistance. , is particularly preferred.
The molecular weight distribution (Mw/Mn) can be measured by a gel permeation chromatography (Gel Permeation Chromatography+; GPC) method using polystyrene as a standard substance.

The viscosity of the polyalkylene oxide (A) at 25° C. is not particularly limited and is appropriately selected depending on the application, but is preferably 1 mPa·s or more and 2000 mPa·s or less, more preferably 2 mPa·s or more and 1000 mPa·s or less. is. If the viscosity of the polyalkylene oxide (A) at 25° C. is 1 mPa·s or more and 2000 mPa·s or less, it is preferable because it is easy to coat with a coating machine or the like to obtain a polyurethane product. Here, the “viscosity” at 25° C. is measured at a shear rate of 0.1 (1/s) using a cone/plate rotational viscometer in accordance with JIS K1557-5 Section 6.2.3. value.

Polyalkylene oxide (A) contains an alkylene oxide residue having 3 or more carbon atoms. The alkylene oxide residue having 3 or more carbon atoms is not particularly limited, and examples thereof include alkylene oxide residues having 3 to 20 carbon atoms. Specifically, propylene oxide residue, 1,2-butylene oxide residue, 2,3-butylene oxide residue, isobutylene oxide residue, butadiene monoxide residue, pentene oxide residue, styrene oxide residue, cyclohexene Examples include oxide residues and the like. Among these alkylene oxide residues, a propylene oxide residue is preferred because the starting material for obtaining the polyalkylene oxide (A) is readily available and the resulting polyalkylene oxide (A) has a high industrial value.

Further, the polyalkylene oxide (A) may contain only a single alkylene oxide residue as the alkylene oxide residue having 3 or more carbon atoms, or may contain two or more types of alkylene oxide residues. good. When two or more kinds of alkylene oxide residues are included, for example, one kind of alkylene oxide residue is linked in a chain, and another alkylene oxide residue is linked in a chain. or two or more alkylene oxide residues randomly linked together. Furthermore, the polyalkylene oxide (A) may contain an alkylene oxide residue having 3 or more carbon atoms, and may additionally contain an ethylene oxide residue having 2 carbon atoms.

Moreover, the polyalkylene oxide (A) has two or more hydroxyl groups in one molecule. The number of hydroxyl groups in the polyalkylene oxide (A) is not particularly limited as long as it has two or more hydroxyl groups in one molecule, but the number of hydroxyl groups in one molecule is preferably 6 or less. When the number of hydroxyl groups in one molecule of the polyalkylene oxide (A) is 6 or less, even when the molecular weight of the polyalkylene oxide (A) is low, the polyurethane obtained by reaction with the isocyanate compound (C) is crosslinked. It is preferable because the structure is less dense and the tensile elongation at break is further increased.

In addition, the polyalkylene oxide (A) is preferably liquid at room temperature because it facilitates handling of the urethane-forming composition (D) containing them.

Here, the polyalkylene oxide (A) having an alkylene oxide residue having 3 or more carbon atoms and two or more hydroxyl groups in one molecule is prepared in the presence of an alkylene oxide polymerization catalyst containing, for example, a phosphazene compound and a Lewis acid. , obtained by ring-opening polymerization of an alkylene oxide using an active hydrogen-containing compound as an initiator. Therefore, polyalkylene oxide (A) will have alkylene oxide residues.

Examples of phosphazene compounds include phosphazenium salts represented by formula (1).

(In formula (1),
R ¹ and R ² are each independently
hydrogen atom,
a hydrocarbon group having 1 to 20 carbon atoms,
a ring structure in which R ¹ and R ² are bonded to each other, or
represents a ring structure in which R ¹ 's or R ² 's are bonded to each other;
X ⁻ represents a hydroxy anion, an alkoxy anion having 1 to 4 carbon atoms, a carboxy anion, an alkyl carboxy anion having 2 to 5 carbon atoms, or a hydrogen carbonate anion;
Y represents a carbon atom or a phosphorus atom;
a is
2 when Y is a carbon atom;
3 when Y is a phosphorus atom; )

Examples of hydrocarbon groups having 1 to 20 carbon atoms include methyl group, ethyl group, vinyl group, n-propyl group, isopropyl group, cyclopropyl group, allyl group, n-butyl group, isobutyl group and t-butyl group. , cyclobutyl group, n-pentyl group, neopentyl group, cyclopentyl group, n-hexyl group, cyclohexyl group, phenyl group, heptyl group, cycloheptyl group, octyl group, cyclooctyl group, nonyl group, cyclononyl group, decyl group, Cyclodecyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group and the like can be mentioned.

R ¹ and R ² are preferably a methyl group, an ethyl group, or an isopropyl group, since they are alkylene oxide polymerization catalysts with excellent catalytic activity and the raw materials are readily available.

X 1 ⁻ in the phosphazenium salt is a hydroxy anion, an alkoxy anion having 1 to 4 carbon atoms, a carboxy anion, an alkyl carboxy anion having 2 to 5 carbon atoms, or a hydrogen carbonate anion.

Examples of alkoxy anions having 1 to 4 carbon atoms include methoxy anion, ethoxy anion, n-propoxy anion, isopropoxy anion, n-butoxy anion, isobutoxy anion and t-butoxy anion.

Examples of alkylcarboxyanions having 2 to 5 carbon atoms include acetoxy anion, ethylcarboxyanion, n-propylcarboxyanion, isopropylcarboxyanion, n-butylcarboxyanion, isobutylcarboxyanion, t-butylcarboxyanion and the like. .

Of these, X 1 ^- is preferably a hydroxy anion or a hydrogen carbonate anion, since they serve as an alkylene oxide polymerization catalyst with excellent catalytic activity.

Examples of the phosphazene compound include tetrakis(1,1,3,3-tetramethylguanidino)phosphazenium hydroxide, tetrakis(1,1,3,3-tetramethylguanidino)phosphazenium hydrogen carbonate, tetrakis Mention may be made of [tris(dimethylamino)phosphoranylideneamino]phosphonium hydroxide.

Examples of Lewis acids include aluminum compounds, zinc compounds, and boron compounds.

Examples of aluminum compounds include trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-normalhexylaluminum, triethoxyaluminum, triisopropoxyaluminum, triisobutoxyaluminum, triphenylaluminum, diphenylmonoisobutylaluminum, monophenyldiisobutylaluminum, and the like. organic aluminum; for example, aluminoxanes such as methylaluminoxane, isobutylaluminoxane, and methyl-isobutylaluminoxane; and the like.

Examples of zinc compounds include organic zinc such as dimethyl zinc, diethyl zinc and diphenyl zinc; and inorganic zinc such as zinc chloride and zinc oxide.

Boron compounds include triethylborane, trimethoxyborane, triethoxyborane, triisopropoxyborane, triphenylborane, tris(pentafluorophenyl)borane, and trifluoroborane.

Among these, organic aluminum, aluminoxane, and organic zinc are preferred, and organic aluminum is particularly preferred, since they serve as alkylene oxide polymerization catalysts with excellent catalytic performance.

The ratio of the phosphazene compound and the Lewis acid in the alkylene oxide polymerization catalyst is arbitrary as long as the action as the alkylene oxide polymerization catalyst is expressed, and is not particularly limited, but among them, the polymerization catalyst having particularly excellent catalytic performance is used. Therefore, the phosphazene compound:Lewis acid is preferably 1:0.002 to 1:500 (molar ratio).

Examples of active hydrogen-containing compounds include, but are not limited to, water, hydroxy compounds, amine compounds, carboxylic acid compounds, thiol compounds, and polyether polyols having hydroxyl groups.
Examples of polyether polyols having hydroxyl groups include polyether polyols having a molecular weight of 200 or more and 3000 or less.
These active hydrogen-containing compounds may be used singly or in combination of several kinds.

<Polyalkylene oxide (B)>
Polyalkylene oxide (B) is not particularly limited as long as it contains one hydroxyl group and ethylene oxide residue in one molecule. The polyalkylene oxide (B ) is preferably one or more selected from the group consisting of polyoxyalkylene glycol monoalkyl ethers, polyoxyalkylene glycol monoalkenyl ethers, and polyoxyalkylene glycol monophenyl ethers.

Here, the polyoxyalkylene glycol monoalkyl ether is not particularly limited, and examples thereof include polyoxyethylene glycol monomethyl ether, polyoxyethylene glycol monobutyl ether, polyoxy(ethylene/propylene) glycol monomethyl ether, polyoxy ( ethylene/propylene)glycol monobutyl ether, polyoxyethylene glycol monolaurate, polyoxyethylene glycol monolaurylamine and the like can be preferably used. In addition, polyoxyalkylene glycol monoalkyl ether salts having an amino group such as polyoxyethylene lauryl ether sulfate triethanolamine salts and inorganic salts such as sulfates can also be used.

The polyoxyalkylene glycol monoalkenyl ether is also not particularly limited, and examples thereof include polyoxyethylene glycol monostearyl ether, polyoxyethylene glycol monooleyl ether, polyoxyethylene glycol monomethacrylate, polyoxyethylene glycol monoacrylate, and the like. and can be preferably used.

The polyoxyalkylene glycol monophenyl ether is also not particularly limited, and examples thereof include polyoxyethylene glycol monooctylphenyl ether and polyoxyethylene glycol monononylphenyl ether, which can be preferably used.

Among these, polyoxyethylene glycol monomethyl ether, poly It preferably contains at least one of oxyethylene glycol monobutyl ether, polyoxy(ethylene/propylene) glycol monomethyl ether, and polyoxy(ethylene/propylene) glycol monobutyl ether.

Although the number average molecular weight of the polyoxyalkylene oxide (B) is not particularly limited, it is preferably 150 or more and 15000 or less, more preferably 200 or more and 5000 or less, and most preferably 250 or more and 1300 or less. If the molecular weight of the polyalkylene oxide (B) is too low, the viscosity of the urethane-forming composition (D) containing it becomes too low, and when the urethane-forming composition (D) is coated with a coating machine, etc. In some cases, a defective phenomenon of liquid flow occurs, resulting in an uneven thickness of the resulting polyurethane coating. On the other hand, when the molecular weight of the polyalkylene oxide (B) is too high, the compatibility with the polyalkylene oxide (A) becomes poor, and the urethane-forming composition (D) containing this is coated with a coating machine or the like. In some cases, the surface of the coating film may become rough or the coating film may become opaque. Therefore, the polyalkylene oxide (B) preferably has a number average molecular weight of 150 or more and 15,000 or less in order to obtain a highly transparent polyurethane coating film having a uniform thickness and a smooth surface.

Incidentally, the number average molecular weight of the polyalkylene oxide (B) is, as in the case of the polyalkylene oxide (A), the hydroxyl value of the polyalkylene oxide (B) calculated by the method described in JIS K-1557-1, It can be calculated from the number of hydroxyl groups in one molecule of the polyalkylene oxide (B).

Moreover, the polyalkylene oxide (B) is preferably liquid at room temperature, since this facilitates handling of the urethane-forming composition (D) containing it.

<Isocyanate compound (C)>
The isocyanate compound (C) is not particularly limited as long as the average number of functional groups of isocyanate groups is 2.0 or more. Examples of the isocyanate compound (C) include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 2,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, and tolidine. Diisocyanate, xylylene diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, lysine diisocyanate, triphenylmethane triisocyanate, tetramethylxylene diisocyanate, 1,6-hexamethylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate , isophorone diisocyanate, 1,4-cyclohexane diisocyanate, norbornane diisocyanate, lysine ester triisocyanate, 1,6,11-undecane triisocyanate, 1,8-diisocyanate-4-isocyanatomethyloctane, 1,3,6-hexamethylenetri Examples include isocyanate, bicycloheptane triisocyanate, trimethylhexamethylene diisocyanate, modified isocyanate obtained by reacting these with polyalkylene oxide, and mixtures of two or more thereof. Furthermore, these isocyanates contain modified products containing urethane groups, carbodiimide groups, allophanate groups, urea groups, biuret groups, isocyanurate groups, amide groups, imide groups, uretonimine groups, uretdione groups or oxazolidone groups, and polymethylene polyphenylene polyisocyanates. Condensates such as (polymeric MDI) can be mentioned.

Among these, aliphatic isocyanate, alicyclic Formula isocyanates, or modifications thereof, are preferred. 1,6-hexamethylene diisocyanate, isophorone diisocyanate, aliphatic isocyanate-containing prepolymers, alicyclic isocyanate-containing prepolymers, or urethane groups, carbodiimide groups, allophanate groups, urea groups, biuret groups of these isocyanates, Modified products containing an isocyanurate group, an amide group, an imide group, a uretonimine group, a uretdione group or an oxazolidone group are more preferred. These isocyanates may be used singly or in combination of two or more.

<Urethane-forming composition (D)>
The urethane-forming composition (D) may be a composition containing the above-described polyalkylene oxide (A), polyalkylene oxide (B), and a specific isocyanate compound (C). The mixing ratio of the polyalkylene oxide (A) and the polyalkylene oxide (B) in the urethane-forming composition (D) is not particularly limited, but the mass ratio (polyalkylene oxide (A)/polyalkylene oxide (B)) , preferably 99.9/0.1 or more and 60/40 or less, more preferably 99.5/0.5 or more and 80/20 or less, and 99/1 or more and 90/10 or less is most preferred. The urethane-forming composition (D) having a mass ratio within this range contains a polyalkylene oxide (A) with a small amount of unsaturated monools, but exhibits good coatability when coated with a coating machine or the like. It is preferable because the resulting polyurethane has even better mechanical properties.

The content of the isocyanate compound (C) in the urethane-forming composition (D) is also not particularly limited. The content of the isocyanate compound (C) in the urethane-forming composition (D) is preferably 0.1% by mass or more and 30% by mass or less, more preferably 0.5% by mass or more and 20% by mass or less. It is preferably 3% by mass or more and 10% by mass or less, most preferably. If the content of the isocyanate compound (C) is 0.1% by mass or more and 30% by mass or less, the curing (hardening) property of the urethane-forming composition (D) when obtaining polyurethane by curing accompanying the reaction of It is excellent and preferred because the polyurethane will have even better mechanical properties.

The polyalkylene oxide (A), the polyalkylene oxide (B), and the isocyanate compound (C) contained in the urethane-forming composition (D) are preferably used after dehydration by vacuum heating or the like. can be used without dehydration.

The preparation of the urethane-forming composition (D) is not particularly limited as long as it can uniformly disperse the raw materials contained in the urethane-forming composition (D). A stirring method can be used, for example, a method of stirring using a stirrer. Examples of the stirrer include a general-purpose stirrer, a rotation-revolution mixer, a disper disperser, a dissolver, a kneader, a mixer, a laboplastomill, a planetary mixer, and the like. When the polyalkylene oxide (A), the polyalkylene oxide (B), and the isocyanate compound (C) are all liquid at the stirring temperature, a rotation-revolution mixer, a general-purpose stirrer, a disper disperser, and a dissolver are preferably used.

Although the viscosity of the urethane-forming composition (D) at 25° C. is not particularly limited, it is usually 100 mPa·s or more and 100000 mPa·s or less, preferably 200 mPa·s or more and 30000 mPa·s or less, more preferably It is 300 mPa-s or more and 3000 mPa-s or less. When the viscosity of the urethane-forming composition (D) at 25° C. is within this range, the urethane-forming composition (D ) is preferable because it facilitates stirring and handling of the composition when stirring is performed as a pre-stage operation when coating with a coating machine or the like.

<Urethane prepolymer (E)>
The urethane prepolymer (E) is a reactant of the urethane-forming composition and has at least one hydroxyl group in one molecule. That is, the urethane prepolymer (E) is obtained by reacting a urethane-forming composition (D) containing a polyalkylene oxide (A), a polyalkylene oxide (B), and an isocyanate compound (C). It is a reactant and a polyurethane having at least one hydroxyl group in one molecule.

Here, the urethane prepolymer (E) has at least one hydroxyl group in one molecule. Therefore, the urethane-forming composition ( _D ) has an amount (M _NCO ) ratio (M _NCO /M _OH ) is preferably less than 1.0, more preferably 0.5 or more and 0.99 or less, and most preferably 0.7 or more and 0.95 or less. is. The ratio (M _NCO /M _OH ) represents a molar ratio. If the ratio (M _NCO /M _OH ) is 0.5 or more and 0.99 or less, gelation (solidification) occurs when the urethane-forming composition (D) is cured to produce the urethane prepolymer (E). is less likely to occur and handling becomes easier, which is preferable.

<Isocyanate compound (F), urethane-forming composition (G)>
The urethane-forming composition (G) is a composition containing a urethane prepolymer (E) and an isocyanate compound (F).

The isocyanate compound (F) is not particularly limited, but the same ones as the isocyanate compound (C) can be mentioned, and preferred isocyanates are also the same. The isocyanate compound (F) and the isocyanate compound (C) may be the same or different.

Here, the urethane-forming composition (G) may be a composition containing the urethane prepolymer (E) and the isocyanate compound (F). Therefore, although the content of the isocyanate compound (F) in the urethane-forming composition (G) is not particularly limited, it should be 0.1% by mass or more and 30% by mass or less in the urethane-forming composition (G). is preferred, more preferably 0.5% by mass or more and 20% by mass or less, and most preferably 3% by mass or more and 10% by mass or less. If the content of the isocyanate compound (F) is 0.1% by mass or more and 30% by mass or less, the curing (hardening) property of the urethane-forming composition (F) when obtaining polyurethane by curing accompanying the reaction of It is excellent and is preferred because the polyurethane will have good mechanical properties.

The urethane prepolymer (E) and the isocyanate compound (F) used in the urethane-forming composition (G) are preferably used after being dehydrated by heating in a vacuum or the like. You may

The method for preparing the urethane-forming composition (G) is not particularly limited as long as it can uniformly disperse the prepolymer and raw materials contained in the urethane-forming composition (G). and a method of stirring using various stirring methods of. Examples of the stirrer include a general-purpose stirrer, a rotation-revolution mixer, a disper disperser, a dissolver, a kneader, a mixer, a laboplastomill, a planetary mixer, and the like. When both the urethane prepolymer (E) and the isocyanate compound (F) are liquid at the stirring temperature, a general-purpose stirrer, a rotation/revolution mixer, a disper disperser, and a dissolver are preferably used.

The viscosity of the urethane-forming composition (G) at 25° C. is not particularly limited, but is usually 100 mPa·s or more and 100000 mPa·s or less, preferably 200 mPa·s or more and 30000 mPa·s or less, more preferably It is 300 mPa-s or more and 3000 mPa-s or less. When the viscosity of the urethane-forming composition (G) at 25° C. is within this range, the urethane-forming composition (G) can be stirred with various stirrers to prepare the urethane-forming composition (G). is preferable because it facilitates stirring and handling of the urethane-forming composition (G) when stirring is performed as a pre-stage operation for coating with a coating machine or the like.

<Urethane-forming composition solution (H), urethane prepolymer solution (I)>
The urethane-forming composition (D) or (G) or the urethane prepolymer (E) may contain an organic A urethane-forming composition solution (H) or a urethane prepolymer solution (I) can be obtained by mixing with a solvent.
At this time, the urethane-forming composition solution (H) is
a urethane-forming composition (D);
an organic solvent;
The concentration of the urethane-forming composition in the urethane-forming composition solution (H) is 10% by mass or more and 90% by mass or less.
Further, the urethane prepolymer solution (I) is
a urethane prepolymer (E) and/or a urethane-forming composition (G);
an organic solvent;
The concentration of the urethane prepolymer (E) in the urethane prepolymer solution (I) is 10% by mass or more and 90% by mass or less.

Examples of organic solvents include methyl ethyl ketone, ethyl acetate, toluene, xylene, acetone, benzene, dioxane, acetonitrile, tetrahydrofuran, diglyme, dimethylsulfoxide, N-methylpyrrolidone, dimethylformamide and the like. Ethyl acetate, toluene, methyl ethyl ketone, or a mixed solvent thereof is particularly preferable in terms of solubility, boiling point of organic solvent, and the like. These solvents are used during preparation of the urethane-forming composition, reaction of the prepared urethane-forming composition, completion of the reaction, and reaction of the urethane-forming composition to obtain a prepolymer. , or at any stage, such as at the end of the reaction.

The concentration of the urethane-forming composition (D), (G), or urethane prepolymer (E) in the urethane-forming composition solution (H) or urethane prepolymer solution (I) is 10% by mass or more and 90% by mass. or less, preferably 30% by mass or more and 70% by mass or less. When the concentration is within this range, good coatability can be obtained when the urethane-forming composition solution (H) or the urethane prepolymer solution (I) is applied with a coating machine or the like. It is possible to facilitate handling of the product solution (H) and the urethane prepolymer solution (I).

The viscosity of the urethane-forming composition solution (H) and the urethane prepolymer solution (I) at 25° C. is also not particularly limited, but is preferably 100 mPa·s or more and 100000 mPa·s or less. When the viscosity is within this range, good coatability can be obtained when the urethane-forming composition solution (H) or the urethane prepolymer solution (I) is applied with a coating machine or the like, and the urethane-forming composition can be used. It is possible to facilitate handling of the product solution (H) and the urethane prepolymer solution (I).

<Additive>
The urethane-forming compositions (D) and (G) may contain urethanization catalysts, antioxidants, light stabilizers, chain extenders, and other additives as necessary.
The content of the additive in the urethane-forming compositions (D) and (G) is not particularly limited, but is preferably 5% by mass or less, more preferably 1% by mass or less. be.

Examples of the urethanization catalyst include tertiary amine-based compounds and organometallic compounds. Examples include triethylenediamine, diazabicycloundecene (also known as DBU) dibutyltin dilaurate (also known as DBTDL), :DOTDL), tin 2-ethylhexanoate and the like can be preferably used.

The chain extender is not particularly limited, and examples thereof include ethylene glycol, 1,4-butanediol, neopentyl glycol, butylethylpentanediol, glycerin, trimethylolpropane, pentaerythritol, and low molecular weights with a molecular weight of 1000 or less. glycols such as polyalkylene glycol; polyvalent amines such as ethylenediamine, N-aminoethylethanolamine, piperazine, isophoronediamine and xylylenediamine;

<Polyurethane (J)>
The polyurethane (J) is a urethane-forming composition (D), a urethane-forming composition (G), a urethane-forming composition (D) in a urethane-forming composition solution (H), or a urethane prepolymer solution. It is the reactant of urethane-forming composition (G) in (I).

The polyurethane (J) is cured (solidified) by reacting the urethane-forming composition (D), (G), the urethane-forming composition solution (H), or the urethane prepolymer solution (I) by various methods. ). The method for producing these polyurethanes (J) is not particularly limited. For example, the urethane-forming compositions (D) and (G), the urethane-forming composition solution (H), or the urethane prepolymer solution (I) may optionally be mixed with a urethanization catalyst, a solvent, and an antioxidant. In the presence of an agent, a light stabilizer, a chain extender, a cross-linking agent, other additives, etc., the urethanization reaction or urea formation reaction can proceed at room temperature or at a high temperature of 150° C. or lower.
Here, the urethane-forming composition (D), (G), the urethane-forming composition solution (H), or the urethane prepolymer solution (I) is used for coating with a coating machine or the like. Since the properties are remarkably excellent, a coating film of polyurethane (J) having a thin and uniform thickness can be obtained.

The thickness of the coating film of polyurethane (J) is not particularly limited. It is even more preferable to have

The application of polyurethane (J) is not particularly limited, and it can be used in any application where ordinary polyurethane is used, but it is particularly suitable for applications requiring mechanical properties, tackiness, adhesive properties, etc. can. Specifically, sealing materials for construction and civil engineering, adhesives such as elastic adhesives for construction, packing tapes and surface protection films, various adhesives represented by optics, paints, elastomers, waterproof coating materials, flooring materials, Applications such as plasticizers, flexible polyurethane foams, semi-rigid polyurethane foams, and rigid polyurethane foams are exemplified and can be preferably used.
Among them, polyurethanes are particularly preferably used as sealants, paints, pressure-sensitive adhesives, and adhesives because they are strongly required to have mechanical properties and tackiness/adhesive properties, and are required to have workability and coatability.

The urethane-forming composition according to one aspect of the present invention has excellent coatability when applied with a coating machine or the like in order to obtain polyurethane, and without using a large amount of a urethanization catalyst, A polyurethane having high productivity and high tensile elongation at break can be obtained by promoting curing (solidification) accompanying reaction with an isocyanate compound.
Moreover, the polyurethane obtained by using the urethane-forming composition according to one aspect of the present invention can be suitably used in a wide range of applications such as sealants, paints, pressure-sensitive adhesives, and adhesives.

EXAMPLES The present invention will now be described in more detail with reference to examples, but the present invention should not be construed as being limited to the following examples as long as the gist thereof is not exceeded. The raw materials and evaluation methods used in the following examples and comparative examples are as follows.

(Raw material 1) Polyalkylene oxide (A or AC) used in Examples and Comparative Examples
The properties of the polyalkylene oxides used in Examples and Comparative Examples were obtained by the following methods.
<Unsaturation of polyalkylene oxide>
The degree of unsaturation of the polyalkylene oxide was measured by scanning 800 times according to the NMR method described in Kobunshi Ronbunshu 1993, 50, 2, 121-126.

<Hydroxyl value and number average molecular weight of polyalkylene oxide>
The hydroxyl value of polyalkylene oxide was measured according to the method described in JIS-K 1557-1. Also, the number average molecular weight of the polyalkylene oxide was calculated from the hydroxyl value of the polyalkylene oxide and the number of hydroxyl groups in one molecule of the polyalkylene oxide.

<Molecular weight distribution (Mw/Mn) of polyalkylene oxide>
The molecular weight distribution (Mw/Mn) of polyalkylene oxide was measured by the following procedure using gel permeation chromatography (GPC).
10 mg of polyalkylene oxide and 10 ml of tetrahydrofuran (THF) are placed in a sample bottle, left to stand for one day to dissolve the polyalkylene oxide in THF, and filtered through a PTFE cartridge filter (0.5 μm) to obtain a sample for GPC measurement. A sample was made.
For GPC measurement, THF is used as a developing solvent, measurement is performed at a column temperature of 40 ° C., and a cubic approximate curve using 8 standard polystyrenes manufactured by Tosoh Corporation with a known molecular weight is used as a calibration curve to determine the molecular weight distribution (Mw / Mn). I did the analysis. HLC-8320GPC manufactured by Tosoh Corporation was used as a measurement apparatus, and HLC-8320GPC-ECOSEC-WorkStation manufactured by Tosoh Corporation was used for analysis.

<Viscosity of polyalkylene oxide>
The viscosity of the polyalkylene oxide was measured according to the method described in JIS K-1557-5. Specifically, it was measured using a cone/plate rotational viscometer at a temperature of 25° C. and a shear rate of 0.1 (1/s).

(Raw material 1-1) Polyalkylene oxide (A) used in Examples
Polyalkylene oxides (A1) and (A2) use an imino group-containing phosphazenium salt (hereinafter referred to as an IPZ catalyst) and triisopropoxyaluminum in combination, perform sufficient dehydration and solvent removal, are bifunctional, and have a molecular weight of 400. obtained by adding sufficiently dehydrated propylene oxide to polyoxypropylene glycol. (A1) and (A2) are polyoxypropylene glycols (diols) having only propylene oxide groups as alkylene oxide groups and two hydroxyl groups in one molecule. The properties of (A1) and (A2) are shown in Table 1. (A1) and (A2) have an extremely small amount of unsaturated monol (extremely low degree of unsaturation) and a narrow molecular weight distribution.

The polyalkylene oxide (A3) is a propylene oxide obtained by using an IPZ catalyst and triisopropoxyaluminum in combination, sufficiently dehydrating and desolvating, and sufficiently dehydrating a bifunctional polyoxypropylene glycol having a molecular weight of 400. and ethylene oxide were added in order. (A3) is a polyoxyalkylene glycol (diol) in which a chain of propylene oxide groups and a chain of ethylene oxide groups are linked, and which has two hydroxyl groups in one molecule. The properties of (A3) are shown in Table 1. (A3) also has an extremely small amount of unsaturated monol (extremely low degree of unsaturation) and a narrow molecular weight distribution.

For the polyalkylene oxides (A4) and (A5), an IPZ catalyst and triisopropoxyaluminum are used in combination to sufficiently dehydrate and remove the solvent, and a trifunctional polyoxypropylene triol having a molecular weight of 600 is sufficiently dehydrated. It was obtained by addition of applied propylene oxide. (A4) and (A5) are polyoxypropylene triols having only propylene oxide groups as alkylene oxide groups and three hydroxyl groups in one molecule. The properties of (A4) and (A5) are shown in Table 1. (A4) and (A5) have an extremely small amount of unsaturated monol (extremely low degree of unsaturation) and a narrow molecular weight distribution.

Polyalkylene oxide (A6) is a polyoxypropylene triol having a molecular weight of 980 and having three hydroxyl groups in one molecule obtained using a potassium hydroxide catalyst. (A6) is commercially available GP1000 manufactured by Sanyo Chemical Industries, Ltd. The properties of (A6) are shown in Table 1. (A6) has a small amount of unsaturated monol (low degree of unsaturation) and a narrow molecular weight distribution, but is somewhat more unsaturated than (A1) to (A5). degree is high.

(Raw material 1-2) Polyalkylene oxide (AC) used in comparative examples
Polyalkylene oxide (AC1) uses only an IPZ catalyst, performs sufficient dehydration and solvent removal, and adds sufficiently dehydrated propylene oxide to a bifunctional polyoxypropylene glycol having a molecular weight of 400. I got it in (AC1) is a polyoxypropylene glycol (diol) having only a propylene oxide group as an alkylene oxide group and two hydroxyl groups in one molecule. The properties of (AC1) are shown in Table 1. (AC1) has a high degree of unsaturation and does not satisfy the range of 0.010 meq/g or less.

Polyalkyloxide (AC2) was obtained by adding propylene oxide to bifunctional polyoxypropylene glycol by a conventional method using a potassium hydroxide catalyst. (AC2) is a polyoxypropylene glycol (diol) having only a propylene oxide group as an alkylene oxide group and two hydroxyl groups in one molecule. The properties of (AC2) are shown in Table 1. (AC2) has a high degree of unsaturation and does not satisfy the range of 0.010 meq/g or less, and (AC2) is more unsaturated than (AC1). High degree.

A polyalkylene oxide (AC3) was also obtained by sequentially adding propylene oxide and ethylene oxide to a trifunctional polyoxypropylene triol using a potassium hydroxide catalyst in a conventional manner. (AC3) is a polyoxyalkylene triol in which a chain of propylene oxide groups and a chain of ethylene oxide groups are linked, and which has three hydroxyl groups in one molecule. The properties of (AC3) are shown in Table 1. (AC3) also has a high degree of unsaturation and does not satisfy the range of 0.010 meq/g or less. and higher than (AC1).

Polyalkylene oxide (AC4) is also polyoxypropylene glycol having two hydroxyl groups in one molecule and a molecular weight of 600, obtained using a potassium hydroxide catalyst. (AC4) is commercially available PP600 manufactured by Sanyo Chemical Industries, Ltd. The properties of (AC4) are shown in Table 1. (AC4) has a low number average molecular weight and does not satisfy the range of 800 or more.

The polyalkylene oxides (A1) to (A6) used in the examples and the polyalkylene oxides (AC1) to (AC4) used in the comparative examples were all used after heating and vacuum dehydration. Moreover, the polyalkylene oxide produced using the IPZ catalyst was used after removing the catalyst.

(Raw material 2) Polyalkylene oxide (B)
(Raw material 2-1) Polyalkylene oxide (B) used in Examples
Polyalkylene oxides (B1) to (B3) are polyethylene glycol monomethyl ethers, each of which has one hydroxyl group and one ethylene oxide group. Properties of (B1) to (B3) are shown in Table 2, but (B1), (B2) and (B3) differ in molecular weight. All of (B1) to (B3) have a high ethylene oxide group content, and the higher the molecular weight, the higher the ethylene oxide group content.

Polyalkylene oxide (B4) is polyethylene glycol monobutyl ether, polyalkylene oxide (B5) is polyethylene glycol monostearyl ether, polyalkylene oxide (B6) is polyethylene glycol monolauryl ether, and polyalkylene oxide (B7) is polyethylene glycol octylphenyl ether. All of them consist of one hydroxyl group and one ethylene oxide group in one molecule. Table 2 shows the properties of (B4) to (B7).

Polyalkylene oxides (B8) and (B9) are poly(ethylene-propylene) glycol monomethyl ethers, each of which has one hydroxyl group, one ethylene oxide group and one propylene oxide group. Properties of (B8) and (B9) are shown in Table 2, and (B8) and (B9) differ in molecular weight and content ratio of ethylene oxide groups. Since (B8) and (B9) contain propylene oxide groups, the content ratio of ethylene oxide groups is low, and (B9) has a lower content ratio of ethylene oxide groups than (B8).

(Raw material 2-2) Polyalkylene oxide (BC) used in Comparative Example
Polyalkylene oxide (BC1) is a polyethylene glycol having two hydroxyl groups in one molecule.

Polyalkylene oxide (BC2) is a polypropylene glycol monomethyl ether which does not contain ethylene oxide groups.

(Raw material 3) Isocyanate compounds (C) and (F) used in Examples and Comparative Examples
In Examples and Comparative Examples, the following three types were used as the isocyanate compounds (C) and (F).
Isocyanate compounds (C1) and (F1): Coronate HXLV manufactured by Tosoh Corporation, which is a modified isocyanate based on 1,6-hexamethylene diisocyanate (HDI). 3.2.
Isocyanate compound (C2): Coronate 2286 manufactured by Tosoh Corporation, which is an HDI-based modified isocyanurate, and the average functional number of isocyanate groups in (C2) is 2.5.
Isocyanate compound (C3): (C3) is HDI. The average functionality of isocyanate groups in (C3) is 2.0.

(Raw material 4) Additive In the examples and comparative examples, a urethanization catalyst was added as an additive. Dioctyltin dilaurate (DOTDL) (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd. (former company name: Wako Pure Chemical Industries, Ltd.)) was used as the urethanization catalyst.

(Raw material 5) Solvent In the examples and comparative examples, when the urethane-forming composition solution was used, ethyl acetate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) or methyl ethyl ketone (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was used as the solvent. board.

(Preparation of urethane-forming composition)
In the examples and comparative examples, all raw materials are liquid at room temperature, and a predetermined amount of each raw material is put into a 50 ml sample bottle, and stirred and degassed at room temperature using a rotation or revolution mixer to produce urethane. A formative composition was obtained. Awatori Mixer ARE-310 manufactured by Thinky Co., Ltd. was used as the rotation and revolution mixer, and the rotation was performed at 2000 rpm for 5 minutes and the revolution was performed at 2200 rpm for 5 minutes.

(Performance evaluation of urethane-forming composition)
<Applicability and curability of urethane-forming composition>
A urethane-forming composition or a solution of a urethane-forming composition is applied onto a 38 μm thick PET film (product name: Lumirror) with an untreated surface manufactured by Toray Industries, Inc. so that the thickness after drying is 100 μm or less. was applied using a Baker applicator. After that, the urethane-forming composition was allowed to stand in an environment of 23° C. and a relative humidity of 50% for one week to obtain a polyurethane coating film. Regarding the solution of the urethane-forming composition, after coating, it is held in an oven set at 100°C for 3 minutes to volatilize the solvent, and then left to stand in an environment of 23°C and a relative humidity of 50% for 1 week. A polyurethane coating was thus obtained.
In the process, the coatability of the urethane-forming composition and its solution is obtained by the reaction of the urethane-forming composition when it is allowed to stand for one week in an environment of 23° C. and 50% relative humidity after coating. Using the surface appearance and thickness of the polyurethane coating film as an index, evaluation was made according to the following criteria. The surface appearance of the polyurethane coating film was visually observed, and the thickness of the polyurethane coating film was measured with a thickness meter.
In addition, regarding the curing (hardening) property of the urethane-forming composition and the urethane-forming composition in its solution, the surface of the polyurethane coating obtained in the process of standing for one week in an environment of 23 ° C. and a relative humidity of 50%. was touched with a finger over time, and the stickiness at that time was used as an index and evaluated according to the following criteria.

<Applicability of urethane-forming composition or urethane-forming composition solution>
A (acceptable coating properties): When visually observed, the surface of the polyurethane coating film is smooth, and the difference in thickness between the center and the edge of the polyurethane coating film is less than 5%.
B (Acceptance of Coatability): The surface of the polyurethane coating film is smooth when visually observed, and the thickness difference between the center and the edge of the polyurethane coating film is in the range of 5% or more and 10% or less.
C (Unacceptable Coatability): When visually observed, the surface of the polyurethane coating film is rough, or the thickness difference between the center and the edge of the polyurethane coating film exceeds 10%.

<Curability of urethane-forming composition>
A (acceptable curability): The stickiness almost disappears after standing for 1 day in an environment of 23°C and 50% relative humidity, and the stickiness does not change over time after holding for 3 days.
B (acceptable curability): The sticky feeling almost disappeared by standing for more than 1 day and up to 3 days in an environment of 23 ° C. and 50% relative humidity, and the sticky feeling disappeared after 7 days. If it does not change over time.
C (hardening failure): sticky feeling after standing for 3 days in an environment of 23 ° C. and 50% relative humidity (insufficient curing), or sticky feeling remaining after holding for 7 days, changes over time (curing is significantly slower).

Furthermore, regarding the toughness of the polyurethane coating film, a dumbbell test piece of ASTM No. 1822 was taken out (punched) from the polyurethane coating film having a thickness of about 100 μm which was coated and cured (solidified) as described above.・Using a tensile tester RTG-1210 manufactured by Day Co., a tensile test is performed at a tensile tester chuck distance of 30 mm and a tensile speed of 50 mm / min. The tensile elongation at break was calculated and evaluated according to the following criteria.

<Tensile elongation at break of polyurethane coating film obtained from urethane-forming composition>
Tensile elongation at break = 100 x (distance between chucks at break - 30 mm) / 30 mm
A (acceptable toughness): when the tensile elongation at break of the polyurethane coating film is 250% or more.
B (acceptable toughness): When the tensile elongation at break of the polyurethane coating film is 150% or more and less than 250%.
C (failed toughness): When the tensile elongation at break of the polyurethane coating film is less than 150%.

The urethane-forming composition (D1) of Example 1 comprises 100 parts by mass of polyalkylene oxide (A1), 3 parts by mass of polyalkylene oxide (B1), an isocyanate compound (C1), and dioctyltine as a urethanization catalyst. and 0.03 parts by weight of dilaurate (DOTDL). Further, in the urethane-forming composition (D1), the amount of hydroxyl groups (M _OH ) derived from (A1) and (B1) and the amount of isocyanate groups (M _NCO ) derived from (C1) are in a molar ratio of M _NCO of (C1)/M _OH of (A1) and (B1) = 1.05.
The results of Example 1 are shown in Table 3. The urethane-forming composition (D1) had good coatability and curability, and the polyurethane (J1) coating film obtained from the composition (D1) was subjected to tensile rupture. The growth was great.

The urethane-forming composition (DC1) of Comparative Example 1 is the same as the urethane-forming composition (D1) of Example 1, except that it does not contain a polyalkylene oxide (B1). The results of Comparative Example 1 are shown in Table 3. Since the composition (DC1) does not contain (B1), the composition (DC1) is inferior in coatability.

The urethane-forming composition (D2) of Example 2 comprises 100 parts by mass of a polyalkylene oxide (A5), 5 parts by mass of a polyalkylene oxide (B3), an isocyanate compound (C2), and 0.2 parts of DOTDL as a urethanization catalyst. 03 parts by mass. Further, in the urethane-forming composition (D2), the amount of hydroxyl groups (M _OH ) derived from (A5) and (B3) and the amount of isocyanate groups (M _NCO ) derived from (C2) are M _NCO /M _OH of (A5) and (B3)]=1.05.
Table 3 shows the results of Example 2. The urethane-forming composition (D2) had good coatability and curability. There was a lot of growth.

Urethane-forming composition (DC2) of Comparative Example 2 is the same as urethane-forming composition (D2) of Example 2, except that it does not contain polyalkylene oxide (B3). The results of Comparative Example 2 are shown in Table 3. Since the composition (DC2) does not contain (B3), the composition (DC2) is inferior in coatability.

The urethane-forming composition (G1) of Example 3 contains a prepolymer (E1) and an isocyanate compound (F1), and the amounts (M _OH ) and (F1) of hydroxyl groups derived from the prepolymer (E1) The amount of isocyanate groups (M _NCO ) derived from is, in molar ratio, M _NCO of (F1)/M _OH of (E1) = 1.05.
A prepolymer (E1) was obtained by reacting the urethane-forming composition (D3).
The urethane-forming composition (D3) comprises 100 parts by mass of a polyalkylene oxide (A2), 3 parts by mass of a polyalkylene oxide (B2), an isocyanate compound (C3), and 0.03 parts by mass of DOTDL as a urethanization catalyst. ,including. Further, in the urethane-forming composition (D3), the amount of hydroxyl groups (M _OH ) derived from (A2) and (B2) and the amount of isocyanate groups (M _NCO ) derived from (C3) are, in molar ratio, M _NCO of (C3)/M _OH of (A2) and (B2) = 0.85.
Table 4 shows the results of Example 3. The urethane-forming composition (G1) had good coatability and curability. The growth was great.

Urethane-forming composition (GC1) of Comparative Example 3 is the same as urethane-forming composition (G1) except that it does not contain polyalkylene oxide (B2). The results of Comparative Example 3 are shown in Table 4. Since the composition (GC1) does not contain (B2), the composition (GC1) is inferior in coatability.

The urethane-forming composition (G2) of Example 4 contains a prepolymer (E2) and an isocyanate compound (F1), and the amounts (M _OH ) and (F1) of hydroxyl groups derived from the prepolymer (E2) The amount of isocyanate groups (M _NCO ) derived from is, in molar ratio, (M _NCO of (F1)/M _OH of (E2) = 1.05.
A prepolymer (E2) was obtained by reacting the urethane-forming composition (D4).
The urethane-forming composition (D4) comprises 80 parts by mass of polyalkylene oxide (A3), 20 parts by mass of polyalkylene oxide (A4), 4 parts by mass of polyalkylene oxide (B1), an isocyanate compound (C3), 0.03 parts by mass of DOTDL as a urethanization catalyst. Further, in the urethane-forming composition (D4), the amount of hydroxyl groups (M _OH ) derived from (A3), (A4), and (B1) and the amount of isocyanate groups (M _NCO ) derived from (C3) are In terms of molar ratio, M _NCO of (C3)/M _OH of (A3), (A4) and (B1) = 0.80.
Table 4 shows the results of Example 4. The urethane-forming composition (G2) had good coatability and curability. The growth was great.

The urethane-forming composition (GC2) of Comparative Example 4 is the same as the urethane-forming composition (G2) of Example 4, except that it does not contain polyalkylene oxide (B1). The results of Comparative Example 4 are shown in Table 4. Since the composition (GC2) does not contain (B1), the composition (GC2) is inferior in coatability.

The urethane-forming composition solution (H1) of Example 5 was obtained by adding ethyl acetate as an organic solvent to the urethane-forming composition (G3).
The urethane-forming composition (G3) contains a prepolymer (E3) and an isocyanate compound (F1), and the amount of hydroxyl groups (M _OH ) derived from the prepolymer (E3) and the isocyanate derived from (F1) The amount of groups (M _NCO ), in molar ratio, is M _NCO of (F1)/M _OH of (E3) = 1.05.
Prepolymer (E3) was obtained by reacting urethane-forming composition (D5).
The urethane-forming composition (D5) comprises 80 parts by mass of polyalkylene oxide (A2), 20 parts by mass of polyalkylene oxide (A4), 3 parts by mass of polyalkylene oxide (B3), an isocyanate compound (C3), 0.03 parts by mass of DOTDL as a urethanization catalyst. Further, in the urethane-forming composition (D5), the amount of hydroxyl groups (M _OH ) derived from (A2), (A4), and (B3) and the amount of isocyanate groups (M _NCO ) derived from (C3) are In terms of molar ratio, M _NCO of (C3)/M _OH of (A2), (A4) and (B3) = 0.90.
The concentration of (F3) in the solution (H1) is 50%.
Table 5 shows the results of Example 5. The urethane-forming composition solution (H1) had good coatability and curability. The tensile elongation at break was also large.

The urethane-forming composition (GC3) of Comparative Example 5 is the same as the urethane-forming composition solution (H1) of Example 5, except that it does not contain polyalkylene oxide (B3). The concentration of (FC3) in the solution (HC1) is 50%.
The results of Comparative Example 5 are shown in Table 5. Since the composition solution (HC1) does not contain (B3), the composition solution (HC1) is inferior in coatability.

The urethane-forming composition solution (H2) of Example 6 was obtained by adding ethyl acetate as an organic solvent to the urethane-forming composition (G4).
The urethane-forming composition (G4) contains a prepolymer (E4) and an isocyanate compound (F1), and has an amount of hydroxyl groups (M _OH ) derived from the prepolymer (E4) and an isocyanate group derived from (F1). (M _NCO ) in molar ratio, M _NCO of (F1)/M _OH of (E4) = 1.05.
Prepolymer (E4) was obtained by reacting urethane-forming composition (D6).
The urethane-forming composition (D6) comprises 96 parts by mass of a polyalkylene oxide (A2), 4 parts by mass of a polyalkylene oxide (A6), 5 parts by mass of a polyalkylene oxide (B3), an isocyanate compound (C3), 0.03 parts by mass of DOTDL as a urethanization catalyst. In the urethane-forming composition (D6), the amount of hydroxyl groups (M _O ) derived from (A2), (A6), and (B3) and the amount of isocyanate groups (M _NCO ) derived from (C3) are In terms of molar ratio, M _NCO of (C3)/M _OH of (A2), (A6), (B3) = 0.85.
The concentration of (G4) in the solution (H2) is 50%.
Table 5 shows the results of Example 6. The composition solution (H2) had good coatability and curability, and the polyurethane (J6) coating film obtained from (H2) had a large tensile elongation at break. .

The urethane-forming composition solution (HC2) of Comparative Example 6 is the same as the urethane-forming composition solution (H2) of Example 6, except that it does not contain polyalkylene oxide (B3). The concentration of (GC4) in the solution (HC2) is 50%. The results of Comparative Example 6 are shown in Table 5. Since the composition solution (HC2) does not contain (B3), the composition solution (HC2) is inferior in coatability.

The urethane-forming composition solution (H3) of Example 7 was obtained by adding ethyl acetate as an organic solvent to the urethane-forming composition (G5).
The urethane-forming composition (G5) contains a prepolymer (E5) and an isocyanate compound (F1). In the urethane-forming composition (G5), the molar ratio of the amount of hydroxyl groups (M _OH ) derived from the prepolymer (E5) to the amount of isocyanate groups (M _NCO ) derived from (F1) is (F1 )/M _OH of ( _E5 ) = 1.5.
Prepolymer (E5) was obtained by reacting urethane-forming composition (D7).
The urethane-forming composition (D7) comprises 92 parts by mass of a polyalkylene oxide (A2), 8 parts by mass of a polyalkylene oxide (A6), 5 parts by mass of a polyalkylene oxide (B3), an isocyanate compound (C3), 0.03 parts by mass of DOTDL as a urethanization catalyst. Further, in the urethane-forming composition (D7), the amount of hydroxyl groups (M _OH ) derived from (A2), (A6), and (B3) and the amount of isocyanate groups (M _NCO ) derived from (C3) are In terms of molar ratio, M _NCO of (C3)/M _OH of (A2), (A6), (B3) = 0.80.
The concentration of (G5) in the solution (H3) is 50%.
Table 5 shows the results of Example 7. The composition solution (H3) had good coatability and curability, and the polyurethane (J7) coating film obtained from (H3) had a large tensile elongation at break. .

The urethane-forming composition solution (H4) of Example 8 was obtained by adding ethyl acetate as an organic solvent to the urethane-forming composition (G6).
The urethane-forming composition (G6) contains a prepolymer (E6) and an isocyanate compound (F1). In addition, in the urethane-forming composition (G6), the amount of hydroxyl groups (M _OH ) derived from the prepolymer (E6) and the amount of isocyanate groups (M _NCO ) of (F1) are in a molar ratio of (F1): M _OH of M _NCO /(E6) = 1.5.
Prepolymer (E6) was obtained by reacting urethane-forming composition (D8).
The urethane-forming composition (D8) comprises 92 parts by mass of a polyalkylene oxide (A2), 8 parts by mass of a polyalkylene oxide (A6), 5 parts by mass of a polyalkylene oxide (B4), an isocyanate compound (C3), 0.03 parts by mass of DOTDL as a urethanization catalyst. Further, in the urethane-forming composition (D8), the amount of hydroxyl groups (M _OH ) derived from (A2), (A6), and (B4) and the amount of isocyanate groups (M _NCO ) derived from (C3) are In molar ratio, M _NCO of (C3)/M _OH of (A2), (A6), (B4) = 0.80.
The concentration of (G6) in the solution (H4) is 50%.
Table 5 shows the results of Example 8. The composition solution (H4) had good coatability and curability, and the polyurethane (J8) coating film obtained from (H4) had a large tensile elongation at break. .

The urethane-forming composition solution (H5) of Example 9 was obtained by adding ethyl acetate as an organic solvent to the urethane-forming composition (G7).
The urethane-forming composition (G7) contains a prepolymer (E7) and an isocyanate compound (F1). Further, in the urethane-forming composition (G7), the molar ratio of the amount of hydroxyl groups (M _OH ) derived from the prepolymer (E7) to the amount of isocyanate groups (M _NCO ) derived from (F1) is (F1 )/M _OH of ( _E7 ) = 1.5.
Prepolymer (E7) was obtained by reacting urethane-forming composition (D9).
The urethane-forming composition (D9) comprises 92 parts by mass of a polyalkylene oxide (A2), 8 parts by mass of a polyalkylene oxide (A6), 5 parts by mass of a polyalkylene oxide (B5), an isocyanate compound (C3), 0.03 parts by mass of DOTDL as a urethanization catalyst. Further, in the urethane-forming composition (D9), the amount of hydroxyl groups (M _OH ) derived from (A2), (A6), and (B5) and the amount of isocyanate groups (M _NCO ) derived from (C3) are In molar ratio, M _NCO of (C3)/M _OH of (A2), (A6), (B5) = 0.80 The concentration of (G7) in the solution (H5) is 50%.
Table 5 shows the results of Example 9. The composition solution (H5) had good coatability and curability, and the polyurethane (J9) coating film obtained from (H5) had a large tensile elongation at break. .

The urethane-forming composition solution (H6) of Example 10 was obtained by adding ethyl acetate as an organic solvent to the urethane-forming composition (G8).
The urethane-forming composition (G8) contains a prepolymer (E8) and an isocyanate compound (F1). Further, in the urethane-forming composition (G8), the molar ratio of the amount of hydroxyl groups (M _OH ) derived from the prepolymer (E8) to the amount of isocyanate groups (M _NCO ) derived from (F1) is (F1 )/M _OH of ( _E8 ) = 1.5.
A prepolymer (E8) was obtained by reacting the urethane-forming composition (D10).
The urethane-forming composition (D10) comprises 92 parts by mass of a polyalkylene oxide (A2), 8 parts by mass of a polyalkylene oxide (A6), 5 parts by mass of a polyalkylene oxide (B6), an isocyanate compound (C3), 0.03 parts by mass of DOTDL as a urethanization catalyst. In the urethane-forming composition (D10), the amount of hydroxyl groups (M _OH ) derived from (A2), (A6), and (B6) and the amount of isocyanate groups (M _NCO ) derived from (C3) are In molar ratio, M _NCO of (C3)/M _OH of (A2), (A6), (B6) = 0.80.
The concentration of (G8) in the solution (H6) is 50%.
Table 5 shows the results of Example 10. The composition solution (H6) had good coatability and curability, and the polyurethane (J10) coating film obtained from (H6) had a large tensile elongation at break. .

The urethane-forming composition solution (H7) of Example 11 was obtained by adding ethyl acetate as an organic solvent to the urethane-forming composition (G9).
The urethane-forming composition (G9) contains a prepolymer (E9) and an isocyanate compound (F1). In the urethane-forming composition (G9), the amount of hydroxyl groups (M _OH ) derived from the prepolymer (E9) and the amount of isocyanate groups (M _NCO ) derived from (F1) are in a molar ratio of (F1). M _NCO /M _OH of (E9) = 1.5.
Prepolymer (E9) was obtained by reacting urethane-forming composition (D11).
The urethane-forming composition (D11) comprises 92 parts by mass of a polyalkylene oxide (A2), 8 parts by mass of a polyalkylene oxide (A6), 5 parts by mass of a polyalkylene oxide (B7), an isocyanate compound (C3), 0.03 parts by mass of DOTDL as a urethanization catalyst. In the urethane-forming composition (D11), the amount of hydroxyl groups (M _OH ) derived from (A2), (A6), and (B7) and the amount of isocyanate groups (M _NCO ) derived from (C3) are In terms of molar ratio, M _NCO of (C3)/M _OH of (A2), (A6), (B7) = 0.80.
The concentration of (G9) in the solution (H7) is 50%.
Table 5 shows the results of Example 11. The composition solution (H7) had good coatability and curability, and the polyurethane (J11) coating film obtained from (H7) had a large tensile elongation at break. .

The urethane-forming composition solution (H8) of Example 12 was obtained by adding ethyl acetate as an organic solvent to the urethane-forming composition (G10).
The urethane-forming composition (G10) contains a prepolymer (E5) and an isocyanate compound (F1). Further, in the urethane-forming composition (G10), the molar ratio of the amount of hydroxyl groups (M _OH ) derived from the prepolymer (E5) to the amount of isocyanate groups (M _NCO ) derived from (F1) is (F1 )/M _OH of ( _E5 ) = 3.5.
Prepolymer (E5) is the same as in Example 7.
The concentration of (G10) in the solution (H8) is 50%.
Table 5 shows the results of Example 12. Compared to Example 7, even if the M _NCO of (F1)/M _OH of (E5) increased, the coating properties of the composition solution (H8) and The curability was good, and the coating film of polyurethane (J12) obtained from (H8) had a large tensile elongation at break.

The urethane-forming composition solution (HC3) of Comparative Example 7 was the same as the urethane-forming composition solutions (H3) to (H7) of Examples 7 to 11, except that they did not contain polyalkylene oxides (B3) to (B7). ) is the same as Table 5 shows the results of Comparative Example 7. Since the composition solution (HC3) does not contain (B3) to (B7), the composition solution (HC3) is inferior in coatability.

The urethane-forming composition solution (H9) of Example 13 was obtained by adding methyl ethyl ketone as an organic solvent to the urethane-forming composition (G11).
The urethane-forming composition (G11) contains a prepolymer (E10) and an isocyanate compound (F1). Further, in the urethane-forming composition (G11), the molar ratio of the amount of hydroxyl groups (M _OH ) derived from the prepolymer (E10) to the amount of isocyanate groups (M _NCO ) derived from (F1) is (F1 )/M _OH of ( _E10 ) = 2.0.
A prepolymer (E10) was obtained by reacting the urethane-forming composition (D12).
The urethane-forming composition (D12) comprises 94 parts by mass of a polyalkylene oxide (A1), 6 parts by mass of a polyalkylene oxide (A6), 6 parts by mass of a polyalkylene oxide (B8), an isocyanate compound (C3), 0.03 parts by mass of DOTDL as a urethanization catalyst. In the urethane-forming composition (D12), the amount of hydroxyl groups (M _OH ) derived from (A1), (A6), and (B8) and the amount of isocyanate groups (M _NCO ) derived from (C3) are In molar ratio, M _NCO of (C3)/M _OH of (A1), (A6), (B8) = 0.80.
The concentration of (G11) in the solution (H9) is 50%.
Table 5 shows the results of Example 13. The composition solution (H9) had good coatability and curability, and the polyurethane (J14) coating film obtained from (H9) had a large tensile elongation at break. .

The urethane-forming composition solution (H10) of Example 14 was obtained by adding methyl ethyl ketone as an organic solvent to the urethane-forming composition (G12).
The urethane-forming composition (G12) contains a prepolymer (E11) and an isocyanate compound (F1). In the urethane-forming composition (G12), the amount of hydroxyl groups (M _OH ) derived from the prepolymer (E11) and the amount of isocyanate groups (M _NCO ) derived from (F1) are in a molar ratio of (F1). M _NCO /M _OH of (E11) = 2.0.
A prepolymer (E11) was obtained by reacting the urethane-forming composition (D13).
The urethane-forming composition (D13) comprises 94 parts by mass of a polyalkylene oxide (A1), 6 parts by mass of a polyalkylene oxide (A6), 6 parts by mass of a polyalkylene oxide (B9), an isocyanate compound (C3), 0.03 parts by mass of DOTDL as a urethanization catalyst. Further, in the urethane-forming composition (D13), the amount of hydroxyl groups (M _OH ) derived from (A1), (A6), and (B9) and the amount of isocyanate groups (M _NCO ) derived from (C3) are In molar ratio, M _NCO of (C3)/M _OH of (A1), (A6), (B9) = 0.80.
The concentration of (G12) in the solution (H10) is 50%.
Table 5 shows the results of Example 14. The composition solution (H10) had good coatability and curability. Since it is less than Cid (B8), the coatability is somewhat inferior to that of Example 13. The polyurethane (J15) coating film obtained from the composition solution (H10) had a large tensile elongation at break.

The urethane-forming composition solution (HC4) of Comparative Example 8 was the same as the urethane-forming composition solutions (H9) to (H10) of Examples 13 and 14, except that they did not contain polyalkylene oxides (B8) to (B9). ) is the same as The results of Comparative Example 8 are shown in Table 5. Since the composition solution (HC4) does not contain (B8) or (B9), the composition solution (HC4) is inferior in coatability.

The urethane-forming composition (DC9) of Comparative Example 9 contains 100 parts by mass of a polyalkylene oxide (AC1), 3 parts by mass of a polyalkylene oxide (B1), an isocyanate compound (C1), and 0.2 parts of DOTDL as a urethanization catalyst. 03 parts by mass. Further, in the urethane-forming composition (DC9), the amount of hydroxyl groups (M _OH ) derived from (AC1) and (B1) and the amount of isocyanate groups (M _NCO ) derived from (C1) are, in molar ratio, M _OH of (C1)/M _OH of (AC1) and (B1) = 1.05. (AC1) is a polyalkylene oxide having a high degree of unsaturation and falling outside the range of 0.010 meq/g or less. The results of Comparative Example 9 are shown in Table 6. Since (AC1) has a high degree of unsaturation (many unsaturated monools), it has excellent coatability but poor curability. The coating film of polyurethane (JC9) obtained from the composition (DC9) had a large tensile elongation at break. However, the surface of the coating film was sticky due to the large amount of unsaturated monool.

The urethane-forming composition (DC10) of Comparative Example 10 contains 100 parts by mass of polyalkylene oxide (AC3), 3 parts by mass of polyalkylene oxide (B3), an isocyanate compound (C2), and 0.2 parts of DOTDL as a urethanization catalyst. 03 parts by mass. Further, in the urethane-forming composition (DC10), the amount of hydroxyl groups (M _OH ) derived from (AC3) and (B3) and the amount of isocyanate groups (M _NCO ) derived from (C2) are, in molar ratio, M _NCO of (C2)/M _OH of (AC3) and (B3) = 1.05. (AC3) is also a polyalkylene oxide having a high degree of unsaturation and falling outside the range of 0.010 meq/g or less. Table 6 shows the results of Comparative Example 10. Since (AC3) has a high degree of unsaturation (many unsaturated monools), it has excellent coatability but poor curability. The coating film of polyurethane (JC10) obtained from the composition (DC10) had a large tensile elongation at break. However, the surface of the coating film was sticky due to the large amount of unsaturated monool.

The urethane-forming composition (DC11) of Comparative Example 11 contains 100 parts by mass of polyalkylene oxide (AC2), 3 parts by mass of polyalkylene oxide (B1), an isocyanate compound (C1), and 0.2 parts of DOTDL as a urethanization catalyst. 03 parts by mass. Further, in the urethane-forming composition (DC11), the amount of hydroxyl groups (M _OH ) derived from (AC2) and (B1) and the amount of isocyanate groups (M _NCO ) derived from (C1) are, in molar ratio, M _NCO of (C1)/M _OH of (AC2) and (B1) = 1.05. (AC2) is a polyalkylene oxide having a high degree of unsaturation and falling outside the range of 0.010 meq/g or less. The results of Comparative Example 11 are shown in Table 6. Since (AC2) has a high degree of unsaturation (high content of unsaturated monools), it is excellent in coatability. In addition, Comparative Example 11 has good curability by using a composition in which the average number of isocyanate groups (C1) is large and the amount of DOTDL as a urethanization catalyst is increased to 0.1 parts by mass. there were. However, in Comparative Example 11, the curability of the composition using polyalkylene oxide with a high degree of unsaturation (many unsaturated monools) was forcibly accelerated, and the polyurethane obtained from the composition (JC11) The coating film of No. 1 formed a dense crosslinked structure and had a small tensile elongation at break. In Comparative Example 11, the surface of the coating film was sticky due to the large amount of unsaturated monool.

The urethane-forming composition solution (HC5) of Comparative Example 12 was obtained by adding ethyl acetate as an organic solvent to the urethane-forming composition (GC7).
The urethane-forming composition (GC7) consists of a prepolymer (EC7) and an isocyanate compound (F1). Further, in the urethane-forming composition (GC7), the molar ratio of the amount of hydroxyl groups (M _OH ) derived from the prepolymer (EC7) to the amount of isocyanate groups (M _NCO ) derived from (F1) is (F1 M _NCO of (EC7)/M _OH of (EC7) = 2.0.
A prepolymer (EC7) was obtained by reacting a urethane-forming composition (DC12).
The urethane-forming composition (DC12) comprises 92 parts by mass of a polyalkylene oxide (AC1), 8 parts by mass of a polyalkylene oxide (A6), 3 parts by mass of a polyalkylene oxide (B3), an isocyanate compound (C3), 0.03 parts by mass of DOTDL as a urethanization catalyst. Further, in the urethane-forming composition (DC12), the amount of hydroxyl groups (M _OH ) derived from (AC1), (A6), and (B3) and the amount of isocyanate groups (M _NCO ) derived from (C3) are In molar ratio, M _NCO of (C3)/M _OH of (AC1), (A6), (B3) = 0.85.
The concentration of (GC7) in the solution (HC5) is 50%.
Table 7 shows the results of Comparative Example 12. Since (AC1) has a high degree of unsaturation (contains a large amount of unsaturated monools), (HC5) has excellent coatability but poor curability. rice field. The coating film of polyurethane (JC12) obtained from the solution (HC5) had a large tensile elongation at break. However, the surface of the coating film was sticky due to the large amount of unsaturated monool.

The urethane-forming composition solution (HC6) of Comparative Example 13 was obtained by adding ethyl acetate as an organic solvent to the urethane-forming composition (GC8).
The urethane-forming composition (GC8) contains a prepolymer (EC8) and an isocyanate compound (F1). Further, in the urethane-forming composition (GC8), the molar ratio of the amount of hydroxyl groups (M _OH ) derived from the prepolymer (EC8) to the amount of isocyanate groups (M _NCO ) derived from (F1) is (F1 M _NCO of (EC8)/M _OH of (EC8) = 2.0.
A prepolymer (EC8) was obtained by reacting a urethane-forming composition (DC13).
Urethane-forming composition (DC13) comprises 90 parts by mass of polyalkylene oxide (AC4), 10 parts by mass of polyalkylene oxide (A6), 3 parts by mass of polyalkylene oxide (B1), an isocyanate compound (C3), 0.03 parts by mass of DOTDL as a urethanization catalyst. In the urethane-forming composition (DC13), the amount of hydroxyl groups (M _OH ) derived from (AC4), (A6), and (B1) and the amount of isocyanate groups (M _NCO ) derived from (C3) were In molar ratio, M _NCO of (C3)/M _OH of (AC4), (A6), (B1) = 0.90.
The concentration of (GC8) in the solution (HC6) is 50%.
Table 7 shows the results of Comparative Example 13. Although (HC6) is excellent in coatability and curability, (AC4) has a low molecular weight, so a polyurethane (JC13) coating film obtained from (HC6) A dense cross-linked structure was formed and the tensile elongation at break was small.

The urethane-forming composition solution (HC7) of Comparative Example 14 was obtained by adding ethyl acetate as an organic solvent to the urethane-forming composition (GC9).
A urethane-forming composition (GC9) comprises a prepolymer (EC9) and an isocyanate compound (F1). Further, in the urethane-forming composition (GC9), the molar ratio of the amount of hydroxyl groups (M _OH ) derived from the prepolymer (EC9) to the amount of isocyanate groups (M _NCO ) derived from (F1) is (F1 M _NCO of (EC9)/M _OH of (EC9) = 2.0.
A prepolymer (EC9) was obtained by reacting a urethane-forming composition (DC14).
The urethane-forming composition (DC14) comprises 92 parts by mass of a polyalkylene oxide (A2), 8 parts by mass of a polyalkylene oxide (A6), 3 parts by mass of a polyalkylene oxide (BC1), an isocyanate compound (C3), 0.03 parts by mass of DOTDL as a urethanization catalyst. Further, in the urethane-forming composition (DC14), the amount of hydroxyl groups (M _OH ) derived from (A2), (A6), and (BC1) and the amount of isocyanate groups (M _NCO ) derived from (C3) are In molar ratio, M _NCO of (C3)/M _OH of (A2), (A6), (BC1) = 0.85.
The concentration of (GC9) in the solution (HC7) is 50%.
Table 7 shows the results of Comparative Example 14. Since (BC1) has two hydroxyl groups in one molecule, the prepolymer obtained by reaction with the isocyanate compound (C3) forms a dense crosslinked structure, Even when the composition solution (HC7) was applied, the solution flowed poorly and the coatability was remarkably inferior, and the resulting polyurethane (JC14) coating film was remarkably inferior in surface appearance.

The urethane-forming composition solution (HC8) of Comparative Example 15 was obtained by adding ethyl acetate as an organic solvent to the urethane-forming composition (GC10).
The urethane-forming composition (GC10) contains a prepolymer (EC10) and an isocyanate compound (F1). In addition, in the urethane-forming composition (GC10), the amount of hydroxyl groups (M _OH ) derived from the prepolymer (EC10) and the amount of isocyanate groups (M _NCO ) derived from (F1) are in a molar ratio of (F1 M _NCO of (EC10)/M _OH of (EC10) = 2.0.
A prepolymer (EC10) was obtained by reacting a urethane-forming composition (DC15).
Urethane-forming composition (DC15) comprises 92 parts by mass of polyalkylene oxide (A2), 8 parts by mass of polyalkylene oxide (A6), 5 parts by mass of polyalkylene oxide (BC2), an isocyanate compound (C3), 0.03 parts by mass of DOTDL as a urethanization catalyst. In the urethane-forming composition (DC15), the amount of hydroxyl groups (M _OH ) derived from (A2), (A6), and (BC2) and the amount of isocyanate groups (M _NCO ) derived from (C3) are in a molar ratio of , and M _NCO of (C3)/M _OH of (A2), (A6) and (BC2) = 0.85.
The concentration of (GC10) in the solution (HC8) is 50%.
Table 7 shows the results of Comparative Example 15. Since the alkylene oxide (BC2) does not contain an ethylene oxide residue, the composition solution (HC8) is inferior in coatability.

As described above in the Examples, the urethane-forming composition according to one aspect of the present disclosure is excellent in coatability when applied with a coating machine or the like, and does not use a large amount of a urethanization catalyst. Curing (solidification) associated with the reaction with the isocyanate compound promotes high productivity, and furthermore, the reaction with the isocyanate compound makes it possible to obtain a polyurethane having high tensile elongation at break and excellent toughness. It was shown that the polyurethane obtained from the urethane-forming composition can be suitably used for sealants, paints, pressure-sensitive adhesives, adhesives and the like by making use of its characteristics.

Claims (12)

A polyalkylene oxide (A) having an alkylene oxide residue having 3 or more carbon atoms in one molecule and two or more hydroxyl groups;
A polyalkylene oxide (B) containing one hydroxyl group and an ethylene oxide residue in one molecule;
an isocyanate compound (C) having an average functionality of isocyanate groups of 2.0 or more;
including
The polyalkylene oxide (A) is
The degree of unsaturation is 0.010 meq/g or less,
number average molecular weight is 800 or more,
A urethane prepolymer (E) that is a reaction product of the urethane-forming composition (D),
The urethane prepolymer (E) has at least one hydroxyl group in one molecule,
The urethane-forming composition (D) contains the amount of isocyanate groups derived from the isocyanate compound (C) relative to the amount of hydroxyl groups (M _OH ) derived from the polyalkylene oxide (A) and the polyalkylene oxide (B) ( M _NCO ) ratio (M _NCO /M _OH ) is less than 1.0 in molar ratio (E). The urethane prepolymer (E) according to claim 1, wherein the alkylene oxide residue having 3 or more carbon atoms is a propylene oxide residue. The polyalkylene oxide (B) is at least one selected from the group consisting of polyoxyalkylene glycol monoalkyl ethers, polyoxyalkylene glycol monoalkenyl ethers, and polyoxyalkylene glycol monophenyl ethers. 3. The urethane prepolymer (E) according to 1 or 2. The number average molecular weight of the polyalkylene oxide (A) is the hydroxyl value of the polyalkylene oxide (A) calculated by the method described in JIS K-1557-1, and 4. The urethane prepolymer (E) according to any one of claims 1 to 3, which is a number average molecular weight calculated from the number of hydroxyl groups. A urethane-forming composition (G) comprising the urethane prepolymer (E) according to any one of claims 1 to 4 and an isocyanate compound (F). The urethane prepolymer (E) according to any one of claims 1 to 4 and/or the urethane-forming composition (G) according to claim 5 ,
A urethane prepolymer solution (I) containing an organic solvent,
A urethane prepolymer solution (I), wherein the concentration of the urethane prepolymer (E) in the urethane prepolymer solution (I) is 10% by mass or more and 90% by mass or less. The urethane-forming composition (G) according to claim 5 or a polyurethane (G) which is a reaction product of the urethane-forming composition (G) in the urethane prepolymer solution (I) according to claim 6 J). A polyurethane sheet comprising the polyurethane (J) according to claim 7 . A sealing material comprising the polyurethane (J) according to claim 7 or the polyurethane sheet according to claim 8 . A paint comprising the polyurethane (J) according to claim 7 or the polyurethane sheet according to claim 8 . A pressure-sensitive adhesive comprising the polyurethane (J) according to claim 7 or the polyurethane sheet according to claim 8 . An adhesive comprising the polyurethane (J) according to claim 7 or the polyurethane sheet according to claim 8 .