JP7283052B2 - 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.
Further, polyurethanes obtained from polyalkylene oxides containing a large amount of unsaturated monools are unlikely to have a high molecular weight, low tensile elongation at break, and low tensile strength at break. On the other hand, even a polyalkylene oxide containing a large amount of unsaturated monool can be reacted with an isocyanate compound having a large average number of isocyanate functional groups to obtain a high molecular weight polyurethane. 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 obtained polyurethane has a low tensile elongation at break and a low tensile strength 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 increases tensile elongation at break and tensile strength at break. However, since polyalkylene oxides containing less unsaturated monools have high viscosities, improvements in coatability are desired for compositions containing such polyalkylene oxides. A further improvement in accompanying tensile strength at break has also been desired.

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 polyurethane having high tensile elongation at break and tensile strength at break, and the urethane-forming composition. It is directed to provide a urethane-forming composition solution comprising:
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 and two or more hydroxyl groups in one molecule;
Polytetramethylene glycol (B) containing tetramethylene-ether in one molecule and having two or more hydroxyl groups,
A polyalkylene oxide (C) containing one hydroxyl group and an ethylene oxide residue in one molecule;
and an isocyanate compound (D) having an average functionality 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.
Urethane-forming composition (E).
[2] A urethane prepolymer (F) that is a reaction product of the urethane-forming composition (E),
The urethane prepolymer (F) has at least one hydroxyl group in one molecule, and among the urethane-forming composition (E), the polyalkylene oxide (A) and the polytetramethylene glycol (B) and The ratio (M _NCO /M _OH ) of the amount (M _NCO ) of isocyanate groups derived from the isocyanate compound (D) to the total amount (M _OH ) of hydroxyl groups derived from the polyalkylene oxide (C) is urethane prepolymer (F), which is less than 1.0.
[3] A urethane-forming composition (H) containing the urethane prepolymer (F) and an isocyanate compound (G).
[4] the urethane-forming composition (E), the urethane prepolymer (F), or the urethane-forming composition (H);
A urethane-forming composition solution (I) comprising an organic solvent,
The concentration of the urethane-forming composition (E), the urethane prepolymer (F), or the urethane-forming composition (H) in the urethane prepolymer solution (I) is 10% by mass or more and 90% by mass. Urethane-forming composition solution (I) which is:
[5] A polyurethane (J) which is a reaction product of the urethane-forming composition (E) or the urethane-forming composition (H) in the urethane-forming composition solution (I).
[6] A polyurethane sheet comprising the above polyurethane (J) [7] A sealing material comprising the above polyurethane (J) or the above polyurethane sheet.
[8] A paint comprising the above polyurethane (J) or the above polyurethane sheet.
[9] A pressure-sensitive adhesive comprising the above polyurethane (J) or the above polyurethane sheet.
[10] An adhesive comprising the above polyurethane (J) or the above polyurethane sheet.

The urethane-forming composition of the present invention has excellent coatability when applied with a coating machine or the like in order to obtain polyurethane, and in addition, it does not use a large amount of a urethanization catalyst, and can be combined with an isocyanate compound. It is possible to obtain a polyurethane having high productivity by proceeding with curing (solidification) accompanying the reaction and having high tensile elongation at break and tensile strength at break.
Moreover, the polyurethane obtained by using the urethane-forming composition of the present invention can be suitably used in a wide range of applications such as sealants, paints, pressure-sensitive adhesives, and adhesives.

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 (E) 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;
Polytetramethylene glycol (B) containing tetramethylene-ether in one molecule and having two or more hydroxyl groups,
A polyalkylene oxide (C) containing one hydroxyl group and an ethylene oxide residue in one molecule;
and an isocyanate compound (D) having an average functionality 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 (E) containing the polyalkylene oxide (A) cures due to the reaction with the isocyanate compound (D). (Solidification) takes a long time, resulting in poor productivity, and the obtained polyurethane does not have a high molecular weight, has a low tensile elongation at break, and a low tensile strength at break. 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 and tensile strength at break become small. If the degree of unsaturation of the polyalkylene oxide (A) is 0.010 meq/g or less, curing ( Solidification is fast, and the resulting polyurethane has a linear high molecular weight and high tensile elongation at break and tensile strength at break. The lower the degree of unsaturation of the polyalkylene oxide (A), the higher the tensile elongation at break and the tensile strength at break of the resulting polyurethane, and 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, since the polyalkylene oxide (A) has a low molecular weight, polytetramethylene glycol (B), polyalkylene oxide (C), and isocyanate The polyurethane obtained by reaction with the compound (D) forms a densely crosslinked structure, resulting in reduced tensile elongation at break and tensile strength at break. If the polyalkylene oxide (A) has a number average molecular weight of 800 or more, the polyurethane obtained by the reaction of the polytetramethylene glycol (B), the polyalkylene oxide (C), and the isocyanate compound (D) will be resistant to tensile rupture. Increased elongation and tensile strength at break. The higher the number average molecular weight of the polyalkylene oxide (A), the higher the tensile elongation at break and the tensile strength at break of the polyurethane, which is preferable. However, if 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) used in the present invention preferably has a molecular weight distribution (weight average molecular weight (Mw)/number average molecular weight (Mn); Mw/Mn) of 1.1 or less. When the Mw/Mn is 1.1 or less, low molecular weight substances that cause contamination are reduced, resulting in excellent contamination resistance, which is preferable.
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. 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 apply 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 polytetramethylene glycol (B) and the polyalkylene oxide (C ) and the isocyanate compound (D), the crosslinked structure of the polyurethane obtained by the reaction with the isocyanate compound (D) is unlikely to become dense, and the tensile elongation at break and the tensile strength at break are further increased.

In addition, the polyalkylene oxide (A) is preferably liquid at room temperature because it facilitates handling of the urethane-forming composition (E) 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 alkyl carboxyanions having 2 to 5 carbon atoms include acetoxy anion, ethyl carboxy anion, n-propyl carboxy anion, isopropyl carboxy anion, n-butyl carboxy anion, isobutyl carboxy anion, t-butyl carboxy anion 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. and aluminoxanes such as methylaluminoxane, isobutylaluminoxane and methyl-isobutylaluminoxane.

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, a 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.

<Polytetramethylene glycol (B)>
Polytetramethylene glycol (B) is not particularly limited as long as it contains tetramethylene-ether in one molecule and has two or more hydroxyl groups. Block, graft and random copolymers containing ethers may also be used.

The viscosity of the polytetramethylene glycol (B) at 40° C. is not particularly limited, and is appropriately selected depending on the application. It is below. If the viscosity of the polytetramethylene glycol (B) at 40° C. is 1 mPa·s or more and 2000 mPa·s or less, it is preferable because it is easy to apply with a coating machine or the like to obtain a polyurethane product. Here, the “viscosity” at 40° 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. The reason why the measurement temperature is 40 ° C. is that polytetramethylene glycol (B) is crystalline, and the viscosity cannot be measured unless (B) is liquid at a temperature higher than the melting point of (B). is.

<Polyalkylene oxide (C)>
Polyalkylene oxide (C) is not particularly limited as long as it contains one hydroxyl group and ethylene oxide residue in one molecule, but polyalkylene oxide (A), polytetramethylene glycol (B) and polyalkylene oxide Since the urethane-forming composition (E) containing (C) and (C) is particularly excellent in coatability when coated with a coating machine, polyoxyalkylene glycol monoalkyl ether, polyoxyalkylene glycol monoalkenyl ether , and polyoxyalkylene glycol monophenyl ether.

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, the urethane-forming composition (E) containing the polyalkylene oxide (A), the polytetramethylene glycol (B), and the polyalkylene oxide (C) is excellent in coatability when applied. Therefore, any one or more of polyoxyethylene glycol monomethyl ether, polyoxyethylene glycol monobutyl ether, polyoxy (ethylene / propylene) glycol monomethyl ether, and polyoxy (ethylene / propylene) glycol monobutyl ether with a high ethylene oxide content preferably included.

Although the number average molecular weight of the polyoxyalkylene oxide (C) is not particularly limited, it is preferably 150 to 15,000, more preferably 200 to 5,000, and most preferably 250 to 1,300. When the molecular weight of the polyalkylene oxide (C) is too low, the viscosity of the urethane-forming composition (E) containing it becomes too low, and when the urethane-forming composition (E) is coated with a coating machine, etc. In some cases, the defect phenomenon of liquid flow occurs, and the thickness of the resulting polyurethane coating film becomes non-uniform. On the other hand, when the molecular weight of the polyalkylene oxide (C) is too high, the compatibility with the polyalkylene oxide (A) becomes poor, and the urethane-forming composition (E) 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 (C) 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 (C) is, as in the case of the polyalkylene oxide (A), the hydroxyl value of the polyalkylene oxide (C) calculated by the method described in JIS K-1557-1, It can be calculated from the number of hydroxyl groups in one molecule of polyalkylene oxide (C).

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

<Isocyanate compound (D)>
The isocyanate compound (D) 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 (D) 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 group, carbodiimide group, allophanate group, urea group, biuret group, isocyanurate group, amide group, imide group, uretonimine group, uretdione group or oxazolidone group, and polymethylene polyphenylene polyisocyanate. Condensates such as (polymeric MDI) can be mentioned.

Among these, a urethane-forming composition that exhibits excellent curing (hardening) properties associated with the reaction of polyalkylene oxide (A), polytetramethylene glycol (B), and polyalkylene oxide (C), is highly transparent, and has little coloration. Aliphatic isocyanates, alicyclic isocyanates, or modified products thereof are preferred because they are easy to obtain. 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 (E)>
The urethane-forming composition (E) is a composition containing the above-described polyalkylene oxide (A), polytetramethylene glycol (B), polyalkylene oxide (C), and a specific isocyanate compound (D). good. The mixing ratio of the polyalkylene oxide (A) and the polytetramethylene glycol (B) in the urethane-forming composition (E) is not particularly limited, but the mass ratio (polyalkylene oxide (A)/polytetramethylene glycol (B) ), preferably 99.9/0.1 or more and 40/60 or less, more preferably 99.5/0.5 or more and 50/50 or less, and 99/1 or more and 60/40 or less is most preferred. A polyurethane obtained from the urethane-forming composition (E) having a mass ratio within this range has high tensile strength at break and good transparency, and is thus preferable.
Also, the mixing ratio of the mixture of polyalkylene oxide (A) and polytetramethylene glycol (B) and polyalkylene oxide (C) is not particularly limited, but the mass ratio [polyalkylene oxide (A) + polytetramethylene glycol ( B)]/polyalkylene oxide (C), 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 preferable. 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. preferred to indicate
The content of the isocyanate compound (D) in the urethane-forming composition (E) is also not particularly limited. The content of the isocyanate compound (D) is _the isocyanate compound ( The ratio (M _NCO /M _OH ) of the amount of isocyanate groups (M _NCO ) derived from D) is preferably 0.5 or more and less than 4.0 in terms of molar ratio, and the content of the isocyanate compound (D) is within the above range, when the polyurethane is obtained by curing accompanying the reaction of the urethane-forming composition (E), the curing (hardening) property is excellent, and the polyurethane has even better mechanical properties. preferable.

The polyalkylene oxide (A), polytetramethylene glycol (B), polyalkylene oxide (C), and isocyanate compound (D) contained in the urethane-forming composition (E) are dehydrated by vacuum heating or the like. It is preferable to use it, but if the operation becomes complicated, it may be used without dehydration.

The preparation of the urethane-forming composition (E) is not particularly limited as long as it can uniformly disperse the raw materials contained in the urethane-forming composition (E). 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), polytetramethylene glycol (B), polyalkylene oxide (C), and isocyanate compound (D) are all liquid at the stirring temperature, a rotation/revolution mixer, a general-purpose stirrer, and a disper disperser , a dissolver is preferably used.

The viscosity of the urethane-forming composition (E) 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 (E) at 25°C is within this range, the urethane-forming composition (E ) 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 (F)>
The urethane prepolymer (F) is a reaction product of the urethane-forming composition (E) and has at least one hydroxyl group per molecule. That is, the urethane prepolymer (F) is a urethane-forming composition ( A reactant obtained by reacting E), which is a polyurethane having at least one hydroxyl group in one molecule.

Among them, the urethane-forming composition (E) for obtaining the urethane prepolymer (F) includes polyalkylene oxide (A), polytetramethylene glycol (B), and hydroxyl groups derived from polyalkylene oxide (C). The ratio (M _NCO /M _OH ) of the amount (M _NCO ) of isocyanate groups derived from the isocyanate compound (D) to the total amount (M _OH ) of the isocyanate compound (D) is preferably less than 1.0, preferably 0.4 to 0.4. It is more preferably 99 or less, and most preferably 0.5 or more and 0.95 or less. 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 prepolymer (F) is produced by reacting the urethane-forming composition (E). ) is less likely to occur and handling becomes easier.

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

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

Here, the urethane-forming composition (H) may be a composition containing the urethane prepolymer (F) and the isocyanate compound (G). Therefore, the content of the isocyanate compound (G) in _the urethane-forming composition (H) is not particularly limited. The ratio (M _NCO /M _OH ) of the amount (M _NCO ) of isocyanate groups derived is preferably 0.5 or more and less than 4.0 in terms of molar ratio. When the content of the isocyanate compound (G) is within the above range, when polyurethane is obtained by curing accompanying the reaction of the urethane-forming composition (H), its curing (hardening) property is excellent, and the polyurethane is excellent in mechanical properties. It is preferable because it has physical properties.

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

The method for preparing the urethane-forming composition (H) is not particularly limited as long as it can uniformly disperse the prepolymer and raw materials contained in the urethane-forming composition (H). 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 (F) and the isocyanate compound (G) 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 (H) 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 (H) at 25° C. is within this range, the urethane-forming composition (H) can be stirred with various stirrers to prepare the urethane-forming composition (H). is preferable because it facilitates stirring and handling of the urethane-forming composition (H) when stirring is performed as a pre-stage operation when coating with a coating machine or the like.

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

The viscosity of the urethane-forming composition solution 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 or the urethane prepolymer solution (I) is applied using a coating machine or the like. The urethane prepolymer solution (I) can be easily handled.

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

Examples of urethanization catalysts include tertiary amine compounds, organometallic compounds, and the like. :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 the urethane-forming composition (E), the urethane-forming composition (H), the urethane-forming composition (E) of the urethane-forming composition solution (I), or the urethane prepolymer solution ( It is the reactant of the urethane-forming composition (H) in I).

The polyurethane (J) is cured (solidified) by reacting the urethane-forming composition (E), (H), the urethane-forming composition solution (I), 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 composition (E) or (H), the urethane-forming composition solution (I), or the urethane prepolymer solution (I), if necessary, a urethanization catalyst, a solvent, 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 (E), (H), the urethane-forming composition solution (I), or the urethane prepolymer solution (I) is used for coating with a coating machine or the like. Since the workability is remarkably excellent, a thin and uniform polyurethane (J) coating film or polyurethane sheet 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 for any application where ordinary polyurethane is used, but it is particularly suitable for applications requiring mechanical properties, viscous/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.

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 the polyalkylene oxide was measured according to the method described in JIS-K1557-1. 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 of
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 polyalkylene oxide was determined 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), (A2), and (A3) are bifunctionally bifunctional, using an imino group-containing phosphazenium salt (hereinafter referred to as an IPZ catalyst) and triisopropoxyaluminum in combination to sufficiently dehydrate and remove the solvent. was obtained by adding sufficiently dehydrated propylene oxide to polyoxypropylene glycol having a molecular weight of 400. (A1), (A2) and (A3) are polyoxypropylene glycols (diols) having only propylene oxide groups as alkylene oxide groups and two hydroxyl groups in one molecule. Table 1 shows the properties of (A1), (A2) and (A3). It has a narrow molecular weight distribution.

The polyalkylene oxide (A4) is a propylene oxide obtained by using an IPZ catalyst and triisopropoxyaluminum in combination, sufficiently dehydrating and removing the solvent, and sufficiently dehydrating a bifunctional polyoxypropylene glycol having a molecular weight of 400. and ethylene oxide were added in order. (A4) 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 (A4) are shown in Table 1. (A4) also has an extremely small amount of unsaturated monol (extremely low degree of unsaturation) and a narrow molecular weight distribution.

For the polyalkylene oxides (A5) and (A6), 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. (A5) and (A6) are polyoxypropylene triols having only propylene oxide groups as alkylene oxide groups and three hydroxyl groups in one molecule. The properties of (A5) and (A6) are shown in Table 1. (A5) and (A6) have an extremely small amount of unsaturated monol (extremely low degree of unsaturation) and a narrow molecular weight distribution.

Polyalkylene oxide (A7) is a polyoxypropylene triol having a molecular weight of 980 and having three hydroxyl groups in one molecule obtained using a potassium hydroxide catalyst. (A7) is commercially available GP1000 manufactured by Sanyo Chemical Industries, Ltd. The properties of (A7) are shown in Table 1. (A7) 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 (A6). 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. is also highly unsaturated.

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. Equivalent to AC2) 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 (A7) 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 2-1) Polytetramethylene glycol (B) used in Examples
Polytetramethylene glycols (B1) and (B2) are commercially available polytetramethylene glycols, (B1) is PTG-1000SN manufactured by Hodogaya Chemical Industry Co., Ltd., (B2) is Hodogaya Chemical Industry Co., Ltd. ) manufactured by PTG-2900SN. (B1) and (B2) are crystalline, and the melting points of the crystals are 27° C. for (B1) and 30° C. for (B2). The properties of (B1) and (B2) are shown in Table 2. (B1) and (B2) are commercially available products, and the property values shown in Table 2 are the values listed in the catalog.
Polytetramethylene glycol (B3) is polytetramethylene glycol whose crystallinity is lowered by partially introducing side chains into the main chain of tetramethylene ether at random. (B3) is PTG-L-2000 manufactured by Hodogaya Chemical Industry Co., Ltd., and has a crystal melting point of 9°C. The properties of (B3) are shown in Table 2. (B3) is a commercial product, and the property values shown in Table 2 are the values listed in the catalog.

(Raw material 3) Polyalkylene oxide (C)
(Raw material 3-1) Polyalkylene oxide (C) used in Examples
Polyalkylene oxides (C1), (C2) and (C3) are polyethylene glycol monomethyl ethers, each of which has one hydroxyl group and one ethylene oxide group. Table 3 shows the properties of (C1), (C2) and (C3), but (C1), (C2) and (C3) differ in molecular weight. All of (C1), (C2) and (C3) have a high ethylene oxide group content, and the higher the molecular weight, the higher the ethylene oxide group content.

Polyalkylene oxide (C4) is polyethylene glycol monobutyl ether, polyalkylene oxide (C5) is polyethylene glycol monostearyl ether, polyalkylene oxide (C6) is polyethylene glycol monolauryl ether, and polyalkylene oxide (C7) is polyethylene glycol octylphenyl ether. All of them consist of one hydroxyl group and one ethylene oxide group in one molecule. Table 3 shows the properties of (C4), (C5), (C6) and (C7).

Polyalkylene oxides (C8) and (C9) 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 (C8) and (C9) are shown in Table 3, and (C8) and (C9) differ in molecular weight and content ratio of ethylene oxide groups. Since (C8) and (C9) contain propylene oxide groups, the content ratio of ethylene oxide groups is low, and (C9) has an even lower content ratio of ethylene oxide groups than (C8).

(Raw material 3-2) Polyalkylene oxide (CC) used in Comparative Example
Polyalkylene oxide (CC1) is a polyethylene glycol having two hydroxyl groups in one molecule. Table 3 shows the properties of (CC1).

Polyalkylene oxides (CC2) are polypropylene glycol monomethyl ethers which do not contain ethylene oxide residues. Table 3 shows the properties of (CC2).

(Raw material 3) Isocyanate compounds (D) and (G) used in Examples and Comparative Examples
In Examples and Comparative Examples, the following three types were used as the isocyanate compounds (D) and (G).
Isocyanate compounds (D1) and (G1): The isocyanate compounds (D1) and (G1) are the same, and the names are used differently depending on the purpose of use. (D1) and (G1) are 1,6-hexamethylene diisocyanate (HDI)-based modified isocyanate Coronate HXLV manufactured by Tosoh Corporation. 3.2.
Isocyanate compound (D2): AQUANATE 105 manufactured by Tosoh Corporation, which is an HDI-based modified isocyanurate, and the average functional number of isocyanate groups in (D2) is 3.4.
Isocyanate compound (D3): (D3) is 1,6-hexamethylene diisocyanate (HDI). The average functionality of isocyanate groups in (D3) is 2.0.

(Raw material 4) Additive In the examples and comparative examples, a urethanization catalyst was added as an additive. Dioctyltin dilaurate (abbreviation: DOTDL) manufactured by 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, the solvent used was ethyl acetate manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd., or ethyl acetate manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd. of methyl ethyl ketone was used.

(Preparation of urethane-forming composition)
In Examples and Comparative Examples, materials other than polytetramethylene glycol (B) were liquid at room temperature, and polytetramethylene glycol (B) was stored at 50°C for about 30 minutes. I used the liquefied material. A predetermined amount of each raw material was placed in a 50 ml sample bottle, and stirred and defoamed at room temperature using a rotation/revolution mixer to obtain a urethane-forming composition. 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 urethane-forming composition solution is applied onto an untreated PET film (product name: Lumirror) with a thickness of 38 μm manufactured by Toray Industries, Inc. so that the thickness after drying becomes 100 μm or less. It was applied using a Baker applicator as follows. 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, the curability of the urethane-forming composition and the urethane-forming composition in its solution was evaluated over time by leaving the surface of the polyurethane coating film obtained in the process of standing for one week in an environment of 23° C. and 50% relative humidity. It was touched with a finger, 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>
⊚ (Acceptance of coating property): When the surface of the polyurethane coating film is smooth and the thickness difference between the center and the edge of the polyurethane coating film is less than 5% by visual observation.
◯ (acceptable coating properties): When visually observed, the surface of the polyurethane coating film is smooth, and the thickness difference between the center and the edge of the polyurethane coating film is in the range of 5 to 10%.
x (Failure for coating): The surface of the polyurethane coating film is rough when visually observed, or the thickness difference between the center and the edge of the polyurethane coating film exceeds 10%.

<Curability of urethane-forming composition>
⊚ (acceptable curability): When the sticky feeling almost disappears after standing for 1 day in an environment of 23°C and 50% relative humidity, and the sticky feeling does not change over time after holding for 3 days.
◯ (acceptable curability): When the sticky feeling is almost lost by standing for 1 to 3 days in an environment of 23° C. and a relative humidity of 50%, and the sticky feeling does not change over time after the holding for 7 days.
× (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, changing over time (curing is significantly slower).

Furthermore, regarding the tensile elongation at break and tensile strength at break of the polyurethane coating, a dumbbell test piece of ASTM 1822 was taken out (punched) from the polyurethane coating having a thickness of about 100 μm which had been coated and cured as described above. Using a tensile tester RTG-1210 manufactured by Kubota Co., Ltd., a tensile test was performed with a distance between the chucks of the tensile tester of 30 mm and a tensile speed of 50 mm / min. The elongation at break was calculated, and the stress at break of the test piece was defined as the tensile breaking strength, which was 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
⊚ (acceptable elongation): When the tensile elongation at break of the polyurethane coating film is 250% or more.
○ (acceptable elongation): when the tensile elongation at break of the polyurethane coating is from 150% to less than 250%.
x (failed elongation): When the tensile elongation at break of the polyurethane coating film is less than 150%.
<Tensile breaking strength of polyurethane coating film obtained from urethane-forming composition>
⊚ (acceptable strength): When the tensile breaking strength of the polyurethane coating film is 2 MPa or more.
○ (acceptable strength): when the tensile elongation at break of the polyurethane coating film is 1 MPa or more and less than 2 MPa.
x (strength failure): When the tensile elongation at break of the polyurethane coating film is less than 1 MPa.

Example 1 contains 80 parts by weight of polyalkylene oxide (A2), 20 parts by weight of polytetramethylene glycol (B2), 3 parts by weight of polyalkylene oxide (C1), an isocyanate compound (D1), and dioctyl as a urethanization catalyst. containing 0.03 parts by weight of tindyl laurate (DOTDL), the amount of hydroxyl groups (M _OH ) derived from (A2), (B2) and (C1) and the amount of isocyanate groups (M _NCO ) derived from (D1) are , the molar ratio of M _NCO of (D1)/M _OH of (A2) and (B2) and (C1) = 1.05 is a urethane-forming composition (E1). Table 4 shows the results of Example 1. The urethane-forming composition (E1) had good coatability and curability. The elongation and tensile breaking strength were large.

Comparative Example 1 contains 80 parts by weight of polyalkylene oxide (A2) and 20 parts by weight of polytetramethylene glycol (B2), which do not contain polyalkylene oxide (C1) with respect to Example 1, and an isocyanate compound (D1) Containing 0.03 parts by weight of DOTDL as a urethanization catalyst, the amount of hydroxyl groups (M _OH ) derived from (A2) and (B2) and the amount of isocyanate groups (M _NCO ) derived from (D1) are in a molar ratio , M _NCO of (D1)/M _OH of (A2) and (B2) = 1.05. The results of Comparative Example 1 are shown in Table 4. Since the composition (DC1) does not contain (B1), the composition (DC1) is inferior in coatability.

A reference example contains 90 parts by weight of polyalkylene oxide (A3), 10 parts by weight of polytetramethylene glycol (B1), 5 parts by weight of polyalkylene oxide (C3), and an isocyanate compound (D1) and 0.5 parts of DOTDL as a urethanization catalyst. 03 parts by weight, and the amount of hydroxyl groups (M _OH ) derived from (A3), (B1) and (C3) and the amount of isocyanate groups (M _NCO ) derived from (D1) are equal to the M _NCO of (D1) / A urethane-forming composition (E2) of (A3), (B1) and (C3) with M _OH =1.05. The results of Reference Examples are shown in Table 4. The urethane-forming composition (E2) had good coatability and curability. and tensile strength at break were large.

Comparative Example 2 contains 100 parts by weight of polyalkylene oxide (A3) and 5 parts by weight of polyalkylene oxide (C3), which does not contain polytetramethylene glycol (B1) compared to Reference Example , and an isocyanate compound (D1) and urethane containing 0.03 parts by weight of DOTDL as a conversion catalyst, the amount of hydroxyl groups (M _OH ) derived from (A3) and (C3) and the amount of isocyanate groups (M _NCO ) derived from (D1) are, in molar ratio, A urethane-forming composition (EC2) in which M _NCO of (D1)/M _OH of (A3) and (C3) = 1.05. Table 4 shows the results of Comparative Example 2. Since the composition (EC2) contains (C3), the composition (EC2) has good coatability, but since it does not contain (B1), the composition (EC2) The obtained coating film of polyurethane (JC2) had a somewhat small tensile elongation at break and a small tensile strength at break.

Example 3 contains 60 parts by weight of polyalkylene oxide (A5), 40 parts by weight of polytetramethylene glycol (B3), 2 parts by weight of polyalkylene oxide (C2), and an isocyanate compound (D3) and DOTDL0 as a urethanization catalyst. .03 parts by weight, and the amount of hydroxyl groups (M _OH ) derived from (A5), (B3) and (C2) and the amount of isocyanate groups (M _NCO ) derived from (D3) are equal to M of (D3) A urethane-forming composition (E3) of _NCO /(A5), (B3) and (C2) with M _OH =1.05. Table 4 shows the results of Example 3. The urethane-forming composition (E3) had good coatability and curability. The elongation and tensile breaking strength were large.
Comparative Example 3 contains 100 parts by weight of polyalkylene oxide (A5), an isocyanate compound (D3), and a urethanization catalyst that does not contain polytetramethylene glycol (B3) and polyalkylene oxide (C3) with respect to Example 3. DOTDL contains 0.03 parts by weight, and the amount of hydroxyl groups (M _OH ) derived from (A5) and the amount of isocyanate groups (M _NCO ) derived from (D3) are in a molar ratio of M _NCO of (D3) / ( A5) urethane-forming composition (EC3) with M _OH =1.05. Table 4 shows the results of Comparative Example 3. Since the composition (EC3) does not contain (C3), the composition (EC3) has poor coatability, and (A5) is trifunctional and has a relatively low molecular weight. , (B3), the polyurethane (JC3) coating film obtained from the composition (EC3) had a low tensile elongation at break and a low tensile strength at break.

Example 4 contains 80 parts by weight of polyalkylene oxide (A1), 20 parts by weight of polytetramethylene glycol (B1), 2 parts by weight of polyalkylene oxide (C2), and a mixture of isocyanate compounds (D2) and (D3) and urethane 0.03 parts by weight of DOTDL as a conversion catalyst, the amount of hydroxyl groups (M OH ) derived from (A1), (B1) and (C2) and the amount of isocyanate groups (M _OH ) derived from (D2) and (D3) _NCO ) is reacted with a urethane-forming composition (E4) in a molar ratio of M _NCO of (D2) and (D3)/M _OH of (A1) and (B1) and (C2) = 0.80 and the isocyanate compound (G1), the amount of hydroxyl groups (M _OH ) derived from the prepolymer (F1) and the amount of isocyanate groups (M _NCO ) derived from (G1) are A urethane-forming composition (H1) having a molar ratio of M _NCO of (G1)/M _OH of (F1) = 1.05. Table 5 shows the results of Example 4. The urethane-forming composition (H1) had good coatability and curability. The elongation and tensile breaking strength were large.

Comparative Example 4 contains 80 parts by weight of polyalkylene oxide (A1) and 20 parts by weight of polytetramethylene glycol (B1), which do not contain polyalkylene oxide (C2) with respect to Example 4, and an isocyanate compound (D2) Containing a mixture of (D3) and 0.03 parts by weight of DOTDL as a urethanization catalyst, the amount of hydroxyl groups (M _OH ) derived from (A1) and (B1) and the amount of isocyanate groups derived from (D2) and (D3) By reacting a urethane-forming composition (EC4) in which the amount (M _NCO ) is, in a molar ratio, M _NCO of (D2) and (D3)/M _OH of (A1) and (B1) = 0.80 The obtained prepolymer (FC1) and an isocyanate compound (G1) are contained, and the amount of hydroxyl groups (M _OH ) derived from the prepolymer (FC1) and the amount of isocyanate groups (M _NCO ) derived from (G1) are mol It is a urethane-forming composition (HC1) with a ratio of (M _NCO ) of (G1)/M _OH of (FC1) = 1.05. The results of Comparative Example 4 are shown in Table 5. Since the composition (HC1) does not contain (C2), the composition (HC1) is inferior in coatability.

Example 5 contains 70 parts by weight of polyalkylene oxide (A3), 10 parts by weight of polyalkylene oxide (A7), 20 parts by weight of polytetramethylene glycol (B2), 2 parts by weight of polyalkylene oxide (C1), and an isocyanate compound (D3) and 0.03 parts by weight of DOTDL as a urethanization catalyst, and the amount of hydroxyl groups (M _OH ) derived from (A3), (A7), (B2) and (C1) and isocyanate derived from (D3) The amount of groups (M _NCO ) is a _urethane -forming _composition (E5 ) obtained by reacting a prepolymer (F2) and an isocyanate compound (G1), the amount of hydroxyl groups (M _OH ) derived from the prepolymer (F2) and the amount of isocyanate groups derived from (G1) ( M _NCO ) is the urethane-forming composition (H2) with a molar ratio of (M _NCO ) of (G1)/M _OH of (F2) = 1.05. Table 5 shows the results of Example 5. The urethane-forming composition (H2) had good coatability and curability. The elongation and tensile breaking strength were large.

Comparative Example 5 contains 87.5 parts by weight of polyalkylene oxide (A3), 12.5 parts by weight of polyalkylene oxide (A7), and polyalkylene oxide ( C1) 2 parts by weight, and containing 0.03 parts by weight of DOTDL as an isocyanate compound (D3) and a urethanization catalyst, and the amount of hydroxyl groups derived from (A3), (A7) and (C1) (M _OH ) and ( A urethane-forming composition in which the amount (M _NCO ) of isocyanate groups derived from D3) is, in a molar ratio, M _NCO of (D3)/M _OH of (A3), (A7) and (C1) = 0.85 The prepolymer (FC2) obtained by reacting (EC5) and an isocyanate compound (G1) containing the amount of hydroxyl groups (M _OH ) derived from the prepolymer (FC2) and the number of isocyanate groups derived from (G1) The amount (M _NCO ) is the urethane-forming composition (HC2) with a molar ratio of M _NCO of (G1)/M _OH of (FC2) = 1.05. Table 5 shows the results of Comparative Example 5. Since (B1) is not included, the coating film of polyurethane (JC5) obtained from the composition (HC2) has a tensile elongation at break of was somewhat smaller, and the tensile strength at break was smaller.

Example 6 contains 90 parts by weight of polyalkylene oxide (A6), 10 parts by weight of polytetramethylene glycol (B2), 2 parts by weight of polyalkylene oxide (C1), and an isocyanate compound (D3) and DOTDL0 as a urethanization catalyst. .03 parts by weight, and the amount of hydroxyl groups (M _OH ) derived from (A6), (B2) and (C1) and the amount of isocyanate groups (M _NCO ) derived from (D3) are, in molar ratio, ( A prepolymer (F3) obtained by reacting M _NCO of D3)/a urethane-forming composition (E6) having M _OH of (A6), (B2) and (C1) = 0.75, and an isocyanate compound ( G1), and the amount of hydroxyl groups (M _OH ) derived from the prepolymer (F3) and the amount of isocyanate groups (M _NCO ) derived from (G1) are in a molar ratio of (M _NCO ) of (G1)/ The urethane-forming composition (H3) of (F3) with M _OH =1.05. Table 5 shows the results of Example 6. The urethane-forming composition (H3) had good coatability and curability. The elongation and tensile breaking strength were large.

Comparative Example 6 contains 100 parts by weight of a polyalkylene oxide (A6), an isocyanate compound (D3), and a urethanization catalyst that does not contain polytetramethylene glycol (B2) and polyalkylene oxide (C1) with respect to Example 6. DOTDL contains 0.03 parts by weight, and the amount of hydroxyl groups (M _OH ) derived from (A6) and the amount of isocyanate groups (M _NCO ) derived from (D3) are in a molar ratio of M _NCO of (D3) / ( The prepolymer (FC3) obtained by reacting the urethane-forming composition (EC6) having M _OH = 0.75 in A6) and the isocyanate compound (G1), containing hydroxyl groups derived from the prepolymer (FC3) The amount (M _OH ) and the amount (M _NCO ) of isocyanate groups derived from (G1) are in a molar ratio of M _NCO of (G1)/M _OH of (FC3) = 1.05 in the urethane-forming composition ( HC3). Table 5 shows the results of Comparative Example 6. Since the composition (HC3) does not contain (C1), the composition (HC3) has poor coatability, and since it does not contain (B2), the composition (HC3) The obtained coating film of polyurethane (JC6) had somewhat low tensile elongation at break and low tensile strength at break.

Example 7 contains 70 parts by weight of polyalkylene oxide (A2), 30 parts by weight of polytetramethylene glycol (B1), 0.5 parts by weight of polyalkylene oxide (C3), and isocyanate compounds (D2) and (D3). The mixture contains 0.03 parts by weight of DOTDL as a urethanization catalyst, and the amount of hydroxyl groups (M _OH ) derived from (A2), (B1) and (C3) and the amount of isocyanate groups derived from (D2) and (D3) The amount (M _NCO ) is the urethane-forming composition (E7), in a molar ratio of M _NCO of (D2) and (D3)/M _OH of (A2), (B1) and (C3) = 0.55. The prepolymer (F4) obtained by the reaction and the isocyanate compound (G1) containing the amount of hydroxyl groups (M _OH ) derived from the prepolymer (F4) and the amount of isocyanate groups derived from (G1) (M _NCO ) is a urethane-forming composition solution obtained by adding ethyl acetate as an organic solvent to a urethane-forming composition (H4) having a molar ratio of M _NCO of (G1) / M _OH of (F4) = 1.2 ( I1). The concentration of (H4) in the solution (I1) is 50%. Table 6 shows the results of Example 7. The urethane-forming composition solution (I1) had good coatability and curability, and the coating film of polyurethane (J7) obtained from composition solution (I1) was The tensile elongation at break and tensile strength at break were large.

Comparative Example 7 contains 70 parts by weight of polyalkylene oxide (A2) and 30 parts by weight of polytetramethylene glycol (B1), which do not contain polyalkylene oxide (C3) with respect to Example 6, and an isocyanate compound (D2) Containing a mixture of (D3) and 0.03 parts by weight of DOTDL as a urethanization catalyst, the amount of hydroxyl groups (M _OH ) derived from (A2) and (B1) and the amount of isocyanate groups derived from (D2) and (D3) By reacting a urethane-forming composition (EC7) in which the amount (M _NCO ) is, in a molar ratio, M _NCO of (D2) and (D3)/M _OH of (A2) and (B1) = 0.55 The obtained prepolymer (FC4) and an isocyanate compound (G1) are contained, and the amount of hydroxyl groups (M _OH ) derived from the prepolymer (FC4) and the amount of isocyanate groups (M _NCO ) derived from (G1) are mol A urethane-forming composition solution (IC1) obtained by adding ethyl acetate as an organic solvent to a urethane-forming composition (HC4) having a ratio of M _NCO of (G1)/M _OH of (FC4) = 1.2. . The concentration of (HC4) in the solution (IC1) is 50%. The results of Comparative Example 7 are shown in Table 6. Since the composition solution (IC1) does not contain (C3), the composition solution (IC1) is inferior in coatability.

Example 8 contains 80 parts by weight of polyalkylene oxide (A4), 20 parts by weight of polytetramethylene glycol (B2), 1 part by weight of polyalkylene oxide (C2), and a mixture of isocyanate compounds (D2) and (D3) Contains 0.03 parts by weight of DOTDL as a urethanization catalyst, the amount of hydroxyl groups (M _O ) derived from (A4), (B2) and (C2) and the amount of isocyanate groups derived from (D2) and (D3) ( M _NCO ) is reacted, in a molar ratio, with M _NCO of (D2) and (D3)/M _OH of (A4), (B2) and (C2) = 0.65 urethane-forming composition (E8) and the isocyanate compound (G1), the amount of hydroxyl groups (M _OH ) derived from the prepolymer (F5) and the amount of isocyanate groups (M _NCO ) derived from (G1) are A urethane-forming composition solution (I2) obtained by adding ethyl acetate as an organic solvent to a urethane-forming composition (H5) having a molar ratio of M _NCO of (G1) / M _OH of (F5) = 1.5. be. The concentration of (H5) in the solution (I2) is 50%. Table 6 shows the results of Example 8. The composition solution (I2) had good coatability and curability. strength was great.

Comparative Example 8 contains 100 parts by weight of polyalkylene oxide (A4) and 1 part by weight of polyalkylene oxide (C2), which does not contain polytetramethylene glycol (B2) with respect to Example 8, and an isocyanate compound (D2) Containing a mixture of (D3) and 0.03 parts by weight of DOTDL as a urethanization catalyst, the amount of hydroxyl groups (M _OH ) derived from (A4) and (C2) and the amount of isocyanate groups derived from (D2) and (D3) By reacting a urethane-forming composition (EC8) in which the amount (M _NCO ) is, in a molar ratio, M _NCO of (D2) and (D3)/M _OH of (A4) and (C2) = 0.65 The obtained prepolymer (FC5) and an isocyanate compound (G1) are included, and the amount of hydroxyl groups (M _OH ) derived from the prepolymer (FC5) and the amount of isocyanate groups (M _NCO ) derived from (G1) are mol A urethane-forming composition solution (IC2) obtained by adding ethyl acetate as an organic solvent to a urethane-forming composition (HC5) having a ratio of M _NCO of (G1) / M _OH of (FC5) = 1.5. . The concentration of (HC5) in the solution (IC2) is 50%. Table 6 shows the results of Comparative Example 8. Since it contains (C2), the composition solution (IC2) has good coatability, but because it does not contain (B2), the composition solution (IC2 ) had a slightly lower tensile elongation at break and a lower tensile strength at break.

Example 9 contains 70 parts by weight of polyalkylene oxide (A2), 10 parts by weight of polyalkylene oxide (A5), 20 parts by weight of polytetramethylene glycol (B3), 2 parts by weight of polyalkylene oxide (C3), and an isocyanate compound (D3) and 0.03 parts by weight of DOTDL as a urethanization catalyst, and the amount of hydroxyl groups derived from (A2), (A5), (B3) and (C3), derived from (M _OH ) and (D3) The _{urethane -} forming composition ₍ E9) containing a prepolymer (F6) obtained by reacting an isocyanate compound (G1), the amount of hydroxyl groups (M _OH ) derived from the prepolymer (F6) and the amount of isocyanate groups derived from (G1) (M _NCO ) is a urethane-forming composition obtained by adding methyl ethyl ketone as an organic solvent to a urethane-forming composition (H6) in which the molar ratio of M _NCO of (G1)/M _OH of (F6) is 1.5. Solution (I4). The concentration of (H6) in the solution (I4) is 50%. The results of Example 9 are shown in Table 6. The composition solution (I4) had good coatability and curability. strength was great.

Comparative Example 9 contains 87.5 parts by weight of polyalkylene oxide (A2) and 12.5 parts by weight of polyalkylene oxide (A5), which does not contain polytetramethylene glycol (B3) and polyalkylene oxide (C3) compared to Example 9. parts by weight, and an isocyanate compound (D3) and 0.03 parts by weight of DOTDL as a urethanization catalyst, the amount of hydroxyl groups derived from (A2) and (A5) (M _OH ) and isocyanate groups derived from (D3) (M _NCO ), in a molar ratio, the preform obtained by reacting the urethane-forming composition (EC9) with M _NCO of (D3)/M _OH of (A2) and (A5) = 1.5 The polymer (FC5) and the isocyanate compound (G1) are contained, and the amount of hydroxyl groups (M _OH ) derived from the prepolymer (FC6) and the amount of isocyanate groups (M _NCO ) derived from (G1) are, in molar ratio, A urethane-forming composition solution (IC4) obtained by adding methyl ethyl ketone as an organic solvent to the urethane-forming composition (HC6) of (G1) M _NCO /(FC6) M _OH =1.5. The concentration of (HC6) in the solution (IC4) is 50%. Table 6 shows the results of Comparative Example 9. Since the composition solution (IC4) does not contain (C3), the composition solution (IC4) is inferior in coatability, and because it does not contain (B3), the composition solution (IC4 ) had a slightly lower tensile elongation at break and a lower tensile strength at break.

Example 10 contains 80 parts by weight of polyalkylene oxide (A3), 20 parts by weight of polytetramethylene glycol (B1), 2 parts by weight of polyalkylene oxide (C4), and a mixture of isocyanate compounds (D2) and (D3) Contains 0.03 parts by weight of DOTDL as a urethanization catalyst, the amount of hydroxyl groups (M _OH ) derived from (A3), (B1) and (C4) and the amount of isocyanate groups derived from (D2) and (D3) ( M _NCO ) is reacted, in a molar ratio, with M _NCO of (D2) and (D3)/M _OH of (A3), (B1) and (C4) = 0.60 urethane-forming composition (E10) and the isocyanate compound (G1), and the amount of hydroxyl groups (M _OH ) derived from the prepolymer (F7) and the amount of isocyanate groups (M _NCO ) of (G1) are A urethane-forming composition solution (I4) obtained by adding ethyl acetate as an organic solvent to a urethane-forming composition (H7) having a ratio of M _NCO of (G1)/M _OH of (F7) = 2.0. . The concentration of (H7) in the solution (I4) is 70%. Table 7 shows the results of Example 10. The composition solution (I4) had good coatability and curability. strength was great.

Example 11 contains 70 parts by weight of polyalkylene oxide (A2), 30 parts by weight of polytetramethylene glycol (B1), 2 parts by weight of polyalkylene oxide (C5), and a mixture of isocyanate compounds (D2) and (D3) Contains 0.03 parts by weight of DOTDL as a urethanization catalyst, the amount of hydroxyl groups (M _OH ) derived from (A2), (B1) and (C5) and the amount of isocyanate groups derived from (D2) and (D3) ( M _NCO ) is reacted, in a molar ratio, with M _NCO of (D2) and (D3)/M _OH of (A2), (B1) and (C5) = 0.60 urethane-forming composition (E11) and the isocyanate compound (G1), the amount of hydroxyl groups (M _OH ) derived from the prepolymer (F8) and the amount of isocyanate groups (M _NCO ) of (G1) are A urethane-forming composition solution (I5) obtained by adding methyl ethyl ketone as an organic solvent to the urethane-forming composition (H8) having a ratio of M _NCO of (G1)/M _OH of (F8) = 2.0. The concentration of (H8) in the solution (I5) is 70%. Table 7 shows the results of Example 11. The composition solution (I5) had good coatability and curability. strength was great.

Example 12 contains 60 parts by weight of polyalkylene oxide (A1), 40 parts by weight of polytetramethylene glycol (B2), 2 parts by weight of polyalkylene oxide (C6), and a mixture of isocyanate compounds (D2) and (D3) Contains 0.03 parts by weight of DOTDL as a urethanization catalyst, the amount of hydroxyl groups (M _OH ) derived from (A1), (B2) and (C6) and the amount of isocyanate groups derived from (D2) and (D3) ( M _NCO ) is reacted, in a molar ratio, with M _NCO of (D2) and (D3)/M _OH of (A1), (B2) and (C6) = 0.60 urethane-forming composition (E12) and the isocyanate compound (G1), and the amount of hydroxyl groups (M _OH ) derived from the prepolymer (F9) and the amount of isocyanate groups (M _NCO ) of (G1) are A urethane-forming composition solution (I6) obtained by adding ethyl acetate as an organic solvent to a urethane-forming composition (H9) having a ratio of M _NCO of (G1)/M _OH of (F9) = 2.0. . The concentration of (H9) in the solution (I6) is 70%. Table 7 shows the results of Example 12. The composition solution (I6) had good coatability and curability. strength was great.

Example 13 contains 70 parts by weight of polyalkylene oxide (A2), 30 parts by weight of polytetramethylene glycol (B1), 2 parts by weight of polyalkylene oxide (C7), and a mixture of isocyanate compounds (D2) and (D3) Contains 0.03 parts by weight of DOTDL as a urethanization catalyst, the amount of hydroxyl groups (M _OH ) derived from (A2), (B1) and (C7) and the amount of isocyanate groups derived from (D2) and (D3) ( M _NCO ) is reacted, in a molar ratio, with M _NCO of (D2) and (D3)/M _OH of (A2), (B1) and (C7) = 0.60 urethane-forming composition (E13) and the isocyanate compound (G1), and the amount of hydroxyl groups (M _OH ) derived from the prepolymer (F10) and the amount of isocyanate groups (M _NCO ) of (G1) are A urethane-forming composition solution (I6) obtained by adding ethyl acetate as an organic solvent to a urethane-forming composition (H10) having a ratio of M _NCO of (G1)/M _OH of (F10) = 2.0. . The concentration of (H10) in the solution (I6) is 40%. Table 7 shows the results of Example 13. The composition solution (I6) had good coatability and curability. strength was great.

Example 14 contains 70 parts by weight of polyalkylene oxide (A3), 30 parts by weight of polytetramethylene glycol (B1), 2 parts by weight of polyalkylene oxide (C8), and a mixture of isocyanate compounds (D2) and (D3) Contains 0.03 parts by weight of DOTDL as a urethanization catalyst, the amount of hydroxyl groups (M _OH ) derived from (A3), (B1) and (C8) and the amount of isocyanate groups derived from (D2) and (D3) ( M _NCO ) is reacted, in a molar ratio, with M _NCO of (D2) and (D3)/M _OH of (A3), (B1) and (C8) = 0.60 urethane-forming composition (E14) and the isocyanate compound (G1), and the amount of hydroxyl groups (M _OH ) derived from the prepolymer (F11) and the amount of isocyanate groups (M _NCO ) of (G1) are A urethane-forming composition solution (I8) obtained by adding ethyl acetate as an organic solvent to a urethane-forming composition (H11) having a ratio of M _NCO of (G1)/M _OH of (F11) = 2.0. . The concentration of (H11) in the solution (I8) is 40%. Table 7 shows the results of Example 14. The composition solution (I8) had good coatability and curability. strength was great.

Example 15 contains 70 parts by weight of polyalkylene oxide (A2), 30 parts by weight of polytetramethylene glycol (B3), 2 parts by weight of polyalkylene oxide (C9), and a mixture of isocyanate compounds (D2) and (D3) Contains 0.03 parts by weight of DOTDL as a urethanization catalyst, the amount of hydroxyl groups (M _OH ) derived from (A2), (B3) and (C9) and the amount of isocyanate groups derived from (D2) and (D3) ( M _NCO ) is reacted, in a molar ratio, with M _NCO of (D2) and (D3)/M _OH of (A2), (B3) and (C9) = 0.60 urethane-forming composition (E15) and the isocyanate compound (G1), and the amount of hydroxyl groups (M _OH ) derived from the prepolymer (F12) and the amount of isocyanate groups (M _NCO ) of (G1) are A urethane-forming composition solution (I9) obtained by adding ethyl acetate as an organic solvent to a urethane-forming composition (H12) having a ratio of M _NCO of (G1)/M _OH of (F12) = 2.0. . The concentration of (H12) in the solution (I9) is 50%. Table 7 shows the results of Example 15. The composition solution (I9) had good coatability and curability. strength was great.

Comparative Example 10 contains 80 parts by weight of polyalkylene oxide (AC1), 20 parts by weight of polytetramethylene glycol (B1), 3 parts by weight of polyalkylene oxide (C2), and an isocyanate compound (D1) and DOTDL0 as a urethanization catalyst. .03 parts by weight, and the amount of hydroxyl groups (M _OH ) derived from (AC1), (B1), and (C2) and the amount of isocyanate groups (M _NCO ) derived from (D1) are in a molar ratio of ( M _NCO of D1)/M _OH of (AC1) and (B1) and (C2) = 1.05 urethane-forming composition (EC10), where (AC1) has a high degree of unsaturation and falls outside the scope of the claim It is a polyalkylene oxide. Table 8 shows the results of Comparative Example 10. Since (AC1) has a high degree of unsaturation (many unsaturated monools), it has excellent coatability but poor curability. The polyurethane (JC10) coating film obtained from the composition (EC10) had a large tensile elongation at break, but a small tensile strength at break. In addition, the surface of the coating film was sticky due to the large amount of unsaturated monool.

Comparative Example 11 contains 80 parts by weight of polyalkylene oxide (AC2), 20 parts by weight of polytetramethylene glycol (B2), 3 parts by weight of polyalkylene oxide (C3), and an isocyanate compound (D1) and DOTDL0 as a urethanization catalyst. .03 parts by weight, and the amount of hydroxyl groups (M _OH ) derived from (AC2), (B2) and (C3) and the amount of isocyanate groups (M _NCO ) derived from (D1) are, in molar ratio, ( M _NCO of D1)/M OH of (AC2) and (B2) and (C3) is a urethane-forming composition (EC11) having a M _OH of 1.05, and (AC2) has a high degree of unsaturation and falls outside the scope of the claim. It is a polyalkylene oxide. The results of Comparative Example 11 are shown in Table 8. Since (AC2) has a considerably high degree of unsaturation (consisting of a considerably large amount of unsaturated monools), it has excellent coatability but poor curability. Curability was improved by increasing the average number of isocyanate functional groups (D1) and increasing the amount of DOTDL as a urethanization catalyst to 0.1 parts by weight, but the degree of unsaturation The curability of a composition using a polyalkylene oxide with a high (high unsaturated monool) polyalkylene oxide is forcibly accelerated. Since (AC2) contains a large amount of unsaturated monool, the coating film of polyurethane (JC11) obtained from the composition (EC11) had low tensile elongation at break and low tensile strength at break. In addition, the surface of the coating film was considerably sticky due to the large amount of unsaturated monool.

Comparative Example 12 contains 80 parts by weight of polyalkylene oxide (AC3), polytetramethylene glycol (B3) and 3 parts by weight of polyalkylene oxide (C3), and an isocyanate compound (D3) and 0.03 weight of DOTDL as a urethanization catalyst. part, the amount of hydroxyl groups (M _OH ) derived from (AC3), (B3) and (C3) and the amount of isocyanate groups (M _NCO ) derived from (D3) are in a molar ratio of (D3) M _NCO /Urethane-forming composition (EC12) with M _OH =1.05 of (AC3) and (B3) and (C3), where (AC3) has a high degree of unsaturation and is a polyalkylene oxide outside the scope of the claim is. Table 8 shows the results of Comparative Example 12. Since (AC3) has a high degree of unsaturation (many unsaturated monools), it is excellent in coatability and has a large average number of isocyanate functional groups (D1 ), and by increasing the amount of DOTDL as a urethanization catalyst to 0.1 parts by weight, the curability was good, but the degree of unsaturation was high (there were many unsaturated monools). The curability of the composition using polyalkylene oxide is forcibly accelerated. Since (AC2) contains a large amount of unsaturated monool, the coating film of polyurethane (JC12) obtained from the composition (EC12) formed a dense crosslinked structure and had a small tensile elongation at break. In addition, the surface of the coating film was very sticky due to the large amount of unsaturated monools.

Comparative Example 13 contains 80 parts by weight of polyalkylene oxide (AC1), 20 parts by weight of polytetramethylene glycol (B1), 3 parts by weight of polyalkylene oxide (C1), and a mixture of isocyanate compounds (D2) and (D3) Contains 0.03 parts by weight of DOTDL as a urethanization catalyst, the amount of hydroxyl groups (M _OH ) derived from (AC1), (B1) and (C1) and the amount of isocyanate groups derived from (D2) and (D3) ( M _NCO ) are reacted, in molar ratio, M _NCO of (D2) and (D3)/M _OH of (AC1) and (B1) and (C1) = 0.85 urethane-forming composition (EC13) _and the isocyanate compound (G1 ₎ . A urethane-forming composition solution (IC5) obtained by adding ethyl acetate as an organic solvent to a urethane-forming composition (HC7) having a molar ratio of M _NCO of (G1)/M _OH of (FC7) = 2.0. is. The concentration of (HC7) in the solution (IC5) is 50%. Table 9 shows the results of Comparative Example 13. Since (AC1) has a high degree of unsaturation (contains a large amount of unsaturated monools), (IC5) has excellent coatability but poor curability. rice field. The coating film of polyurethane (JC13) obtained from the solution (IC5) had somewhat low tensile elongation at break and somewhat low tensile strength at break. Moreover, the surface of the coating film was sticky due to the large amount of unsaturated monool.

Comparative Example 14 contains 70 parts by weight of polyalkylene oxide (AC2), 30 parts by weight of polytetramethylene glycol (B2), 3 parts by weight of polyalkylene oxide (C2), and a mixture of isocyanate compounds (D2) and (D3) Contains 0.03 parts by weight of DOTDL as a urethanization catalyst, the amount of hydroxyl groups (M _OH ) derived from (AC2), (B2) and (C2) and the amount of isocyanate groups derived from (D2) and (D3) ( M _NCO ) is reacted, in molar ratio, M _NCO of (D2) and (D3)/M _OH of (AC2) and (B2) and (C2) = 0.85 urethane-forming composition (EC14) and the isocyanate compound (G1), the amount of hydroxyl groups (M _OH ) derived from the prepolymer (FC8) and the amount of isocyanate groups (M _NCO ) derived from (G1) are A urethane-forming composition solution (IC6) obtained by adding ethyl acetate as an organic solvent to a urethane-forming composition (HC8) having a molar ratio of M _NCO of (G1)/M _OH of (FC8) = 2.0. is. The concentration of (HC8) in the solution (IC6) is 50%. Table 9 shows the results of Comparative Example 14. Since (AC2) has a higher degree of unsaturation (more unsaturated monools) than (AC1) used in Comparative Example 13, (IC6) has good coatability. Although it was excellent in hardening property, it was inferior in curability. Since the degree of unsaturation of (AC2) is quite high, the coating film of polyurethane (JC14) obtained from the solution (IC6) had a low tensile elongation at break and a low tensile strength at break. Moreover, the surface of the coating film was sticky due to the large amount of unsaturated monool.

Comparative Example 15 contains 80 parts by weight of polyalkylene oxide (AC4), 20 parts by weight of polytetramethylene glycol (B1), 2 parts by weight of polyalkylene oxide (C3), and a mixture of isocyanate compounds (D2) and (D3) Contains 0.03 parts by weight of DOTDL as a urethanization catalyst, the amount of hydroxyl groups (M _OH ) derived from (AC4), (B1) and (C3) and the amount of isocyanate groups derived from (D2) and (D3) ( M _NCO ) are reacted, in molar ratio, M _NCO of (D2) and (D3)/M _OH of (AC4) and (B1) and (C3) = 0.90 urethane-forming composition (EC15) The prepolymer (FC9) obtained by and the isocyanate compound (G1) are included, and the amount of hydroxyl groups (M _OH ) derived from the prepolymer (FC9) and the amount of isocyanate groups (M _NCO ) derived from (G1) are A urethane-forming composition solution (IC7) obtained by adding ethyl acetate as an organic solvent to a urethane-forming composition (HC9) having a molar ratio of M _NCO of (G1)/M _OH of (FC9) = 2.0. is. The concentration of (HC9) in the solution (IC7) is 50%. Table 9 shows the results of Comparative Example 15. Although (IC7) is excellent in coatability and curability, (AC4) has a low molecular weight, so the polyurethane (JC15) coating film obtained from (IC7) A dense cross-linked structure was formed and the tensile elongation at break was small.

Comparative Example 16 contains 70 parts by weight of polyalkylene oxide (A2), 30 parts by weight of polytetramethylene glycol (B3), 1 part by weight of polyalkylene oxide (CC1), and a mixture of isocyanate compounds (D2) and (D3). Contains 0.03 parts by weight of DOTDL as a urethanization catalyst, the amount of hydroxyl groups (M _OH ) derived from (A2), (B3) and (CC1) and the amount of isocyanate groups derived from (D2) and (D3) ( M _NCO ) is reacted in a molar ratio of M _NCO of (D2) and (D3)/M _OH of (A2) and (B3) and (CC1) = 0.85 urethane-forming composition (EC16) The prepolymer (FC10) obtained by and the isocyanate compound (G1) are contained, and the amount of hydroxyl groups (M _OH ) derived from the prepolymer (FC10) and the amount of isocyanate groups (M _NCO ) derived from (G1) are A urethane-forming composition solution (IC8) obtained by adding ethyl acetate as an organic solvent to a urethane-forming composition (HC10) having a molar ratio of M _NCO of (G1)/M _OH of (FC10) = 2.0. is. The concentration of (HC10) in the solution (IC8) is 50%. Table 9 shows the results of Comparative Example 16. Since (CC1) has two hydroxyl groups in one molecule, the prepolymer obtained by reaction with a mixture of isocyanate compounds (D2) and (D3) is densely crosslinked. Even when a structure is formed and the composition solution (IC8) is applied, the solution does not flow well and the coatability is remarkably poor, and the resulting polyurethane (JC16) coating film has a remarkably poor surface appearance. It was something.

Comparative Example 17 contains 70 parts by weight of polyalkylene oxide (A2), polytetramethylene glycol (B1) and 3 parts by weight of polyalkylene oxide (CC2), and a mixture of isocyanate compounds (D2) and (D3) and a urethanization catalyst. and the amount of hydroxyl groups (M _{OH )} derived from (A2), (B1) and (CC2) and the amount of isocyanate groups (M _NCO ) derived from (D2) and (D3). reacts a urethane-forming composition (EC17) with a molar ratio of M _NCO of (D2) and (D3)/M _OH of (A2) and (A2) and (B1) and (CC2) = 0.80. and the isocyanate compound (G1), the amount of hydroxyl groups (M _OH ) derived from the prepolymer (FC11) and the amount of isocyanate groups (M _NCO ) derived from (G1) is a urethane-forming _composition solution ( _IC9 ). The concentration of (HC11) in the solution (IC9) is 50%. Table 9 shows the results of Comparative Example 17. Since the alkylene oxide (CC2) does not contain an ethylene oxide residue, the composition solution (IC9) has poor coatability.

As described above in the examples, the urethane-forming composition in the present development is excellent in coatability when applied with a coating machine or the like, and can be combined with isocyanate compounds without using a large amount of urethane catalyst. It has high productivity by promoting curing (solidification) accompanying the reaction, and furthermore, a polyurethane having high tensile elongation at break and high tensile strength at break can be obtained by reaction with an isocyanate compound. 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 (15)

Propylene oxide residue, 1,2-butylene oxide residue, 2,3-butylene oxide residue, isobutylene oxide residue, butadiene monoxide residue, pentene oxide residue having 3 or more carbon atoms in one molecule , a polyalkylene oxide (A) having at least one alkylene oxide residue and two or more hydroxyl groups from the group consisting of a styrene oxide residue and a cyclohexene oxide residue;
Polytetramethylene glycol (B) containing tetramethylene-ether in one molecule and having two or more hydroxyl groups,
A polyalkylene oxide (C) containing one hydroxyl group and an ethylene oxide residue in one molecule;
and an isocyanate compound (D) having an average functionality of isocyanate groups of 2.0 or more,
The polyalkylene oxide (A) is
The degree of unsaturation is 0.010 meq/g or less,
number average molecular weight is 800 or more,
and a urethane-forming composition (E) in which the weight ratio of the polyalkylene oxide (C) to 100 parts by weight of the polyalkylene oxide (A) is 5/7 or more and 3.75 or less. 2. The urethane-forming composition (E) according to claim 1, wherein the alkylene oxide residue having 3 or more carbon atoms is a propylene oxide residue. The polyalkylene oxide (C) 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-forming composition (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-forming composition (E) according to any one of claims 1 to 3, characterized by having a number of hydroxyl groups and a number average molecular weight calculated from the number of hydroxyl groups. A urethane prepolymer (F) that is a reaction product of the urethane-forming composition (E) according to any one of claims 1 to 4,
The urethane prepolymer (F) has at least one hydroxyl group in one molecule,
Among the urethane-forming composition ₍ E), the isocyanate compound (D ) in which the ratio (M _NCO /M _OH ) of the amount (M _NCO ) of isocyanate groups derived from ) is less than 1.0 in terms of molar ratio. A urethane-forming composition (H) comprising the urethane prepolymer (F) according to claim 5 and an isocyanate compound (G). The urethane-forming composition (E) according to any one of claims 1 to 4;
A urethane-forming composition solution (I) comprising an organic solvent,
A urethane-forming composition solution (I), wherein the concentration of the urethane-forming composition (E) in the urethane-forming composition solution (I) is 10% by mass or more and 90% by mass or less. A urethane prepolymer solution (I) containing the urethane prepolymer (F) according to claim 5 and an organic solvent, wherein the concentration of the urethane prepolymer (F) in the urethane prepolymer solution (I) is 10 mass % or more and 90 mass % or less of the urethane prepolymer solution (I). A urethane-forming composition solution (I) comprising the urethane-forming composition (H) according to claim 6 and an organic solvent, wherein the urethane-forming composition in the urethane-forming composition solution (I) A urethane prepolymer solution (I), wherein the concentration of the curable composition (H) is 10% by mass or more and 90% by mass or less. The urethane-forming composition (E) according to any one of claims 1 to 4, the urethane-forming composition (H) according to claim 6, and the urethane-forming composition solution according to claim 7 ( Urethane-forming composition (E) in I) or polyurethane (J) which is the reactant of urethane-forming composition (H) in urethane-forming composition solution (I) according to claim 9 . A polyurethane sheet comprising the polyurethane (J) according to claim 10. A sealing material comprising the polyurethane (J) according to claim 10 or the polyurethane sheet according to claim 11. A paint comprising the polyurethane (J) according to claim 10 or the polyurethane sheet according to claim 11. A pressure-sensitive adhesive comprising the polyurethane (J) according to claim 10 or the polyurethane sheet according to claim 11. An adhesive comprising the polyurethane (J) according to claim 10 or the polyurethane sheet according to claim 11.