JP2021130781A - Urethane forming composition - Google Patents

Abstract

To provide a composition composed of a polyalkylene oxide having an alkylene oxide residue having 3 or more carbon atoms and an isocyanate compound which produces a polyurethane having excellent coatability, high productivity associated with reaction (curing) and less stickiness.SOLUTION: There is provided a urethane forming composition which comprises: a silicone-based compound having an alkylene oxide residue having 3 or more carbon atoms and one or more hydroxy groups in one molecule; an alkylene oxide containing one hydroxy group and an ethylene oxide residue in one molecule; and an isocyanate compound having an average functional group number of isocyanate groups of 2.0 or more, wherein a polyalkylene oxide satisfies the following (a1) and (a2). (a1) The degree of unsaturation is 0.010 meq/g or less. (a2) The number average molecular weight of the polyalkylene oxide is 800 or more.SELECTED DRAWING: None

Description

The present disclosure relates to urethane-forming compositions.

A polyalkylene oxide containing a large amount of by-product monool having an unsaturated group at one end (hereinafter referred to as unsaturated monool) is used as a raw material for polyurethane. However, when trying to obtain polyurethane using this polyalkylene oxide, there arises a problem that it takes time to cure (solidify) due to the reaction with the isocyanate compound and the productivity is impaired.
Further, polyurethane obtained from polyalkylene oxide containing a large amount of unsaturated monool is difficult to have a high molecular weight and is often sticky. On the other hand, even with a polyalkylene oxide containing a large amount of unsaturated monool, a polyurethane having a high molecular weight and less stickiness can be obtained by reacting with an isocyanate compound having a large average number of functional groups of isocyanate groups. However, in this case, the polyurethane does not have a linear high molecular weight, but becomes a crosslinked body having a dense crosslinked structure, so that the obtained polyurethane has a small tensile elongation at break and a small tensile strength at break.

On the other hand, since unsaturated monools have a relatively low molecular weight, conventional compositions containing polyalkylene oxides containing a large amount of unsaturated monools have a low viscosity, and a coating machine is used to obtain polyurethane from those compositions. When it is coated with such a material, it has the advantage of being easy to apply.

Here, Patent Document 1 discloses that a polyalkylene oxide having a small amount of unsaturated monool can be obtained by using an iminophosphazenium salt and a Lewis acid as catalysts. By using these polyalkylene oxides, the productivity problem of the polyalkylene oxide containing a large amount of unsaturated monool is solved, and the stickiness is reduced. However, since a polyalkylene oxide containing a small amount of unsaturated monool has a high viscosity, it has been desired to improve the coatability of the composition containing the polyalkylene oxide, and further to eliminate the stickiness. ..

Japanese Unexamined Patent Publication No. 2017-25274

One aspect of the present invention is a urethane-forming composition having excellent coatability and high productivity and contributing to the formation of a polyurethane having less stickiness, and a urethane-forming composition containing the urethane-forming composition. It is aimed at providing a solution.
Another aspect of the present invention is directed to providing a urethane prepolymer which is a reaction product of the urethane-forming composition and a urethane prepolymer solution containing the urethane prepolymer.
Yet another aspect of the present invention is directed to providing polyurethane which is a reactant of the urethane-forming composition.
Yet another aspect of the present invention is directed to providing a polyurethane sheet made of the polyurethane.

Each aspect of the present invention is [1] to [15] shown below.
[1] Polyalkylene oxide (A) having an alkylene oxide residue having 3 or more carbon atoms and 2 or more hydroxyl groups in one molecule, and
Silicone compound (B) having one or more hydroxyl groups in one molecule,
Polyalkylene oxide (C) containing one hydroxyl group and ethylene oxide residue in one molecule, and
The isocyanate compound (D) having an average number of functional groups of 2.0 or more is included.
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] The urethane-forming composition (E) according to the above [1], wherein the alkylene oxide residue having 3 or more carbon atoms is a propylene oxide residue.
A urethane prepolymer (F) which is a reaction product of the urethane-forming composition (E).
[3] The polyalkylene oxide (C) is at least one selected from the group consisting of polyoxyalkylene glycol monoalkyl ether, polyoxyalkylene glycol monoalkenyl ether, and polyoxyalkylene glycol monophenyl ether. The urethane-forming composition (E) according to the above [1] or [2].
[4] 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 1 of the polyalkylene oxide (A). The urethane-forming composition (E) according to any one of the above [1] to [3], which has a number average molecular weight calculated from the number of hydroxyl groups in the molecule.
[5] The urethane prepolymer (F) which is a reaction product of the urethane-forming composition (E) according to any one of the above [1] to [4], and the urethane prepolymer (F) is 1 It has at least one hydroxyl group in the molecule and is derived from the polyalkylene oxide (A), the silicone-based compound (B) and the polyalkylene oxide (C) among the urethane-forming compositions (E). _{Urethane prepolymer (MNCO} / M _OH ) in which the ratio ( _{MNCO / M OH) of the amount of isocyanate groups (MNCO} ) derived from the isocyanate compound (D) to the total amount of hydroxyl groups (M _OH ) is less than 1.0 in terms of molar ratio. F).
[6] A urethane-forming composition (H) containing the urethane prepolymer (F) according to the above [5] and an isocyanate compound (G).
[7] The urethane-forming composition (E), the urethane prepolymer (F), or the urethane-forming composition (H) according to any one of the above [1] to [4].
A urethane-forming composition solution (I) containing 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. The following urethane-forming composition solution (I).
[8] The urethane prepolymer solution (I) containing the urethane prepolymer (F) according to the above [5] and an organic solvent, and the urethane prepolymer solution (I) in the urethane prepolymer solution (I). The urethane prepolymer solution (I), wherein the concentration of F) is 10% by mass or more and 90% by mass or less.
[9] A urethane-forming composition solution (I) containing the urethane-forming composition (H) according to the above [6] and an organic solvent, which is contained in the urethane-forming composition solution (I). The urethane prepolymer solution (I), wherein the concentration of the urethane-forming composition (H) is 10% by mass or more and 90% by mass or less.
[10] The urethane-forming composition (E) according to any one of the above [1] to [4], the urethane-forming composition (H) according to the above [6], and the urethane according to the above [7]. The urethane-forming composition (E) in the forming composition solution (I), or the reaction product of the urethane-forming composition (H) in the urethane-forming composition solution (I) according to the above [9]. Polyurethane (J).
[11] Polyurethane sheet made of polyurethane (J) according to the above [10] [12] Sealing material made of the polyurethane (J) according to the above [10] or the polyurethane sheet according to the above [11].
[13] A paint comprising the polyurethane (J) according to the above [10] or the polyurethane sheet according to the above [11].
[14] An adhesive comprising the polyurethane (J) according to the above [10] or the polyurethane sheet according to the above [11].
[15] An adhesive made of the polyurethane (J) according to the above [10] or the polyurethane sheet according to the above [11].

The urethane-forming composition of the present invention has excellent coatability when coated with a coating machine or the like in order to obtain polyurethane, and can be combined with an isocyanate compound without using a large amount of urethanization catalyst. It is possible to obtain polyurethane having high productivity and less stickiness by advancing curing (solidification) accompanying the reaction.
Further, the polyurethane obtained by using the urethane-forming composition of the present invention can be suitably used for a wide range of applications such as sealing materials, paints and elastomers.

An exemplary embodiment for carrying out the present invention will be described in detail below.

<Polyalkylene oxide (A)>
The urethane-forming composition (E) according to one aspect of the present invention is
Polyalkylene oxide (A) having an alkylene oxide residue having 3 or more carbon atoms and 2 or more hydroxyl groups in one molecule, and
Silicone compound (B) having one or more hydroxyl groups in one molecule,
Polyalkylene oxide (C) containing one hydroxyl group and ethylene oxide residue in one molecule, and
The isocyanate compound (D) having an average number of functional groups of 2.0 or more is included.
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, and 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) is cured by the reaction with the isocyanate compound (D). It takes time to (solidify) and is inferior in productivity. Even if the degree of unsaturation is more than 0.010 meq / g, a high molecular weight polyurethane can be obtained by reacting with an isocyanate compound having a large average number of functional groups of isocyanate groups. In this case, polyurethane Is a crosslinked body having a dense crosslinked structure, and the tensile elongation at break and the tensile strength at break are reduced. When the degree of unsaturation of the polyalkylene oxide (A) is 0.010 meq / g or less, the silicone compound (B) is cured (solidified) due to the reaction of the polyalkylene oxide (C) and the isocyanate compound (D). ) Is fast, the obtained polyurethane has a linear high molecular weight, and the tensile elongation at break and the tensile strength at break increase. The lower the degree of unsaturation of the polyalkylene oxide (A), 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 in 1 g of the polyalkylene oxide, and the unsaturated monool contained in the polyalkylene oxide. Corresponds to the number. That is, if the degree of unsaturation is high, the amount of unsaturated monool is large, and if the degree of unsaturation is low, the amount of unsaturated monool is small.

In this embodiment, the degree of unsaturation of polyalkylene oxide was measured according to the NMR method described in Polymer Papers 1993, 50, 2, 121-126. In this embodiment, since the polyalkylene oxide having a small amount of unsaturated monool is targeted for measurement, the number of scans in the 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 30,000 or less, and more preferably 3000 or more and 13000 or less. When the number average molecular weight of the polyalkylene oxide (A) is less than 800, the silicone compound (B), the polyalkylene oxide (C), and the isocyanate compound are produced because the polyalkyloxide (A) has a low molecular weight. The polyurethane obtained by the reaction with (D) forms a dense crosslinked structure, and the tensile elongation at break and the tensile strength at break are reduced. When the number average molecular weight of the polyalkylene oxide (A) is 800 or more, the polyurethane obtained by the reaction of the silicone compound (B) with the polyalkylene oxide (C) and the isocyanate compound (D) is stretched at tensile strength. And the tensile breaking strength becomes large. The larger the number average molecular weight of the polyalkylene oxide (A), the larger the tensile elongation at break and the tensile strength at break of polyurethane, which is preferable. However, if the number average molecular weight of the polyalkylene oxide (A) exceeds 30,000, the obtained 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 Mw / Mn is 1.1 or less, low molecular weight substances that cause contamination are reduced, so that excellent contamination resistance is obtained, which is preferable.
The molecular weight distribution (Mw / Mn) can be measured by a 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 may be appropriately selected depending on the intended use, but is preferably 1 mPa · s or more and 2000 mPa · s or less, and more preferably 2 mPa · s or more and 1000 mPa · s or less. Is. When 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 becomes easy to coat when coating with a coating machine or the like in order 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 6.2.3. The value.

The 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 an alkylene oxide residue having 3 to 20 carbon atoms. Specifically, propylene oxide residue, 1,2-butylene oxide residue, 2,3-butylene oxide residue, isobutylene oxide residue, butadiene monooxide residue, pentene oxide residue, styrene oxide residue, cyclohexene. Examples include oxide residues. Among these alkylene oxide residues, the propylene oxide residue is preferable because the raw material for obtaining the polyalkylene oxide (A) is easily available and the obtained polyalkylene oxide (A) has a high industrial value.

Further, the polyalkylene oxide (A) may contain only a single alkylene oxide residue as an 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 types contain alkylene oxide residues, for example, one type of alkylene oxide residue is linked in a chain, and the other alkylene oxide residues are linked in a chain. It may be the one in which two or more kinds of alkylene oxide residues are randomly connected. Further, the polyalkylene oxide (A) may contain an alkylene oxide residue having 3 or more carbon atoms, and may further contain an ethylene oxide residue having 2 carbon atoms.

Further, 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, the silicone compound (B) and the polyalkylene oxide (C) are formed even when the molecular weight of the polyalkylene oxide (A) is low. The crosslinked structure of the polyurethane obtained by the reaction with the isocyanate compound (D) is less likely to be dense, and the tensile elongation at break and the tensile strength at break are further increased, which is preferable.

Further, the polyalkylene oxide (A) is preferably liquid at room temperature because the urethane forming composition (E) containing them can be easily handled.

Here, the polyalkylene oxide (A) having an alkylene oxide residue having 3 or more carbon atoms and 2 or more hydroxyl groups in one molecule is, for example, in the presence of an alkylene oxide polymerization catalyst containing a phosphazene compound and Lewis acid. , It is obtained by ring-opening polymerization of an alkylene oxide using an active hydrogen-containing compound as an initiator. Therefore, the polyalkylene oxide (A) will have an alkylene oxide residue.

Examples of the phosphazene compound include a phosphazenium salt represented by the formula (1).

(In equation (1),
R ¹ and R ² are independent of each other.
Hydrogen atom,
Hydrocarbon groups with 1 to 20 carbon atoms,
A ring structure in which R ¹ and R ² are bonded to each other, or
R ¹ together or R ² together represent a bond and the ring structure;
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 bicarbonate anion;
Y represents a carbon atom or a phosphorus atom;
a is
When Y is a carbon atom, it is 2,
It is 3 when Y is a phosphorus atom. )

Examples of the hydrocarbon group having 1 to 20 carbon atoms include a methyl group, an ethyl group, a vinyl group, an n-propyl group, an isopropyl group, a cyclopropyl group, an allyl group, an n-butyl group, an isobutyl group and a 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, nonadecil group and the like can be mentioned.

As R ¹ and R ² , methyl group, ethyl group and isopropyl group are preferable from the viewpoint that they are alkylene oxide polymerization catalysts having excellent catalytic activity and raw materials are easily available.

^{Further, X −} 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 the alkoxy anion having 1 to 4 carbon atoms include methoxy anion, ethoxy anion, n-propoxy anion, isopropoxy anion, n-butoxy anion, isobutoxy anion, t-butoxy anion and the like.

Examples of the alkylcarboxy anion 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. ..

Among these, ^{as X −} , a hydroxy anion and a hydrogen carbonate anion are preferable because they serve as an alkylene oxide polymerization catalyst having excellent catalytic activity.

Examples of the phosphazene compound include tetrakis (1,1,3,3-tetramethylguanidino) phospasenium hydroxide, tetrakis (1,1,3,3-tetramethylguanidino) phosphasenium hydrogen carbonate, and tetrakis. [Tris (dimethylamino) phosphoranilideneamino] Phosphonium hydroxide can be mentioned.

Examples of the Lewis acid include an aluminum compound, a zinc compound, a boron compound and the like.

Examples of the aluminum compound include trimethylaluminum, triethylaluminum, triisobutylaluminum, trinormalhexylaluminum, triethoxyaluminum, triisopropoxyaluminum, triisobutoxyaluminum, triphenylaluminum, diphenylmonoisobutylaluminum, monophenyldiisobutylaluminum and the like. Organic aluminum, for example, aluminoxane such as methylaluminoxane, isobutylaluminoxane, and methyl-isobutylaluminoxan can be mentioned.

Examples of the zinc compound include organic zinc such as dimethylzinc, diethylzinc and diphenylzinc; and inorganic zinc such as zinc chloride and zinc oxide.

Examples of the boron compound include triethylborane, trimethoxyborane, triethoxyborane, triisopropoxyborane, triphenylborane, tris (pentafluorophenyl) borane, trifluoroborane and the like.

Among these, organoaluminum, aluminoxane, and organozinc are preferable, and organoaluminum is particularly preferable, because it is an alkylene oxide polymerization catalyst having excellent catalytic performance.

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

The active hydrogen-containing compound is not particularly limited, and examples thereof include water, a hydroxy compound, an amine compound, a carboxylic acid compound, a thiol compound, and a polyether polyol having a hydroxyl group.
Examples of the polyether polyol having a hydroxyl group include a polyether polyol having a molecular weight of 200 or more and 3000 or less.
Then, these active hydrogen-containing compounds may be used alone or in combination of several kinds.

<Silicone compound (B)>
The silicone-based compound (B) is not particularly limited as long as it is a silicone-based compound having one or more hydroxyl groups in one molecule. Polyether-modified polyorganosiloxane having an ether group introduced, polyester-modified polyorganosiloxane having a polyester group introduced into the main chain or side chain of the polyorganosiloxane skeleton, and an organic compound introduced into the main chain or side chain of the polyorganosiloxane skeleton. Polyorganosiloxane with organic compound introduced, silicone-modified (meth) acrylic resin with polyorganosiloxane introduced into (meth) acrylic resin, silicone-modified organic compound with polyorganosiloxane introduced into organic compound, both organic compound and silicone compound Examples thereof include polymerized silicone-containing organic compounds. In these, the hydroxyl group may be contained in a polyorganosiloxane skeleton, or may be contained in a polyether group, a polyester group, a (meth) acryloyl group, or an organic compound. Examples of such hydroxyl group-containing silicones as commercially available products include trade names "X-22-4015", "X-22-4039", "KF6000", "KF6001", <KF6002>, <KF6003>, and < Examples thereof include X-22-170BX>, <X-22-170DX>, <X-22-176DX>, and <X-22-176F> [manufactured by Shin-Etsu Chemical Co., Ltd.]. Of these, those having only one hydroxyl group are particularly preferable because the resulting polyurethane coating film tends to be less sticky.

The viscosity of the silicone compound (B) at 25 ° C. is not particularly limited and may be appropriately selected depending on the intended use, but is preferably 1 mPa · s or more and 2000 mPa · s or less, and more preferably 2 mPa · s or more and 1000 mPa · s or less. Is. When the viscosity of the silicone compound (B) at 25 ° C. is 1 mPa · s or more and 2000 mPa · s or less, it is preferable because it becomes easy to apply the silicone compound (B) when it is applied with a coating machine or the like in order 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 6.2.3. The value.

<Polyalkylene oxide (C)>
The polyalkylene oxide (C) is not particularly limited as long as it contains one hydroxyl group and ethylene oxide residue in one molecule, but the polyalkylene oxide (A), the silicone compound (B), and the polyalkylene oxide ( Since the coatability of the urethane-forming composition (E) containing C) is particularly excellent when coated with a coating machine or the like, polyoxyalkylene glycol monoalkyl ether, polyoxyalkylene glycol monoalkenyl ether, etc. It is preferably one or more selected from the group consisting of polyoxyalkylene glycol monophenyl ether.

Here, the polyoxyalkylene glycol monoalkyl ether is not particularly limited, but for example, polyoxyethylene glycol monomethyl ether, polyoxyethylene glycol monobutyl ether, polyoxy (ethylene / propylene) glycol monomethyl ether, polyoxy ( Examples thereof include (ethylene / propylene) glycol monobutyl ether, polyoxyethylene glycol monolaurate, and polyoxyethylene glycol monolaurylamine, which can be preferably used. Further, a polyoxyalkylene glycol monoalkyl ether salt having an amino group such as polyoxyethylene lauryl ether sulfate triethanolamine salt or an inorganic salt such as sulfate can also be used.

The polyoxyalkylene glycol monoalkenyl ether is not particularly limited, but for example, polyoxyethylene glycol monostearyl ether, polyoxyethylene glycol monooleyl ether, polyoxyethylene glycol monomethacrylate, polyoxyethylene glycol monoacrylate, etc. Can be preferably used.

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

Among these, because the urethane-forming composition (E) containing the polyalkylene oxide (A), the silicone-based compound (B), and the polyalkylene oxide (C) is excellent in coatability. Contains at least one of polyoxyethylene glycol monomethyl ether, polyoxyethylene glycol monobutyl ether, polyoxy (ethylene / propylene) glycol monomethyl ether, and polyoxy (ethylene / propylene) glycol monobutyl ether, which have a high content of ethylene oxide. Is preferable.

Here, the number average molecular weight of the polyoxyalkylene oxide (C) is not particularly limited, but is preferably 150 or more and 15,000 or less, more preferably 200 or more and 5000 or less, and most preferably 250 or more and 1300 or less. If the molecular weight of the polyalkylene oxide (C) is too low, the viscosity of the urethane-forming composition (E) containing the polyalkylene oxide (C) becomes too low, and when the urethane-forming composition (E) is coated with a coating machine or the like. In some cases, a defective phenomenon called liquid flow occurs, and the thickness of the obtained polyurethane coating film becomes non-uniform. On the other hand, if the molecular weight of the polyalkylene oxide (C) is too high, the compatibility with the polyalkylene oxide (A) deteriorates, and the urethane-forming composition (E) containing the polyalkylene oxide (C) is coated with a coating machine or the like. At that time, the surface of the coating film may be roughened or the coating film may become opaque. Therefore, the number average molecular weight of the polyalkylene oxide (C) is preferably 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.
The number average molecular weight of the polyalkylene oxide (C) is the hydroxyl value of the polyalkylene oxide (C) calculated by the method described in JIS K-1557-1, as in the case of the polyalkylene oxide (A). It can be calculated from the number of hydroxyl groups in one molecule of polyalkylene oxide (C).

Further, the polyalkylene oxide (C) is preferably liquid at room temperature because the urethane forming composition (E) containing the polyalkylene oxide (C) can be easily handled.

<Isocyanate compound (D)>
The isocyanate compound (D) is not particularly limited as long as the average number of functional groups of the 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-naphthalenedisocyanate, and tridine. Diisocyanate, xylylene diisocyanate, 1,3-phenylenediocyanate, 1,4-phenylenediocyanate, lysine diisocyanate, triphenylmethane triisocyanate, tetramethylxylene diisocyanate, 1,6-hexamethylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate , Isophorone diisocyanate, 1,4-cyclohexanediisocyanate, norbornandiisocyanate, lysine ester triisocyanate, 1,6,11-undecantryisocyanate, 1,8-diisocyanate-4-isocyanatemethyloctane, 1,3,6-hexamethylenetri Examples thereof include isocyanates, bicycloheptanetriisocyanates, trimethylhexamethylene diisocyanates, modified isocyanates obtained by reacting these with polyalkylene oxides, and mixtures of two or more of these. Further, modified products containing urethane group, carbodiimide group, allophanate group, urea group, burette group, isocyanurate group, amide group, imide group, uretonimine group, uretdione group or oxazolidone group in these isocyanates, and polymethylenepolyphenylene polyisocyanate. Examples thereof include a condensate such as (Polymeric MDI).

Among these, a urethane-forming composition having excellent curability (solidification) property associated with the reaction of the polyalkylene oxide (A), the silicone compound (B), and the polyalkylene oxide (C), and being highly transparent and having little coloring. Aliphatic isocyanates, alicyclic isocyanates, or modified compounds thereof are preferable because they can be easily obtained. 1,6-Hexamethylene diisocyanate, isophorone diisocyanate, prepolymer containing aliphatic isocyanate, prepolymer containing alicyclic isocyanate, or urethane group, carbodiimide group, allophanate group, urea group, burette group, etc. A modified product containing an isocyanurate group, an amide group, an imide group, a uretonimine group, a uretdione group or an oxazolidone group is more preferable. One of these isocyanates may be used alone, or two or more of these isocyanates may be mixed and used.

<Urethane-forming composition (E)>
The urethane-forming composition (E) may be a composition containing the above-mentioned polyalkylene oxide (A), silicone-based compound (B), polyalkylene oxide (C), and a specific isocyanate compound (D). .. The mixing ratio of the polyalkylene oxide (A) and the silicone-based compound (B) in the urethane-forming composition (E) is not particularly limited, but the mass ratio (polyalkylene oxide (A) / silicone-based compound (B)) is used. , 99.99 / 0.01 to 90/10, more preferably 99.95 / 0.05 to 95/5, and 99.9 / 0.1 to 99/1. Is the most preferable. Polyurethane obtained from the urethane-forming composition (E) having a mass ratio within this range is preferable because it is less sticky and has good transparency.
Further, the mixing ratio of the mixture of the polyalkylene oxide (A) and the silicone compound (B) and the polyalkylene oxide (C) is not particularly limited, but the mass ratio [polyalkylene oxide (A) + silicone compound (B)) ] / Polyalkylene oxide (C), preferably 99.9 / 0.1 to 60/40, more preferably 99.5 / 0.5 to 80/20, 99/1 to 90. Most preferably, it is 1/10. Although the urethane-forming composition (D) having a mass ratio within this range contains polyalkylene oxide (A) having a small amount of unsaturated monool, it has good coatability when coated with a coating machine or the like. It is preferable to show.
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 (D) with respect to _{the total amount (MOH} ) of the hydroxyl groups derived from the polyalkylene oxide (A), the silicone compound (B) and the polyalkylene oxide (C). the ratio of the amount of isocyanate groups _{(M NCO)} derived from) _(M NCO _/ M _OH) is 0.5 or more in the molar ratio is preferably less than 4.0, the content of the isocyanate compound (D) is Within the above range, when polyurethane is obtained by curing with the reaction of the urethane-forming composition (E), the curing (solidification) property is excellent, and the polyurethane has even better mechanical properties, which is preferable. ..

The polyalkylene oxide (A), the silicone compound (B), the polyalkylene oxide (C), and the isocyanate compound (D) contained in the urethane-forming composition (E) are dehydrated by vacuum heating or the like before use. However, if the work becomes complicated, it may be used without dehydration.

The preparation of the urethane-forming composition (E) is not particularly limited as long as it is a method capable of uniformly dispersing the raw materials contained in the urethane-forming composition (E), and various conventionally known methods are used. A stirring method can be used, and examples thereof include a method of stirring using a stirrer. Examples of the stirrer include a general-purpose stirrer, a rotation / revolution mixer, a disperser, a dissolver, a kneader, a mixer, a lab plast mill, a planetary mixer, and the like. When the polyalkylene oxide (A), the silicone compound (B), the polyalkylene oxide (C), and the isocyanate compound (D) are all liquid at the stirring temperature, a rotation / revolution mixer, a general-purpose stirrer, a disper disperser, etc. 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 100,000 mPa · s or less, preferably 200 mPa · s or more and 30,000 mPa · s or less, and 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) may be stirred with various stirrers to prepare the urethane-forming composition (E), or the urethane-forming composition (E) may be stirred. ) Is preferable because it facilitates stirring and handling of the composition when stirring is performed as a pre-stage work 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 in one molecule. That is, the urethane prepolymer (F) is a urethane-forming composition (E) containing a polyalkylene oxide (A), a silicone-based compound (B), a polyalkylene oxide (C), and an isocyanate compound (D). ) Is a reaction product obtained by reacting the above, and 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 a polyalkylene oxide (A), a silicone-based compound (B), and a hydroxyl group derived from the polyalkylene oxide (C). The ratio ( _MNCO / M _{OH ) of the amount of isocyanate groups (MNCO} ) derived from the isocyanate compound (D) to the total amount (M _OH ) is preferably less than 1.0, preferably 0.4 or more and 0.99. It is more preferably 0.5 or more, and most preferably 0.95 or less. The ratio ( _MNCO / M _OH ) represents a molar ratio. When the ratio ( _MNCO / 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 unlikely to occur and is easy to handle, which is preferable.

<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, and examples thereof include the same isocyanate compounds as the isocyanate compound (D), and preferred isocyanates include the same isocyanate compounds. 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 a urethane prepolymer (F) and an isocyanate compound (G). Therefore, there is no particular limitation on the content of the urethane-forming composition (H) isocyanate compound in (G), the isocyanate compound to the total amount of hydroxyl groups derived from the urethane prepolymer _{(F) (M OH) (} G) the ratio of the amount of from isocyanate groups _{(M NCO) (M NCO /} M OH) is 0.5 or more in molar ratio, preferably less than 4.0. When the content of the isocyanate compound (G) is within the above range, when the polyurethane is obtained by curing with the reaction of the urethane-forming composition (H), the curing (solidification) property is excellent and the polyurethane is a good machine. 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 vacuum heating or the like, but are used without dehydration when the work becomes complicated. You may.

The preparation of the urethane-forming composition (H) is not particularly limited as long as it is a method capable of uniformly dispersing the prepolymer and raw materials contained in the urethane-forming composition (H), and is conventionally known. There is a method of stirring using various stirring methods of. Examples of the stirrer include a general-purpose stirrer, a rotation / revolution mixer, a disperser, a dissolver, a kneader, a mixer, a lab plast mill, a planetary mixer, and the like. When both the urethane prepolymer (F) and the isocyanate compound (G) are liquid at a 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 100,000 mPa · s or less, preferably 200 mPa · s or more and 30,000 mPa · s or less, and 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) may be agitated with various stirrers to prepare the urethane-forming composition (H), or the urethane-forming composition (H) may be agitated. Is preferable because the urethane-forming composition (H) can be easily stirred and handled when stirring is performed as a pre-stage work 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 urethane prepolymer (F), is organic to facilitate their handling or to obtain the desired viscosity and coatability. It can be mixed with a solvent to obtain a urethane-forming composition solution or a urethane prepolymer solution (I).
At this time, the urethane-forming composition solution (I) is
Urethane-forming composition (E) and
Containing with 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.
In addition, the urethane prepolymer solution (I) is
Urethane prepolymer (F) and
Containing with 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.
In addition, the urethane-forming composition solution (I) is
Urethane-forming composition (H) and
Containing with organic solvent,
The concentration of the urethane-forming composition (H) is 10% by mass or more and 90% by mass or less.

Examples of the organic solvent include methyl ethyl ketone, ethyl acetate, toluene, xylene, acetone, benzene, dioxane, acetonitrile, tetrahydrofuran, diglime, dimetholsulfoxide, N-methylpyrrolidone, dimethylformiamide and the like. Ethyl acetate, toluene, methyl ethyl ketone, or a mixed solvent thereof is particularly preferable from the viewpoint of solubility, boiling point of the organic solvent, and the like. It should be noted that these solvents are used at the time of preparing the urethane-forming composition, at the time of the reaction of the prepared urethane-forming composition, at the end of the reaction, and at the time of the reaction when obtaining the prepolymer by the reaction of the urethane-forming composition. , 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. It is preferably 30% by mass or more and 70% by mass or less. When the concentration is in this range, good coatability can be obtained when the urethane-forming composition solution or the urethane prepolymer solution (I) is coated with a coating machine or the like, and the urethane-forming composition solution or the urethane-forming composition solution or The urethane prepolymer solution (I) can be easily handled.

Further, the viscosity of the urethane-forming composition solution or the urethane prepolymer solution (I) at 25 ° C. is not particularly limited, but is preferably 100 mPa · s or more and 100,000 mPa · s or less. When the viscosity is in this range, good coatability can be obtained when the urethane-forming composition solution or the urethane prepolymer solution (I) is coated with a coating machine or the like, and the urethane-forming composition solution or the urethane-forming composition solution or The handling of the urethane prepolymer solution (I) can be facilitated.

<Additives>
Urethane-forming compositions (E) and (H) may contain a urethanization catalyst, an antioxidant, a light stabilizer, a chain extender, 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, and more preferably 1% by mass or less. be.

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

The chain extender is also not particularly limited, and is, for example, ethylene glycol, 1,4-butanediol, neopentyl glycol, butylethylpentanediol, glycerin, trimethylolpropane, pentaerythritol, and a low molecular weight of 1000 or less. Glycols such as polyalkylene glycol; polyvalent amines such as ethylenediamine, N-aminoethylethanolamine, piperazine, isophoronediamine, and xylylenediamine; can be mentioned.

<Polyurethane (J)>
The polyurethane (J) is a urethane-forming composition (E), a urethane-forming composition (H), a urethane-forming composition (E) of a urethane-forming composition solution (I), or a urethane prepolymer solution ( It is a reaction product 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. ) Can be obtained. The method for producing these polyurethanes (J) is not particularly limited. For example, the urethane-forming composition (E), (H), or the urethane-forming composition solution (I), or the urethane prepolymer solution (I) is, if necessary, a urethanization catalyst, a solvent, and an antioxidant. It can be produced by proceeding with a urethanization reaction and a urea conversion reaction at room temperature or a high temperature of 150 ° C. or lower in the presence of an agent, a light stabilizer, a chain extender, a cross-linking agent, and other additives.
Here, the urethane-forming composition (E), (H), or the urethane-forming composition solution (I), or the urethane prepolymer solution (I) is coated when it is applied by a coating machine or the like. Since the workability is remarkably excellent, a polyurethane (J) coating film or a polyurethane sheet having a thin thickness and a uniform thickness can be obtained.

The thickness of the polyurethane (J) coating film is not particularly limited, but the thickness of the coating film is preferably 1 μm or more and 1000 μm or less, preferably 20 μm or more and 300 μm or less, because the appearance of the coating film is particularly good. It is more preferable to have.

The application of polyurethane (J) is not particularly limited, and it can be used in any application in which ordinary polyurethane is used, but it can be particularly preferably used in applications requiring mechanical properties. Specifically, applications such as sealing materials for construction / civil engineering, paints, elastomers, waterproofing materials for coating films, flooring materials, plasticizers, flexible polyurethane foams, semi-rigid polyurethane foams, rigid polyurethane foams, etc. are exemplified and can be preferably used. ..
Among them, polyurethane is particularly preferably used as a sealing material, a paint, and an elastomer because the mechanical properties are strongly required and workability and coatability are required.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention will not be construed as being limited to the following Examples as long as the gist thereof is not exceeded. The raw materials used in the following Examples and Comparative Examples and the evaluation method are as shown below.

(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 determined by the following methods.
<Degree of unsaturation of polyalkylene oxide>
The degree of unsaturation of the polyalkylene oxide was measured at 800 scans according to the NMR method described in Polymer Papers 1993, 50, 2, 121-126.
<Hydroxyl group 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. Further, 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 of polyalkylene oxide (Mw / Mn)>
The molecular weight distribution (Mw / Mn) of the polyalkylene oxide was measured by the following procedure using a gel permeation chromatography (GPC) method.
10 mg of polyalkylene oxide and 10 ml of tetrahydrofuran (THF) are placed in a sample bottle, and the mixture is allowed to stand for 1 day to dissolve the polyalkylene oxide in THF and filtered through a PTFE cartridge filter (0.5 μm) for GPC measurement. Samples were prepared.
For GPC measurement, THF was used as the developing solvent, the column temperature was 40 ° C., and the molecular weight distribution (Mw / Mn) was measured using a cubic approximation curve using eight standard polystyrenes manufactured by Tosoh Corporation with known molecular weights as the calibration curve. The analysis was performed. Tosoh's HLC-8320GPC was used as the measuring device, and Tosoh's HLC-8320GPC-ECOSEC-Workstation was used for the analysis.

<Viscosity of polyalkylene oxide>
The viscosity of the polyalkylene oxide was determined according to the method described in JIS K-1557-5. Specifically, the measurement was performed at a temperature of 25 ° C. and a shear rate of 0.1 (1 / s) using a cone-plate rotational viscometer, and MCR-300 manufactured by Antonio-Par was used as the measuring device.

(Raw Material 1-1) Polyalkylene Oxide (A) Used in Examples
The polyalkylene oxides (A1), (A2) and (A3) are bifunctional by using an imino group-containing phosphazenium salt (hereinafter referred to as IPZ catalyst) and triisopropoxyaluminum in combination to sufficiently dehydrate and desolvate. It 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 a propylene oxide group as an alkylene oxide group and having two hydroxyl groups in one molecule. The properties of (A1), (A2) and (A3) are shown in Table 1. In (A1), (A2) and (A3), the amount of unsaturated monool is extremely small (the degree of unsaturation is extremely low). It has a narrow molecular weight distribution.

The polyalkylene oxide (A4) is a propylene oxide obtained by sufficiently dehydrating and desolving the IPZ catalyst and triisopropoxyaluminum, and then sufficiently dehydrating polyoxypropylene glycol having a bifunctionality and a molecular weight of 400. And ethylene oxide were added in order. (A4) is a polyoxyalkylene glycol (diol) having two hydroxyl groups in one molecule, in which a chain of propylene oxide groups and a chain of ethylene oxide groups are bonded. The properties of (A4) are shown in Table 1, and (A4) also has an extremely small amount of unsaturated monool (extremely low degree of unsaturation) and a narrow molecular weight distribution.

The polyalkylene oxides (A5) and (A6) are sufficiently dehydrated and desolvated by using an IPZ catalyst and triisopropoxyaluminum in combination, and sufficiently dehydrated to a trifunctional polyoxypropylene triol having a molecular weight of 600. Obtained by adding the applied propylene oxide. (A5) and (A6) are polyoxypropylene triols having only a propylene oxide group as an alkylene oxide group and having three hydroxyl groups in one molecule. The properties of (A5) and (A6) are shown in Table 1. In (A5) and (A6), the amount of unsaturated monool is extremely small (the degree of unsaturation is extremely low), and the molecular weight distribution is narrow.

The polyalkylene oxide (A7) is a polyoxypropylene triol having three hydroxyl groups in one molecule obtained by using a potassium hydroxide catalyst and having a molecular weight of 980. (A7) is a commercially available GP1000 manufactured by Sanyo Chemical Industries, Ltd. The properties of (A7) are shown in Table 1. In (A7), the amount of unsaturated monool is small (the degree of unsaturation is low) and the molecular weight distribution is narrow, but (A1) to (A6) are somewhat unsaturated. The degree is high.

(Raw Material 1-2) Polyalkylene Oxide (AC) Used in Comparative Example
For polyalkylene oxide (AC1), use only an IPZ catalyst, sufficiently dehydrate and desolvate, and add fully dehydrated propylene oxide to 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 having two hydroxyl groups in one molecule. The properties of (AC1) are shown in Table 1. In (AC1), the degree of unsaturation is high and the degree of unsaturation does not satisfy the range of 0.010 meq / g or less.

Polyalkylene oxide (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 having two hydroxyl groups in one molecule. The properties of (AC2) are shown in Table 1. (AC2) has a high degree of unsaturation and does not satisfy the range of 0.010 meq / g or less, and (AC2) is more than (AC1). Is even more unsaturated.

Polyalkylene oxide (AC3) was also obtained by sequentially adding propylene oxide and ethylene oxide to trifunctional polyoxypropylene triol using a potassium hydroxide catalyst. (AC3) is a polyoxyalkylene triol having a chain of propylene oxide groups and a chain of ethylene oxide groups bonded to each other and having three hydroxyl groups in one molecule. The properties of (AC3) are shown in Table 1. (AC3) also has a high degree of unsaturation and does not satisfy the range of 0.010 meq / g or less, and the degree of unsaturation of (AC3) is (AC3). Equivalent to AC2) and higher than (AC1).

Polyalkylene oxide (AC4) is also a polyoxypropylene glycol having two hydroxyl groups in one molecule obtained by using a potassium hydroxide catalyst and having a molecular weight of 600. (AC4) is a commercially available PP600 manufactured by Sanyo Chemical Industries, Ltd. The properties of (AC4) are shown in Table 1. In (AC4), the number average molecular weight is low and the number average molecular weight 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 being heated and vacuum dehydrated. Further, the polyalkylene oxide prepared by using the IPZ catalyst was used after removing the catalyst.

(Raw Material 2-1) Silicone Compound (B) Used in Examples
The silicone compounds (B1) and (B2) used in the examples are silicone compounds having a hydroxyl group introduced at the end, and (B1) has a hydroxyl group at one end and is manufactured by Shin-Etsu Chemical Co., Ltd. X-22-170BX, (B2) has hydroxyl groups at both ends and is KF-6001 manufactured by Shin-Etsu Chemical Co., Ltd. Table 2 shows the properties of (B1) and (B2). (B1) and (B2) are commercial products, and the property values shown in Table 2 are the values listed in the catalog.
The silicone-based compound (B3) is a silicone-based compound in which a side chain containing a partially hydroxyl group is randomly introduced into the main chain composed of a siloxane bond, and (B3) is X-22-4015 manufactured by Shin-Etsu Chemical Co., Ltd. Is. Table 2 shows the properties of (B3). (B3) is a commercially available 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
The polyalkylene oxides (C1), (C2) and (C3) are polyethylene glycol monomethyl ethers, which are composed of one hydroxyl group and an ethylene oxide group in one molecule. Table 3 shows the properties of (C1), (C2), and (C3), but (C1), (C2), and (C3) have different molecular weights. (C1), (C2), and (C3) all have a high ethylene oxide group content ratio, but the higher the molecular weight, the higher the ethylene oxide group content ratio.

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. In each case, one hydroxyl group and one ethylene oxide group are contained 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, which are composed of one hydroxyl group, ethylene oxide group, and propylene oxide group in one molecule. Table 3 shows the properties of (C8) and (C9), but (C8) and (C9) have different molecular weights and ethylene oxide group content ratios. Since (C8) and (C9) contain propylene oxide groups, the content ratio of ethylene oxide groups is low, and (C9) has a lower content ratio of ethylene oxide groups than (C8).

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

Polyalkylene oxide (CC2) is a polypropylene glycol monomethyl ether that does 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), (G1): The isocyanate compounds (D1) and (G1) are the same, and the names are used according to the purpose of use. (D1) and (G1) are coronate HXLV manufactured by Tosoh Corporation, which is a 1,6-hexamethylene diisocyanate (HDI) -based modified isocyanate, and the average number of functional groups of the isocyanate groups in (D1) and (G1) is It is 3.2.
Isocyanate compound (D2): Aquanate 105 manufactured by Tosoh Corporation, which is an HDI-based modified isocyanurate, has an average number of functional groups of isocyanate groups of 3.4 in (D2).
Isocyanate compound (D3): (D3) is 1,6-hexamethylene diisocyanate (HDI). The average number of functional groups of the isocyanate group in (D3) is 2.0.

(Raw Material 4) Additive In Examples and Comparative Examples, a urethanization catalyst was added as an additive. As the urethanization catalyst, dioctyltin dilaurate (abbreviation: DOTDL) manufactured by Wako Pure Chemical Industries, Ltd. was used.

(Raw Material 5) Solvent When the urethane-forming composition solution was used in Examples and Comparative Examples, the solvent was ethyl acetate manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. or Fujifilm Wako Pure Chemical Industries, Ltd. Methyl ethyl ketone was used.

(Preparation of urethane-forming composition)
In both Examples and Comparative Examples, those which were liquid at room temperature were used. A predetermined amount of each raw material was placed in a 50 ml sample bottle, and a urethane-forming composition was obtained by stirring and defoaming at room temperature using a rotation / revolution mixer. As the rotation / revolution mixer, Awatori Rentaro ARE-310 manufactured by Shinky Co., Ltd. was used, and the rotation was performed at a rotation speed of 2000 rpm for 5 minutes and the revolution was performed at a rotation speed of 2200 rpm for 5 minutes.

(Performance evaluation of urethane-forming composition)
<Colability and curability of urethane-forming composition>
A urethane-forming composition or a urethane-forming composition solution is placed on a surface-untreated PET film (product name: Lumirror) manufactured by Toray Industries, Inc. with a thickness of 38 μm, and the thickness after drying is 100 μm or less. As described above, the coating was applied using a baker-type applicator. Then, the urethane-forming composition was allowed to stand in an environment of 23 ° C. and a relative humidity of 50% for 1 week to obtain a polyurethane coating film. The solution of the urethane-forming composition is kept in an oven set at 100 ° C. for 3 minutes to volatilize the solvent after coating, and then allowed to stand in an environment at 23 ° C. and a relative humidity of 50% for 1 week. As a result, a polyurethane coating film was obtained.
In that step, the coatability of the urethane-forming composition and its solution was obtained by the reaction of the urethane-forming composition when it was allowed to stand in an environment of 23 ° C. and a relative humidity of 50% for 1 week after coating. The surface appearance and thickness of the polyurethane coating film were used as indicators for evaluation according to the following criteria. The surface appearance of the polyurethane coating film was visually measured, and the thickness of the polyurethane coating film was measured with a thickness gauge.
Regarding the curability of the urethane-forming composition and the urethane-forming composition in the solution, the surface of the polyurethane coating film obtained in the process of allowing to stand in an environment of 23 ° C. and a relative humidity of 50% for one week over time. The evaluation was made according to the following criteria, using the sticky feeling at that time as an index.

<Coatability of urethane-forming composition or urethane-forming composition solution>
◎ (Applicability passed): When the surface of the polyurethane coating film is smooth by visual observation and the thickness difference between the center and the edge of the polyurethane coating film is less than 5%.
○ (passed coatability): When the surface of the polyurethane coating film is smooth by visual observation and the thickness difference between the center and the edge of the polyurethane coating film is in the range of 5 to 10%.
× (Applicability rejected): When the surface of the polyurethane coating film is rough by visual observation, or when the thickness difference between the center and the edge of the polyurethane coating film exceeds 10%.

<Currability of urethane-forming composition>
◎ (Passing curability): When the stickiness disappears by leaving it to stand in an environment of 23 ° C. and a relative humidity of 50% for 1 day, and the sticky feeling does not change with time after holding for 3 days.
○ (Passing curability): When the stickiness disappears by leaving it to stand in an environment of 23 ° C. and a relative humidity of 50% for 1 to 3 days, and the stickiness does not change over time after holding for 7 days.
× (Curability failed): There is a sticky feeling even after standing for 3 days in an environment of 23 ° C and 50% relative humidity (curing is insufficient), or a sticky feeling remains even after holding for 7 days and changes over time. If you do (curing is extremely slow).

Further, regarding the stickiness of the polyurethane coating film, the polyurethane coating film having a thickness of about 100 μm, which was coated and cured as described above, was ^{contacted with a columnar probe (bottom area 0.2 cm 2} ) made of SUS at a load of 190 g for 300 seconds. After that, the force required for peeling at a peeling speed of 10 mm / min was set as the maximum tack value, and was evaluated according to the following criteria.

<Stickiness of polyurethane coating film obtained from urethane-forming composition>
◎ (No stickiness): When the maximum tack value of the polyurethane coating film is less than 1N.
○ (less sticky): When the maximum tack value of the polyurethane coating film is 1N or more and less than 2N.
× (with stickiness): When the maximum tack value of the polyurethane coating film is 2N or more.

In Example 1, 99 parts by weight of the polyalkylene oxide (A2), 1 part by weight of the silicone compound (B2), 3 parts by weight of the polyalkylene oxide (C1), and the isocyanate compound (D1) and dioctyltin as a urethanization catalyst. includes dilaurate (DOTDL) 0.03 parts by weight, (A2) and (B2) the amount of isocyanate groups derived from the amount of hydroxyl groups derived from _{(M OH)} and (D1) to _{(C1) (M NCO),} in molar ratios, it is _M NCO / (A2) and (B2) and urethane forming composition _M OH = 1.05 in (C1) of (D1) (E1). Table 4 shows the results of Example 1. The urethane-forming composition (E1) has good coatability and curability, and the polyurethane (J1) coating film obtained from the composition (E1) is sticky. There were few.

In Comparative Example 1, 99 parts by weight of the polyalkylene oxide (A2) and 1 part by weight of the silicone compound (B2), and the isocyanate compound (D1) and urethane, which do not contain the polyalkylene oxide (C1), as compared with Example 1. of include DOTDL0.03 parts by weight as a catalyst, the (A2) and the amount of hydroxyl groups derived from the _{(B2) (M OH)} to the amount of isocyanate groups derived from _{(D1) (M NCO),} in molar ratio, is _{(D1) M NCO / (A2} ) and urethane forming composition _M OH = 1.05 in (B2) (EC1). Table 4 shows the results of Comparative Example 1. Since (C1) is not contained, the composition (EC1) is inferior in coatability, but the polyurethane (JC1) obtained from the composition (EC1) is coated. The membrane was less sticky.

In Example 2, 99.9 parts by weight of the polyalkylene oxide (A3), 0.1 part by weight of the silicone compound (B1), 5 parts by weight of the polyalkylene oxide (C3), and the isocyanate compound (D1) and the urethanization catalyst were used. includes DOTDL0.03 parts by weight as, (A3) and (B1) to the amount of isocyanate groups derived from the amount of hydroxyl groups derived from _{(M OH)} and (D1) to _{(C3) (M NCO)} is, (D1 ) _MNCO / (A3), (B1) and (C3) _MOH = 1.05 urethane-forming composition (E2). Table 4 shows the results of Example 2. The urethane-forming composition (E2) has good coatability and curability, and the polyurethane (J2) coating film obtained from the composition (E2) is sticky. There wasn't.

In Comparative Example 2, 100 parts by weight of polyalkylene oxide (A3) and 5 parts by weight of polyalkylene oxide (C3), and isocyanate compound (D1) and urethane, which do not contain silicone compound (B1), are compared with Example 2. of include DOTDL0.03 parts by weight as a catalyst, the (A3) to the amount of isocyanate groups derived from the amount of hydroxyl groups derived from the _{(C3) (M OH)} and _{(D1) (M NCO),} in molar ratio, is _{(D1) M NCO / (A3} ) and urethane forming composition _M OH = 1.05 in (C3) (EC2). Table 4 shows the results of Comparative Example 2. Since (C3) is contained, the coating property of the composition (EC2) is good, but since (B1) is not contained, the composition (EC2) is used. The obtained polyurethane (JC2) coating film was sticky.

In Example 3, 95 parts by weight of the polyalkylene oxide (A5), 5 parts by weight of the silicone compound (B3), 2 parts by weight of the polyalkylene oxide (C2), and the isocyanate compound (D3) and DOTDL 0. It comprises 03 parts by weight, (A5) and (B3) to the amount of hydroxyl groups derived from _{(C2) (M OH)} to the amount of isocyanate groups derived from _{(D3) (M NCO),} M NCO of (D3) a / (A5) and (B3) and urethane forming composition _M OH = 1.05 in (C2) (E3). Table 4 shows the results of Example 3. The urethane-forming composition (E3) has good coatability and curability, and the polyurethane (J3) coating film obtained from the composition (E3) is sticky. There were few.
In Comparative Example 3, 100 parts by weight of the polyalkylene oxide (A5), the isocyanate compound (D3), and DOTDL0 as a urethanization catalyst, which do not contain the silicone compound (B3) and the polyalkylene oxide (C2), as compared with Example 3. includes a .03 parts by weight, the amount of isocyanate groups derived from the amount of hydroxyl groups derived from _{(M OH)} and (D3) to _{(A5) (M NCO)} is in molar ratio, _M NCO / (A5 of (D3) ) _MOH = 1.05 urethane-forming composition (EC3). Table 4 shows the results of Comparative Example 3. Since (C2) is not contained, the composition (EC3) is inferior in coatability, and the coating film of polyurethane (JC3) obtained from the composition (EC3) is coated. It was sticky.

In Example 4, 99 parts by weight of the polyalkylene oxide (A1), 1 part by weight of the silicone compound (B1), 2 parts by weight of the polyalkylene oxide (C2), and a mixture (D2 /) of the isocyanate compound (D2) and (D3). D3 = 3/7 (weight ratio)) comprises DOTDL0.03 parts as urethanization catalyst, (A1) and (B1) and (the amount of the hydroxyl group derived from C2) _{(M OH)} and (D2) the amount of isocyanate groups derived from (D3) _{(M NCO)} is in molar ratio, _M NCO / (A1) and (B1) _M OH = 0.80 in (C2) of (D2) and (D3) _{The amount of hydroxyl groups (MOH} ) and (G1) derived from the prepolymer (F1) containing the prepolymer (F1) obtained by reacting the urethane-forming composition (E4) and the isocyanate compound (G1) A urethane-forming composition (H1) in which the amount of derived isocyanate groups ( _MNCO ) is (G1) _MNCO / (F1) M _{OH = 1.05 in molar ratio.} Table 5 shows the results of Example 4. The urethane-forming composition (H1) has good coatability and curability, and the polyurethane (J4) coating film obtained from the composition (H1) is sticky. There wasn't.

In Comparative Example 4, 99 parts by weight of the polyalkylene oxide (A1), 1 part by weight of the silicone compound (B1), and the isocyanate compound (D2), which did not contain the polyalkylene oxide (C2), were compared with the fourth example. mixtures of D3) (D2 / D3 = 3 /7 ( weight ratio)) comprises DOTDL0.03 parts as urethane catalysts, and (A1) and (the amount of hydroxyl groups derived from B1) _{(M OH)} ( the amount of isocyanate groups derived from D2) and _{(D3) (M NCO)} is in molar ratio, urethane _M OH = 0.80 in (D2) and _M NCO / (A1) and the (D3) (B1) a prepolymer obtained by reacting the formed composition (EC4) (FC1), from containing an isocyanate compound (G1), the amount of hydroxyl groups derived from the prepolymer _{(FC1) (M OH)} and the (G1) the amount of isocyanate groups _{(M NCO)} which is, in molar ratio, a (G1) of the _{(M NCO) / (FC1)} M OH = 1.05 urethane-forming composition of (HC1). Table 5 shows the results of Comparative Example 4. Since (C2) is not contained, the composition (HC1) is inferior in coatability, but the polyurethane (JC4) obtained from the composition (HC1) is coated. The membrane was not sticky.

In Example 5, 89 parts by weight of polyalkylene oxide (A3), 10 parts by weight of polyalkylene oxide (A7), 1 part by weight of silicone compound (B2), 2 parts by weight of polyalkylene oxide (C1), and an isocyanate compound ( D3) and includes a DOTDL0.03 parts as urethanization catalysts, isocyanate group derived from the (A3) and (A7) and (B2) and (the amount of the hydroxyl group derived from C1) _{(M OH)} (D3) the amount _{(M NCO)} is in molar ratio, _M NCO / (A3) and (A7) and (B2) and urethane forming composition _M OH = 0.85 in (C1) of (D3) (E5) prepolymer (F2) obtained by reacting, wherein the isocyanate compound (G1), the amount of isocyanate groups derived from the amount of hydroxyl groups derived from the prepolymer (F2) _{(M OH)} and the (G1) (M _NCO ) is a urethane-forming composition (H2) of (G1) ( _MNCO ) / (F2) with _{MOH = 1.05 in a molar ratio.} Table 5 shows the results of Example 5. The urethane-forming composition (H2) has good coatability and curability, and the polyurethane (J5) coating film obtained from the composition (H2) is sticky. There were few.

Comparative Example 5 contains 90 parts by weight of the polyalkylene oxide (A3), 10 parts by weight of the polyalkylene oxide (A7), and 2 parts by weight of the polyalkylene oxide (C1), which does not contain the silicone compound (B2). , and comprise isocyanate compound (D3) a DOTDL0.03 parts by weight of a urethane catalyst, derived from (A3) and (A7) and the amount of hydroxyl groups derived from _{(C1) (M OH) (} D3) A urethane-forming composition (EC5) having an isocyanate group amount ( _MNCO ) of (D3) _MNCO / (A3), (A7) and (C1) M _{OH = 0.85 is reacted in a molar ratio.} prepolymer (FC2) obtained by causing an isocyanate compound (G1) includes the amount of hydroxyl groups derived from the prepolymer _{(FC2) (M OH)} to the amount of isocyanate groups derived from the (G1) _{(M NCO)} but a molar ratio is _M NCO / (FC2) urethane forming composition _M OH = 1.05 in (G1) (HC2). Table 5 shows the results of Comparative Example 5. Since (B2) was not contained, the coating film of polyurethane (JC5) obtained from the composition (HC2) was sticky.

In Example 6, 99 parts by weight of the polyalkylene oxide (A6), 1 part by weight of the silicone compound (B2), 2 parts by weight of the polyalkylene oxide (C1), and the isocyanate compound (D3) and DOTDL 0. comprises 03 parts by weight, a molar ratio (A6) and (B2) the amount of isocyanate groups derived from the amount of hydroxyl groups derived from _{(M OH)} and (D3) to _{(C1) (M NCO),} (D3 ) _MNCO / (A6), (B2) and (C1) _MOH = 0.75 urethane-forming composition (E6) obtained by reacting the prepolymer (F3) and the isocyanate compound (G1). ) wherein the amount of isocyanate groups derived from the amount of hydroxyl groups derived from the prepolymer (F3) _{(M OH)} and the (G1) _{(M NCO)} is in molar ratio, (G1) of the _(M NCO) / ( F3) is a urethane-forming composition (H3) having _{M OH = 1.05.} Table 5 shows the results of Example 6. The urethane-forming composition (H3) has good coatability and curability, and the polyurethane (J6) coating film obtained from the composition (H3) is sticky. There were few.

In Comparative Example 6, 100 parts by weight of the polyalkylene oxide (A6), the isocyanate compound (D3), and DOTDL0 as a urethanization catalyst, which do not contain the silicone compound (B2) and the polyalkylene oxide (C1), as compared with Example 6. includes a .03 parts by weight, the amount of hydroxyl groups derived from the (A6) the amount of isocyanate groups derived from the _{(M OH)} and (D3) _{(M NCO)} is in molar ratio, _M NCO / (A6 of (D3) ), _{Which contains the prepolymer (FC3) obtained by reacting the urethane-forming composition (EC6) having M OH} = 0.75 and the isocyanate compound (G1), and the amount of hydroxyl groups derived from the prepolymer (FC3). the amount of isocyanate groups derived from the _{(M OH)} and _{(G1) (M NCO)} is in molar _{ratio, M NCO / (FC3) M} OH = 1.05 urethane-forming composition of (G1) (HC3 ). Table 5 shows the results of Comparative Example 6. Since the composition (HC3) is inferior in coatability because it does not contain (C1), and does not contain (B2), it is derived from the composition (HC3). The obtained polyurethane (JC6) coating film was sticky.

Example 7 is a mixture of 99 parts by weight of the polyalkylene oxide (A2), 1 part by weight of the silicone compound (B1), 0.5 parts by weight of the polyalkylene oxide (C3), and the isocyanate compounds (D2) and (D3). It includes DOTDL0.03 parts by weight as (D2 / D3 = 2/8 ( weight ratio)) and urethane catalyst, and (A2) and (B1) to the amount of hydroxyl groups derived from the _{(C3) (M OH)} ( the amount of isocyanate groups derived from D2) and _{(D3) (M NCO)} is in molar ratio, _M OH = 0 and _{(D2) (D3) M NCO} / (A2) and the (B1) (C3) urethane forming composition .55 prepolymer obtained by reacting (E7) (F4), wherein the isocyanate compound (G1), the amount of hydroxyl groups derived from the prepolymer (F4) _{(M OH)} and ( The amount of isocyanate groups ( _MNCO ) derived from G1) is in a molar ratio, as an organic solvent in the urethane-forming composition (H4) of _{(G1) MNCO} / (F4) _{MOH = 1.2.} It is a urethane-forming composition solution (I1) to which ethyl acetate is added. The concentration of (H4) in the solution (I1) is 50%. Table 6 shows the results of Example 7. The urethane-forming composition solution (I1) has good coatability and curability, and the polyurethane (J7) coating film obtained from the composition solution (I1) has a coating film of polyurethane (J7). There was no stickiness.

Comparative Example 7 contains 99 parts by weight of the polyalkylene oxide (A2), 1 part by weight of the silicone compound (B1), and the isocyanate compound (D2), which does not contain the polyalkylene oxide (C3), as compared with Example 6. mixtures of D3) (D2 / D3 = 2 /8 ( weight ratio)) comprises DOTDL0.03 parts as urethane catalysts, and (A2) and (the amount of hydroxyl groups derived from B1) _{(M OH)} ( the amount of isocyanate groups derived from D2) and _{(D3) (M NCO)} is in molar ratio, urethane _M OH = 0.55 in (D2) and _M NCO / (A2) and of (D3) (B1) a prepolymer obtained by reacting the formed composition (EC7) (FC4), derived include isocyanate compound (G1), the amount of hydroxyl groups derived from the prepolymer _{(FC4) (M OH)} and the (G1) Ethyl acetate is added as an organic solvent to the urethane-forming composition (HC4) having an isocyanate group content ( _MNCO ) of (G1) _MNCO / (FC4) M _{OH = 1.2 in a molar ratio.} Urethane-forming composition solution (IC1). The concentration of (HC4) in the solution (IC1) is 50%. Table 6 shows the results of Comparative Example 7. Since the composition solution (IC1) is inferior in coatability because it does not contain (C3), the polyurethane (JC7) obtained from the composition solution (IC1) The coating film was not sticky.

In Example 8, 99 parts by weight of the polyalkylene oxide (A4), 1 part by weight of the silicone compound (B2), 1 part by weight of the polyalkylene oxide (C2), and a mixture (D2) of the isocyanate compound (D2) and (D3). / D3 = 3/7 includes DOTDL0.03 parts by weight as (weight ratio)) and urethane catalyst, (A4) and (B2) and (the amount of the hydroxyl group derived from C2) _{(M O)} and (D2) the amount of isocyanate groups derived from _{(D3) (M NCO)} is in molar ratio, _M OH = 0.65 in (D2) and _{(D3) M NCO / (A4} ) and the (B2) (C2) The prepolymer (F5) obtained by reacting the urethane-forming composition (E8) of the above and the isocyanate compound (G1) are contained, _{and the amount of hydroxyl groups (MOH} ) and (G1) derived from the prepolymer (F5) are combined. Ethyl acetate as an organic solvent was added to a urethane-forming composition (H5) in which the amount of derived isocyanate groups ( _MNCO ) was (G1) _MNCO / (F5) M _{OH = 1.5 in a molar ratio.} The added urethane-forming composition solution (I2). The concentration of (H5) in the solution (I2) is 50%. Table 6 shows the results of Example 8. The coatability and curability of the composition solution (I2) were good, and the coating film of polyurethane (J8) obtained from (I2) was less sticky.

Comparative Example 8 contains 100 parts by weight of the polyalkylene oxide (A4) and 1 part by weight of the polyalkylene oxide (C2), and the isocyanate compound (D2), which does not contain the silicone compound (B2), as compared with Example 8. mixtures of D3) and (D2 / D3 = 3/7 ( weight ratio)) comprises DOTDL0.03 parts as urethane catalysts, and (A4) and (the amount of the hydroxyl group derived from C2) _{(M OH)} ( the amount of isocyanate groups derived from D2) and _{(D3) (M NCO)} is in molar ratio, urethane _M OH = 0.65 in (D2) and _M NCO / (A4) and of (D3) (C2) a prepolymer obtained by reacting the formed composition (EC8) (FC5), derived include isocyanate compound (G1), the amount of hydroxyl groups derived from the prepolymer _{(FC5) (M OH)} and the (G1) Ethyl acetate is added as an organic solvent to the urethane-forming composition (HC5) having an isocyanate group content ( _MNCO ) of (G1) _MNCO / (FC5) M _{OH = 1.5 in a molar ratio.} Urethane-forming composition solution (IC2). The concentration of (HC5) in the solution (IC2) is 50%. Table 6 shows the results of Comparative Example 8. Since (C2) is contained, the coatability of the composition solution (IC2) is good, but since (B2) is not contained, the composition solution (IC2) is not contained. The coating film of polyurethane (JC8) obtained from) was sticky.

In Example 9, 89 parts by weight of polyalkylene oxide (A2), 10 parts by weight of polyalkylene oxide (A5), 1 part by weight of silicone compound (B3), 2 parts by weight of polyalkylene oxide (C3), and an isocyanate compound ( D3) and includes a DOTDL0.03 parts as urethanization catalysts, isocyanates derived from (A2) and (A5) and (B3) (C3), the amount of hydroxyl groups derived from the _{(M OH)} and (D3) Urethane-forming composition (E9) in which the amount of groups ( _{MNCO ) is M OH = 0.70 of (D3) MNCO} / (A2), (A5), (B3) and (C3) in molar ratio. ) prepolymer obtained by reacting (F6), wherein the isocyanate compound (G1), the amount of isocyanate groups derived from the amount of hydroxyl groups derived from the prepolymer (F6) _{(M OH)} and the (G1) ( _MNCO ) is a urethane-forming composition solution (H6) in which methyl ethyl ketone is added as an organic solvent to a urethane-forming composition (H6) having _MNCO / (F6) M _OH = 1.5 in a molar ratio. (I3). The concentration of (H6) in the solution (I3) is 50%. Table 6 shows the results of Example 9. The coatability and curability of the composition solution (I3) were good, and the coating film of polyurethane (J9) obtained from (I4) was less sticky.

Comparative Example 9 contains 90 parts by weight of the polyalkylene oxide (A2), 10 parts by weight of the polyalkylene oxide (A5), and 10 parts by weight of the polyalkylene oxide (A5), which does not contain the silicone compound (B3) and the polyalkylene oxide (C3) with respect to the example 9. wherein the isocyanate compound (D3) a DOTDL0.03 parts by weight of a urethane catalyst, the amount of isocyanate groups derived from the (A2) and the amount of hydroxyl groups derived from _{(A5) (M OH) (} D3) (M NCO ) it is, in molar ratio, and (D3) _M NCO / (A2) and the (urethane forming composition _M OH = 1.5 to A5) (prepolymer obtained by reacting the EC9) (FC5) comprise isocyanate compound (G1), the amount of isocyanate groups derived from the amount of hydroxyl groups derived from the prepolymer _{(FC6) (M OH)} and the _{(G1) (M NCO)} is in molar ratio of (G1) M the _{NCO / (FC6) M OH =} 1.5 urethane-forming composition of (HC6), a urethane-forming composition was added methyl ethyl ketone as an organic solvent solution (IC3). The concentration of (HC6) in the solution (IC3) is 50%. Table 6 shows the results of Comparative Example 9. Since the composition solution (IC3) is inferior in coatability because it does not contain (C3), and does not contain (B3), the composition solution (IC4) is not contained. The coating film of polyurethane (JC9) obtained from) was sticky.

In Example 10, 99 parts by weight of the polyalkylene oxide (A3), 1 part by weight of the silicone compound (B1), 2 parts by weight of the polyalkylene oxide (C4), and a mixture (D2) of the isocyanate compound (D2) and (D3). / D3 = 2/8 comprises DOTDL0.03 parts by weight as (weight ratio)) and urethane catalyst, (A3) and (B1) and (the amount of hydroxyl groups derived from C4) _{(M OH)} and (D2) the amount of isocyanate groups derived from _{(D3) (M NCO)} is in molar ratio, _M OH = 0.60 in (D2) and _{(D3) M NCO / (A3} ) and the (B1) (C4) _{The amount of hydroxyl groups (MOH} ) and (G1) of the prepolymer (F7) obtained by reacting the urethane-forming composition (E10) of the above, which contains the isocyanate compound (G1) and is derived from the prepolymer (F7). Ethyl acetate was added as an organic solvent to the urethane-forming composition (H7) having an isocyanate group amount ( _MNCO ) of (G1) of _MNCO / (F7) of _{MOH = 2.0 in a molar ratio.} Urethane-forming composition solution (I4). The concentration of (H7) in the solution (I4) is 70%. Table 7 shows the results of Example 10. The coatability and curability of the composition solution (I4) were good, and the coating film of polyurethane (J10) obtained from (I4) was not sticky.

In Example 11, 99 parts by weight of the polyalkylene oxide (A2), 1 part by weight of the silicone compound (B1), 2 parts by weight of the polyalkylene oxide (C5), and a mixture (D2) of the isocyanate compound (D2) and (D3). / D3 = 2/8 comprises DOTDL0.03 parts by weight as (weight ratio)) and urethane catalyst, (A2) and (B1) and (the amount of hydroxyl groups derived from C5) _{(M OH)} and (D2) the amount of isocyanate groups derived from _{(D3) (M NCO)} is in molar ratio, _M OH = 0.60 in (D2) and _{(D3) M NCO / (A2} ) and the (B1) (C5) urethane forming composition and (E11) prepolymer obtained by reacting (F8), wherein the isocyanate compound (G1), the amount of hydroxyl groups derived from the prepolymer _{(F8) (M OH)} and (G1) Methyl ethyl ketone was added as an organic solvent to the urethane-forming composition (H8) having an isocyanate group amount ( _MNCO ) of (G1) of _MNCO / (F8) of M _{OH = 2.0 in a molar ratio.} It is a urethane-forming composition solution (I5). The concentration of (H8) in the solution (I5) is 70%. Table 7 shows the results of Example 11, and the coatability and curability of the composition solution (I5) were good, and the coating film of polyurethane (J11) obtained from (I5) was not sticky.

In Example 12, 98 parts by weight of the polyalkylene oxide (A1), 2 parts by weight of the silicone compound (B2), 2 parts by weight of the polyalkylene oxide (C6), and a mixture (D2) of the isocyanate compound (D2) and (D3). / D3 = 2/8 comprises DOTDL0.03 parts by weight as (weight ratio)) and urethane catalyst, (A1) and (B2) and (the amount of hydroxyl groups derived from C6) _{(M OH)} and (D2) the amount of isocyanate groups derived from _{(D3) (M NCO)} is in molar ratio, _M OH = 0.60 in (D2) and _{(D3) M NCO / (A1} ) and the (B2) (C6) urethane forming composition and (E12) prepolymer obtained by reacting (F9), wherein the isocyanate compound (G1), the amount of hydroxyl groups derived from the prepolymer _{(F9) (M OH)} and (G1) Ethyl acetate was added as an organic solvent to the urethane-forming composition (H9) having an isocyanate group amount ( _MNCO ) of (G1) of _MNCO / (F9) of _{MOH = 2.0 in a molar ratio.} Urethane-forming composition solution (I6). The concentration of (H9) in the solution (I6) is 70%. Table 7 shows the results of Example 12. The coatability and curability of the composition solution (I6) were good, and the coating film of polyurethane (J12) obtained from (I6) was less sticky.

In Example 13, 99 parts by weight of the polyalkylene oxide (A2), 1 part by weight of the silicone compound (B1), 2 parts by weight of the polyalkylene oxide (C7), and a mixture (D2) of the isocyanate compound (D2) and (D3). / D3 = 2/8 comprises DOTDL0.03 parts by weight as (weight ratio)) and urethane catalyst, (A2) and (B1) and (the amount of hydroxyl groups derived from C7) _{(M OH)} and (D2) the amount of isocyanate groups derived from _{(D3) (M NCO)} is in molar ratio, _M OH = 0.60 in (D2) and _{(D3) M NCO / (A2} ) and the (B1) (C7) _{The amount of hydroxyl groups (MOH} ) and (G1) of the prepolymer (F10) obtained by reacting the urethane-forming composition (E13) of the above, which contains the isocyanate compound (G1) and is derived from the prepolymer (F10). Ethyl acetate was added as an organic solvent to the urethane-forming composition (H10) having an isocyanate group amount ( _MNCO ) of (G1) of _MNCO / (F10) of _{MOH = 2.0 in a molar ratio.} Urethane-forming composition solution (I7). The concentration of (H10) in the solution (I7) is 40%. Table 7 shows the results of Example 13. The coatability and curability of the composition solution (I6) were good, and the coating film of polyurethane (J13) obtained from (I7) was not sticky.

In Example 14, 99 parts by weight of the polyalkylene oxide (A3), 1 part by weight of the silicone compound (B1), 2 parts by weight of the polyalkylene oxide (C8), and a mixture (D2) of the isocyanate compound (D2) and (D3). / D3 = 2/8 (weight ratio)) and include DOTDL0.03 parts as urethanization catalyst, (A3) and (B1) and (the amount of hydroxyl groups derived from C8) _{(M OH)} and (D2) the amount of isocyanate groups derived from _{(D3) (M NCO)} is in molar ratio, _M OH = 0.60 in (D2) and _{(D3) M NCO / (A3} ) and the (B1) (C8) urethane forming composition and (E14) prepolymer obtained by reacting (F11), wherein the isocyanate compound (G1), the amount of hydroxyl groups derived from the prepolymer _{(F11) (M OH)} and (G1) Ethyl acetate was added as an organic solvent to the urethane-forming composition (H11) having an isocyanate group amount ( _MNCO ) of (G1) of _MNCO / (F11) of _{MOH = 2.0 in a molar ratio.} Urethane-forming composition solution (I8). The concentration of (H11) in the solution (I8) is 40%. Table 7 shows the results of Example 14, and the coatability and curability of the composition solution (I8) were good, and the coating film of polyurethane (J14) obtained from (I8) was not sticky.

Example 15 shows 99 parts by weight of the polyalkylene oxide (A2), 1 part by weight of the silicone compound (B3), 2 parts by weight of the polyalkylene oxide (C9), and a mixture (D2) of the isocyanate compound (D2) and (D3). / D3 = 2/8 comprises DOTDL0.03 parts by weight as (weight ratio)) and urethane catalyst, (A2) and (B3) and (the amount of hydroxyl groups derived from C9) _{(M OH)} and (D2) the amount of isocyanate groups derived from _{(D3) (M NCO)} is in molar ratio, _M OH = 0.60 in (D2) and _{(D3) M NCO / (A2} ) and the (B3) (C9) urethane forming composition and a prepolymer obtained by reacting (E15) (F12), wherein the isocyanate compound (G1), the amount of hydroxyl groups derived from the prepolymer _{(F12) (M OH)} and (G1) To a urethane-forming composition (H12) having an isocyanate group amount ( _MNCO ) of (G1) of _MNCO / (F12) of _MOH = 2.0 in a molar ratio, ethyl acetate was added as an organic solvent. Urethane-forming composition solution (I9). 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, and the polyurethane (J15) coating film obtained from (I9) was less sticky.

In Comparative Example 10, 99 parts by weight of the polyalkylene oxide (AC1), 1 part by weight of the silicone compound (B1), 3 parts by weight of the polyalkylene oxide (C2), and the isocyanate compound (D1) and DOTDL 0. comprises 03 parts by weight, a molar ratio (AC1) and (B1) to the amount of hydroxyl groups derived from _{(C2) (M OH)} to the amount of isocyanate groups derived from _{(D1) (M NCO),} (D1 ) _MNCO / (AC1), (B1) and (C2) _MOH = 1.05 urethane-forming composition (EC10), and (AC1) is a poly that has a high degree of unsaturation and is out of the claimed range. It is an alkylene oxide. Table 8 shows the results of Comparative Example 10. Since (AC1) has a high degree of unsaturation (many unsaturated monools), it is excellent in coatability but inferior in curability. The coating film of polyurethane (JC10) obtained from the composition (EC10) was sticky because it contained a large amount of unsaturated monool.

In Comparative Example 11, 99 parts by weight of the polyalkylene oxide (AC2), 1 part by weight of the silicone compound (B2), 3 parts by weight of the polyalkylene oxide (C3), and the isocyanate compound (D1) and DOTDL 0. comprises 1 part by weight, the (AC2) and (B2) the amount of isocyanate groups derived from the amount of hydroxyl groups derived from the _{(C3) (M OH)} and _{(D1) (M NCO),} in molar ratio, (D1 ) and _M NCO / in (AC2) and (B2) and (urethane forming composition _M OH = 1.05 in C3) (EC11), (AC2) it has a high degree of unsaturation, poly departing from claims It is an alkylene oxide. Table 8 shows the results of Comparative Example 11. Since (AC2) has a considerably high degree of unsaturation (a considerable amount of unsaturated monool), it is excellent in coatability but inferior in curability. By using a composition in which the average number of functional groups of isocyanate groups is large (D1) and the amount of DOTDL as a urethanization catalyst is increased to 0.1 parts by weight, the curability is improved, but the degree of unsaturation is improved. The curability of a composition using a polyalkylene oxide having a high degree of unsaturation (mostly unsaturated monool) is forcibly accelerated. Since (AC2) has a large amount of unsaturated monool, the coating film of polyurethane (JC11) obtained from the composition (EC11) has a large amount of unsaturated monool, so that the surface is considerably sticky.

In Comparative Example 12, 99 parts by weight of the polyalkylene oxide (AC3), 1 part by weight of the silicone compound (B3), 3 parts by weight of the polyalkylene oxide (C3), and the isocyanate compound (D1) and DOTDL 0. comprises 1 part by weight, the (AC3) and (B3) to the amount of isocyanate groups derived from the amount of hydroxyl groups derived from the _{(C3) (M OH)} and _{(D1) (M NCO),} in molar ratio, (D1 ) and _M NCO / (AC3) and the (B3) and (urethane forming composition _M OH = 1.05 in C3) (EC 12), (AC3) has high degree of unsaturation, poly departing from claims It is an alkylene oxide. 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 functional groups of isocyanate groups (D1). ) And the composition in which the amount of DOTDL as a urethanization catalyst was increased to 0.1 parts by weight, the curability was good, but the degree of unsaturation was high (many unsaturated monools). The curability of the composition using the polyalkylene oxide is forcibly accelerated. Since (AC2) contains a large amount of unsaturated monool, the surface of the polyurethane (JC12) coating film obtained from the composition (EC12) was considerably sticky.

Comparative Example 13 shows 99 parts by weight of the polyalkylene oxide (AC1), 1 part by weight of the silicone compound (B1), 3 parts by weight of the polyalkylene oxide (C1), and a mixture (D2) of the isocyanate compounds (D2) and (D3). / D3 = 2/8 (weight ratio)) and include DOTDL0.03 parts as urethanization catalyst, (AC1) and (B1) and (the amount of the hydroxyl group derived from C1) _{(M OH)} and (D2) the amount of isocyanate groups derived from _{(D3) (M NCO)} is in molar ratio, _M OH = 0.85 and _{(D2) (D3) M NCO} / (AC1) and the (B1) (C1) urethane forming composition and a prepolymer obtained by reacting (EC13) (FC7), consists isocyanate compound (G1), the amount of hydroxyl groups derived from the prepolymer _{(FC7) (M OH)} and (G1) In a urethane-forming composition (HC7) in which the amount of isocyanate groups ( _MNCO ) derived from the above is (G1) _MNCO / (FC7) M _{OH = 2.0 in molar ratio, ethyl acetate as an organic solvent} Is a urethane-forming composition solution (IC4) to which the above is added. The concentration of (HC7) in the solution (IC4) is 50%. Table 9 shows the results of Comparative Example 13. Since (AC1) has a high degree of unsaturation (many unsaturated monools), (IC4) is excellent in coatability but inferior in curability. rice field. The surface of the polyurethane (JC13) coating film obtained from the solution (IC4) was sticky due to the large amount of unsaturated monool.

Comparative Example 14 shows 99 parts by weight of the polyalkylene oxide (AC2), 1 part by weight of the silicone compound (B2), 3 parts by weight of the polyalkylene oxide (C2), and a mixture (D2) of the isocyanate compounds (D2) and (D3). / D3 = 2/8 comprises DOTDL0.03 parts by weight as (weight ratio)) and urethane catalyst, (AC2) and (B2) and (the amount of the hydroxyl group derived from C2) _{(M OH)} and (D2) the amount of isocyanate groups derived from _{(D3) (M NCO)} is in molar ratio, _M OH = 0.85 in (D2) and _{(D3) M NCO / (AC2} ) and the (B2) (C2) urethane forming composition and a prepolymer obtained by reacting (EC14) (FC8), consists isocyanate compound (G1), the amount of hydroxyl groups derived from the prepolymer _{(FC8) (M OH)} and (G1) an amount _{(M NCO)} is the molar ratio of isocyanate groups derived from, the _{M NCO / (FC8) M OH} = 2.0 urethane forming composition of (G1) (HC8), ethyl acetate as an organic solvent Is a urethane-forming composition solution (IC5) to which the above is added. 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 monool) than (AC1) used in Comparative Example 13, (IC5) has a coatability. However, it was inferior in curability. Since the degree of unsaturation of (AC2) is quite high, the surface of the polyurethane (JC14) coating film obtained from the solution (IC5) was considerably sticky.

Comparative Example 15 shows 99 parts by weight of the polyalkylene oxide (AC4), 1 part by weight of the silicone compound (B1), 2 parts by weight of the polyalkylene oxide (C3), and a mixture (D2) of the isocyanate compounds (D2) and (D3). / D3 = 2/8 (weight ratio)) comprises DOTDL0.03 parts as urethanization catalyst, (AC4) and (B1) and (the amount of hydroxyl groups derived from C3) _{(M OH)} and (D2) the amount of isocyanate groups derived from _{(D3) (M NCO)} is in molar ratio, _M OH = 0.90 and _{(D2) (D3) M NCO} / and (AC4) and (B1) (C3) urethane forming composition and a prepolymer obtained by reacting (EC15) (FC9), wherein an isocyanate compound (G1), the amount of hydroxyl groups derived from the prepolymer _{(FC9) (M OH)} and (G1) an amount _{(M NCO)} is the molar ratio of isocyanate groups derived from, the _{M NCO / (FC9) M OH} = 2.0 urethane forming composition of (G1) (HC9), ethyl acetate as an organic solvent Is a urethane-forming composition solution (IC6) to which the above is added. The concentration of (HC9) in the solution (IC6) is 50%. Table 9 shows the results of Comparative Example 15. (IC6) had good coatability and curability, and the polyurethane (JC15) coating film obtained from (IC7) was not sticky.

Comparative Example 16 shows 99 parts by weight of the polyalkylene oxide (A2), 1 part by weight of the silicone compound (B3), 1 part by weight of the polyalkylene oxide (CC1), and a mixture (D2) of the isocyanate compound (D2) and (D3). / D3 = 2/8 (weight ratio)) and include DOTDL0.03 parts as urethanization catalyst, (A2) and (B3) and (the amount of hydroxyl groups derived from CC1) _{(M OH)} and (D2) the amount of isocyanate groups derived from _{(D3) (M NCO)} is in molar ratio, _M OH = 0.85 in (D2) and _{(D3) M NCO / (A2} ) and the (B3) (CC1) urethane forming composition and a prepolymer obtained by reacting (EC16) (FC10), wherein an isocyanate compound (G1), the amount of hydroxyl groups derived from the prepolymer _{(FC10) (M OH)} and (G1) an amount _{(M NCO)} is the molar ratio of isocyanate groups derived from, the _{M NCO / (FC10) M OH} = 2.0 urethane forming composition of (G1) (HC10), ethyl acetate as an organic solvent Is a urethane-forming composition solution (IC7) to which the above is added. The concentration of (HC10) in the solution (IC7) is 50%. Table 9 shows the results of Comparative Example 16. Since (CC1) has two hydroxyl groups in one molecule, the prepolymer obtained by the reaction with the mixture of the isocyanate compounds (D2) and (D3) is densely crosslinked. Even if a structure is formed and the composition solution (IC7) is applied, the flow of the solution is poor and the coatability is significantly inferior, and the obtained polyurethane (JC16) coating film is significantly inferior in surface appearance. It was a thing.

Comparative Example 17 shows 99 parts by weight of the polyalkylene oxide (A2), 3 parts by weight of the silicone compound (B1) and the polyalkylene oxide (CC2), and a mixture (D2 / D3 =) of the isocyanate compounds (D2) and (D3). 2/8 (weight ratio)) comprises DOTDL0.03 parts as urethanization catalyst, (A2) and (B1) and (the amount of hydroxyl groups derived from CC2) _{(M OH)} and (D2) (D3 the amount of isocyanate groups derived from) _{(M NCO)} is in molar ratio, _M OH = 0 of (D2) and _{(D3) M NCO / (A2} ) and the (A2) and (B1) (CC2). 80 urethane-forming composition and a prepolymer obtained by reacting (EC17) (FC11), wherein an isocyanate compound (G1), the amount of hydroxyl groups derived from the prepolymer _{(FC11) (M OH)} and (G1 the amount of isocyanate groups derived from) _{(M NCO)} is in molar ratio, the _{(M NCO / (FC11 M OH} = 2.0 urethane forming composition) of G1) (HC11), acetic acid as the organic solvent It is a urethane-forming composition solution (IC8) to which ethyl is added. The concentration of (HC11) in the solution (IC8) is 50%. Table 9 shows the results of Comparative Example 17. Since the alkylene oxide (CC2) does not contain ethylene oxide residues, the composition solution (IC8) is inferior in coatability, but is obtained from the composition solution (IC8). The coating film of polyurethane (JC17) was not sticky.

As described above, as shown in Examples, the urethane-forming composition in the present development has excellent coatability when coated with a coating machine or the like, and can be used with an isocyanate compound without using a large amount of urethanization catalyst. It has high productivity by advancing curing (solidification) accompanying the reaction, and further, it is possible to obtain polyurethane with less stickiness by reaction with an isocyanate compound. It was shown that the polyurethane obtained from the urethane-forming composition can be suitably used for a sealing material, a paint, an elastomer and the like by taking advantage of its characteristics.

Claims (15)

Polyalkylene oxide (A) having an alkylene oxide residue having 3 or more carbon atoms and 2 or more hydroxyl groups in one molecule, and
Silicone compounds having one or more hydroxyl groups in one molecule,
Polyalkylene oxide (C) containing one hydroxyl group and ethylene oxide residue in one molecule, and
The isocyanate compound (D) having an average number of functional groups of 2.0 or more is included.
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). 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 claim is that the polyalkylene oxide (C) is at least one selected from the group consisting of polyoxyalkylene glycol monoalkyl ether, polyoxyalkylene glycol monoalkenyl ether, and polyoxyalkylene glycol monophenyl ether. 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 the hydroxyl value of the polyalkylene oxide (A) in one molecule of the polyalkylene oxide (A). The urethane-forming composition (E) according to any one of claims 1 to 3, which has a number average molecular weight calculated from the number of hydroxyl groups. A urethane prepolymer (F) which 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 and has at least one hydroxyl group.
The urethane-forming compositions among the (E), the polyalkylene oxide (A) and the silicone compound (B) and the isocyanate compound to the amount of hydroxyl groups derived from the polyalkylene oxide _{(C) (M OH) (} D) the amount of isocyanate groups derived from the ratio of _{(M NCO) (M NCO /} M OH) is 1.0 less than a molar ratio of the urethane prepolymer (F). The urethane-forming composition (H) containing the urethane prepolymer (F) according to claim 5 and the isocyanate compound (G). The urethane-forming composition (E) according to any one of claims 1 to 4, and the urethane-forming composition (E).
A urethane-forming composition solution (I) containing an organic solvent.
The 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. The urethane prepolymer solution (I) containing the urethane prepolymer (F) according to claim 5 and an organic solvent, and the concentration of the urethane prepolymer (F) in the urethane prepolymer solution (I). Is a urethane prepolymer solution (I), characterized in that the amount is 10% by mass or more and 90% by mass or less. The urethane-forming composition solution (I) containing the urethane-forming composition (H) according to claim 6 and an organic solvent, and the urethane-forming in the urethane-forming composition solution (I). The urethane prepolymer solution (I), wherein the concentration of the sex 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. Polyurethane (J), which is a reaction product of the urethane-forming composition (E) in I) or the urethane-forming composition (H) in the urethane-forming composition solution (I) according to claim 9. .. The polyurethane sheet made of polyurethane (J) according to claim 10. A sealing material made of the polyurethane (J) according to claim 10 or the polyurethane sheet according to claim 11. A coating material comprising the polyurethane (J) according to claim 10 or the polyurethane sheet according to claim 11. The pressure-sensitive adhesive comprising the polyurethane (J) according to claim 10 or the polyurethane sheet according to claim 11. The adhesive comprising the polyurethane (J) according to claim 10 or the polyurethane sheet according to claim 11.