JP2020158552A - Urethane prepolymer composition - Google Patents

Abstract

To provide: a urethane prepolymer composition having a sufficiently long pot life even when using a highly reactive polyol; and polyurethane using the same.SOLUTION: A urethane prepolymer composition comprises: a urethane prepolymer; an active methylene compound having keto-enol tautomerism; a urethanization catalyst containing a metal component. The urethane prepolymer has a weight average molecular weight of 3,000 or more, contains alkylene oxide residues having 3 or more carbon atoms, unsaturated groups of 0.010 meq/g or less, and ethylene oxide residues as essential components, and further contains any one or more residues selected from a tetramethylene ether residue, C6 or more sugar residues, and aromatic amine residues.SELECTED DRAWING: None

Description

The present disclosure relates to urethane prepolymer compositions.

Polyalkylene oxides containing a large amount of by-product monool having an unsaturated group at one end (hereinafter referred to as unsaturated monool) and urethane prepolymers using the same are used as raw materials for polyurethane. However, the polyalkylene oxide containing a large amount of such unsaturated monool and the urethane prepolymer using the same have a problem that the curing (solidification) accompanying the reaction with the isocyanate compound takes time and the productivity is impaired. Occurs.

Further, the polyurethane obtained from such a polyalkylene oxide containing a large amount of unsaturated monool is unlikely to have a high molecular weight, has a small tensile elongation at break, and has a low tensile strength at break.

On the other hand, since unsaturated monool is monofunctional, the conventional polyalkylene oxide containing a large amount of unsaturated monool and the urethane prepolymer obtained by using the unsaturated monool undergo a urethanization reaction with an isocyanate compound. However, since the molecular weight does not easily increase, it is easy to maintain a low viscosity even when it takes time after mixing with the isocyanate compound, and when it is coated with a coating machine to obtain polyurethane from those compositions, It has the advantage that it has a long pot life and is 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 improved, and the tensile elongation at break and the tensile strength at break are increased. However, polyalkylene oxides containing less unsaturated monool and urethane prepolymers obtained by using them tend to increase in molecular weight as the urethanization reaction with the isocyanate compound proceeds, so that the thickening after mixing of the isocyanate compound is quick. It has been desired to improve the pot life, further improve the productivity (curability), and further improve the tensile breaking strength of the obtained polyurethane.

On the other hand, in order to improve productivity and increase tensile breaking strength, in addition to polyalkylene oxide containing less unsaturated monool, highly reactive polyoxytetramethylene glycol and sugar residues having a high number of functional groups are added. When a polyol having a polyol or a polyol having a highly reactive and highly functional group aromatic amine residue is introduced into the urethane prepolymer, the molecular weight tends to increase immediately when the urethanization reaction with the isocyanate compound proceeds. There is a problem that the viscosity is easily thickened when it takes time after mixing with the isocyanate compound, and it is more difficult to apply the polyurethane when it is applied with a coating machine or the like in order to obtain polyurethane from those compositions.

That is, urethane obtained by using a polyol such as polyoxytetramethylene glycol, a polyol having a sugar residue having a high number of functional groups, and a polyol having an aromatic amine residue, in addition to a polyalkylene oxide having a small amount of unsaturated monool. Even when a prepolymer is used, there has been a demand for a urethane prepolymer composition capable of obtaining a polyurethane exhibiting a high tensile breaking strength without impairing productivity and having a remarkably long pot life.

Japanese Unexamined Patent Publication No. 2017-25274

One aspect of the present invention includes a urethane prepolymer that contributes to the formation of polyurethane having a high tensile breaking strength, has a long pot life, and has high productivity, and the urethane prepolymer composition. It is directed to provide urethane prepolymer composition solutions.

Another aspect of the invention is directed to providing polyurethane, which is a reactant of the urethane prepolymer 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 [12] shown below.
[1] A urethane prepolymer composition comprising a urethane prepolymer (E), an active methylene group-containing compound (F) having keto-enol tectabilism, and a urethanization catalyst (G) containing a metal component.
The urethane prepolymer (E)
With a weight average molecular weight of 3000 or more
It contains an alkylene oxide residue having 3 or more carbon atoms, an unsaturated group of 0.010 meq / g or less, and an ethylene oxide residue as essential constituents.
Further, it contains at least one of a tetramethylene-ether residue, a sugar residue having 6 or more carbon atoms, and an aromatic amine residue as a constituent component.
Urethane prepolymer composition (H).
[2] The urethane prepolymer (E) contains a polyalkylene oxide (A) having an alkylene oxide residue having 3 or more carbon atoms and 2 or more hydroxyl groups in one molecule, a tetramethylene-ether residue, and a carbon number of carbon atoms. A polyol (B) having at least one of 6 or more sugar residues and an aromatic amine residue, a polyalkylene oxide (C) containing one hydroxyl group and an ethylene oxide residue in one molecule, and an isocyanate group. It is a reaction product with the isocyanate compound (D) having an average number of functional groups of 2.0 or more.
The polyalkylene oxide (A) is
The degree of unsaturation is 0.010 meq / g or less,
The number average molecular weight is 800 or more.
The urethane prepolymer composition (H) according to [1].
[3] The urethane prepolymer (E) has at least one hydroxyl group in one molecule, and the total amount of hydroxyl groups derived from the polyalkylene oxide (A), the polyol (B) and the polyalkylene oxide (C). the isocyanate compound to the _{(M OH)} ratio _(M NCO _/ M _OH) of the amount of isocyanate groups derived from _{(D) (M NCO)} is a less than 1.0 in a molar ratio, according to [2] urethane Prepolymer composition (H).
[4] The urethane prepolymer composition according to any one of [1] to [3], wherein the active methylene group-containing compound (F) having keto-enol tautomerism is acetylacetone or ethyl acetoacetate. H).
[5] A urethane prepolymer composition solution (I) containing the urethane prepolymer composition (H) according to [1] to [4] and an organic solvent.
A urethane prepolymer composition in which the concentration of the urethane-forming composition (E) or the urethane-forming composition (H) in the urethane-forming composition solution (I) is 10% by mass or more and 99% by mass or less. Solution (I).
[6] Polyurethane containing the urethane prepolymer composition (E) according to [1] to [4] or the urethane prepolymer composition solution (I) according to [5] and an isocyanate compound (J). Formable composition (K).
[7] Polyurethane (L), which is a reaction product of the urethane-forming composition (K) according to [6].
[8] The polyurethane sheet made of the polyurethane (L) according to [7].
[9] A sealing material made of the polyurethane (L) according to [7] or the polyurethane sheet according to [8].
[10] A paint comprising the polyurethane (L) according to [7] or the polyurethane sheet according to [8].
[11] An adhesive comprising the polyurethane (L) according to [7] or the polyurethane sheet according to [8].
[12] An adhesive comprising the polyurethane (L) according to [7] or the polyurethane sheet according to [8].

The urethane prepolymer composition of the present invention has excellent pot life and coatability when coated with a coating machine or the like in order to obtain polyurethane, and does not use a large amount of urethanization catalyst. It is possible to obtain polyurethane having high productivity and high tensile breaking strength by advancing curing (solidification) accompanying the reaction with the isocyanate compound.

In addition, the polyurethane obtained by using the urethane prepolymer composition of the present invention can be suitably used in a wide range of applications such as sealants, paints, adhesives and adhesives.

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

The urethane prepolymer composition (H) according to one aspect of the present invention is
A urethane prepolymer composition comprising a urethane prepolymer (E), an active methylene group-containing compound (F) having keto-enol tectabilism, and a urethanization catalyst (G) containing a metal component.
The urethane prepolymer (E)
With a weight average molecular weight of 3000 or more
It contains an alkylene oxide residue having 3 or more carbon atoms, an unsaturated group of 0.010 meq / g or less, and an ethylene oxide residue as essential constituents.
Further, it contains any residue of tetramethylene-ether residue, sugar residue having 6 or more carbon atoms, and aromatic amine residue as a constituent component.
<Polyalkylene oxide (A)>
The degree of unsaturation of the polyalkylene oxide (A) is preferably 0.010 meq / g or less, more preferably 0.007 meq / g or less, and most preferably 0.004 meq / g or less.

If the degree of unsaturation of the polyalkylene oxide (A) is 0.010 meq / g or less, the urethane prepolymer (E) obtained by using the polyalkylene oxide (A) is cured (solidified) due to the reaction with the isocyanate compound (J). It is preferable because the polyurethane tends to be faster and the obtained polyurethane has a linear high molecular weight, and the tensile elongation at break and the tensile strength at break tend to increase.

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 is the amount of unsaturated monool contained in the polyalkylene oxide. Corresponds to the number. That is, if the degree of unsaturation is high, there are many unsaturated monools, and if the degree of unsaturation is low, there are few unsaturated monools.

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) preferably has a number average molecular weight of 800 or more, more preferably 1000 or more and 30,000 or less, and most preferably 3000 or more and 9000 or less. When the number average molecular weight of the polyalkylene oxide (A) is 800 or more, the urethane prepolymer (E) and the isocyanate obtained by the reaction of the polyol (B), the polyalkylene oxide (C), and the isocyanate compound (D) The pot life tends to be long during the reaction with compound (J), and the obtained polyurethane tends to have large tensile elongation at break and tensile strength at break, which is preferable.

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 the Gel Permeation Chromatography +; GPC method using polystyrene as a standard substance.

The polyalkylene oxide (A) preferably 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 oxide. Oxide residues and the like can be mentioned. 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 also contain an ethylene oxide residue having 2 carbon atoms.

The polyalkylene oxide (A) preferably has two or more hydroxyl groups in one molecule, and the upper limit of the number of hydroxyl groups is not particularly limited, but the number of hydroxyl groups in one molecule is further 6 or less. Preferably, the number of hydroxyl groups in one molecule is 3 or less. When the number of hydroxyl groups in one molecule of the polyalkylene oxide (A) is 6 or less, the urethane prepolymer (E) obtained by using the polyalkylene oxide (A) even when the molecular weight of the polyalkylene oxide (A) is low, It is preferable because the crosslinked structure of the polyurethane obtained by the reaction with the isocyanate compound (J) is difficult to be dense, and the tensile elongation at break and the tensile strength at break are further increased.

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. , 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. Organoaluminium, for example, aluminoxane such as methylaluminoxane, isobutylaluminoxane, and methyl-isobutylaluminoxan.

Examples of the zinc compound include organic zinc such as dimethyl zinc, diethyl zinc and diphenyl zinc; 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.
<Polyprethane (B)>
The polyol (B) preferably has any one of a tetramethylene-ether residue, a sugar residue having 6 or more carbon atoms, and an aromatic amine residue. The same polyol may contain one or more of the above residues, and two or more polyols (B) may be used.

When the polyol (B) contains a sugar residue having 6 or more carbon atoms in one molecule, it is not particularly limited, but contains a sugar residue having 6 or more carbon atoms in one molecule, an alkylene oxide residue and four. A polyol having the above hydroxyl groups is preferable, one is a sugar having 6 or more carbon atoms linked with one type of alkylene oxide, the other is a sugar having 6 or more carbon atoms linked with a plurality of alkylene oxides in a chain, or randomly. It may be connected.

Among them, since alkylene oxide is industrially easily available and easily synthesized, only propylene oxide is linked to a sugar having 6 or more carbon atoms, and only ethylene oxide is linked to a sugar having 6 or more carbon atoms. It is preferable that propylene oxide and ethylene oxide are chained or randomly linked to a sugar having 6 or more carbon atoms.

When the polyol (B) contains a sugar residue having 6 or more carbon atoms in one molecule, the polyol (B) preferably further has four or more hydroxyl groups in one molecule, and more preferably in one molecule. The number of hydroxyl groups is 4 or more and 12 or less, and most preferably 5 or more and 8 or less.

When the number of hydroxyl groups in one molecule of the polyol (B) containing a sugar residue having 6 or more carbon atoms in one molecule is 4 or more and 12 or less, even when the molecular weight of the polyalkylene oxide (A) is low. , The crosslinked structure of the polyurethane obtained by the reaction between the urethane prepolymer (E) obtained by using the urethane prepolymer (E) and the isocyanate compound (J) tends to be uniform, and the tensile breaking strength is further increased, which is preferable.

The number average molecular weight of the polyol (B) containing a sugar residue having 6 or more carbon atoms in one molecule is not particularly limited and is appropriately selected depending on the intended use, but is preferably 100 or more and 3000 or less, and more preferably 500. More than 2000 or less. When the number average molecular weight of the polyol (B) containing a sugar residue having 6 or more carbon atoms in one molecule is 3000 or less, a large number of sugar residues having 6 or more carbon atoms are contained and the tensile strength at break is easily improved. preferable.

The number average molecular weight of the polyol (B) is calculated from the hydroxyl value of the polyol (B) calculated by the method described in JIS K-1557-1 and the number of hydroxyl groups in one molecule of the polyol (B). Can be done.

The structure of the sugar residue of the polyol (B) containing a sugar residue having 6 or more carbon atoms in one molecule is not particularly limited, but a sugar residue having 6 or more and 20 or less carbon atoms in one molecule is preferable. It is more preferably 6 or more and 12 or less sugar residues. When the polyol (B) does not contain a sugar residue having 6 or more carbon atoms, the tensile breaking strength tends to be insufficient, and it is preferable to use a polyol containing either a tetramethylene-ether residue or an aromatic amine residue.

Examples of such sugar residues include multitoll residues, maltose residues, glucose residues, fructose residues, shoecrose residues, sorbitol residues, and the like, and the raw materials are preferably easily available. It is a shoe fructose residue or a sorbitol residue that easily develops good curability and tensile breaking strength. Among them, it is most preferable to contain a shoe-closed residue because it has a cyclic structure and easily develops a high tensile breaking strength.

The polyol (B) containing a sugar residue having 6 or more carbon atoms in one molecule can be generally obtained by ring-opening polymerization of alkylene oxide using a sugar having 6 or more carbon atoms such as shoeclaw or sorbitol as an initiator. , Diethylene triamine, triethanolamine, diethylene glycol, glycerin, propylene glycol and other low-viscosity active hydrogen compounds that do not contain sugar residues with 6 or more carbon atoms may be synthesized in combination with the initiator. It may contain a component having.

For example, normally, the number of hydroxyl groups of sorbitol is 6 and the number of hydroxyl groups of shoeclose is 8, but the number of hydroxyl groups decreases due to the combined use of an initiator containing no shoeclose residue or sorbitol residue or sealing of the terminal. There is.

Commercially available polyalkylene oxides containing shoe-close residues include JEFFOLSA-499 (nominal functional group number 4.3, hydroxyl value 495), JEFFOLSD-361 (nominal functional group number 4.4, hydroxyl value 360), JEFFOLSG- As a polyalkylene oxide containing 522 (nominal functional group number 5.0, hydroxyl value 520), Toho polyol O-850 (nominal functional group number 8, hydroxyl value 380) manufactured by Toho Chemical Industry Co., Ltd., and sorbitol residue, JEFFOLS-manufactured by Huntsman Co., Ltd. 490 (nominal number of functional groups 4.7, hydroxyl value 490) and the like can be mentioned and can be preferably used.

When the polyol (B) contains a tetramethylene-ether residue, it is not particularly limited, but it is preferable that the polyol (B) contains tetramethylene-ether in one molecule and has two or more hydroxyl groups, and the continuous weight of the tetramethylene-ether. It may be coalesced or a block, graft or random copolymer containing tetramethylene-ether.

The number average molecular weight of the polyol (B) containing the tetramethylene-ether residue is not particularly limited and is appropriately selected depending on the intended use, but is preferably 100 or more and 3000 or less, and more preferably 500 or more and 2000 or less. When the number average molecular weight of the polyol (B) containing the tetramethylene-ether residue is 3000 or less, the tensile strength at break is likely to be improved, which is preferable.

The content of the tetramethylene-ether residue in the polyol (B) containing the tetramethylene-ether residue is not particularly limited and is appropriately selected depending on the intended use, but is preferably in the range of 70 to 100%. It is preferably in the range of 90 to 100%. When the content of the tetramethylene-ether residue is 70% or more, the desired tensile breaking strength is likely to be developed, which is preferable.

When the polyol (B) contains an aromatic amine residue, it is not particularly limited, but a polyol containing an aromatic amine residue in one molecule and having an alkylene oxide residue and two or more hydroxyl groups is preferable, and aromatic. It may be either one in which one kind of alkylene oxide is linked to the amine in a chain, one in which a plurality of alkylene oxides are linked in a chain to an aromatic amine, or one in which a plurality of alkylene oxides are randomly linked.

Among them, alkylene oxides are industrially easily available and easily synthesized, so that only propylene oxide is linked to aromatic amines in a chain reaction, and only ethylene oxide is linked to aromatic amines in a chain chain. It is preferable that propylene oxide and ethylene oxide are linked to the aromatic amine in a chained manner or randomly linked.
When the polyol (B) contains an aromatic amine residue, the polyol (B) preferably has two or more hydroxyl groups in one molecule, and more preferably the number of hydroxyl groups in one molecule is 3 or more and 12 or less. Yes, most preferably 4 or more and 6 or less.

When the number of hydroxyl groups in one molecule of the polyol (B) containing an aromatic amine residue in one molecule is 3 or more and 12 or less, even if the molecular weight of the polyalkylene oxide (A) is low, it can be used. It is preferable because the crosslinked structure of the polyurethane obtained by the reaction of the urethane prepolymer (E) obtained in use with the isocyanate compound (J) tends to be uniform and the tensile breaking strength is further increased.

The number average molecular weight of the polyol (B) containing an aromatic amine residue in one molecule is not particularly limited and is appropriately selected depending on the intended use, but is preferably 100 or more and 3000 or less, and more preferably 300 or more and 2000 or less. Is. It is preferable that the number average molecular weight of the polyol (B) containing a sugar residue having 6 or more carbon atoms in one molecule is 3000 or less because it contains a large amount of aromatic amine residues and the tensile strength at break is easily improved.

The number average molecular weight of the polyol (B) is calculated from the hydroxyl value of the polyol (B) calculated by the method described in JIS K-1557-1 and the number of hydroxyl groups in one molecule of the polyol (B). Can be done.

The structure of the aromatic amine residue of the polyol (B) containing the aromatic amine residue in one molecule is not particularly limited, but preferably the aromatic amine having an aromatic ring number of 1 or more and 20 or less in one molecule. It is a residue, more preferably an aromatic amine residue of 1 or more and 3 or less. When the polyol (B) does not contain an aromatic amine residue, the tensile breaking strength tends to be insufficient, and it is preferable to use a polyol containing either a tetramethylene-ether residue or an aromatic amine residue.
Examples of such aromatic amine residues include aniline residue, 2,4-tolylenediamine residue, 2,6-tolylenediamine residue, 2,4'-diphenylmethanediamine residue, and 4,4. '-Diphenylmethane diamine residue, polyphenylene polyamine residue, 1,5-naphthalenediamine residue, trizine diamine residue, xylylenediamine residue, 1,3-phenylenediamine residue, 1,4-phenylenediamine residue, In addition, a mixed residue of two or more of these may be mentioned, preferably a 2,4-tolylenediamine residue, 2,6 which is easily available as a raw material and easily develops good curability and tensile breaking strength. -Trylenediamine residues, as well as mixed residues of two or more of these.

The polyol (B) containing an aromatic amine residue in one molecule is generally obtained by ring-opening polymerization of an alkylene oxide using an aromatic amine such as tolylenediamine or diphenylmethanediamine as an initiator. Ethylenediamine and diethylenetriamine , Triethanolamine, diethylene glycol, glycerin, propylene glycol and other low-viscosity active hydrogen compounds that do not contain aromatic amine residues may be synthesized in combination with the initiator, and include components having the above residues. You may.

For example, normally, the number of hydroxyl groups of a tolylene amine-initiated polyol is 4, and the number of hydroxyl groups of an aniline-initiated polyol is 2, but a combination of an initiator containing no tolylene amine residue or an aniline residue or alkylene oxide is not added. The number of hydroxyl groups may decrease due to the residual amino groups.

Examples of the commercially available polyol (B) containing an aromatic amine residue include JEFFOLAD-310 (nominal functional group number 3.2, hydroxyl value 310), JEFFOLAD-500 (nominal functional group number 3.2, hydroxyl value 360) manufactured by Huntsman. Toho polyol AB-250 (nominal functional group number 2.0, hydroxyl value 440) manufactured by Toho Chemical Industry Co., Ltd. AR-2589 (nominal functional group number 4.0, hydroxyl value 360) manufactured by Toho Chemical Industry Co., Ltd. 750 (nominal number of functional groups 4.0, hydroxyl value 300) and the like can be mentioned and can be preferably used.

The polyol (B) may be used in combination of two or more types, and is not particularly limited. For example, a combination of a polyol (B1) having a tetramethylene-ether residue and a polyol (B2) containing a sugar residue having 6 or more carbon atoms, a polyol (B1) having a tetramethylene-ether residue and an aromatic amine residue. Examples thereof include a combination of a polyol (B3) having a group, a polyol (B2) containing a sugar residue having 6 or more carbon atoms, and a polyol (B3) having an aromatic amine residue, and examples thereof include (B1) and (B2). ) And (B3) may be combined in combination of three or more.
<Polyalkylene oxide (C)>
The polyalkylene oxide (C) preferably contains one hydroxyl group and ethylene oxide residue in one molecule. Although not particularly limited, the polyoxyalkylene is particularly excellent when the urethane prepolymer composition (H) containing the urethane prepolymer (E) obtained by using the urethane prepolymer composition (H) is coated with a coating machine or the like. It is more preferable that the amount is one or more selected from the group consisting of glycol monoalkyl ether, polyoxyalkylene glycol monoalkenyl ether, and polyoxyalkylene glycol monophenyl ether.

Here, the polyoxyalkylene glycol monoalkyl ether is not particularly limited, and for example, polyoxyethylene glycol monomethyl ether, polyoxyethylene glycol monobutyl ether, polyoxy (ethylene / propylene) glycol monomethyl ether, polyoxy ( Ethylene / propylene) glycol monobutyl ether, polyoxyethylene glycol monolaurate, polyoxyethylene glycol monolaurylamine and the like can be preferably used. 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, in order to have excellent coatability when coating the urethane prepolymer composition (H) containing the urethane prepolymer (E) obtained by using the polyalkylene oxide (C), the ethylene oxide residue is used. One or more of polyoxyethylene glycol monomethyl ether, polyoxyethylene glycol monobutyl ether, polyoxy (ethylene / propylene) glycol monomethyl ether, and polyoxy (ethylene / propylene) glycol monobutyl ether having a content of 50% or more. It is preferable to include it.

Here, the number average molecular weight of the polyalkylene 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 prepolymer composition (H) becomes too low, and the liquid flow when the urethane prepolymer composition (H) is applied by a coating machine or the like. The defective phenomenon may occur, and the thickness of the obtained polyurethane coating film may become uneven. On the other hand, if the molecular weight of the polyalkylene oxide (C) is too high, the surface of the coating film becomes rough or the coating film becomes opaque when the urethane prepolymer composition (H) is applied with a coating machine or the like. It may happen. 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).
<Isocyanate compound (D)>
The isocyanate compound (D) is preferably, but 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, an aliphatic isocyanate, an alicyclic isocyanate, or a modified product thereof is preferable because it is easy to obtain the urethane prepolymer composition (H) which is highly transparent and has little coloring. 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. of these isocyanates. 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 thereof may be mixed and used.
<Urethane prepolymer (E)>
The urethane prepolymer (E) contains an alkylene oxide residue having 3 or more carbon atoms, an unsaturated group having 0.010 meq / g or less, and an ethylene oxide residue as essential constituents, and further contains a tetramethylene-ether residue. It is characterized by containing a residue of any of a sugar residue having 6 or more carbon atoms and an aromatic amine residue as a constituent component.

If the urethane prepolymer contains an unsaturated group exceeding 0.010 meq / g, it is easy to maintain a low viscosity even when it takes time after mixing with the isocyanate compound, and it is coated to obtain polyurethane from those compositions. When it is applied by a machine or the like, it has a long pot life and is easy to apply, but it is difficult to use because the tensile breaking strength of the obtained polyurethane is low.

If the urethane prepolymer does not contain alkylene oxide residues or ethylene oxide residues having 3 or more carbon atoms as essential constituents, the coatability when coating with an coating machine after mixing with the isocyanate compound is poor. The actual production is difficult, and the obtained polyurethane does not exhibit the desired tensile breaking strength, so that it is difficult to use.

Furthermore, when any of the tetramethylene-ether residue, sugar residue having 6 or more carbon atoms, and aromatic amine residue is not contained as a constituent component, it is low even when it takes time after mixing with the isocyanate compound. It is easy to maintain the viscosity, and when it is applied with a coating machine to obtain polyurethane from those compositions, it has a long pot life and is easy to apply, but the obtained polyurethane exhibits the desired tensile breaking strength. It is difficult to use because it does not.

The content of any of the tetramethylene-ether residue, sugar residue having 6 or more carbon atoms, and aromatic amine residue in the urethane prepolymer (E) is preferably 1% by mass to 50% by mass. It is in the range of 5% by mass to 30% by mass, more preferably. If the content is less than 1% by mass, the obtained polyurethane may not easily exhibit the desired tensile breaking strength, and if it exceeds 50% by mass, the pot life may be shortened and the workability may be inferior.

The content of the unsaturated group in the urethane prepolymer (E) is not particularly limited as long as it is 0.010 meq / g or less, but it is 0.007 meq / g or less because the tensile breaking strength of the obtained polyurethane tends to be high. It is preferable, it is more preferably 0.003 meq / g or less, and most preferably 0.0015 meq / g or less. In this embodiment, the content of unsaturated groups was measured by the same method as for polyalkylene oxide (A).

The urethane prepolymer (E) is characterized by having a weight average molecular weight of 3000 or more. Among them, the weight average molecular weight is preferably in the range of 5,000 to 1,000,000, and more preferably the weight average molecular weight is in the range of 10,000 to 100,000. If the weight average molecular weight is less than 3000, it takes time to cure and the productivity is inferior, and the obtained polyurethane also has a low tensile strength, which makes it difficult to use. If the weight average molecular weight exceeds 1,000,000, the pot life may be shortened and the coatability (workability) may be inferior. The weight average molecular weight of the urethane prepolymer (E) can be measured by a conventional method using a gel permeation chromatography (GPC) method.

Among them, the urethane prepolymer (E) is a reaction product obtained by reacting a polyalkylene oxide (A), a polyol (B), a polyalkylene oxide (C), and an isocyanate compound (D). It is preferable that the polyurethane has at least one hydroxyl group in one molecule.

The urethane prepolymer (E) Among them, from a polyalkylene oxide (A), the polyol (B), the isocyanate compound (D) to the total amount of hydroxyl groups derived from the polyalkylene oxide _(C) (M _OH) The ratio of the amount of isocyanate groups ( _MNCO ) ( _MNCO / _MOH ) is preferably less than 1.0. It is more preferably 0.20 or more and 0.95 or less, and further preferably 0.20 or more and 0.80 or less. The ratio ( _MNCO / _MOH ) represents a molar ratio. When the ratio ( _MNCO / M _OH ) is less than 1.0, gelation (solidification) is unlikely to occur when the urethane prepolymer (E) is produced, and the coating property of the obtained urethane prepolymer is low. It is preferable because it has excellent storage stability and is easy to handle.

The content ratio of the polyalkylene oxide (A) and the polyol (B) in producing the urethane prepolymer (E) is not particularly limited, but the mass ratio (polyalkylene oxide (A) / polyol (B)) is 99. It is preferably in the range of 9 / 0.1 to 40/60, more preferably in the range of 99/1 to 50/50, and most preferably in the range of 95/5 to 70/30. Polyurethane obtained from the urethane prepolymer (E) having a mass ratio within this range is preferable because it has a large tensile breaking strength and good transparency.

Further, the mass ratio of the total mass of the polyalkylene oxide (A) and the polyol (B) to the polyalkylene oxide (C) in producing the urethane prepolymer (E) is not particularly limited, but the mass ratio [polyalkylene] Oxide (A) + polyol (B)] / polyalkylene oxide (C), preferably in the range of 99.9 / 0.1 to 60/40, preferably 99.5 / 0.5 to 80/20. The range is more preferable, and the range of 99/1 to 90/10 is most preferable. The urethane prepolymer (E) having a mass ratio within this range contains polyalkylene oxide (A) having a small amount of unsaturated monool, but exhibits good coatability when coated with a coating machine or the like. preferable.

The average number of functional groups of the mixture of the polyalkylene oxide (A), the polyol (B) and the polyalkylene oxide (C) is not particularly limited, but is preferably 1.9 or more, and more preferably 2 or more and 6 or less. preferable. The urethane-forming composition (E) having an average functional group number of 1.9 or more calculated from the number of each functional group and the molar ratio is excellent in curing (solidification) property when polyurethane is obtained by curing accompanying the reaction, and the polyurethane is excellent. Further, it is preferable because it has good mechanical properties.

The polyalkylene oxide (A), polyol (B), polyalkylene oxide (C), and isocyanate compound (D) used in producing the urethane prepolymer (E) can be dehydrated by vacuum heating or the like before use. Although it is preferable, it may be used without dehydration when the work becomes complicated.
<Urethane prepolymer composition (H)>
The urethane prepolymer composition (H) of the present invention contains, in addition to the urethane prepolymer (E), an active methylene group-containing compound (F) having keto-enol twill mutation and a urethanization catalyst (G) containing a metal component as essential components. It is characterized by being contained as.

When the keto-enol tally-mutable active methylene group-containing compound (F) and the urethanization catalyst (G) containing a metal component are not contained, the polyalkylene oxide (A) having significantly less unsaturated groups, high reactivity, and high functionality When the urethane prepolymer obtained by using the polyol (B) of the group number and isocyanate are mixed, cross-linking proceeds immediately, and the pot life is remarkably short, which makes coating difficult and prolongs the pot life. When the amount of catalyst is reduced or an acid retarder is introduced, a side reaction with water in the air proceeds, so that curing (solidification) takes time and productivity is impaired, which makes it difficult to use. In this embodiment, simple ketones such as acetone and methyl ethyl ketone do not contain a substantial enol form, and therefore are considered to have no keto-enol tautomerism and are not included in (F).

The active methylene group-containing compound (F) having keto-enol tachivariability is not particularly limited as long as it is a compound having an active methylene group and exhibiting keto-enol timivariability, for example, malononitrile, diethyl malonate, acetylacetone, acetacetic acid. Ethyl and the like can be mentioned, but it is preferable to contain one or more of β-diketone and β-ketoester because it exhibits good productivity while significantly extending the pot life and does not impair the tensile strength of the obtained polyurethane. ..

Among them, even if it contains a polyalkylene oxide (A) having remarkably few unsaturated groups and a urethane prepolymer using a highly reactive and highly functional group polyol (B) and having a particularly short pot life, it can withstand practical use. It is more preferable to contain one or more of acetylacetone and ethyl acetoacetate in order to develop a long pot life, and most preferably acetylacetone having a boiling point of 150 ° C. or lower and can be removed at a low temperature.

The content of the keto-enol tangle-containing active methylene group-containing compound (F) in the urethane prepolymer composition (H) of the present invention is not particularly limited, but is in the range of 0.1% by mass to 10% by mass. The mass ratio (mass of (G) / mass of (F)) to the content of the urethanization catalyst (G) containing a metal component is in the range of 0.1 / 99.9 to 3/97. Is preferable.

By setting the mass ratio of the urethanization catalyst (G) containing a metal component and the active methylene group-containing compound (F) having keto-enol tectrate to 3/97 or less, a remarkable pot life extension effect can be exhibited. When it is set to 1 / 99.9 or more, it can be cured in a short time and good productivity is exhibited, and the obtained polyurethane exhibits high tensile breaking strength, which is preferable.

Among them, the content of the active methylene group-containing compound (F) having keto-enol tectabilism in the urethane prepolymer composition (H) of the present invention is in the range of 0.3% by mass to 3% by mass, and the metal. The mass ratio (mass of (G) / mass of (F)) to the content of the urethanization catalyst (G) containing the component is preferably in the range of 0.15 / 99.85-2 / 98.

The urethanization catalyst (G) containing a metal component is not particularly limited as long as it is a compound containing a metal component and exhibiting catalytic activity in the urethanization reaction, but for example, dibutyltin dilaurate (also known as DBTDL) and dioctyltin dilaurate (also known as dioctyltin dilaurate). : DOTDL), tin 2-ethylhexanoate, tin acetylacetonate, iron trisacetylacetonate and the like.

Among them, dibutyltin dilaurate and tin 2-ethylhexanoate have high catalytic activity and may have a short pot life, and acetylacetone metal salts such as acetylacetonate tin and trisacetylacetonate iron are curable at room temperature. Dioctyltin dilaurate (also known as DOTDL), which tends to significantly extend the pot life without impairing curability when an active methylene group-containing compound (F) having keto-enol tautomerism is introduced, is likely to be inferior. Is the most preferable.

The preparation of the urethane prepolymer composition (H) of the present invention is not particularly limited as long as it is a method capable of uniformly dispersing the raw materials contained in the urethane prepolymer composition (H), and is conventionally known. Various stirring methods 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 dispar disperser, a dissolver, a kneader, a mixer, a lab plast mill, a planetary mixer and the like. When the urethane prepolymer (E), the keto-enol tally-mutable active methylene group-containing compound (F), and the urethanization catalyst (G) containing a metal component are all liquid at the stirring temperature, a rotation / revolution mixer, general-purpose stirring Machines, dispersers, and dissolvers are preferably used.

The urethane prepolymer composition (H) may contain an antioxidant, a light stabilizer, a chain extender, an acid retarder, and other additives, if necessary.

The content of the additive in the urethane prepolymer composition (H) is not particularly limited, but is preferably 5% by mass or less, and more preferably 1% by mass or less.

The chain extender is 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. Examples thereof include glycols such as polyalkylene glycol; polyvalent amines such as ethylenediamine, N-aminoethylethanolamine, piperazin, isophoronediamine and xylylenediamine;

The acid retarder is not particularly limited, and examples thereof include acidic phosphoric acid esters and carboxylic acids.
<Urethane prepolymer composition solution (I)>
The urethane prepolymer composition (H) is mixed with the urethane prepolymer solution (I) in order to facilitate their handling or to obtain the desired viscosity and coatability. can do.

At this time, the urethane prepolymer composition solution (I) is
Urethane prepolymer composition (H) and
Contains organic solvent,
The concentration of the urethane prepolymer composition in the urethane prepolymer composition solution (I) is 10% by mass or more and 90% by mass or less.

Examples of the organic solvent include methyl ethyl ketone, ethyl acetate, butyl 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. In addition, these solvents should be added at an arbitrary stage, such as when obtaining the urethane prepolymer composition (H) using the prepared urethane prepolymer (E) before or after the synthesis of the urethane prepolymer (E). Can be done.

The concentration of the urethane prepolymer composition in the urethane prepolymer composition solution (I) is 10% by mass or more and 90% by mass or less, preferably 30% by mass or more and 70% by mass or less. When the concentration is in this range, the urethane prepolymer composition solution (I) and the isocyanate compound are mixed, and good coatability can be obtained when coating with a coating machine or the like, which facilitates handling. be able to.

The viscosity of the urethane prepolymer composition 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, the urethane prepolymer composition solution (I) and the isocyanate compound are mixed, and good coatability can be obtained when coating with a coating machine or the like, which facilitates handling. be able to.
<Urethane-forming composition (K)>
The urethane-forming composition (K) is a composition containing the urethane prepolymer composition (H) or the urethane prepolymer composition solution (I) and an isocyanate compound (J).

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

Here, the urethane-forming composition (K) may be a urethane prepolymer composition (H) or a composition containing the urethane prepolymer composition solution (I) and an isocyanate compound (J). Therefore, there is no particular limitation on the content of the urethane prepolymer composition (H) isocyanate compound in (J), the total amount of hydroxyl groups derived from the urethane prepolymer _(E) (M _OH) isocyanate compound to the (J) The ratio of the amount of derived isocyanate groups ( _MNCO ) ( _MNCO / _MOH ) is preferably 0.5 or more and less than 4.0 in terms of molar ratio. The mass ratio of the urethane prepolymer (E) to the isocyanate compound (J) (mass of (E) / mass of (J)) is preferably in the range of 99/1 to 70/30.

When the content of the isocyanate compound (J) is within the above range, when the polyurethane is obtained by curing with the reaction of the urethane-forming composition (K), the curing (solidification) property is excellent and the polyurethane is a good machine. It is preferable because it has physical properties.

The urethane prepolymer composition (H) and the isocyanate compound (J) used in the urethane-forming composition (K) are preferably dehydrated by vacuum heating or the like, but are not dehydrated when the work becomes complicated. May be used for.

The preparation of the urethane-forming composition (K) is not particularly limited as long as it is a method capable of uniformly dispersing the prepolymer and the raw material contained in the urethane-forming composition (K), 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 dispar disperser, a dissolver, a kneader, a mixer, a lab plast mill, a planetary mixer and the like. When the urethane prepolymer composition (H) or the urethane prepolymer composition solution (I) and the isocyanate compound (J) are both liquid at a stirring temperature, a general-purpose stirrer, a rotation / revolution mixer, and a disper disperser , Dissolver is preferably used.

The viscosity of the urethane-forming composition (K) 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 10,000 mPa · s or less. When the viscosity of the urethane-forming composition (K) at 25 ° C. is within this range, the urethane-forming composition (K) may be stirred with various stirrers to prepare the urethane-forming composition (K), or the urethane-forming composition (K) may be stirred. Is preferable because the urethane-forming composition (K) can be easily stirred and handled when stirring is performed as a pre-stage work when coating with a coating machine or the like.
<Polyurethane (L)>
Polyurethane (L) is a reaction product of the urethane-forming composition (K), and is a reaction product of the urethane prepolymer (E) and the isocyanate compound (J) in the urethane-forming composition (K).

Polyurethane (L) can be obtained by reacting the urethane-forming composition (K) by various methods and curing (solidifying) it. The method for producing these polyurethanes (L) is not particularly limited. For example, the urethane-forming composition (K) can be mixed at room temperature or 150 in the presence of a urethanization catalyst, a solvent, an antioxidant, a light stabilizer, a chain extender, a cross-linking agent, and other additives, if necessary. It can be produced by advancing the urethanization reaction and the urea conversion reaction at a high temperature of ° C. or lower.

Further, in order to exhibit good curability, a step of activating at a high temperature and a step of removing the solvent may be included, if necessary.
Here, since the urethane-forming composition (K) is remarkably excellent in coatability when coated with a coating machine or the like, a polyurethane (L) coating film having a thin thickness and a uniform thickness can be used. A polyurethane sheet is obtained.

The thickness of the polyurethane (L) coating film is not particularly limited, but the thickness of the coating film is preferably 1 μm or more and 1000 μm or less, and 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 (L) is not particularly limited, and it can be used in any application in which ordinary polyurethane is used, but it is particularly preferably used in applications requiring mechanical properties, adhesiveness, adhesive properties, etc. it can. Specifically, sealants for construction and civil engineering, adhesives such as elastic adhesives for construction, gum tapes and surface protective films, various adhesives typified by optics, paints, elastomers, coating waterproof materials, flooring materials, etc. Applications such as plasticizers, flexible polyurethane foams, semi-rigid polyurethane foams, and rigid polyurethane foams are exemplified and can be preferably used.

Among them, polyurethane is particularly preferably used as a sealing material, a paint, an adhesive, and an adhesive because it is strongly required to have mechanical properties and adhesive / adhesive properties, 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 Oxyd (A or AC) Used in Examples and Comparative Examples
The properties of the polyalkylene oxide 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.
(Raw Material 1-1) Polyalkylene Oxyd (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 desolve. It was obtained by adding fully 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). The molecular weight distribution is narrow.
(Raw Material 1-2) Polyalkylene Oxyd (AC) Used in Comparative Example
For polyalkylene oxide (AC1), only the IPZ catalyst is used, dehydration and desolvation are sufficiently performed, and sufficiently dehydrated propylene oxide is added to polyoxypropylene glycol which is bifunctional and has 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, and (AC1) has a high degree of unsaturation and 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.

The polyalkylene oxide (AC3) is a polyoxypropylene glycol having two hydroxyl groups in one molecule obtained by using a potassium hydroxide catalyst and having a molecular weight of 600. (AC3) is a commercially available PP600 manufactured by Sanyo Chemical Industries, Ltd. The properties of (AC3) are shown in Table 1. In (AC3), 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 (A3) used in the examples and the polyalkylene oxides (AC1) to (AC3) used in the comparative examples were all used after heating and vacuum dehydration. Further, the polyalkylene oxide prepared using the IPZ catalyst was used after removing the catalyst.

(Raw material 2) polyol (B)
(Raw material 2-1) Polyester (B) used in Examples
The polyol (B1) was a commercially available polytetramethylene glycol, and PTG-1000SN manufactured by Hodogaya Chemical Co., Ltd. having a hydroxyl value of 112 mgKOH / g and a molecular weight of 1000 was used.

The polyol (B2) is a commercially available shoe-closed polyol, and O-855W manufactured by Toho Chemical Industry Co., Ltd. having a nominal number of functional groups of 8.0, a hydroxyl value of 377 mgKOH / g, and a molecular weight of 1190 was used.

The polyol (B3) is a commercially available tolylene diamine-based polyol, and AR-2589 manufactured by Toho Chemical Industry Co., Ltd. having a nominal number of functional groups of 4.0, a hydroxyl value of 360 mgKOH / g, and a molecular weight of 620 was used.
(Raw material 2-2) Polyol (BC) used in Comparative Example
The polyol (BC1) was a commercially available polycarbonate diol, and Nipponlan 965 having a nominal number of functional groups of 2.0, a hydroxyl value of 113 mgKOH / g, and a molecular weight of 990 was used.

The polyol (BC2) is a commercially available acrylic polyol, and Acridic A801 manufactured by DIC Corporation having a hydroxyl value of 50 mgKOH / g was used.
(Raw material 3) Polyalkylene oxide (C)
(Raw Material 3-1) Polyalkylene Oxyd (C) Used in Examples
As the polyalkylene oxide (C1), a hydroxyl value of 80 mgKOH / g and a molecular weight of 700 polyethylene glycol monomethyl ether were used.

As the polyalkylene oxide (C2), a hydroxyl value of 160 mgKOH / g and a molecular weight of 350 polyethylene glycol monomethyl ether were used.
Both (C1) and (C2) had one hydroxyl group in one molecule and had a high content ratio of ethylene oxide groups.
(Raw Material 3-2) Polyalkylene Oxyd (CC) Used in Comparative Example
The polyalkylene oxide (CC1) is a polypropylene glycol monomethyl ether having a hydroxyl value of 56 mgKOH / g and a molecular weight of 1000, and does not contain ethylene oxide residues.
(Raw material 4) Isocyanate compounds (D) and (J) used in Examples and Comparative Examples.
The isocyanate compound (D1) is Aquanate 105 manufactured by Toso Co., Ltd., which is an HDI-based modified isocyanurate, and the average number of functional groups of the isocyanate group in (D1) is 3.4.

The isocyanate compound (D2) is 1,6-hexamethylene diisocyanate (HDI), and the average number of functional groups of the isocyanate group in (D2) is 2.0.
The isocyanate compound (J1) is a 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 group in (J1) is 3.2.
(Raw Material 5) Keto-enol Active Methylene Group-Containing Compound Compound (F) with Tautomerism
(Raw Material 5-1) Active Methylene Group-Containing Compound (F) with Keto-enol Tautomerism Used in Examples and Comparative Examples
As the active methylene group-containing compound (F1) having keto-enol tautomerism, acetylacetone, which is a β-diketone, was used.

As the active methylene group-containing compound (F2) having keto-enol tautomerism, ethyl acetoacetate, which is a β-keto ester, was used.
(Raw Material 5-2) Compound (FC) used in Examples and Comparative Examples
The compound (FC1) is a 2-ethylhexyl acid phosphate which is an acidic phosphoric acid ester, and the compound (FC2) which is a delaying agent for the urethanization reaction which does not have keto-enol tvariability and does not have an active methylene group is It is a bis (2-ethylhexyl) hydrogen phosphite, and is a compound having keto-enol tvariability but not having a methylene group activated by an electron-withdrawing group or the like.

The compound (FC3) is a methyl ethyl ketone, which has substantially no keto-enol tautomerism and does not have a methylene group activated by an electron-withdrawing group or the like.
(Raw Material 6) Urethaneization Catalyst Used in Examples and Comparative Examples Dioctyltin dilaurate (abbreviation: DOTDL) manufactured by Wako Pure Chemical Industries, Ltd. was used as the urethanization catalyst (G1) having a metal component.

Further, as the urethanization catalyst having no metal component (GC1), triethylenediamine (abbreviated as TEDA) was used.
(Raw Material 7) Solvent When the urethane prepolymer composition solution was used in Examples and Comparative Examples, ethyl acetate manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. was used as the solvent.
(Preparation of urethane prepolymer composition and urethane prepolymer composition solution)
A predetermined amount of polyalkylene oxide (A), polyol (B) and polyalkylene oxide (C) is added to a four-necked eggplant flask equipped with a stirrer, a reflux condenser tube, a nitrogen introduction tube and a thermometer, and the temperature is 100 ° C. Vacuum dehydration was performed for 2 hours.

A predetermined amount of isocyanate compound (D), urethanization catalyst (G), and if necessary ethyl acetate as a solvent were added, and the temperature was raised to 76 ° C. to carry out the reaction. The amount of NCO groups in the reactor contents was tracked using an infrared spectrophotometer, and after confirming the completion of the reaction, an active hydrogen compound (F) having keto-enol tvariability was added to the urethane prepolymer composition (H) or It was designated as a urethane prepolymer composition solution (I).

The weight average molecular weight of the urethane prepolymer was calculated by the GPC method using tetrahydrofuran as a solvent and polystyrene as a standard substance.
(Preparation of urethane-forming composition)
In Examples and Comparative Examples, a predetermined amount of each raw material (urethane prepolymer composition (H) or urethane prepolymer composition solution (I), isocyanate (J)) was placed in a 50 ml sample bottle, and a rotation / revolution mixer was used. Then, the urethane-forming composition was obtained by stirring and defoaming at room temperature. Awatori Rentaro ARE-310 manufactured by Shinky Co., Ltd. was used as the rotation / revolution mixer, 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 to obtain a urethane-forming composition (K). ..
(Performance evaluation)
The urethane-forming composition (K) was coated on a PET film having a thickness of 38 μm using a baker-type applicator so that the thickness after drying was 100 μm or less. Then, the solvent was kept in an oven set at 130 ° C. for 3 minutes to volatilize the solvent and the like, and the mixture was allowed to stand in an environment at 23 ° C. and a relative humidity of 50% for 1 week to obtain a coating film.
Further, regarding the tensile breaking strength of the polyurethane coating, the dumbbell test piece of ASTM1822 was taken out (punched) from the cured polyurethane coating having a thickness of about 100 μm by coating as described above, and manufactured by Orientec Co., Ltd. A tensile test was performed using a tensile tester RTG-1210 at a distance between chucks of the tensile tester of 30 mm and a tensile speed of 50 mm / min, and the stress when the test piece broke was defined as the tensile breaking strength.

In that process, the urethane-forming composition was evaluated according to the following evaluation criteria as an index of performance. The urethane prepolymer composition (H) and the urethane prepolymer composition solution (I) are coated with 1.5 equivalents of the isocyanate compound C-HXLV as a curing agent with respect to the OH group of the prepolymer. The properties, curability, and physical properties were evaluated in the same manner as the urethane-forming composition, and used as an index of the performance of the urethane prepolymer composition and the urethane prepolymer composition solution.
<Available time>
◎ (Passed pot life): Maintains fluidity for more than 48 hours after mixing the curing agent, and the viscosity increase rate after 24 hours is 50% or less 〇 (Passing pot life): After mixing the curing agent, When the fluidity is maintained for more than 30 hours and the viscosity increase rate after 18 hours is 50% or less × (failure of pot life): When the fluidity is lost within 30 hours after mixing the curing agent (gelation) Or, if the viscosity increase rate after 18 hours exceeds 50% XX (failed pot life): If the fluidity is lost within 12 hours (gelation) after mixing the curing agent, or after 6 hours When the viscosity increase rate exceeds 50% <Coatability>
◎ (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%.
<Curable>
◎ (Passed 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 stickiness does not change over time after 3 days of holding.
○ (passed 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.
XX (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, over time. If it changes (curing is significantly slower).
<Tensile breaking strength>
◎ (Strength passed): Tensile breaking strength after standing in an environment of 23 ° C and 50% relative humidity for 3 days or more △ (Strength failed): After standing in an environment of 23 ° C and relative humidity of 50% for 3 days Tensile breaking strength of 3MPa or more and less than 10MPa XX (strength failure): Tensile breaking strength of less than 3MPa after standing for 3 days in an environment of 23 ° C. and relative humidity of 50%. It was judged that the urethane prepolymer composition contributes to the formation of polyurethane having high breaking strength, has a long pot life, does not require time for coating and curing, and has high productivity.

Example 1 is a urethanization catalyst containing 70 parts by weight of polyalkylene oxide (A1), 30 parts by weight of polyol (B1), 0.5 parts by weight of polyalkylene oxide (C1), and isocyanate compound (D2) and a metal. G1) includes 0.02 parts by weight, (A1) and (B1) and (the amount of isocyanate groups derived from the amount of the hydroxyl group derived from C1) _{(M OH)} and (D2) _{(M NCO),} the molar ratio in, _M NCO / (A1) and (B1) an active hydrogen compound having a keto-enol tautomerism obtained urethane prepolymer (E1) in _M OH = 0.60 in (C1) (F1) 3 in (D2) It is a urethane prepolymer composition (H1) containing 0.0 part by weight.
The results of Example 1 are shown in Table 2. The urethane prepolymer composition (H1) has a remarkably long pot life, has good coatability and curability, and is obtained from the composition (H1). The coating film of polyurethane (L1) had a high tensile breaking strength.

Comparative Example 1 contains 70 parts by weight of polyalkylene oxide (A1), 30 parts by weight of polyalkylene oxide (B1), and polyalkylene oxide, which does not contain an active hydrogen compound (F1) having keto-enol tachimbling with respect to Example 1. (C1) 0.5 parts by weight and 0.02 parts by weight of a urethanization catalyst (G1) containing an isocyanate compound (D1) and a metal, and the hydroxyl groups derived from (A1), (B1) and (C1) the amount the amount of isocyanate groups derived from the _{(M OH)} and (D2) _{(M NCO)} is in molar ratio, was obtained in _{M M} OH = 0.60 in NCO / (A1) and (B1) of (D2) It is a urethane prepolymer composition (HC1) containing a urethane prepolymer (EC1). Since the composition (HC2) does not contain (F1), it thickens by 50% or more in 6 hours and loses fluidity in 12 hours, and the pot life is remarkably short, and the obtained polyurethane (LC1) is subjected to tensile fracture. Although it has high strength, it was difficult to actually manufacture it.

Example 2 is a urethanization catalyst (G1) containing 80 parts by weight of polyalkylene oxide (A3), 20 parts by weight of polyol (B2), 5 parts by weight of polyalkylene oxide (C2), and isocyanate compound (D1) and metal. includes 0.05 parts by weight, a molar ratio (A3) and (B2) to the amount of hydroxyl groups derived from _{(C2) (M OH)} to the amount of isocyanate groups derived from _{(D1) (M NCO),} active hydrogen compound having an _M NCO / (A3) and (B2) and keto-enol tautomerism obtained urethane prepolymer (E2) in _M OH = 0.23 in (C2) of (D1) (F1) 5.0 It is a urethane prepolymer composition (H2) containing a part by weight.
Table 2 shows the results of Example 2. The urethane prepolymer composition (H2) has a remarkably long pot life, has good coatability and curability, and is obtained from the composition (H2). The coating film of polyurethane (L2) had a high tensile breaking strength.

Comparative Example 2 contains 80 parts by weight of the polyalkylene oxide (A3), 20 parts by weight of the polyol (B2), and the polyalkylene oxide (C2), which do not contain the active hydrogen compound (F1) having keto-enol tvariability with respect to Example 2. ) 5 parts by weight, and includes a urethane catalyst (G1) 0.05 parts by weight comprising isocyanate compound (D1) of metal, the amount of hydroxyl groups derived from the (C2) (A3) and (B2) _{(M OH} ) and (the amount of isocyanate groups derived from D1) _{(M NCO)} is in molar ratio, was obtained in _M OH = 0.23 in (D1) _M NCO / (A3) and the (B2) (C2) It is a urethane prepolymer composition (HC2) containing a urethane prepolymer (E2). Since the composition (HC2) does not contain (F1), it loses fluidity in 1 hour and has a remarkably short pot life, resulting in poor coatability, and the obtained polyurethane (LC2) has a high tensile strength at break. However, the actual production was difficult.

Example 3 is a urethanization catalyst (G1) containing 90 parts by weight of polyalkylene oxide (A2), 10 parts by weight of polyol (B3), 1 part by weight of polyalkylene oxide (C1), and isocyanate compound (D1) and metal. comprises 0.005 parts by weight, a molar ratio (A2) and (B3) to the amount of isocyanate groups derived from the amount of hydroxyl groups derived from _{(M OH)} and (D1) to _{(C1) (M NCO),} (D1) of _M NCO / (A2) and (B3) with an active hydrogen compound having a keto-enol tautomerism a urethane prepolymer (E3) obtained in _M OH = 0.40 in (C1) (F2) 0.5 It is a urethane prepolymer composition (H3) containing a part by weight. The results of Example 3 are shown in Table 2. The urethane prepolymer composition (H3) has a remarkably long pot life, has good coatability and curability, and is obtained from the composition (H3). The coating film of polyurethane (L3) had a high tensile breaking strength.

Comparative Example 3 contains 90 parts by weight of the polyalkylene oxide (A2) and 10 parts by weight of the polyol (B3), and the isocyanate compound (D1) and the metal, which are free of the polyalkylene oxide (C1) with respect to Example 3. comprising a urethane catalyst (G1) 0.005 parts by weight, (A2) and the amount of hydroxyl groups derived from the _{(B3) (M OH)} to the amount of isocyanate groups derived from _{(D1) (M NCO),} the molar ratio in, _M NCO / (A2) and (B3) an active hydrogen compound having a keto-enol tautomerism a urethane prepolymer (EC3) obtained in _M OH = 0.40 in (F2) 0.5 parts by weight of (D1) It is a urethane prepolymer composition (HC3) containing. Although the composition (HC3) has a long pot life, it does not contain (C1) and therefore has poor coatability, and the obtained polyurethane (LC1) has a somewhat low tensile breaking strength, which makes it difficult to actually manufacture and cannot be used. Met.

Example 4 is a urethanization catalyst containing 95 parts by weight of polyalkylene oxide (A1), 5 parts by weight of polyol (B1), 0.5 parts by weight of polyalkylene oxide (C1), and isocyanate compound (D2) and metal. G1) comprises 0.02 volume part, the (A1) and (B1) and (the amount of isocyanate groups derived from the amount of the hydroxyl group derived from C1) _{(M OH)} and (D2) _{(M NCO),} the molar ratio in, _M NCO / (A1) and (B1) an active hydrogen compound having a keto-enol tautomerism obtained urethane prepolymer (E4) with _M OH = 0.60 in (C1) (F1) 3 in (D2) It is a urethane prepolymer composition (H4) containing 0.0 part by weight. The results of Example 4 are shown in Table 2. The urethane prepolymer composition (H4) has a remarkably long pot life, has good coatability and curability, and is obtained from the composition (H4). The coating film of polyurethane (L4) had a high tensile breaking strength.

Comparative Example 4 contains 100 parts by weight of the polyalkylene oxide (A1) and 0.5 parts by weight of the polyalkylene oxide (C1), and the isocyanate compound (D2) and the metal, which do not contain the polyol (B1) as compared with Example 4. comprising a urethane catalyst (G1) 0.02 amounts portion containing, the (A1) to the amount of isocyanate groups derived from the amount of hydroxyl groups derived from _{(M OH)} and (D2) to _{(C1) (M NCO),} a molar ratio, _M NCO / (A1) with an active hydrogen compound having a keto-enol tautomerism obtained urethane prepolymer (EC4) at _M OH = 0.60 in (C1) of (D2) (F1) 3.0 It is a urethane prepolymer composition (HC4) containing a part by weight.
Although the composition (HC4) has a long pot life and a somewhat good curability, the polyurethane (LC4) obtained because it does not contain the polyol (B1) has a low tensile strength at break and is difficult to use.

Example 5 contains 85 parts by weight of the polyalkylene oxide (A3) and 15 parts by weight of the polyol (B1), 2 parts by weight of the polyalkylene oxide (C1), and a mixture and metal of the isocyanate compounds (D1) and (D2). comprising a urethane catalyst (G1) 0.03 parts by weight, the amount of isocyanate groups derived from the (A3) and (B1) and the amount of hydroxyl groups derived from _{(C1) (M OH)} and (D1) (D2) _{(M NCO)} is in molar ratio, and (D1) and _{(D2) M NCO / (A3} ) and the (B1) and the urethane prepolymer was obtained by _M OH = 0.75 in (C1) (E5) ketoenols It is a urethane prepolymer composition solution (I1) containing ethyl acetate as an organic solvent in a urethane prepolymer composition (H5) containing 2.0 parts by weight of an active hydrogen compound (F1) having remutability. The concentration of (H5) in the solution (I1) is 50%.

Table 3 shows the results of Example 5. The urethane prepolymer composition solution (I1) has a remarkably long pot life, has good coatability and curability, and is obtained from the composition (I1). The coating film of polyurethane (L5) had a high tensile breaking strength.

Comparative Example 5 contains 85 parts by weight of the polyalkylene oxide (A3) and 15 parts by weight of the polyol (B1), and isocyanate compounds (D1) and (D2), which do not contain the polyalkylene oxide (C1) as compared with Example 5. comprises a mixture of, (A3) and the amount of hydroxyl groups derived from _{(B1) (M OH)} to the amount of isocyanate groups derived from the (D1) and _{(D2) (M NCO),} in molar ratio, (D1) in the _M NCO / (A3) and (B1) a urethane prepolymer composition comprising the urethane prepolymer (EC5) obtained in _M OH = 0.75 in (D2) (HC5), including ethyl acetate as the organic solvent It is a urethane prepolymer composition solution (IC1). The concentration of (HC5) in the solution (IC1) is 50%. Although the composition (IC1) has a long pot life, it does not contain (C1), so that it has poor coatability, and the obtained polyurethane (LC5) has a slightly low tensile breaking strength. It was something I couldn't do.

In Example 6, 90 parts by weight of the polyalkylene oxide (A2) and 10 parts by weight of the polyol (B2), 0.5 parts by weight of the polyalkylene oxide (C2), and a mixture of the isocyanate compounds (D1) and (D2) and a metal. comprising a urethane catalyst (G1) 0.005 parts by weight containing, isocyanate group derived from (A2) and (B2) and (C2) to the amount of hydroxyl groups derived from the _{(M OH)} and (D1) (D2) Urethane prepolymer (E6) obtained by the amount ( _MNCO ) of _MNCO / (A2) and (B2) and (C2) M _OH = 0.45 of (D1) and (D2) in molar ratio. A urethane prepolymer composition solution (I2) containing ethyl acetate as an organic solvent in a urethane prepolymer composition (H6) containing 1.0 part by weight of an active hydrogen compound (F1) having a reciprocity with ketoenol. The concentration of (H6) in the solution (I2) is 85%.

Table 3 shows the results of Example 6. The urethane prepolymer composition solution (I2) has a remarkably long pot life, has good coatability and curability, and is obtained from the composition (I2). The coating film of polyurethane (L6) had a high tensile breaking strength.

Comparative Example 6 contains 90 parts by weight of the polyalkylene oxide (A2), 10 parts by weight of the polyol (B2), and the polyalkylene oxide (C2), which do not contain the active hydrogen compound (F1) having ketoenol homomorphism with respect to Example 6. ) 0.5 parts by weight, and 0.005 parts by weight of a prepolymerized catalyst (G1) containing a mixture of isocyanate compounds (D1) and (D2) and a metal, in (A2), (B2) and (C2). the amount of isocyanate groups derived from the amount of derived hydroxyl _{(M OH)} and (D1) to _{(D2) (M NCO)} is in molar ratio, and _M NCO / (A2) of (D1) and (D2) ( B2) a urethane prepolymer composition comprising the urethane prepolymer (EC 6) obtained in _M OH = 0.45 of (C2) to (HC6), urethane prepolymer composition solution containing ethyl acetate as the organic solvent (IC 2) Is. The concentration of (HC6) in the solution (IC2) is 85%.

Since the composition (IC2) does not contain (F1), it thickens by 50% or more in 1 hour and loses fluidity in 3 hours, and the pot life is remarkably short. The obtained polyurethane (LC2) is tensile. Although the breaking strength was high, the actual production was difficult.

Example 7 is a urethanization catalyst containing 70 parts by weight of polyalkylene oxide (A1), 30 parts by weight of polyol (B3), 0.5 parts by weight of polyalkylene oxide (C1), and isocyanate compound (D2) and metal. G1) contains 0.005 parts by weight, (A1) and (B3) and (the amount of isocyanate groups derived from the amount of the hydroxyl group derived from C1) _{(M OH)} and (D2) _{(M NCO),} the molar ratio in, _M NCO / (A1) and (B3) with an active hydrogen compound having a keto-enol tautomerism obtained urethane prepolymer (E7) by _M OH = 0.50 in (C1) (F1) 3 in (D2) A urethane prepolymer composition solution (I3) containing ethyl acetate as an organic solvent in a urethane prepolymer composition (H7) containing 0.0 parts by weight. The concentration of (H7) in the solution (I3) is 75%.

Table 3 shows the results of Example 7. The urethane prepolymer composition solution (I3) has a remarkably long pot life, has good coatability and curability, and is obtained from the composition (I3). The coating film of polyurethane (L7) had a high tensile breaking strength.

Comparative Example 7 contains 70 parts by weight of the polyalkylene oxide (A1), 30 parts by weight of the polyol (B3), and the polyalkylene oxide (C1), which do not contain the active hydrogen compound (F1) having keto-enol tvariability with respect to Example 7. ) 0.5 parts by weight and 0.005 parts by weight of the urethanization catalyst (G1) containing the isocyanate compound (D2) and the metal, and the amount of hydroxyl groups derived from (A1), (B3) and (C1) ( the amount of isocyanate groups derived from M _OH) and (D2) _{(M NCO)} is in molar ratio in _M OH = 0.50 and _M NCO / (A1) of (D2) and (B3) (C1) It is a urethane prepolymer composition solution (IC3) containing ethyl acetate as an organic solvent in the urethane prepolymer composition (HC7) containing the obtained urethane prepolymer (EC7). The concentration of (HC7) in the solution (IC3) is 75%.

Since the composition (IC3) does not contain (F1), it loses fluidity in 1 hour and has a remarkably short pot life, resulting in poor coatability and a high tensile strength at break of the obtained polyurethane (LC7). It was small, and it was difficult to actually manufacture and use it.

Example 8 contains 95 parts by weight of the polyalkylene oxide (A1) and 5 parts by weight of the polyol (B3), 2 parts by weight of the polyalkylene oxide (C1), and a mixture and a metal of the isocyanate compounds (D1) and (D2). comprising a urethane catalyst (G1) 0.005 parts by weight, the amount of isocyanate groups derived from the (A1) and (B3) and the amount of hydroxyl groups derived from _{(C1) (M OH)} and (D1) (D2) _{(M NCO)} is in molar ratio, and (D1) and _{(D2) M NCO / (A1} ) and the (B3) and the urethane prepolymer was obtained by _M OH = 0.75 in (C1) (E8) ketoenols A urethane prepolymer composition solution (I4) containing ethyl acetate as an organic solvent in a urethane prepolymer composition (H8) containing 0.5 parts by weight of a remutable active hydrogen compound (F2). The concentration of (H8) in the solution (I4) is 75%.

Table 3 shows the results of Example 8. The urethane prepolymer composition solution (I4) has a remarkably long pot life, has good coatability and curability, and is obtained from the composition (I4). The coating film of polyurethane (L8) had a high tensile breaking strength.

Comparative Example 8 contains 100 parts by weight of the polyalkylene oxide (A1) and 2 parts by weight of the polyalkylene oxide (C1), and isocyanate compounds (D1) and (D2), which do not contain the polyol (B3) as compared with Example 8. mixture with a metal comprising a urethane catalyst (G1) 0.005 parts by weight containing, isocyanate group derived from the (A1) to the amount of hydroxyl groups derived from _{(C1) (M OH)} and (D1) (D2) of the amount of _{(M NCO)} is in molar ratio, (D1) and (D2) of _M NCO / (A1) and (C1) of _M OH = 0.75 obtained in the urethane prepolymer (EC8) and ketoenols tautomeric A urethane prepolymer composition solution (IC4) containing ethyl acetate as an organic solvent in a urethane prepolymer composition (HC8) containing 0.5 parts by weight of an active hydrogen compound (F2) having a property. The concentration of (HC8) in the solution (IC4) is 75%.
Although the composition (IC4) has a long pot life and a somewhat good curability, the polyurethane (LC8) obtained because it does not contain the polyol (B3) has a low tensile strength at break and is difficult to use.

Example 9 shows 70 parts by weight of polyalkylene oxide (A1) and 30 parts by weight of polyol (B1), 0.5 parts by weight of polyalkylene oxide (C1), a mixture of isocyanate compounds (D1) and (D2), and a metal. comprising a urethane catalyst (G1) 0.03 parts by weight containing, isocyanate group derived from the (A1) and (B1) and the amount of hydroxyl groups derived from _{(C1) (M OH)} and (D1) (D2) Urethane prepolymer (E9) obtained by the amount ( _MNCO ) of _MNCO / (A1) and (B1) and (C1) M _OH = 0.75 of (D1) and (D2) in molar ratio. Ethyl acetate as an organic solvent, isocyanate compound (J1) as a curing agent, and isocyanate (J1) in a urethane prepolymer composition (H9) containing 2.0 parts by weight of an active hydrogen compound (F1) having reciprocity with ketoenol. It is a urethane-forming composition (K1) containing M _OH = 2.0 of the _MNCO / urethane prepolymer (E9) of the above. The combined concentration of (H9) and (J1) in the solution (K1) is 50%.

Table 4 shows the results of Example 9. The urethane-forming composition (K1) has a remarkably long pot life, has good coatability and curability, and is obtained from the composition (K1). The coating film of polyurethane (L9) had a high tensile breaking strength.

In Comparative Example 9, 70 parts by weight of the polyalkylene oxide (A1), 30 parts by weight of the polyol (B1), and 0 parts of the polyalkylene oxide (C1), which did not contain the urethanization catalyst (G1) containing a metal, as compared with Example 9. It contains 5 parts by weight and a mixture of isocyanate compounds (D1) and (D2), and the amount of hydroxyl groups ( _MOH ) and (D1) and (D2) derived from (A1), (B1) and (C1). the amount of from isocyanate groups _{(M NCO)} is in molar ratio, urethane obtained by _M OH = 0.75 in (D1) and _{(D2) M NCO / (A1} ) and the (B1) (C1) A urethane prepolymer composition (HC9) containing 2.0 parts by weight of an active hydrogen compound (F1) having a remutability between a polymer (EC9) and ketoenol is mixed with ethyl acetate as an organic solvent and an isocyanate compound (J1) as a curing agent. a urethane-forming composition comprising at _M OH = 2.0 of _{M NCO} / urethane prepolymer isocyanate (J1) (EC9) (KC1 ). The combined concentration of (HC9) and (J1) in the solution (K1) is 50%.

Although the composition (KC1) has a long pot life, it does not contain (G1) and therefore has poor curability, and the obtained polyurethane (LC9) has a low tensile breaking strength, which makes it difficult to actually manufacture and cannot be used. ..

Example 10 shows 85 parts by weight of polyalkylene oxide (A1), 15 parts by weight of polyol (B2), 0.5 parts by weight of polyalkylene oxide (C1), a mixture of isocyanate compounds (D1) and (D2), and a metal. comprising a urethane catalyst (G1) 0.005 parts by weight containing, isocyanate group derived from the (A1) and (B2) and the amount of hydroxyl groups derived from _{(C1) (M OH)} and (D1) (D2) Urethane prepolymer (E10) obtained with the amount ( _MNCO ) of _MNCO / (A1) and (B2) and (C1) M _OH = 0.35 of (D1) and (D2) in molar ratio. Ethyl acetate as an organic solvent, isocyanate compound (J1) as a curing agent, and isocyanate (J1) in a urethane prepolymer composition (H10) containing 1.0 part by weight of an active hydrogen compound (F1) having reciprocity with ketoenol. It is a urethane-forming composition (K2) containing M _OH = 0.9 of the _MNCO / urethane prepolymer (E10) of the above. The combined concentration of (H10) and (J1) in the solution (K2) is 83%.

Table 4 shows the results of Example 10. The urethane-forming composition (K2) has a remarkably long pot life, has good coatability and curability, and is obtained from the composition (K2). The coating film of polyurethane (L10) had a high tensile breaking strength.

Comparative Example 10 contains 85 parts by weight of polyalkylene oxide (A1), 15 parts by weight of polyol (B2), and polyalkylene oxide (C1), which does not contain an active hydrogen compound (F1) having ketoenol homomorphism with respect to Example 10. ) 0.5 parts by weight, a mixture of isocyanate compounds (D1) and (D2), and 0.005 parts by weight of a urethanization catalyst (G1) containing a metal, in (A1), (B2), and (C1). the amount of isocyanate groups derived from the amount of derived hydroxyl _{(M OH)} and (D1) to _{(D2) (M NCO)} is in molar ratio, and _M NCO / (A1) of (D1) and (D2) ( B2) and (C1) a urethane prepolymer composition comprising the urethane prepolymer (EC10) was obtained by _M OH = 0.35 in the (HC10), ethyl acetate as an organic solvent, an isocyanate compound as a curing agent (J1), a urethane-forming composition comprising at _M OH = 0.9 of _{M NCO} / urethane prepolymer isocyanate (J1) (EC10) (KC2 ). The combined concentration of (HC10) and (J1) in the solution (KC2) is 83%.

Since the composition (KC2) does not contain (F1), it loses fluidity in 3 hours and has a remarkably short pot life. Although the obtained polyurethane (LC10) has a high tensile breaking strength, it is difficult to actually manufacture it. It was something like that.

Example 11 shows 80 parts by weight of polyalkylene oxide (A1), 20 parts by weight of polyol (B3), 0.5 parts by weight of polyalkylene oxide (C1), a mixture of isocyanate compounds (D1) and (D2), and a metal. comprising a urethane catalyst (G1) 0.005 parts by weight containing, isocyanate group derived from the (A1) and (B3) and the amount of hydroxyl groups derived from _{(C1) (M OH)} and (D1) (D2) Urethane prepolymer (E11) obtained by the amount ( _MNCO ) of _MNCO / (A1), (B3) and (C1) of (D1) and (D2) in molar ratio of M _OH = 0.50. Ethyl acetate as an organic solvent, isocyanate compound (J1) as a curing agent, and isocyanate (J1) in a urethane prepolymer composition (H11) containing 3.0 parts by weight of an active hydrogen compound (F1) having reciprocity with ketoenol. It is a urethane-forming composition (K3) containing M _OH = 1.7 of the _MNCO / urethane prepolymer (E11) of the above. The combined concentration of (H11) and (J1) in the solution (K3) is 80%.

Table 4 shows the results of Example 11. The urethane-forming composition (K3) has a remarkably long pot life, has good coatability and curability, and is obtained from the composition (K3). The coating film of polyurethane (L11) had a high tensile breaking strength.

Comparative Example 11 contains 80 parts by weight of polyalkylene oxide (A1) and 20 parts by weight of polyol (B3), and isocyanate compounds (D1) and (D2), which do not contain polyalkylene oxide (C1) as compared with Example 11. the mixture contains a urethanization catalyst (G1) 0.005 parts by weight containing a metal, isocyanate group derived from the (A1) to the amount of hydroxyl groups derived from the _{(B3) (M OH)} and (D1) and (D2) of the amount of _{(M NCO)} is in molar ratio, (D1) and (D2) of _M NCO / (A1) and (B3) of _M OH = 0.50 obtained in the urethane prepolymer (EC11) and ketoenols tautomeric Ethyl acetate as an organic solvent, isocyanate compound (J1) as a curing agent, and _MNCO / of isocyanate (J1) in a urethane prepolymer composition (HC11) containing 3.0 parts by weight of an active hydrogen compound (F1) having a property. a urethane-forming composition comprising at _M OH = 1.7 urethane prepolymer (EC11) (KC3). The combined concentration of (HC11) and (J1) in the solution (KC3) is 80%.

Although the composition (KC3) has a long pot life, it does not contain (C1) and therefore has poor coatability, and the obtained polyurethane (LC11) has a slightly low tensile breaking strength. It was something I couldn't do.

Example 12 contains 95 parts by weight of polyalkylene oxide (A2) and 5 parts by weight of polyol (B2), 2 parts by weight of polyalkylene oxide (C2), a mixture of isocyanate compounds (D1) and (D2), and a metal. comprising a urethane catalyst (G1) 0.005 parts by weight, the amount of isocyanate groups derived from the (A2) and (B2) and (C2) to the amount of hydroxyl groups derived from the _{(M OH)} and (D1) (D2) _{(M NCO)} is in molar ratio, and (D1) and _{(D2) M NCO / (A2} ) and the (B2) and the urethane prepolymer was obtained by _M OH = 0.55 in (C2) (E12) ketoenols In a urethane prepolymer composition (H12) containing 0.5 parts by weight of a remutable active hydrogen compound (F2), ethyl acetate is used as an organic solvent, an isocyanate compound (J1) is used as a curing agent, and M of isocyanate (J1) is used. a urethane-forming composition comprising at _M OH = 1.3 of _NCO / urethane prepolymer (E12) (K4). The combined concentration of (H12) and (J1) in the solution (K4) is 75%.

Table 4 shows the results of Example 12. The urethane-forming composition (K4) had a remarkably long pot life, had good coatability and curability, and was obtained from the composition (K4). The coating film of polyurethane (L12) had a high tensile breaking strength.

Comparative Example 12 contains 100 parts by weight of polyalkylene oxide (A2) and 2 parts by weight of polyalkylene oxide (C2), and isocyanate compounds (D1) and (D2), which do not contain polyol (B2) with respect to Example 12. the mixture contains a urethanization catalyst (G1) 0.005 parts by weight containing a metal, isocyanate group derived from the (A2) and the amount of hydroxyl groups derived from _{(C2) (M OH)} and (D1) (D2) of the amount _{(M NCO)} is in molar ratio, (D1) and (D2) of _M NCO / (A2) and _M OH = 0.55 obtained in the urethane prepolymer (EC 12) and keto-enol tautomeric of (C2) Ethyl acetate as an organic solvent, isocyanate compound (J1) as a curing agent, and _MNCO / of isocyanate (J1) in a urethane prepolymer composition (HC12) containing 0.5 parts by weight of an active hydrogen compound (F2) having a property. a urethane-forming composition comprising at _M OH = 1.3 urethane prepolymer (EC12) (KC4). The combined concentration of (HC12) and (J1) in the solution (KC4) is 75%.

Although the composition (KC4) has a long pot life and a somewhat good curability, the polyurethane (LC12) obtained because it does not contain the polyol (B2) has a low tensile strength at break and is difficult to use.

In Example 13, 80 parts by weight of the polyalkylene oxide (A3), 15 parts by weight of the polyol (B1), 5 parts by weight of the polyol (B2), 2 parts by weight of the polyalkylene oxide (C1), and the isocyanate compound (D1) and ( The mixture of D2) contains 0.005 parts by weight of the metal-containing prepolymerized catalyst (G1), and the amount of hydroxyl groups ( _MOH ) and (D1) derived from (A3), (B1), (B2) and (C1). ) and (the amount of isocyanate groups derived from D2) _{(M NCO)} is in molar ratio, M of (D1) and _M NCO / (A3) and the (D2) and (B1) and (B2) (C1) An isocyanate compound (H13) containing 0.5 parts by weight of a urethane prepolymer (E13) obtained at _OH = 0.40 and an active hydrogen compound (F1) having ketoenol homomorphism as a curing agent was added to an isocyanate compound (H13). A urethane-forming composition (K5) containing J1) at M _OH = 1.3 of an isocyanate (J1) _MNCO / urethane prepolymer (E13).
Table 5 shows the results of Example 13. The urethane-forming composition (K5) has a remarkably long pot life, has good coatability and curability, and is obtained from the composition (K5). The coating film of polyurethane (L13) had a high tensile breaking strength.

In Comparative Example 13, 80 parts by weight of the polyalkylene oxide (AC1) in which the polyalkylene oxide (A3) having a significantly lower unsaturated degree than that of Example 13 was changed to the polyalkylene oxide (AC1) having a higher degree of unsaturated degree. 15 parts by weight of polyol (B1), 5 parts by weight of polyol (B2), 2 parts by weight of polyalkylene oxide (C1), a mixture of isocyanate compounds (D1) and (D2), and a urethanization catalyst (G1) containing a metal. The amount of hydroxyl groups (M _OH ) derived from (AC1), (B1), (B2) and (C1) and the amount of isocyanate groups derived from (D1) and (D2) (M) containing 0.005 parts by weight. _NCO) is in molar ratio, (D1) and (D2) _M NCO / in (AC1) and (B1) and (B2) and (urethane prepolymer obtained by _M OH = 0.40 for C1) (EC 13) an active hydrogen compound having a keto-enol tautomerism (F1) urethane prepolymer composition containing 0.5 parts by weight (HC13), an isocyanate compound as a curing agent (J1), _{M NCO} / urethane isocyanate (J1) urethane-forming composition comprising at _M OH = 1.3 polymer (EC 13) is (KC5).
Although the composition (KC5) has a long pot life and good coatability, it does not contain polyalkylene oxide (A3) having a significantly low degree of unsaturation, so that it is inferior in curability and sticky. LC13) had a low tensile breaking strength and was difficult to use.

In Example 14, 80 parts by weight of the polyalkylene oxide (A3) and 15 parts by weight of the polyol (B1), 5 parts by weight of the polyol (B3), 2 parts by weight of the polyalkylene oxide (C1), and the isocyanate compound (D1) and ( The mixture of D2) contains 0.005 parts by weight of the metal-containing prepolymerized catalyst (G1), and the amount of hydroxyl groups ( _MOH ) and (D1) derived from (A3), (B1), (B3) and (C1). ) and (the amount of isocyanate groups derived from D2) _{(M NCO)} is in molar ratio, M of (D1) and _M NCO / (A3) and the (D2) and (B1) and (B3) (C1) An isocyanate compound (H14) containing 0.5 parts by weight of a urethane prepolymer (E14) obtained at _OH = 0.40 and an active hydrogen compound (F1) having ketoenol homomorphism as a curing agent was added to an isocyanate compound (H14). the J1), a urethane-forming composition comprising at _M OH = 1.3 isocyanate _{(M NCO} / urethane prepolymer J1) (E14) (K6) .

Table 5 shows the results of Example 14. The urethane-forming composition (K6) had a remarkably long pot life, had good coatability and curability, and was obtained from the composition (K6). The coating film of polyurethane (L14) had a high tensile breaking strength.

In Comparative Example 14, 80 weights of polyalkylene oxide (AC2) obtained by changing polyalkylene oxide (A3) having a significantly lower degree of unsaturatedity from Example 14 to general-purpose polyalkylene oxide (AC2) having a higher degree of unsaturated degree. A urethanization catalyst (G1) containing 15 parts by weight of a polyol (B1), 5 parts by weight of a polyol (B3), 2 parts by weight of a polyalkylene oxide (C1), a mixture of isocyanate compounds (D1) and (D2), and a metal. ) include 0.005 part by weight, the amount of isocyanate groups derived from the (AC2) and (B1) and (B3) and (the amount of the hydroxyl group derived from C1) _{(M OH)} and (D1) (D2) ( M _NCO) is in molar ratio, (D1) and (D2) of _M NCO / (AC2) and (B1) and (B3) and the urethane prepolymer (EC14 obtained in _M OH = 0.40 in (C1) ) and the active hydrogen compound having a keto-enol tautomerism (F1) urethane prepolymer composition containing 0.5 parts by weight (HC14), an isocyanate compound as a curing agent (J1), _{M NCO} / urethane isocyanate (J1) a urethane-forming composition comprising at _M OH = 1.3 prepolymer (EC14) (KC6).

Although the composition (KC6) has a long pot life and good coatability, it does not contain polyalkylene oxide (A3) having a significantly low degree of unsaturation, so that it is inferior in curability and sticky. LC14) had a low tensile breaking strength and was difficult to use.

Example 15 contains 70 parts by weight of polyalkylene oxide (A3), 30 parts by weight of polyol (B3), 2 parts by weight of polyalkylene oxide (C1), a mixture of isocyanate compounds (D1) and (D2), and a metal. comprising a urethane catalyst (G1) 0.005 parts by weight, the amount of isocyanate groups derived from the (A3) and (B3) and the amount of hydroxyl groups derived from _{(C1) (M OH)} and (D1) (D2) _{(M NCO)} is in molar ratio, and (D1) and _{(D2) M NCO / (A3} ) and the (B3) and the urethane prepolymer was obtained by _M OH = 0.40 in (C1) (E15) ketoenols A urethane prepolymer composition (H15) containing 3.0 parts by weight of a remutable active hydrogen compound (F1) and 0.001 part by weight of a compound (FC1) as a reaction modifier, and an isocyanate compound (J1) as a curing agent. Isocyanate (J1) _MNCO / urethane prepolymer (E15) in a urethane-forming composition (K7) containing M _OH = 1.3.
The results of Example 15 are shown in Table 5. The urethane-forming composition (K7) has a remarkably long pot life, has good coatability and curability, and is obtained from the composition (K7). The coating film of polyurethane (L15) had a high tensile breaking strength.

In Comparative Example 15, 70 parts by weight of the polyalkylene oxide (AC3) was obtained by changing the polyalkylene oxide (A3) having a significantly lower degree of unsaturatedness to the polyalkylene oxide (AC3) having a molecular weight as low as 600. It contains 30 parts by weight of polyol (B3), 2 parts by weight of polyalkylene oxide (C1), a mixture of isocyanate compounds (D1) and (D2), and 0.005 parts by weight of urethanization catalyst (G1) containing metal. the amount of isocyanate groups derived from the AC3) and (B3) and (the amount of the hydroxyl group derived from C1) _{(M OH)} and _{(D1) (D2) (M} NCO) is in molar ratio, and (D1) ( _M NCO / (AC3) and (B3) and (C1) an active hydrogen compound having a urethane prepolymer (EC15) and keto-enol tautomerism obtained in _M OH = 0.40 in (F1) 3.0 weight D2) parts, the compound as a reaction modifier (FC1) urethane prepolymer composition comprising 0.001 part by weight (HC15), an isocyanate compound as a curing agent (J1), _{M NCO} / urethane prepolymer isocyanate (J1) (EC15 ) Is a urethane-forming composition (KC7) containing M _OH = 1.3.

Since the composition (KC7) contains a large amount of polyalkylene oxide (AC3) having a low molecular weight of 600 and does not contain polyalkylene oxide (A3), the weight average molecular weight of the urethane prepolymer (EC15) is as low as less than 3000, and the coating is applied. Although the workability and curability were good, the pot life was short, and the obtained polyurethane (LC15) had a low tensile breaking strength and was difficult to use.

Comparative Example 16 shows 70 parts by weight of polyalkylene oxide (A2), 30 parts by weight of polyol (B2), 0.5 parts by weight of polyalkylene oxide (C2), a mixture of isocyanate compounds (D1) and (D2), and a metal. comprising a urethane catalyst (G1) 0.005 parts by weight containing, isocyanate group derived from (A2) and (B2) and (C2) to the amount of hydroxyl groups derived from the _{(M OH)} and (D1) (D2) the amount _{(M NCO)} is in molar ratio, (D1) and _{(D2) M NCO / (A2} ) and the (B2) and (C2) a urethane prepolymer obtained by _M OH = 0.35 in (EC16) And ethyl acetate as an organic solvent in a urethane prepolymer composition (HC16) containing 1.0 part by weight of compound (FC1) as a reaction modifier instead of containing active hydrogen compound (F) having ketoenol remutability. , an isocyanate compound as a curing agent (J1), an isocyanate _{M NCO} / urethane-forming composition comprising at _M OH = 1.3 urethane prepolymer (EC16) of (J1) (KC8). The combined concentration of (HC16) and (J1) in the solution (KC8) is 80%.

Since (FC1) is used instead of (F) in the composition (KC8), the pot life is long, but the curability is remarkably poor, and the obtained polyurethane (LC16) is also stretched without losing its tack. The breaking strength was small, and it was difficult to actually manufacture and use it.

Comparative Example 17 shows 70 parts by weight of polyalkylene oxide (A2), 30 parts by weight of polyol (B2), 0.5 parts by weight of polyalkylene oxide (C2), a mixture of isocyanate compounds (D1) and (D2), and a metal. comprising a urethane catalyst (G1) 0.005 parts by weight containing, isocyanate group derived from (A2) and (B2) and (C2) to the amount of hydroxyl groups derived from the _{(M OH)} and (D1) (D2) the amount _{(M NCO)} is in molar ratio, (D1) and _{(D2) M NCO / (A2} ) and the (B2) and (C2) a urethane prepolymer obtained by _M OH = 0.35 in (EC 17) In a urethane prepolymer composition (HC17) containing 1.0 part by weight of the compound (FC2) instead of the active hydrogen compound (F) having ketoenol remutability, ethyl acetate as an organic solvent and a curing agent as a curing agent. isocyanate compound (J1), an isocyanate _{M NCO} / urethane-forming composition comprising at _M OH = 1.3 urethane prepolymer (EC 17) of (J1) (KC9). The combined concentration of (HC17) and (J1) in the solution (KC9) is 80%.

Since the composition (KC9) does not contain (F) having an active methylene group, the pot life that loses fluidity in 3 hours is remarkably short, and the obtained polyurethane (LC17) has a tensile breaking strength. Although large, it was difficult to actually manufacture.

Comparative Example 18 shows 70 parts by weight of polyalkylene oxide (A2), 30 parts by weight of polyol (B2), 0.5 parts by weight of polyalkylene oxide (C2), a mixture of isocyanate compounds (D1) and (D2), and a metal. comprising a urethane catalyst (G1) 0.005 parts by weight containing, isocyanate group derived from (A2) and (B2) and (C2) to the amount of hydroxyl groups derived from the _{(M OH)} and (D1) (D2) the amount _{(M NCO)} is in molar ratio, (D1) and _{(D2) M NCO / (A2} ) and the (B2) and (C2) a urethane prepolymer obtained by _M OH = 0.35 in (ec18) In a urethane prepolymer composition (HC18) containing 1.0 part by weight of the compound (FC3) instead of the active hydrogen compound (F) having ketoenol remutability, ethyl acetate as an organic solvent and a curing agent as a curing agent. isocyanate compound (J1), an isocyanate _{M NCO} / urethane-forming composition comprising at _M OH = 1.3 urethane prepolymer (ec18) of (J1) (KC10). The combined concentration of (HC18) and (J1) in the solution (KC10) is 80%.

Since the composition (KC10) does not contain (F) having an active methylene group, the pot life that loses fluidity in 4 hours is remarkably short, and the obtained polyurethane (LC18) has a tensile breaking strength. Although large, it was difficult to actually manufacture.

Comparative Example 19 shows 70 parts by weight of polyalkylene oxide (A2), 30 parts by weight of polyol (B2), 0.5 parts by weight of polyalkylene oxide (C2), a mixture of isocyanate compounds (D1) and (D2), and a metal. free of urethane catalyst (G1) comprising, instead include amine urethane catalyst (GC1) 0.005 parts by weight, the amount of hydroxyl groups derived from the (A2) and _{(B2) (C2) (M} OH ), (D1), and (D2) are derived from (D1) and (D2), and the amount of isocyanate groups ( _MNCO ) is the molar ratio of _MNCO / (A2), (B2), and (C2) of (D1) and (D2). Ethyl acetate as an organic solvent in a urethane prepolymer composition (HC19) containing 1.0 part by weight of a urethane prepolymer (EC19) obtained at _OH = 0.35 and an active hydrogen compound (F1) having ketoenol homomorphism. , an isocyanate compound as a curing agent (J1), an isocyanate _{M NCO} / urethane-forming composition comprising at _M OH = 1.3 urethane prepolymer (EC 19) of (J1) (KC11). The combined concentration of (HC19) and (J1) in the solution (KC11) is 80%.

Since the composition (KC11) does not contain a urethanization catalyst (G1) containing a metal, it loses its fluidity in 4 hours and has a remarkably short pot life, and its curability is somewhat low. Although the tensile breaking strength of (LC19) was high, it was difficult to actually manufacture it.

In Comparative Example 20, 70 parts by weight of polyalkylene oxide (A2), 30 parts by weight of polyol (B2), and 0.5 parts of polyalkylene oxide (CC1) containing no ethylene oxide residue instead of containing polyalkylene oxide (C). It contains 0.005 parts by weight of a mixture of isocyanate compounds (D1) and (D2) and a metal-containing urethanization catalyst (G1), and is derived from (A2), (B2) and (CC1). the amount of isocyanate groups derived from the amount of the hydroxyl group _{(M OH)} and _{(D1) (D2) (M} NCO) is in molar ratio, and _M NCO / (A2) of (D1) and (D2) (B2) and urethane prepolymer was obtained by _M OH = 0.35 in (CC1) (EC20), active hydrogen compound having a keto-enol tautomerism (F1) urethane prepolymer composition containing 1.0 parts by weight (HC20) , ethyl acetate as an organic solvent, an isocyanate compound as a curing agent (J1), is a urethane-forming composition comprising at _M OH = 1.3 of _{M NCO} / urethane prepolymer isocyanate (J1) (EC20) (KC12 ) .. The combined concentration of (HC20) and (J1) in the solution (KC12) is 80%.

Although the composition (KC12) has a long pot life, it does not contain polyalkylene oxide (C2) containing ethylene oxide residues, so that the coatability is poor and the tensile breaking strength of the obtained polyurethane (LC20) is somewhat small. It was a thing, and the actual production was difficult and unusable.

In Comparative Example 21, 90 parts by weight of the polyalkylene oxide (A2), 10 parts by weight of the polyol (BC1) having a polycarbonate residue instead of the polyol (B), 0.5 parts by weight of the polyalkylene oxide (C2), and isocyanate. mixture of compound (D1) and (D2), wherein the urethane catalyst (G1) 0.005 parts by weight containing a metal, and (A2) and the amount of hydroxyl groups derived from the (BC1) and _{(C2) (M OH)} the amount of isocyanate groups derived from the (D1) and _{(D2) (M NCO)} is in molar ratio, _{M OH} of (D1) and _{(D2) M NCO / (A2} ) and the (BC1) (C2) = A urethane prepolymer composition (HC21) containing 1.0 part by weight of the urethane prepolymer (EC21) obtained in 0.35 and an active hydrogen compound (F1) having ketoenol remutability was cured with ethyl acetate as an organic solvent. isocyanate compound (J1) as agent, an isocyanate _{M NCO} / urethane-forming composition comprising at _M OH = 1.3 urethane prepolymer (EC21) of (J1) (KC13). The combined concentration of (HC21) and (J1) in the solution (KC13) is 80%.

Although the composition (KC13) has a long pot life and good curability, it does not contain the polyol (B) and contains a polycarbonate residue (BC1), so that the coatability is poor, and the obtained polyurethane (LC21) Has a low tensile breaking strength and is difficult to use.

In Comparative Example 22, 90 parts by weight of the polyalkylene oxide (A2), 10 parts by weight of the polyol (BC2) having an acrylic residue instead of the polyol (B), 0.5 parts by weight of the polyalkylene oxide (C2), and isocyanate. mixture of compound (D1) and (D2), wherein the urethane catalyst (G1) 0.005 parts by weight containing a metal, and (A2) and the amount of hydroxyl groups derived from the (BC1) and _{(C2) (M OH)} the amount of isocyanate groups derived from the (D1) and _{(D2) (M NCO)} is in molar ratio, _{M OH} of (D1) and _{(D2) M NCO / (A2} ) and the (BC1) (C2) = A urethane prepolymer composition (HC21) containing 1.0 part by weight of the urethane prepolymer (EC21) obtained in 0.35 and an active hydrogen compound (F1) having ketoenol remutability was cured with ethyl acetate as an organic solvent. isocyanate compound (J1) as agent, an isocyanate _{M NCO} / urethane-forming composition comprising at _M OH = 1.3 urethane prepolymer (EC21) of (J1) (KC14). The combined concentration of (HC21) and (J1) in the solution (KC14) is 80%.

Since the composition (KC14) does not contain the polyol (B) but contains an acrylic residue (BC1), precipitation components are generated and coating is difficult, and the physical properties of polyurethane (LC22) can be evaluated. Was difficult to manufacture.

In Comparative Example 23, 70 parts by weight of the polyalkylene oxide (A2), 30 parts by weight of the polyol (B2), 0.5 parts by weight of the polyalkylene oxide (C2), 0.005 parts by weight of the urethanization catalyst (G1) containing a metal, active hydrogen compound having a keto-enol tautomerism (F1) 1.0 part by weight of ethyl acetate as organic solvent, an isocyanate compound (J1) isocyanate _{(J1) M NCO / (A2} ) and the (B2) as the curing agent ( wherein in _M OH = 1.3 of C2), which is (A2) and (B2) and (C2) with an isocyanate compound (D) a urethane prepolymer (E) is not formed composition (KC15). The combined concentration of (A2), (B2), (C2), (G1), (F1) and (J1) in the solution (KC15) is 80%.

Since the composition (KC15) does not contain the urethane prepolymer (E), it has a low viscosity and poor coatability, and although it has a long pot life, it takes a long time to react and has poor curability. The obtained polyurethane (LC23) had a low tensile breaking strength, and it was difficult to actually manufacture and use it.

In each of the urethane prepolymer compositions (H) exemplified in Examples 1 to 15, the urethane prepolymer (E) has an alkylene oxide residue having a weight average molecular weight of 3000 or more and a carbon number of 3 or more. , 0.010 meq / g or less unsaturated group, ethylene oxide residue, and further constitutes any residue of tetramethylene-ether residue, sugar residue having 6 or more carbon atoms, and aromatic amine residue. It was included as an ingredient.

As described above, as shown in the examples, the urethane prepolymer composition in the present development has a remarkably long pot life when coated with a coating machine or the like, has excellent coatability, and contains a large amount of urethanization catalyst. It has high productivity by advancing curing (solidification) accompanying the reaction with the isocyanate compound without using it, and further, it is possible to obtain polyurethane having a large tensile breaking strength by the reaction with the isocyanate compound. By taking advantage of its characteristics, it was shown that the polyurethane obtained from the urethane prepolymer composition can be suitably used as a sealant, a paint, an adhesive, an adhesive and the like.

Claims (12)

A urethane prepolymer composition comprising a urethane prepolymer (E), an active methylene group-containing compound (F) having keto-enol tachism, and a urethanization catalyst (G) containing a metal component.
The urethane prepolymer (E)
With a weight average molecular weight of 3000 or more
It contains an alkylene oxide residue having 3 or more carbon atoms, an unsaturated group of 0.010 meq / g or less, and an ethylene oxide residue as essential components.
Further, it contains at least one of a tetramethylene-ether residue, a sugar residue having 6 or more carbon atoms, and an aromatic amine residue.
Urethane prepolymer composition (H). The urethane prepolymer (E) contains a polyalkylene oxide (A) having an alkylene oxide residue having 3 or more carbon atoms and 2 or more hydroxyl groups in one molecule, a tetramethylene-ether residue, and 6 or more carbon atoms. A polyol (B) having at least one of a sugar residue and an aromatic amine residue, a polyalkylene oxide (C) containing one hydroxyl group and an ethylene oxide residue in one molecule, and an average functional group of isocyanate groups. A reaction product with an isocyanate compound (D) having a group number of 2.0 or more.
The polyalkylene oxide (A) is
The degree of unsaturation is 0.010 meq / g or less,
The number average molecular weight is 800 or more.
The urethane prepolymer composition (H) according to claim 1. Urethane prepolymer (E) has at least one hydroxyl group in one molecule, the polyalkylene oxide (A) and the polyol (B) and the total amount of the hydroxyl group derived from a polyalkylene oxide (C) (M _OH The urethane prepolymer composition according to claim 2, wherein the ratio ( _MNCO / M _OH ) of the amount ( _MNCO ) of the isocyanate groups derived from the isocyanate compound (D) to the above-mentioned isocyanate compound (D) is less than 1.0 in terms of molar ratio. Thing (H). The urethane prepolymer composition (H) according to any one of claims 1 to 3, wherein the active methylene group-containing compound (F) having keto-enol tautomerism is acetylacetone or ethyl acetoacetate. A urethane prepolymer composition solution (I) containing the urethane prepolymer composition (H) according to claims 1 to 4 and an organic solvent.
A urethane prepolymer composition in which the concentration of the urethane-forming composition (E) or the urethane-forming composition (H) in the urethane-forming composition solution (I) is 10% by mass or more and 99% by mass or less. Solution (I). A polyurethane-forming composition (K) containing the urethane prepolymer composition (E) according to claims 1 to 4 or the urethane prepolymer composition solution (I) according to claim 5 and an isocyanate compound (J). ). Polyurethane (L), which is a reaction product of the urethane-forming composition (K) according to claim 6. The polyurethane sheet made of the polyurethane (L) according to claim 7. A sealing material made of the polyurethane (L) according to claim 7 or the polyurethane sheet according to claim 8. A coating material comprising the polyurethane (L) according to claim 7 or the polyurethane sheet according to claim 8. The pressure-sensitive adhesive comprising the polyurethane (L) according to claim 7 or the polyurethane sheet according to claim 8. An adhesive comprising the polyurethane (L) according to claim 7 or the polyurethane sheet according to claim 8.