JP2020083972A - Urethane prepolymer, polyurethane and sealing material using the same - Google Patents

Abstract

To provide a polyurethane that has a low tackiness property and is high strength and high transparency.SOLUTION: Provided is a NCO-terminated liquid urethane prepolymer represented by formula (1), containing a structural unit having a number average molecular weight of 200 or more and 3,000 or less, in which the degree of unsaturation is 0.020 meq/g or less, and the terminal is a NCO group. In formula (1), Q represents a polymer component containing a halogenated oxypropylene group, m represents an integer of 2 to 8, and Rrepresents an active hydrogen-containing compound residue.SELECTED DRAWING: None

Description

The present disclosure relates to a urethane prepolymer, a polyurethane using the same, and a sealing material.

The curing polyurethane composition used as a sealing material, paint, coating material, pressure-sensitive adhesive, or adhesive agent is a one-component type that is cured by moisture in the air, or a two-component type that is cured by mixing a curing agent with a polyol or polyamine. And a 1.5-pack type containing a latent curing agent. A curable resin composition containing an NCO-terminated urethane prepolymer obtained by reacting an isocyanate with a polyol, a filler, and an additive is widely used as a main component for forming such a polyurethane. As the polyol, a polyester polyol is used. And polyalkylene oxide polyols.

The polyurethane obtained by using the polyester polyol has an ester group and therefore has a problem of poor water resistance due to hydrolysis.

Polyalkylene oxide industrially produced by addition polymerization of alkylene oxide such as propylene oxide using an alkali metal such as potassium hydroxide as a catalyst contains a large amount of impurities, and thus has poor curability and sufficient resin strength. There was a problem that was not obtained.

A halogen-containing polyether polyol is known as a raw material for a polyurethane-based adhesive having excellent shear strength, moisture resistance, and water resistance (see, for example, Patent Document 1). Such a halogen-containing polyether polyol can be synthesized by ring-opening polymerization of a halogen-containing alkylene oxide using an acid catalyst such as a boron trifluoride compound.

JP-A-2-202573

However, the polyol used as the raw material of the adhesive composition according to Patent Document 1 contains a large amount of impurities and unsaturated components because it uses the Lewis acid catalyst to open the epichlorohydrin. Therefore, the resulting cured product has many defective portions and the cross-linking density is lowered, so that unless the filler is contained in a large amount, sufficient resin strength is not exhibited and the resin surface becomes sticky.

The respective aspects of the present invention are [1] to [6] shown below.
[1] A liquid urethane prepolymer having an NCO terminal,
The urethane prepolymer is
A structural unit having a number average molecular weight of 200 or more and 3,000 or less, represented by the formula (1), and
The degree of unsaturation is 0.020 meq/g or less,
Liquid urethane prepolymer terminated with NCO groups:

In formula (1),
Q represents a polymer component containing a structural unit represented by the formula [I],
m represents an integer of 2 to 8,
R ¹ represents an active hydrogen-containing compound residue;

In formula [I], X represents a halogen atom.
[2]
The liquid urethane prepolymer according to [1], which has an unsaturation degree of 0.016 meq/g or less.
[3]
Containing the urethane prepolymer according to any one of [1] and [2], and one or more of a filler and another polyol, a urethane-forming catalyst, a foam stabilizer, an antioxidant, and a plasticizer. , A liquid urethane prepolymer composition.
[4]
The liquid urethane prepolymer according to any one of [1] to [2] or the liquid urethane prepolymer composition according to [3] is reacted with water in air or a curing agent (active hydrogen-containing compound). Cured polyurethane.
[5]
A composition for a sealing material, comprising the urethane prepolymer according to any one of [1] to [2] or the urethane prepolymer composition according to [3].
[6]
A sealing material obtained by curing the composition for a sealing material according to [5] by reaction with water in air or a curing agent (active hydrogen-containing compound).

According to one aspect of the present invention, a polyurethane having low tackiness, high strength, and high transparency can be provided, and can be suitably used for applications such as sealing materials.

Hereinafter, exemplary embodiments for carrying out the present invention will be described in detail.
<Urethane prepolymer>
The urethane prepolymer according to one aspect of the present invention,
It can be obtained by reacting a halogen-containing polyether polyol with an isocyanate compound.
<<Halogen-containing polyether polyol>>
The halogen-containing polyether polyol is
It is shown by formula (2),
The average molecular weight is 200 or more and 3,000 or less:

In formula (2),
Q represents a polymer component containing a structural unit represented by the formula [I],
m represents an integer of 2 to 8,
R ¹ represents an active hydrogen-containing compound residue;

In formula [I], X represents a halogen atom.

In formula [I], the halogen atom represented by X is not particularly limited, and examples thereof include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Among these, a fluorine atom, a chlorine atom and a bromine atom are preferable, and a fluorine atom or a chlorine atom is more preferable, from the viewpoint of easy handling.

In formulas (1) and (2), the active hydrogen-containing compound residue represented by R ¹ is not particularly limited, and examples thereof include a hydroxy residue, an amine residue, a carboxylic acid residue, and a thiol. Examples thereof include residues.

Further, the active hydrogen-containing compound containing such an active hydrogen-containing compound residue is not particularly limited, but examples thereof include a hydroxy compound, an amine compound, a carboxylic acid compound, a thiol compound, and a polyether polyol having a hydroxyl group. Etc.

Examples of the hydroxy compound include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol and 2,3-butanediol. 1,6-hexanediol, 1,9-nonanediol, 2,5-hexanediol, 1,3-cyclohexanediol, 2-methylpentane-2,4-diol, 2,5-dimethyl-2,5- Examples thereof include hexanediol, glycerin, trimethylolpropane, hexanetriol, pentaerythritol, diglycerin, sorbitol, sucrose, glucose, 2-naphthol and bisphenol.

Examples of the amine compound include ethylenediamine, 1,3-propylenediamine, 1,4-butylenediamine, and 1,2-butylenediamine.

Examples of the carboxylic acid compound include phthalic acid and adipic acid.

Examples of the thiol compound include ethanedithiol and butanedithiol.

Examples of the polyether polyol having a hydroxyl group include polyether polyols having a molecular weight of 200 or more and 1000 or less.

Among these active hydrogen-containing compounds, since it becomes possible to efficiently produce a halogen-containing polyether polyol, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,9-nonanediol, 2,5-hexanediol, 1,6-hexanediol, 2-methylpentane-2,4-diol, ethylenediamine, and polyether polyol having a molecular weight of 200 or more and 1,000 or less are preferable, and tripropylene glycol or 2,5-hexane is preferable. Diol, 1,9-nonanediol, and polyether polyol having a molecular weight of 200 or more and 1,000 or less are particularly preferable.

The number-average molecular weight of the halogen-containing polyether polyol is 200 or more and 3,000 or less, and it is preferable that the number-average molecular weight is 200 or more and 2,000 or less, since handling property and polyurethane production efficiency are excellent. It is particularly preferable that it is 2,000 or less.

The degree of unsaturation of the halogen-containing polyether polyol is preferably 0.02 meq/g or less, and particularly preferably 0.01 meq/g or less, because the curability of the polyurethane is improved.

The ratio (Mw/Mn) of the weight average molecular weight Mw to the number average molecular weight Mn of the halogen-containing polyether polyol is preferably 2.00 or less, and particularly preferably 1. It is 50 or less. However, the number average molecular weight determined by gel permeation chromatography measurement using polystyrene as the standard substance is Mn, and the mass average molecular weight is Mw.

The rate of primary conversion of the terminal hydroxyl group in the halogen-containing polyether polyol is not particularly limited, but the variation in reactivity is small, the reaction is uniform, and the molecular weight distribution and composition of the resulting polyurethane are likely to be uniform. It is preferably less than 10%, more preferably 8% or less, and particularly preferably 5% or less.
<<Production Method of Halogen-Containing Polyether Polyol>>
The method for producing the halogen-containing polyether polyol is not particularly limited and can be produced by a conventionally known production method.

For example, (A) a method of adding a halogen-containing alkylene oxide to a predetermined molecular weight to a bifunctional or higher functional hydrogen compound using a Lewis acid catalyst or a complex metal cyanide complex catalyst; (B) a bifunctional or higher functional hydrogen compound And a onium salt catalyst such as a phosphazenium salt or an ammonium salt or a phosphonium salt, and a Lewis acid catalyst in the presence of a ring-opening polymerization of a halogen-containing alkylene oxide.

Examples of the Lewis acid catalyst include aluminum compounds, zinc compounds, boron compounds and the like.

Examples of the aluminum compound include trimethylaluminum, triethylaluminum, triisobutylaluminum, trinormalhexylaluminum, triethoxyaluminum, triisopropoxyaluminum, triisobutoxyaluminum, triphenylaluminum, diphenylmonoisobutylaluminum, monophenyldiisobutylaluminum and the like. Aluminoxane such as methylaluminoxane, isobutylaluminoxane and methyl-isobutylaluminoxane; inorganic aluminum such as aluminum chloride, aluminum hydroxide and aluminum oxide;

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

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

Among these, organoaluminum, aluminoxane, and organozinc are preferable, and organoaluminum is particularly preferable, because they are catalysts for producing halogen-containing polyether polyols having excellent catalytic performance.

The halogen-containing alkylene described in (B) has a low degree of unsaturation and is easy to obtain a halogen-containing polyalkylene oxide having a narrow molecular weight distribution, and is easy to improve the handling property when the prepolymer is prepared and the curability of the obtained prepolymer is excellent. It is preferable to produce a halogen-containing polyether polyol by carrying out ring-opening polymerization of an oxide.

The structure of the phosphazenium salt used in the production of the halogen-containing polyether polyol is not particularly limited.

The phosphazenium salt is, for example, a phosphazenium salt represented by the formula (3):

In formula (3),
R ² and R ³ are each independently
Hydrogen atom,
A hydrocarbon group having 1 to 20 carbon atoms,
A ring structure in which R ² and R ³ are bonded to each other,
Represents a ring structure in which R ^{2 s} or R ^{3 s} are bonded to each other;
Z ⁻ represents a hydroxy anion, an alkoxy anion having 1 to 4 carbon atoms, a carboxy anion, an alkylcarboxy anion having 2 to 5 carbon atoms, a chlorine anion, a bromine anion, an iodine anion or a hydrogen carbonate anion;
Y represents a carbon atom or a phosphorus atom;
a is
2 when Y is a carbon atom,
3 when Y is a phosphorus atom.

In formula (3), the hydrocarbon group having 1 to 20 carbon atoms represented by R ² and R ³ is not particularly limited, and examples thereof include a methyl group, an ethyl group, a vinyl group, and n-propyl. Group, isopropyl group, cyclopropyl group, allyl group, n-butyl group, isobutyl group, t-butyl group, cyclobutyl group, n-pentyl group, neopentyl group, cyclopentyl group, n-hexyl group, cyclohexyl group, phenyl group, Heptyl group, cycloheptyl group, octyl group, cyclooctyl group, nonyl group, cyclononyl group, decyl group, cyclodecyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group , Nonadecyl group and the like.

Examples of the case where R ² and R ³ are bonded to each other to form a ring structure include a pyrrolidinyl group, a pyrrolyl group, a piperidinyl group, an indolyl group and an isoindolyl group.

The ring structure in which R ^{2 s} or R ^{3 s} are bonded to each other is not particularly limited, but for example, two R ^{2 s} or two R ^{3 s} are independently a methylene group, an ethylene group, or a propylene group. A ring structure in which one alkylene group and the other alkylene group are bonded to each other to form one group selected from alkylene groups such as a butylene group and the like.

Of these, R ² and R ³ are preferably a methyl group, an ethyl group, or an isopropyl group from the viewpoints of an alkylene oxide polymerization catalyst having particularly excellent catalytic activity and easy availability of raw materials.

Z ⁻ in the formula (3) is a hydroxy anion, an alkoxy anion having 1 to 4 carbon atoms, a carboxy anion, an alkylcarboxy anion having 2 to 5 carbon atoms, or a hydrogen carbonate anion.

The alkoxy anion having 1 to 4 carbon atoms is not particularly limited, and examples thereof include methoxy anion, ethoxy anion, n-propoxy anion, isopropoxy anion, n-butoxy anion, isobutoxy anion, t-butoxy anion. Etc.

The alkylcarboxy anion having 2 to 5 carbon atoms is not particularly limited, but, for example, acetoxy anion, ethylcarboxy anion, n-propylcarboxy anion, isopropylcarboxy anion, n-butylcarboxy anion, isobutylcarboxy anion, Examples include t-butyl carboxy anion.

Among these, as Z ⁻ , a hydroxy anion and a hydrogen carbonate anion are particularly preferable because they are halogen-containing alkylene oxide polymerization catalysts having excellent catalytic activity.

The phosphazenium salt represented by the formula (3) is not particularly limited, but specifically, tetrakis(1,1,3,3-tetramethylguanidino)phosphonium hydroxide, tetrakis(1,1, 3,3-Tetraethylguanidino)phosphonium hydroxide, tetrakis(1,1,3,3-tetra(n-propyl)guanidino)phosphonium hydroxide, tetrakis(1,1,3,3-tetraisopropylguanidino)phosphonium hydroxide , Tetrakis(1,1,3,3-tetra(n-butyl)guanidino)phosphonium hydroxide, tetrakis(1,1,3,3-tetraphenylguanidino)phosphonium hydroxide, tetrakis(1,1,3,3) -Tetrabenzylguanidino)phosphonium hydroxide, tetrakis(1,3-dimethylimidazolidine-2-imino)phosphonium hydroxide, tetrakis(1,3-diethylimidazolidin-2-imino)phosphonium hydroxide, tetrakis(1,1) ,3,3-Tetramethylguanidino)phosphonium hydrogen carbonate, tetrakis(1,1,3,3-tetraethylguanidino)phosphonium hydrogen carbonate, tetrakis(1,1,3,3-tetra(n-propyl)guanidino)phosphonium hydrogengen Carbonate, tetrakis(1,1,3,3-tetraisopropylguanidino)phosphonium hydrogen carbonate, tetrakis(1,1,3,3-tetra(n-butyl)guanidino)phosphonium hydrogen carbonate, tetrakis(1,1,3,3) 3-tetraphenylguanidino)phosphonium hydrogen carbonate, tetrakis(1,1,3,3-tetrabenzylguanidino)phosphonium hydrogen carbonate, tetrakis(1,3-dimethylimidazolidine-2-imino)phosphonium hydrogen carbonate, tetrakis(1, Examples thereof include 3-diethylimidazolidin-2-imino)phosphonium hydrogen carbonate.

Further, tetrakis[tris(dimethylamino)phosphoranylideneamino]phosphonium hydroxide, tetrakis[tris(diethylamino)phosphoranylideneamino]phosphonium hydroxide, tetrakis[tris(di-n-propylamino)phosphoranylideneamino]phosphonium hydroxy. De, 1-tert-butyl-4,4,4-tris(dimethylamino)-2,2-bis(tris(dimethylamino)phosphoranylideneamino)-2λ5,4λ5-catenadi(phosphazene), tetrakis[tris( Diisopropylamino)phosphoranylideneamino]phosphonium hydroxide, tetrakis[tris(di-n-butylamino)phosphoranylideneamino]phosphonium hydroxide, tetrakis[tris(diphenylamino)phosphoranylideneamino]phosphonium hydroxide, tetrakis[tris (1,3-Dimethylimidazolidin-2-imino)phosphoranylideneamino]phosphonium hydroxide, tetrakis[tris(dimethylamino)phosphoranylideneamino]phosphonium hydrogen carbonate, tetrakis[tris(diethylamino)phosphoranylideneamino]phosphonium Hydrogen carbonate, tetrakis[tris(di-n-propylamino)phosphoranylideneamino]phosphonium hydrogen carbonate, tetrakis[tris(diisopropylamino)phosphoranylideneamino]phosphonium hydrogen carbonate, tetrakis[tris(di-n-butylamino)phosphorani Examples include rideneamino]phosphonium hydrogencarbonate, tetrakis[tris(diphenylamino)phosphoranylideneamino]phosphonium hydrogencarbonate, tetrakis[tris(1,3-dimethylimidazolidine-2-imino)phosphoranylideneamino]phosphonium hydrogencarbonate, etc. can do.

Among them, tetrakis(1,1,3,3-tetramethylguanidinophosphonium hydroxide, tetrakis(1,1,3,3-tetramethyl), since it is a halogen-containing polyether polyol production catalyst having excellent catalytic performance, Guanidino)phosphonium hydrogen carbonate and tetrakis[tris(dimethylamino)phosphoranylideneamino]phosphonium hydroxide are particularly preferred.

The structure of ammonium salt or phosphonium salt is represented by formula (4):

In formula (4),
D represents a nitrogen atom or a phosphorus atom;
R ⁴ , R ⁵ , R ⁶ and R ⁷ are each independently
An alkyl group, an aryl group, an alkoxy group, or a dialkylamino group having 1 to 20 carbon atoms,
A halogen atom, or
Represents a hydrogen atom;
E ⁻ represents a counter ion composed of an inorganic or organic group;
Two to four of R ^{4 to} R ⁷ may be bonded to each other to form a cyclic structure, and the cyclic structure may contain a hetero atom.

In formula (4), the alkyl group having 1 to 20 carbon atoms and the aryl group represented by R ⁴ , R ⁵ , R ⁶ and R ⁷ are not particularly limited, and examples thereof include a methyl group and an ethyl group. Group, vinyl group, normal propyl group, isopropyl group, cyclopropyl group, allyl group, normal butyl group, isobutyl group, t-butyl group, cyclobutyl group, normal pentyl group, neopentyl group, cyclopentyl group, normal hexyl group, cyclohexyl group , Phenyl group, heptyl group, cycloheptyl group, benzyl group, tolyl group, octyl group, cyclooctyl group, xylyl group and the like.

In formula (4), the alkoxy group having 1 to 20 carbon atoms represented by R ⁴ , R ⁵ , R ⁶ and R ⁷ is a methoxy group, an ethoxy group, a vinyloxy group, a normal propoxy group, an isopropoxy group, a cyclo group. Propoxy group, allyloxy group, normal butoxy group, isobutoxy group, t-butoxy group, cyclobutoxy group, normal pentyloxy group, neopentyloxy group, cyclopentyloxy group, normalhexyloxy group, cyclohexyloxy group, phenoxy group, heptyloxy group Group, cycloheptyloxy group, octyloxy group, benzyloxy group, tolyloxy group, cyclooctyloxy group, xylyloxy group.

In formula (4), the dialkylamino group having 1 to 20 carbon atoms represented by R ⁴ , R ⁵ , R ⁶ and R ⁷ is a dimethylamino group, a diethylamino group, a pyrrolidino group, a piperidino group, or dinormalpropylamino. Group, diisopropylamino group, dicyclopropylamino group and the like.

The halogen atom is not particularly limited, but examples thereof include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

Since it becomes a halogen-containing polyether polyol production catalyst having excellent catalytic activity, R ⁴ , R ⁵ , R ⁶ and R ⁷ are each independently a C 1-10 alkyl group which may contain a hetero atom, or An aryl group is preferable, and a methyl group, an ethyl group, a normal butyl group, a normal octyl group, or a phenyl group is particularly preferable.

Of R ^{4 to} R ⁷ , 2 to 4 may combine to form a cyclic structure, and it is preferable that 2 or 3 combine to form a cyclic structure. The cyclic structure may contain a hetero atom.

Examples of the structure of the ammonium salt in which two or three of R ^{4 to} R ⁷ are bonded to each other to form a cyclic structure include a pyridinium salt and an imidazolium salt, and a halogen-containing polyether polyol production catalyst having excellent catalytic activity is obtained. Therefore, it is preferably an imidazolium salt.

In formula (4), the inorganic or organic group represented by E ⁻ is not particularly limited, but specifically, a halogen atom, a hydroxyl group, an alkoxyl group, an amino group, a carboxyl group, a sulfonic acid. Examples thereof include groups, borohydride groups and hexafluorophosphate groups. It is preferable that E ⁻ be a bromine atom, a chlorine atom, an iodine atom, or a hexafluorophosphate group because it becomes a halogen-containing polyether polyol production catalyst having excellent catalytic activity.

The ammonium salt or phosphonium salt represented by the formula (4) is not particularly limited, and specifically, tetramethylammonium bromide, tetraethylammonium bromide, tetranormalpropylammonium bromide, tetranormalbutylammonium bromide. , Tetranormal pentyl ammonium bromide, tetra normal hexyl ammonium bromide, tetra normal heptyl ammonium bromide, tetra normal octyl ammonium bromide, tetramethyl ammonium chloride, tetraethyl ammonium chloride, tetra normal propyl ammonium chloride, tetra normal butyl ammonium chloride, tetra normal pentyl ammonium Chloride, tetranormalhexyl ammonium chloride, tetranormal heptyl ammonium chloride, tetranormal octyl ammonium chloride, 1-butyl-3-methylimidazolium chloride, 1-butyl-2,3-dimethylimidazolium chloride, 1-ethyl-3- Methylimidazolium chloride, tetramethylphosphonium bromide, tetraethylphosphonium bromide, tetranormal propylphosphonium bromide, tetranormal butylphosphonium bromide, tetranormal pentyl phosphonium bromide, tetranormal hexyl phosphonium bromide, tetranormal heptylphosphonium bromide, tetranormaloctylphosphonium bromide Tetramethylphosphonium chloride, tetraethylphosphonium chloride, tetra-normal propyl phosphonium chloride, tetra-normal butyl phosphonium chloride, tetra-normal pentyl phosphonium chloride, tetra-normal hexyl phosphonium chloride, tetra-normal heptyl phosphonium chloride, tetra-normal octyl phosphonium chloride, bromotris (dimethylamino) Examples include phosphonium hexafluorophosphate and the like.

Among these, since it becomes a halogen-containing polyether polyol production catalyst having excellent catalytic activity, tetra-normal octyl ammonium chloride, tetra-normal octyl ammonium bromide, tetra-normal butyl ammonium chloride, tetra-normal butyl ammonium bromide, tetra-normal ethyl ammonium chloride , Tetranormal ethylammonium bromide and tetranormal butylphosphonium bromide are preferably used.

The polymerization temperature at the time of producing the halogen-containing polyether polyol is not particularly limited, but the range of 70 to 150° C. is because the polyalkylene oxide is decomposed and the molecular weight distribution is difficult to spread and the catalytic activity is easily expressed. Is more preferable, and the range of 90 to 110° C. is more preferable.

In the method for producing a halogen-containing polyether polyol, the polymerization reaction is preferably carried out without a solvent, but it can also be carried out in a solvent. Examples of the solvent used include benzene, toluene, xylene, cyclohexane, 1,2-dichloroethane, chlorobenzene, dichlorobenzene, 1,4-dioxane, 1,2-dimethoxyethane and the like.
<< Isocyanate compound >>
The isocyanate compound is not particularly limited, and examples thereof include aromatic isocyanate compounds, aliphatic isocyanate compounds, alicyclic isocyanate compounds (monocyclic alicyclic isocyanate compounds, cross-linked alicyclic isocyanate compounds), and polys thereof. An isocyanate derivative etc. are mentioned.

As the aromatic isocyanate compound, for example, tolylene diisocyanate (2,4- or 2,6-tolylene diisocyanate or a mixture thereof) (TDI), phenylene diisocyanate (m- or p-phenylene diisocyanate, or These mixtures), 4,4'-diphenyl diisocyanate, diphenylmethane diisocyanate (4,4'-, 2,4'- or 2,2'-diphenylmethane diisocyanate, or a mixture thereof) (MDI), 4,4'- Toluidine diisocyanate (TODI), 4,4'-diphenyl ether diisocyanate, xylylene diisocyanate (1,3- or 1,4-xylylene diisocyanate, or a mixture thereof) (XDI), tetramethyl xylylene diisocyanate (1,3- Alternatively, 1,4-tetramethylxylylene diisocyanate, or a mixture thereof (TMXDI), ω,ω′-diisocyanate-1,4-diethylbenzene, naphthalene diisocyanate (1,5-, 1,4- or 1,8- Naphthalene diisocyanate, or a mixture thereof (NDI), triphenylmethane triisocyanate, tris(isocyanatophenyl)thiophosphate, polymethylene polyphenylene polyisocyanate, nitrodiphenyl-4,4'-diisocyanate, 3,3'-dimethyldiphenylmethane- 4,4'-diisocyanate, 4,4'-diphenylpropane diisocyanate, 3,3'-dimethoxydiphenyl-4,4'-diisocyanate and the like can be mentioned.

Examples of the aliphatic isocyanate compound include trimethylene diisocyanate, 1,2-propylene diisocyanate, butylene diisocyanate (tetramethylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene. Diisocyanate), hexamethylene diisocyanate, pentamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, 2,6-diisocyanate methylcaptoate, lysine diisocyanate, lysine ester triisocyanate, 1,6,11-undecane triisocyanate, 1,3,6-hexamethylene triisocyanate, trimethylhexamethylene diisocyanate, decamethylene diisocyanate and the like can be mentioned.

Examples of the monocyclic alicyclic isocyanate compound include 1,3-cyclopentane diisocyanate, 1,3-cyclopentene diisocyanate, cyclohexane diisocyanate (1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate), 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate, IPDI), methylene bis (cyclohexyl isocyanate (4,4'-, 2,4'- or 2,2'-methylene bis(cyclohexyl isocyanate, or these Mixture (hydrogenated MDI), methylcyclohexane diisocyanate (methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, bis(isocyanatomethyl)cyclohexane (1,3- or 1,4-bis) (Isocyanate methyl)cyclohexane, or a mixture thereof (hydrogenated XDI), dimer acid diisocyanate, transcyclohexane 1,4-diisocyanate, hydrogenated tolylene diisocyanate (hydrogenated TDI), hydrogenated tetramethylxylylene diisocyanate (hydrogenated TMXDI) and the like.

Examples of the crosslinked cyclic alicyclic isocyanate compound include norbornene diisocyanate, norbornane diisocyanate methyl, bicycloheptane triisocyanate, cyisocyanatomethyl bicycloheptane, di(diisocyanatomethyl)tricyclodecane, and the like.

Examples of the derivatives of these polyisocyanates include, for example, multimers of the above isocyanate compounds (dimers, trimers, pentamers, heptamines, uretidinediones, ureytonimines, isocyanurate modified products, polycarbodiimides, etc.) , Urethane modified products (for example, urethane modified products obtained by modifying or reacting a part of the isocyanate groups in the above isocyanate compound or multimer with monool or polyol), biuret modified products (for example, reaction between the above isocyanate compound and water) Modified biuret, etc.), allophanate modified (eg, allophanate modified produced by the reaction of the isocyanate compound with a monool or a polyol component), urea modified (eg, the reaction of the isocyanate compound with a diamine) Modified urea, etc.), oxadiazinetrione (for example, oxadiazinetrione generated by the reaction of the isocyanate compound with carbon dioxide gas, etc.) and the like.

The above isocyanate compounds or their derivatives may be used alone or in combination of two or more.

The addition amount of the isocyanate compound is not particularly limited as long as the terminal is NCO, but since the free isocyanate that deteriorates the working environment such as free TDI and HDI is hard to be generated, the total amount of NCO groups contained in the isocyanate compound and the halogen-containing polyisocyanate are included. The ratio of the total amount of OH groups contained in the ether polyol (described as NCO/OH ratio) is preferably 1.2 or more and 3.0 or less, and more preferably 1.5 or more and 2.5 or less.
<<Liquid urethane prepolymer composition>>
The urethane prepolymer composition according to one embodiment of the present invention contains one or more of a filler and another polyol, a urethane-forming catalyst, a foam stabilizer, an antioxidant, and a plasticizer. The mixing order when using these is not particularly limited and can be appropriately selected.

Examples of the filler include inorganic fillers and organic fillers.

As the inorganic filler, silica, alumina, zinc oxide, titanium oxide, calcium oxide, magnesium oxide, iron oxide, tin oxide, antimony oxide, ferrites, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, basic magnesium carbonate , Calcium carbonate, zinc carbonate, barium carbonate, dawsonite, hydrotalcite, calcium sulfate, barium sulfate, calcium silicate, talc, clay, mica, montmorillonite, bentonite, sepiolite, imogolite, sericite, glass fiber, glass beads, silica Examples include balun, aluminum nitride, boron nitride, silicon nitride, carbon black, graphite, carbon fiber, carbon balun, zinc borate, and various magnetic powders.

As the organic filler, polystyrene, polyacrylonitrile, polymethylmethacrylate, polypropylene, polyethylene, polyvinyl chloride, synthetic organic fine particles such as polyurethane, wood powder, bamboo powder, sawdust, paper pulp, wood obtained from paper pulp Examples include natural organic fine particles such as purified cellulose powder.

The antioxidant is not particularly limited, and examples thereof include compounds having an effect of suppressing the oxidation of the polymer chain such as thioether compounds, phosphorus antioxidants and hindered phenol compounds.

Other polyols are not particularly limited as long as they do not deviate from the purpose, for example, polyether polyols obtained by ring-opening polymerization of alkylene oxide, polymer polyols obtained by radical polymerization of vinyl monomer in polyether polyol. , Polyester polyols obtained by polycondensation of polyhydric alcohols and polycarboxylic acids, polyesteramide polyols obtained by polycondensation of polyhydric alcohols with polycarboxylic acids and amino alcohols, ring opening of lactones Polylactone polyols obtained by polymerization, polycarbonate polyols obtained by polycondensation of polyhydric alcohols and carbonates, acrylic polyols, polybutadiene polyol and hydrogenated products thereof, polyisoprene polyol and hydrogenated products thereof, Examples thereof include partially saponified ethylene-vinyl acetate copolymers and natural oil-based polyols such as soybean oil and castor oil.

As the urethanization catalyst, a known urethanization catalyst can be used. For example, a tertiary amine compound, an organometallic compound, etc. may be mentioned.

The tertiary amine compound is not particularly limited, and examples thereof include triethylamine, triethylenediamine, N,N-dimethylbenzylamine, N-methylmorpholine, diazabicycloundecene (alias: DBU), and the like. These can be used alone or in combination of two or more.

The organometallic compound is not particularly limited, but includes tin compounds and non-tin compounds.

The tin-based compound is not particularly limited, and examples thereof include dibutyltin dichloride, dibutyltin oxide, dibutyltin dibromide, dibutyltin dimaleate, dibutyltin dilaurate (also known as DBTDL), dibutyltin diacetate, dibutyltin sulfide, tributyltin. Sulfide, tributyltin oxide, tributyltin acetate, triethyltin ethoxide, tributyltin ethoxide, dioctyltin oxide, tributyltin chloride, tributyltin trichloroacetate, dioctyltin dilaurylate (also known as DOTDL), tin 2-ethylhexanoate and the like can be mentioned. ..

The non-tin compound is not particularly limited, but examples thereof include titanium compounds such as dibutyl titanium dichloride, tetrabutyl titanate, butoxy titanium trichloride, lead oleate, lead 2-ethylhexanoate, lead benzoate, lead naphthenate, etc. Lead-based, iron 2-ethylhexanoate, iron acetylacetonate and other iron-based, cobalt benzoate, cobalt 2-ethylhexanoate and other cobalt-based, zinc naphthenate, zinc 2-ethylhexanoate and other zinc-based, Examples thereof include zirconium naphthenate.

Among the above urethanization catalysts, dibutyltin dilaurate (alias: DBTDL), dioctyltin dilaurate (alias: DOTDL), tin 2-ethylhexanoate and the like are preferable in terms of reactivity and hygiene.

The above-mentioned catalysts such as tertiary amine compounds and organometallic compounds can be used alone or in combination of two or more kinds.

The plasticizer is not particularly limited, and examples thereof include phthalic acid esters, non-aromatic dibasic acid esters, aliphatic esters, polyalkylene glycol esters, phosphoric acid esters, trimellitic acid esters, chlorine. Examples thereof include modified paraffins, hydrocarbon oils, process oils, polyethers, epoxy plasticizers, polyester plasticizers, and the like, and phthalic acid esters are preferable. Specifically, dibutyl phthalate, diheptyl phthalate, di(2-ethylhexyl) phthalate, dioctyl phthalate, dioctyl adipate, dioctyl sebacate, dibutyl sebacate, isodecyl succinate, tricresyl phosphate, tributyl phosphate, epoxidized soybean oil. , Benzyl epoxy stearate and the like.

The foam stabilizer is not particularly limited, but examples thereof include silicone compounds.
<Polyurethane>
The polyurethane according to one embodiment of the present invention is obtained by curing the above-mentioned liquid urethane prepolymer or urethane prepolymer composition by the reaction with water in air or a curing agent (active hydrogen-containing compound).

When the urethane prepolymer composition is cured, it may be cured with one liquid due to moisture in the air (one liquid type), or may be cured with two liquids by using a curing agent (active hydrogen-containing compound). Good (2 liquid type).

The one-pack type is a one-pack moisture curing type that is cured by a reaction with moisture in the air, and one-pack latent curing agent type (1.5-pack type that is cured by an active hydrogen-containing compound obtained from a latent curing agent. And the like. Examples include a two-component curing type in which a main component containing the liquid urethane prepolymer of the present invention is mixed with a curing agent and other auxiliary materials to cure in two or more liquids. Any one can be suitably used by selecting it according to the required characteristics.

The active hydrogen-containing compound is not particularly limited as long as it contains at least one compound having at least one active hydrogen group. For example, water, polypropylene glycol, polyethylene propylene glycol, ethylene glycol (EG), diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,4-butanediol (1,4-BD), 1, Diols such as 6-hexanediol, neopentyl glycol, 1,4-cyclohexanedimethanol, and 1,4-dihydroxycyclohexane, polypropylene triol, polyethylene propylene triol, glycerin, trimethylolpropane (TMP), triethanolamine, etc. Modified with triols, polypropylene tetraol, polyethylene propylene tetraol, castor oil, sucrose, tetrafunctional or higher functional polyols such as sorbitol, 3,3'-dichloro-4,4'-diaminodiphenylmethane (MOCA), aniline, etc. Modified polyamines such as modified MOCA, aromatic amines such as toluenediamine, diphenylmethanediamine and diethyltoluenediamine, aliphatic amines such as ethylenediamine, polyamines such as Jeffamine ED, amino alcohols such as ethanolamine and diethanolamine, and the like. Examples include a mixture of two or more species. Examples of the curing agent combination system include a MOCA-polyol combination curing agent obtained by mixing a polyalkylene oxide with an aromatic amine.

The reaction temperature and reaction time for producing the polyurethane may be appropriately set according to the purpose, and among them, the reaction temperature is preferably 20 to 220° C. and the reaction time is preferably 0.1 minute to 24 hours.

The coating method when using polyurethane is not particularly limited, for example, coating with a spatula, comb, roller, trowel, rake, etc., extrusion or spray with a sealing gun, hand coating or mechanical coating. Thus, a coating film, a film sheet, a thick material or the like having an arbitrary thickness can be formed. It is also possible to form a coating film or a cured product by compounding a compound having an anti-sagging property and applying the surface, wall surface, surface, depression or the like with a roller, a resin gun, an airless gun or the like.

The specific application of the polyurethane according to one aspect of the present invention is not particularly limited, but for example, a waterproof film for roofs such as balconies and buildings, a waterproof sheet, a waterproof film for vehicles, a condominium and Examples include detached houses, flooring materials for hospitals, elastic pavement materials for sports facilities, civil engineering, sealing materials for construction, vehicle sealing materials such as direct glazing and body sealers, medical potting agents, and siding joint caulks.
<Sealant composition>
The sealant composition of the present invention is preferably a one-pack type because it forms a uniform composition and cures, and is easily excellent in foaming resistance.
<Sealing material>
A sealing material according to one aspect of the present invention includes the above polyurethane.

Examples of the method for applying the sealing material include a method in which the material is usually filled in a sealing gun and, if necessary, washed or directly coated with a primer coated/dried and then allowed to stand to cure. For automobile applications, there may be mentioned a method of directly extruding a base material such as a steel plate on which a primer is applied/dried as required, a method of laminating glass or the like and curing the base material or moisture in the air. For construction purposes, the adhesive surface is usually cleaned and a backup material or bond breaker is installed. A masking tape is applied around the joints, and then a pretreatment is performed by applying a primer to the application site. After that, the steps of filling the target points such as joints with a sealing gun and performing a spatula finishing, cleaning, and curing are performed.

At that time, if the curable resin composition is viscous, it takes time to extrude in a filling operation into joints and the like and workability tends to deteriorate, so that the cartridge extruding time is preferably completed within 5 seconds. More preferably, it is within 4 seconds. If the sealing material is too viscous, it may take time to clean the adhered substances to the surroundings and the curable resin composition may adhere to the spatula at the time of spatula finishing, which may make the construction and molding difficult. It is preferable that the composition has such a viscosity that it can be applied with a spatula or a trowel, which is a construction method, and has a handling property.

In the two-pack type, a method in which a mixture of a main agent liquid containing a curable resin composition and a curing agent liquid is washed or a primer is applied/dried directly on a dried substrate as required, and the mixture is allowed to stand and cured. Examples include a method of directly applying while washing or applying a primer to a substrate to which the primer has been applied and dried by mechanical coating while mixing and then allowing to stand and cure.

The use of the sealing material according to one aspect of the present invention is not particularly limited, but examples thereof include sealing materials for civil engineering and construction, and sealing materials for vehicles such as direct glazing and body sealers.

Hereinafter, the present invention will be described with reference to examples, but the examples do not limit the present invention. The raw materials used in the following examples and comparative examples and the evaluation methods are as follows.
<Polyol>
In Examples and Comparative Examples, a polyol having a structure represented by formula (5) was used. The properties of the polyol are shown in Table 1.

The following materials were used as the raw materials shown in Tables 1 to 3, respectively.
<<Halogen-containing polyether polyol (A), (C)>>
Tetra-normal butyl ammonium bromide (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.) and triisopropoxyaluminum are used in combination for sufficient dehydration and desolvation, and polypropylene glycol having a molecular weight of 400 (manufactured by Sanyo Kasei Kogyo, trade name: Sun Nix PP-400), by adding 17.3 mol equivalents of epichlorohydrin (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), a bifunctional halogen-containing polyether polyol (A) having a molecular weight of 2,000. Was produced.

Furthermore, in the production of the halogen-containing polyether polyol (A), the molecular weight was 1, except that 6.5 mol equivalents of epichlorohydrin were added instead of 17.3 mol equivalents of epichlorohydrin. At 000, a bifunctional halogen-containing polyether polyol (C) was prepared.
<<Halogen-containing polyether polyol (B), (D)>>
Tetra-normal butyl ammonium bromide (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) and triisopropoxyaluminum are used together for dehydration and desolvation, and 1,6-hexanediol (manufactured by Fuji Film Wako Pure Chemical Industries). On the other hand, by adding 20.3 mol equivalent of epichlorohydrin (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), a bifunctional halogen-containing polyether polyol (B) having a molecular weight of 2000 was prepared.

Further, in the production of the halogen-containing polyether polyol (B), instead of adding 20.3 mol equivalent of epichlorohydrin, 9.5 mol equivalent is added, whereby a bifunctional halogen-containing polyether having a molecular weight of 1000 is added. A polyol (D) was produced.
<<Halogen-containing polyether polyol (E)>>
Tetra-normal butyl ammonium bromide (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.) and triisopropoxyaluminum are used in combination for sufficient dehydration and desolvation, and polypropylene glycol having a molecular weight of 600 (manufactured by Sanyo Chemical Industry Co., Ltd., trade name: Sun (Knicks PP-600), 4.3 mol equivalents of epichlorohydrin (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) are added to give a bifunctional halogen-containing polyether polyol (E having a molecular weight of 1,000). ) Was produced.
<<Halogen-containing polyether polyol (F)>>
By using BF ₃ -Et ₂ O as a Lewis acid catalyst and adding epichlorohydrin to polypropylene glycol having a molecular weight of 400 (manufactured by Sanyo Chemical Industry Co., Ltd., trade name: Sannix PP-400), the molecular weight is 2. At 000, a bifunctional polyether polyol (F) was produced.
<Isocyanate compound>
In all Examples and Comparative Examples, 4,4′-MDI (manufactured by Aldrich) was used as it was without purification.
(Analysis of polyol properties)
<Unsaturation>
It measured according to the method of JIS-K1557-6.
<Molecular weight distribution (Mw/Mn)>
A sample was obtained by adding 10 mg of polyol and 10 ml of THF to a sample bottle, allowing it to stand overnight and dissolving it, and filtering with a PTFE cartridge filter (0.5 μm).

RI detector RI8020 was used as a detector, TSKgelGMR-HHRL x 2 series, HLC-8020GPC were used as a measuring column (all manufactured by Tosoh Corporation).

As the measurement conditions, the column temperature is 40° C., the flow rate is 1.0 ml/min, and the solvent is THF, and the molecular weight distribution (Mw/Mn) of the third-order approximation curve using standard polystyrene manufactured by Tosoh Corporation is used as a calibration curve. Analysis was performed.

Production example (production of NCO-terminated prepolymer solution)
100 g of the halogen-containing polyether polyol A was placed in a 4-neck separable flask equipped with a stirring blade, and dehydration under reduced pressure was carried out at 80° C. for 2 hours. After cooling to room temperature, 25 g of 4,4′-MDI was added under nitrogen and the reaction was carried out at 100° C. Prepolymer 1 was synthesized by back titration of the reactor contents with dibutylamine, stirring until the consumption of NCO groups ceased.

Prepolymers 2 to 8 were produced in the same manner as in the production example of Prepolymer 1 except that the prescribed raw materials shown in Table 2 were used in prescribed amounts.

(Polyurethane evaluation method)
<Preparation of polyurethane sheet>
The prepolymer obtained in the synthesis example of NCO-terminated prepolymer was coated on a PET film (Purex A31 manufactured by Teijin Film Solutions Co., Ltd.) which had been subjected to a mold release treatment, using an applicator (manufactured by YOSHIMITSU SEIKI) so as to have a desktop coater of 150 μm. (TC-1 manufactured by Mitsui Electric Seiki Co., Ltd.) was applied at a speed of 1.0 m/min, and left standing in a thermostatic chamber at 23 to 25° C. and 50% RH for 7 days to prepare a polyurethane sheet.
<Breaking strength>
A JIS No. 3 dumbbell was punched out, and a tensile tester (Tensilon TG-1210 manufactured by A&D Company) was used to perform a tensile test at a tensile speed of 200 mm/min to measure the breaking strength. The measurement was performed in an atmosphere of 23 to 25° C. and 50% RH. The number of tests was set to 5 and the average value not including the maximum value and the minimum value was calculated as the breaking strength.
A: 10 MPa or more B: 5 MPa or more and less than 10 MPa
C: less than 5 MPa <tackiness>
A thumb was pressed against the produced polyurethane and the resistance when peeled off was evaluated.
A: Almost no resistance is felt B: There is resistance C: Sticky <Transparency>
The haze of the produced polyurethane sheet was measured with a haze meter (NDH-5000 manufactured by Nippon Denshoku Industries Co., Ltd.).
A: less than 5% B: 5% or more and less than 10% C: 10% or more Examples 1 to 5.
According to the polyurethane evaluation method, a polyurethane sheet was prepared using Prepolymers 1 to 5 and evaluated. All of them were polyurethane sheets having high breaking strength, low tack, and high transparency.
Comparative Example 1.
According to the polyurethane evaluation method, a polyurethane sheet was prepared using Prepolymer 7 and evaluated. The transparency was good, but the curing was poor and stickiness occurred, and the breaking strength was poor.
Comparative example 2.
According to the polyurethane evaluation method, a polyurethane sheet was prepared using Prepolymer 8 and evaluated. The breaking strength of the dumbbell pieces was high, but when the thumb was pressed against the surface of the sheet, a resistance was felt and the transparency was low.
Comparative Example 3.
According to the polyurethane evaluation method, a polyurethane sheet was prepared using Prepolymer 8 and evaluated. The breaking strength of the dumbbell pieces was inferior, and a resistance was felt when the thumb was pressed against the surface of the sheet, and the transparency was low.

The above Examples 1 to 6 are shown in Table 3 and the results of Comparative Examples 1 to 3 are shown in Table 4.

(Evaluation as a sealing material)
<Production of sealing material>
To 100 parts by weight of the prepolymer obtained in the synthesis example of NCO-terminated prepolymer, 80 parts by weight of heavy calcium carbonate (Whiten SB manufactured by Maruo Calcium Co., Ltd.) as a filler, and Iganox 1010 (manufactured by BASF) as an antioxidant. 0.1 part by weight and 0.1 part by weight of bismuth octylate (Pucat 25 manufactured by Nippon Kagaku Sangyo Co., Ltd.) as a catalyst were added and kneaded with a kneader to obtain a paste-like sealing material composition.

The obtained sealing material composition was applied to a 25 mm width SUS304 test piece (manufactured by Paltec Co., Ltd., one side #320 HL) in a width of 5 mm and a thickness of 2 mm, adhered and allowed to stand for 24 hours to proceed with curing, and then tested. A piece was prepared and evaluated as a sealing material.
<Curability>
After the test piece obtained above was allowed to stand for 24 hours, the feel of the sealing material portion when touched with a finger was evaluated.
A: Not sticky B: Sticky C: Sealant adheres to finger (not cured)
<Adhesiveness>
The test piece obtained above was subjected to a hand peel test and evaluated by visually observing the fracture surface.
A: Cohesive failure B: Interface peeling <Shear peel strength>
Using a tensile tester (Tensilon TG-1210 manufactured by A&D Co., Ltd.), a shear peeling test was performed at a pulling speed of 50 mm/min to measure the shear peeling strength.
A: 5 MPa or more B: 2 MPa or more, less than 5 MPa C: Less than 2 MPa Application Example 1.
According to the method for evaluating a sealing material, a sealing material was prepared using Prepolymer 3 and evaluated. It was easy to apply and showed good curability, adhesiveness and shear peel strength.
Application Comparative Example 1.
According to the method for evaluating a sealing material, a sealing material was prepared using Prepolymer 6 and evaluated. During coating, sagging occurred, workability was poor, it did not cure sufficiently, and adhesiveness and shear peel strength were poor.

Table 5 shows the results of the above application example.

Claims (6)

NCO-terminated liquid urethane prepolymer,
The urethane prepolymer is
A structural unit having a number average molecular weight of 200 or more and 3,000 or less, represented by the formula (1), and
The degree of unsaturation is 0.020 meq/g or less,
Liquid urethane prepolymer terminated with NCO groups:
In formula (1),
Q represents a polymer component containing a structural unit represented by the formula [I],
m represents an integer of 2 to 8,
R ¹ represents an active hydrogen-containing compound residue;
In formula [I], X represents a halogen atom. The liquid urethane prepolymer according to claim 1, wherein the degree of unsaturation is 0.016 meq/g or less. The urethane prepolymer according to any one of claims 1 and 2, and one or more of a filler and another polyol, a urethane-forming catalyst, a foam stabilizer, an antioxidant, and a plasticizer. , A liquid urethane prepolymer composition. The liquid urethane prepolymer according to any one of claims 1 to 2 or the liquid urethane prepolymer composition according to claim 3 is reacted with water in air or a curing agent (active hydrogen-containing compound). Cured polyurethane. A composition for a sealant, comprising the urethane prepolymer according to claim 1 or the urethane prepolymer composition according to claim 3. A sealant obtained by curing the composition for sealant according to claim 5 by reaction with water in air or a curing agent (compound containing active hydrogen).