JP2002128853A - Water dispersing polyurethane composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a water dispersing polyurethane composition having a high dispersion stability in which a hydrolyzable silyl group and/or its hydrolyzed silyl group is introduced into a polyurethane molecule. SOLUTION: The water dispersing polyurethane composition comprises a polyol, a polyisocyanate, a polyamine compound having two primary amino groups at its terminals, and a polyurethane compound having a silyl group at its terminal which is derived from an epoxy-silane derivative having one epoxy group in a molecule and a hydrolyzable silyl group and/or its hydrolyzed silyl group at its terminal represented by general formula (I) (wherein R refers to a 1-8C alkyl group; X refers to a hydrogen atom or a 1-4C alkyl group; and n refers to 1, 2 or 3).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a water-dispersible polyurethane composition having a specific structure, and more particularly to a water-dispersible polyurethane having a terminal hydrolyzable silyl group and / or a hydrolyzable silyl group. It relates to a polyurethane composition.

[0002]

2. Description of the Related Art Polyurethane compositions have been widely applied to paints, adhesives, surface modifiers and the like.
A water-dispersed composition that does not use an organic solvent in the composition is desired. However, the aqueous dispersion type has a problem that water resistance, substrate adhesion, strength, and the like are insufficient as compared with the solvent type or the non-solvent type.

[0003] In order to solve the above problems, methods for introducing a hydrolyzable silyl group and / or a hydrolyzable silyl group into the polyurethane molecule have been studied. For example, a method using a silane derivative having an isocyanate group is reported in JP-A-5-7407, and a method using a silane derivative having an amino group is described in JP-A-51-90391.
JP-A-8-504230, JP-A-9-128
No. 64, and JP-A-11-60939.

However, the above-mentioned method using a silane derivative having an isocyanate group or an amino group is liable to react with other functional groups such as water, anionic group and cationic group, and its application is limited. If stored for a long period of time, there is a problem that gelation or precipitation occurs.

Further, a method using a silane derivative having an epoxy group is described in JP-A-11-60939, JP-A-7-138469, and JP-A-7-138524. However, these are not satisfactory in physical properties such as dispersion stability and water resistance of a coating film obtained from the water-dispersible polyurethane composition, and satisfactory ones have not been obtained.

Accordingly, an object of the present invention is to provide a water-dispersible polyurethane composition having high dispersion stability in which a hydrolyzable silyl group and / or a hydrolyzed silyl group is introduced into a polyurethane molecule. is there.

[0007]

As a result of repeated studies, the present inventors have found that the use of a polyamine compound having two terminal primary amino groups at the end and an epoxysilane derivative having a specific structure has led to the problems described above. And found that the present invention can be solved, and arrived at the present invention.

The present invention relates to a polyol, a polyisocyanate, a polyamine compound having two terminal primary amino groups, an epoxy group in a molecule and a compound represented by the following general formula (I):
And / or a water-dispersible polyurethane composition containing a silyl group-terminated polyurethane compound obtained from a hydrolyzed silyl group-terminated epoxysilane derivative represented by the following formula: .

Embedded image (Wherein, R represents an alkyl group having 1 to 8 carbon atoms;
Represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and n
Represents 1, 2 or 3)

[0009]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, embodiments of the present invention will be described in detail.

The polyol used in the water-dispersible polyurethane composition of the present invention is not particularly limited, and one or more known polyols can be used in combination. Examples of the polyol include a low molecular polyol, a polyether polyol, a polybutadiene polyol, a silicone polyol, and a polyol having an ester bond. When anionic or cationic ionic groups are introduced into the polyurethane compound, the ionic group-introduced polyol can be used alone or in combination with the above polyols.

The low molecular polyol includes, for example,
Ethylene glycol, 1,2-propanediol, 1,
3-propanediol, 2-methyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,4-butanediol, neopentyl glycol, 3-methyl-2,4- Pentanediol, 2,
4-pentanediol, 1,5-pentanediol, 3
-Methyl-1,5-pentanediol, 2-methyl-
2,4-pentanediol, 2,4-diethyl-1,5
-Pentanediol, 1,6-hexanediol, 1,
7-heptanediol, 3,5-heptanediol,
Aliphatic diols such as 1,8-octanediol, 2-methyl-1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, diethylene glycol, triethylene glycol, cyclohexanedimethanol, cyclohexanediol Alicyclic diols such as, trimethylolethane, trimethylolpropane,
Hexitols, pentitols, glycerin, pentaerythritol, trihydric or higher alcohols such as tetramethylolpropane.

Examples of the above-mentioned polyether polyols include ethylene oxide and / or propylene oxide adducts of the above-mentioned low molecular weight polyols, and polytetramethylene glycol.

Examples of the silicone polyol include silicone oils having a siloxane bond in the molecule and having a hydroxyl group at the end.

Examples of the polyol having an ester bond include polyester polyol, polyester polycarbonate polyol, and polycarbonate polyol.

The polyester polyol includes a low-molecular-weight polyhydric alcohol exemplified above and a polyhydric carboxylic acid in an amount smaller than the stoichiometric amount of the polyhydric alcohol or an ester-forming ester such as an ester, an anhydride or a halide thereof. Those obtained by a direct esterification reaction and / or a transesterification reaction with a derivative may be mentioned. Examples of the polycarboxylic acid or its ester-forming derivative include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecane diacid, and 2-methylsuccinic acid , 2-methyladipic acid, 3
-Methyladipic acid, 3-methylpentanedioic acid, 2-methyloctanedioic acid, 3,8-dimethyldecandioic acid, 3,
Aliphatic dicarboxylic acids such as 7-dimethyldecandioic acid, hydrogenated dimer acid and dimer acid, phthalic acid, terephthalic acid,
Polycarboxylic acids such as aromatic dicarboxylic acids such as isophthalic acid and naphthalenedicarboxylic acid, alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid, and tricarboxylic acids such as trimellitic acid, trimesic acid, and trimer of castor oil fatty acid. Acid anhydrides of polyvalent carboxylic acids, halides such as chlorides and bromides of the polyvalent carboxylic acids, lower esters such as methyl ester, ethyl ester, propyl ester, isopropyl ester, butyl ester, isobutyl ester, amyl ester of the polyvalent carboxylic acid Esters and lactones such as γ-caprolactone, δ-caprolactone, ε-caprolactone, dimethyl-ε-caprolactone, δ-valerolactone, γ-valerolactone, γ-butyrolactone, and the like.

Of these polyols, low molecular polyols, polyether polyols and polyester polyols are preferred because of their low cost and easy availability.

As the polyol used for introducing the ionic group, those containing an anionic group include, for example, polyols containing a carboxyl group such as dimethylolpropionic acid, dimethylolbutyric acid and dimethylolvaleric acid. And polyols containing a sulfonic acid group, such as 1,4-butanediol-2-sulfonic acid. Examples of those that introduce a cationic group include N, N-dialkylalkanolamines, N-methyl-N, N-diethanolamine, N-butyl-N,
Examples include N-alkyl-N, N-dialkanolamines such as N-diethanolamine and trialkanolamines.

The polyisocyanate used in the water-dispersible polyurethane composition of the present invention is not particularly limited, and one or two or more well-known common ones can be used. The polyisocyanate includes diisocyanate and triisocyanate.

As the diisocyanate, for example,
2,4- and / or 2,6-tolylene diisocyanate, diphenylmethane-4,4'-diisocyanate,
p-phenylene diisocyanate, xylylene diisocyanate, 1,5-naphthylene diisocyanate, 3,
Aromatic diisocyanates such as 3'-dimethyldiphenyl-4,4'-diisocyanate, dianisidine diisocyanate, tetramethylxylylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, trans-1,4
Alicyclic diisocyanates such as cyclohexyl diisocyanate and norbornene diisocyanate, 1,6-
Hexamethylene diisocyanate, 2,2,4 (2,
Aliphatic diisocyanates such as 4,4) -trimethylhexamethylene diisocyanate and lysine diisocyanate are exemplified. Of these, alicyclic diisocyanates are preferred because of their excellent hydrolysis resistance.

Further, as the above triisocyanate,
Examples include triphenylmethane triisocyanate, 1-methylbenzol-2,4,6-triisocyanate, isocyanurate trimer of the above diisocyanate, buret trimer, and trimethylolpropane adduct.

The water-dispersible polyurethane composition of the present invention comprises:
Although it is not always necessary because of its excellent dispersion stability, for example, when it is desired to impart further dispersion stability such as storage stability at a high temperature, the following general formula (A) having the effect of improving the dispersion stability is used. May be used.

[0022]

Embedded image (Wherein D represents a group derived from a triisocyanate, and E represents a group derived from an ethylene oxide adduct of an alkylene glycol monoalkyl ether)

In the diisocyanate compound represented by the general formula (A), the above effect is remarkable as an ethylene oxide adduct of an alkylene glycol monoalkyl ether for introducing a nonionic group.
Ethylene oxide adduct or ethylene oxide / propylene oxide co-adduct of alcohol is preferred because of its low cost. The alcohols constituting this include methanol, ethanol, propyl alcohol, isopropyl alcohol, butyl alcohol, isobutyl alcohol, secondary butyl alcohol, tertiary butyl alcohol,
Amyl alcohol, octyl alcohol, lauryl alcohol, stearyl alcohol and the like can be mentioned. When the molecular weight of these polyalkylene glycol monoalkyl ethers is less than 400, the use effect may not be obtained, and when the molecular weight is more than 4000, the water resistance of a coating film or the like obtained from the water-dispersible polyurethane composition may deteriorate. Therefore, 400 to 4000 is preferable.

When the amount of the polyalkylene glycol used is less than 0.01 in terms of the molar ratio of diisocyanate to 1, the effect of use may not be obtained. On the other hand, when the amount is more than 1, the polyalkylene glycol may not be obtained from the water-dispersible polyurethane composition. Since the water resistance of the resulting coating film or the like may deteriorate, it is preferably 0.01 to 1, more preferably 0.05 to 0.5.

The polyamine compound having two terminal amino groups at the terminal used in the water-dispersible polyurethane composition of the present invention is intended to increase the molecular weight by extending the chain of the polyurethane and to react with the epoxysilane derivative. Used to introduce sites. Examples of the polyamine compound include low-molecular-weight polyamines in which the alcoholic hydroxyl group of the low-molecular-weight polyol exemplified above such as ethylenediamine and propylenediamine is substituted with a primary amino group, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, and polyethylene. Polyether polyamines such as oxypropylenediamine and polyoxypropylenetriamine, mensendiamine, isophoronediamine, norbornenediamine, bis (4-amino-3-methyldicyclohexyl) methane, diaminodicyclohexylmethane, bis (aminomethyl) cyclohexane, Alicyclic polyamines such as 2,9-bis (3-aminopropyl) 2,4,8,10-tetraoxaspiro (5,5) undecane, m-xylenediamine, α- (m / p amino Eniru) ethylamine, m- phenylenediamine, diaminodiphenylmethane, diaminodiphenyl sulfone, diaminodiphenyl diethyl dimethyl methane, diamino diethyl diphenyl methane, dimethylthiotoluenediamine, diethyltoluenediamine, alpha,. Alpha .'- bis (4-
Aromatic polyamines such as aminophenyl) -p-diisopropylbenzene and dithiodianiline; dicarboxylic acid dihydrazides such as adipic dihydrazide and isophthalic dihydrazide; and hydrazine.
One type or a mixture of two or more types can be used.

Among these, when low molecular weight polyamines such as ethylenediamine and propylenediamine are used in combination with dicarboxylic acid dihydrazide, coloring due to heat can be suppressed. Therefore, it is preferable to use low molecular weight polyamines and dicarboxylic acid dihydrazide together.

When the low-molecular-weight polyamines and the dicarboxylic acid dihydrazide are used in combination, any molar ratio can be selected without any particular limitation. If the dihydrazide is less than 0.05, the anti-coloring effect may not be obtained, and if it is more than 10, not only the anti-coloring effect is not improved, but also the dispersion stability of the obtained water-dispersible polyurethane composition is affected. Therefore, 0.05 to 10 is preferable, and 0.1 to 5 is preferable.

The polyurethane compound according to the present invention includes trimethylolethane, trimethylolpropane, hexitols, pentitols, and the like, which are used in the polyurethane as required and impart a branch to the polyurethane.
Tri- or higher-valent polyols such as glycerin, pentaerythritol, and tetramethylolpropane may be used, and tri- or higher-valent polyamines and melamines may be used. The use of these branching compounds gives the resulting polyurethane compound a form such as a dendrimer, a comb polymer, or a star polymer, and has the effect of improving the strength and thermal properties of the coating film, as well as the molecular weight. It is effective to provide a preferable silicon content described later without reducing the content.

The epoxysilane derivative having one epoxy group and the hydrolyzable silyl group of the formula (I) and / or the hydrolyzed silyl group at the terminal in the molecule according to the present invention comprises an epoxy group and one epoxy group. By the reaction of the secondary amino group,
Introducing a hydrolyzable silyl group and / or a hydrolyzable silyl group into the water-dispersible polyurethane,
This method has an advantage that it can be used without considering a reaction with other functional groups such as an anionic group and a cationic group.

In the above general formula (I), examples of the alkyl having 1 to 8 carbon atoms represented by R include methyl, ethyl, propyl, isopropyl, butyl, sec-butyl,
Tertiary butyl, isobutyl, amyl, isoamyl, tertiary amyl, hexyl, cyclohexyl, heptyl, isoheptyl, tertiary heptyl, n-octyl, isooctyl, tertiary octyl, 2-ethylhexyl, and the number of carbon atoms represented by X Examples of the alkyl group of 1 to 4 include methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, and isobutyl.

As the epoxysilane derivative, a silane coupling agent having a corresponding structure can be used without any particular limitation. Examples of the epoxysilane derivative include those represented by the following formula (II).

[0032]

Embedded image (Wherein X and R represent the same groups as in the above general formula (I),
Rep represents an organic group having one epoxy group;
Is a single bond, -O-, -S-, -N-, -NH-, -N
R'- represents, Z represents an alkylene group having 1 to 4 carbon atoms, and m represents A as a single bond, -O-, -S-, -NH-,-
NR'- represents 1; A represents -N- represents 2; R 'represents an organic group having 1 to 18 carbon atoms)

In the above formula (II), Rep is, for example, a glycidyl-derived group such as glycidyl, glycidyloxyalkyl or glycidyloxycarbonyl; or an alicyclic group such as epoxycyclohexyl, epoxycyclopentyl, epoxycycloheptyl or epoxycyclooctyl. Epoxy group and the like; and Z is methylene, ethylene,
Propylene, 1-methylethylene, 2-methylethylene, butylene, 1-methylpropylene, 2-methylpropylene, and R ′ is methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, octyl, lauryl, Stearyl, phenyl, naphthyl, 2-
Methylphenyl, 3-methylphenyl, 4-methylphenyl, 4-vinylphenyl, 3-isopropylphenyl, benzyl, phenethyl, 2-phenylpropane-2
-Yl, diphenylmethyl, triphenylmethyl, styryl, cinnamyl, vinyl, allyl and the like.

Among the above, those represented by the following formulas (1) and (2) are preferable because they give excellent dispersion stability.

[0035]

Embedded image (In the formula, R, Y, X, and n are the same as those in the general formula (I), and Y represents an alkylene group having 1 to 4 carbon atoms.)

The method for producing the water-dispersible polyurethane composition of the present invention is not particularly limited, and well-known general methods can be applied. For example, a polyol is reacted with a polyisocyanate to synthesize a prepolymer having a terminal isocyanate group, and then reacted with a polyamine compound having two primary amino groups at a terminal to form a polyurethane compound having a terminal primary amino group. And reacting it with an epoxysilane derivative (a), a prepolymer of terminal isocyanate groups obtained from a polyol and a polyisocyanate, a polyamine compound having two primary amino groups at terminals and an epoxysilane derivative. A method of reacting a primary amino group-terminated epoxy silane obtained by the reaction (b), a polyol, a polyisocyanate, and a polyamine compound having two terminal primary amino groups at the terminal to react with each other to form a terminal primary amino group; Synthesize polyurethane compound and react it with epoxysilane derivative The method (c) can be given to.

With respect to the above-mentioned production method, the method (a) is preferable because the composition and the reaction can be easily controlled.
The polyol and the polyisocyanate are reacted in a solvent which is inert to the reaction and has a high affinity for water to form a prepolymer, and then the prepolymer is mixed with water and a polyamine compound having two terminal primary amino groups. This method is more preferable because good dispersibility can be obtained.

Examples of the solvent which is inert to the reaction and has a high affinity for water used in the above preferred production method include, for example,
Acetone, methyl ethyl ketone, dioxane, tetrahydrofuran, N-methyl-2-pyrrolidone and the like can be mentioned. These solvents are usually added to the total amount of the above-mentioned raw materials used for producing the prepolymer by 3%.
１００100% by mass is used. Among these solvents, those having a boiling point of 100 ° C. or lower are preferably distilled off under reduced pressure after the synthesis of the prepolymer.

The mixing ratio of the polyol, the polyisocyanate, the polyamine compound having two terminal primary amino groups and the epoxysilane derivative compound in the production of the polyurethane compound according to the present invention depends on the final water-dispersible polyurethane composition. It is set in a range where the terminal of the product becomes the silane group represented by the general formula (I).

In the above mixing ratio, the polyol and the polyisocyanate have a hydroxyl group of 0.33 or more and a mole number of 1 of the isocyanate group of 1.
A range of less than 0 is preferable because it gives good dispersibility. As for the molar ratio of the polyamine compound having two primary amino groups at the terminals, the coloring is small in a range of more than 0.5 and 2.5 or less with respect to 1 mole of the isocyanate group to be reacted. It is preferable because the hydrolysis property is improved. Also, regarding the molar ratio of the epoxysilane derivative,
If the number of moles of the primary amino group to be reacted is less than 0.5, a sufficient effect of introducing a silane group may not be obtained if it is less than 0.5, and if it is more than 2.5, the dispersion stability of the water-dispersible polyurethane may be insufficient. 0.5 to 2.5 is preferable, and 0.8 to 2.0 is more preferable, because it may decrease.

The silicon content of the solid content of the polyurethane compound according to the present invention can be arbitrarily selected by changing the composition of the raw materials.
If it is smaller than the above, the silane group content becomes small, the effect of introducing a sufficient silane group may not be obtained, and the adhesion may not be improved. If it is more than 2.0% by mass, the dispersion stability of the composition may be impaired. Is preferably 0.1 to 2.0% by mass.

When the molecular weight of the polyurethane compound according to the present invention is smaller than 4000, sufficient strength and sufficient strength can be obtained for a coating film obtained from the water-dispersible urethane composition.
Elongation and water resistance may not be obtained.
If it is larger than 00, it becomes difficult to obtain a preferable silicon content.
0 to 50,000 is more preferable.

The state of the water-dispersible polyurethane composition of the present invention includes an emulsion, a suspension, a colloidal dispersion, and an aqueous solution. Methods for obtaining these water-dispersible polyurethane compositions include an ionic method for introducing an ionic group of an anionic group or a cationic group into a polyurethane molecule, a nonionic method for introducing a nonionic group into a polyurethane molecule, and a surfactant. Examples thereof include a method using an emulsifier such as an emulsifier, and two or more of these may be used in combination.

As the above-mentioned ion method, there is a method of introducing an ionic group from the above-mentioned ionic group-introduced polyol into the primary amino group-terminated polyurethane molecule according to the present invention, and neutralizing the ionic group with a neutralizing agent. It is preferable because it is easy and costs are small. The amount of the polyol used to introduce the ionic group can be appropriately selected without particular limitation, but the molar ratio of the polyol (ionic group-introduced polyol / other polyol) is smaller than 0.1. And the dispersion stability is reduced, and if it is larger than 50, the water resistance of a coating film or the like obtained from the water-dispersible polyurethane composition may be deteriorated. Therefore, 0.1 to 50 is preferable, and 1.0 to 20 is more preferable. preferable.

Examples of the anionic group neutralizing agent used in the above ion method include trialkylamines such as trimethylamine and triethylamine, N, N-dialkylalkanolamines, N-alkyl-N, N-dialkanolamines. , Tertiary amines such as trialkanolamines, and basic compounds such as ammonia, sodium hydroxide, potassium hydroxide, and lithium hydroxide. Examples of the neutralizing agent for the cationic group include organic carboxylic acids such as formic acid, acetic acid, lactic acid, succinic acid, glutaric acid, and citric acid; organic sulfonic acids such as paratoluenesulfonic acid and alkyl sulfonate; hydrochloric acid, phosphoric acid, and nitric acid. , Inorganic acids such as sulfonic acid,
In addition to epoxy compounds such as epihalohydrin, quaternizing agents such as dialkyl sulfates and alkyl halides are exemplified.
When the amount of the neutralizing agent used is generally too large or small with respect to 1 mol of the ionic group, physical properties such as water resistance, strength, and elongation of a coating film obtained from the water-dispersible polyurethane composition are reduced. 0.8 to 1.2 is preferable because there is a possibility of it.

The nonionic method is a method in which a nonionic hydrophilic group such as an oxyethylene chain is introduced into a main chain or a side chain of a polyurethane molecule to give water dispersibility. The method for introducing a hydrophilic group includes a method using polyoxyethylene glycol as a polyol and a method using a diisocyanate compound represented by the above general formula (A).

In the nonionic method, if the content (mass ratio) of the nonionic hydrophilic group is less than 0.05 with respect to the terminal polyurethane of the primary amino group, sufficient dispersibility may not be obtained in some cases. If it exceeds 0.75, the water resistance, strength, and properties such as elongation of the coating film obtained from the water-dispersible polyurethane composition may be reduced.
5 is preferable, and 0.1 to 0.5 is more preferable.

Examples of the emulsifier include well-known general anionic surfactants, nonionic surfactants, cationic surfactants, amphoteric surfactants, and polymer surfactants used in water-dispersible polyurethanes. , A reactive surfactant and the like can be used. Among them, anionic surfactants, nonionic surfactants, or cationic surfactants are preferred because they are low in cost and can provide good emulsification.

Examples of the anionic surfactant include alkyl sulfates such as ammonium dodecyl sulfate such as sodium dodecyl sulfate and potassium dodecyl sulfate; sodium dodecyl polyglycol ether sulfate; sodium sulfolicine; alkali metal salt of sulfonated paraffin Alkyl sulfonates such as ammonium salts of sulfonated paraffins; fatty acid salts such as sodium laurate, triethanolamine oleate and toluethanolamine aviate; alkyl aryl sulfonates such as sodium benzene sulfonate and alkali metal sulfate of alkali phenol hydroxyethylene; Alkyl naphthalene sulfonate; Naphthalene sulfonic acid formalin condensate; Dialkyl Ruhokohaku salt; polyoxyethylene alkyl sulfate salts, polyoxyethylene alkylaryl sulfate salts.

Examples of the nonionic surfactant include ethylene oxide and / or propylene oxide adducts of alcohols having 1 to 18 carbon atoms, ethylene oxide and / or propylene oxide adducts of alkyl phenol, alkylene glycol and / or alkylenediamine. Examples include ethylene oxide and / or propylene oxide adducts.

The alcohol having 1 to 18 carbon atoms constituting the nonionic surfactant includes methanol, ethanol, propanol, 2-propanol, butanol, and the like.
2-butanol, tert-butanol, amyl alcohol,
Examples include isoamyl alcohol, tertiary amyl alcohol, hexanol, octanol, decane alcohol, lauryl alcohol, myristyl alcohol, palmityl alcohol, stearyl alcohol and the like. Alkyl phenols include phenol, methyl phenol,
2,4-di-tert-butylphenol, 2,5-di-tert-butylphenol, 3,5-di-tert-butylphenol, 4-
(1,3-tetramethylbutyl) phenol, 4-isooctylphenol, 4-nonylphenol, 4-tert-octylphenol, 4-dodecylphenol, 2-
(3,5-dimethylheptyl) phenol, 4- (3
5-dimethylheptyl) phenol, naphthol, bisphenol A, bisphenol F and the like. As the alkylene glycol, ethylene glycol, 1,
2-propanediol, 1,3-propanediol, 2
-Methyl-1,3-propanediol, 2-butyl-2
-Ethyl-1,3-propanediol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 3-methyl-1,5-pentanediol,
2,4-diethyl-1,5-pentanediol, 1,6
-Hexanediol and the like. Examples of the alkylene diamine include those in which the alcoholic hydroxyl group of these alkylene glycols is substituted with an amino group.
The ethylene oxide and propylene oxide adducts may be random adducts or block adducts.

Examples of the cationic surfactant include primary to tertiary amine salts; pyridinium salts, and quaternary ammonium salts.

The amount of the emulsifier used is not particularly limited and may be an arbitrary amount. However, if the mass ratio to the polyurethane compound is smaller than 0.01, sufficient dispersibility may not be obtained. If it exceeds 0.3, the properties such as water resistance, strength and elongation of the coating film obtained from the water-dispersible polyurethane composition may be reduced.
Is preferable, and 0.05 to 0.2 is more preferable.

The solid content in the water-dispersible polyurethane composition of the present invention is not particularly limited and may be any value, but is usually 1 to 90% by mass, more preferably 5 to 80% by mass. It is adjusted so that

The water-dispersed polyurethane composition of the present invention may contain various commonly used additives, if necessary. Examples of the additives include pigments, dyes, film-forming auxiliaries, curing agents, coupling agents, antiblocking agents, viscosity modifiers, leveling agents, defoamers, antigelling agents, dispersion stabilizers, and light stabilizers. Agents, antioxidants, ultraviolet absorbers, radical scavengers, heat-resistance additives, inorganic and organic fillers, plasticizers, lubricants, antistatic agents, reinforcing agents, catalysts, thixotropic agents, antibacterial agents, fungicides, Preservatives, hydrolyzable silyl group stabilizers and the like can be mentioned. When particularly strong adhesion to the substrate is required, colloidal silica, tetraalkoxysilane, and a condensation polymer thereof may be used.

The water-dispersed polyurethane composition of the present invention can be used for coatings, adhesives, surface modifiers, organic and / or inorganic powder binders, and forming materials. Specifically, a glass fiber sizing agent, a thermal paper coating agent, an inkjet paper coating agent, a binder for a printing ink, a coating agent for a steel plate, a coating material for inorganic structural materials such as glass, slate, concrete, a fiber treatment agent, and the like. No.

[0057]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples (Production Examples and Evaluation Examples). However, the present invention is not limited at all by the following Examples (Production Examples and Evaluation Examples). In addition, about the abbreviation in an Example,
It is as follows. All ratios in the following abbreviations are molar ratios.

(Polyol) 1,6HD / AA / IPA; 1,6-hexanediol and adipic acid: isophthalic acid = 1: 1 polyester polyol 1,6HD / NPG / AA; 1,6-hexanediol: neopentyl Polyester polyol of glycol = 1: 1 and adipic acid PEG / PPG; diol obtained by block-polymerizing 3 mol of polyethylene oxide and 7 mol of polypropylene oxide PPG; polypropylene glycol BIA; propylene oxide adduct of bisphenol A

(Branched Group-Introducing Compound) TMP; Trimethylolpropane MM; Melamine

(Polyisocyanate) HMDI; dicyclohexylmethane diisocyanate IPDI; isophorone diisocyanate HMDI / noHDI; dicyclohexylmethane diisocyanate: nonisocyanate diisocyanate obtained from isocyanurate trimer of 1,6-hexamethylene diisocyanate and PEG having a molecular weight of 400 = 4: 1

(Polyamine Compound Having Two Primary Amino Groups at Terminals) EDA; Ethylenediamine ADH; Adipic dihydrazide IPDH; Isophthalic dihydrazide EDA / ADH; Ethylenediamine: Adipic dihydrazide mixture EDA / IPDH; Ethylenediamine: Isophthalic dihydrazide mixture

(Epoxysilane derivative); γ-glycidoxypropylmethyldiethoxysilane; 2- (3,4-epoxycyclohexylethyl) trimethoxysilane

(Aminosilane compound); 3-aminopropylmethyldiethoxysilane

[Production Example 1] <Production of water-dispersible polyurethane composition of Examples 1 to 13> An anionic water-dispersible polyurethane composition was produced by the following procedure and formulation.

(Procedure and Formulation) A polyisocyanate and a branch-introduced compound having a mole ratio of 0.35 mole of polyol, 0.31 mole of dimethylolpropionic acid and a compound shown in Tables 1 and 2 based on the total mass thereof are used. 11% by mass of N-methyl-2-pyrrolidone was charged into a reaction flask and reacted at 90 ° C. for 2 hours under a nitrogen stream, and dimethylolpropionic acid and an equimolar amount of triethylamine were added to the obtained prepolymer composition. Neutralized. This solution was added dropwise to an aqueous solution to which a polyamine compound having two primary amino groups at the ends was added so that the solid content became 30% by mass, and the epoxysilane derivative was added to a dispersion obtained by adding the epoxysilane derivative to the dispersion at 65 ° C. for 6 hours. By reacting, an anionic water-dispersed polyurethane shown in Tables 1 and 2 below was produced. The molecular weight is the average molecular weight determined by GPC, and the silicon content is that in the solid content, and is a value measured by an ash analysis method.

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[Table 1]

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[Table 2]

[Comparative Production Example 1] <Production of water-dispersible polyurethane compositions of Comparative Examples 1 to 4>
As a comparative composition, as shown in Table 3 below, an epoxysilane derivative was not added, an aminosilane compound was used instead of an epoxysilane derivative without using a polyamine compound having two terminal primary amino groups. Was manufactured.

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[Table 3]

[Comparative Production Example 2] <Production of water-dispersible polyurethane composition of Comparative Example 5> Further, as a comparative composition, a primary amino group-terminated polyurethane compound not using a chain extender was prepared by the following procedure and formulation. And a water-dispersible polyurethane composition of Comparative Example 5 obtained from an epoxysilane derivative.

(Procedure, blending) 1,6- having a molecular weight of 1750
Hexanediol and adipic acid: isophthalic acid = 1: 1
0.35 mol of a polyester polyol polyol, 0.31 mol of dimethylolpropionic acid, 1.0 mol of dicyclohexylmethane diisocyanate, and 11% by mass of N-methyl-2-pyrrolidone based on the total mass thereof were charged into a reaction flask, Dimethylolpropionic acid and an equimolar amount of triethylamine were added to the prepolymer composition obtained by reacting at 90 ° C. for 2 hours under a nitrogen stream to neutralize the prepolymer. A monoketimine compound obtained from 2 mole ratio of ethylenediamine and 1 mole ratio of acetone is added to this solution in an equimolar amount with the isocyanate group of the prepolymer.
After the reaction at 60 ° C. for 2 hours, 10% of the total mass of water was added, and the reaction was performed at 60 ° C. for 1 hour. The obtained reaction system solution was added dropwise to an aqueous solution so that the solid content became 30% by mass, and an epoxysilane derivative having the same mole as the primary amino group was added to the dispersion and reacted at 65 ° C. for 6 hours to obtain a molecular weight. A water-dispersible polyurethane composition having a silicon content of 3,500 and a silicon content of 1.6% by mass (solid content) was obtained.

[Evaluation Example 1] <Evaluation of dispersion stability> The above Production Example 1 and Comparative Production Examples 1 to
20 m of the water-dispersible polyurethane composition obtained in Step 2
10 ml into a 1-ml glass sample bottle.
The solution was stored in a high-temperature bath at 40 ° C. and 40 ° C., and the storage stability was evaluated based on the number of days when precipitation occurred. The results are shown in Tables 4 and 5.

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[Table 4]

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[Table 5]

[Evaluation Example 2] <Evaluation of coating film> The water-dispersible polyurethane compositions obtained in Production Example 1 and Comparative Production Examples 1 and 2 were subjected to JIS K54.
According to 00, with a film applicator, a glass plate,
1g / 100cm each for cold rolled steel plate and slate plate
² and dried at 60 ° C. for 10 minutes, and further dried at 100 ° C. for 20 minutes. Was cut into 100 squares of 2 mm square, and a cellophane tape was pressure-bonded. Then, the cellophane tape was peeled off, and the number of squares remaining on the base material) and the appearance were evaluated. The results are shown in Tables 6 to 8.

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[Table 6]

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[Table 7]

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[Table 8]

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The present invention can provide a water-dispersible polyurethane composition having high dispersion stability in which a hydrolyzable silyl group and / or a hydrolyzable silyl group is introduced into a polyurethane molecule.

Continued on front page F term (reference) 4J034 BA05 CA03 CA04 CA05 CA13 CA15 CA16 CA17 CA22 CA31 CA34 CB03 CB04 CB05 CB07 CB08 CC02 CC03 CC05 CC12 CC23 CC26 CC45 CC52 CC54 CC55 CC61 CC62 CC65 CC67 CD04 CD08 CD09 CD15 CE03 DA01 DA03 DB03 DB03 DB05 DB07 DF01 DF02 DF11 DF12 DF16 DF20 DF21 DF22 DG03 DG04 DG06 DG08 DG09 DG14 DM01 HA01 HA02 HA07 HA08 HB05 HB07 HB08 HB11 HB12 HC03 HC12 HC13 HC17 HC22 HC35 HC46 HC52 HC54 HC61 HC71 HC07 HC67 HC67 HC07 HC67

Claims (5)

[Claims] 1. A polyol, a polyisocyanate, a polyamine compound having two primary amino groups at a terminal, one epoxy group in a molecule and a hydrolyzable silyl group represented by the following general formula (I) and / or Or a water-dispersible polyurethane composition comprising a silyl group-terminated polyurethane compound obtained from a hydrolyzed silyl group-terminated epoxysilane derivative. Embedded image (Wherein, R represents an alkyl group having 1 to 8 carbon atoms;
Represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and n
Represents 1, 2 or 3) 2. The water-dispersible polyurethane composition according to claim 1, wherein the solid content of the polyurethane compound is 0.1 to 2% by mass. 3. The water-dispersible polyurethane composition according to claim 1, wherein the polyurethane compound has an anionic hydrophilic group. 4. The water-dispersible polyurethane composition according to claim 1, wherein the polyamine compound having two terminal amino groups at the terminal contains dicarboxylic dihydrazide. 5. The water-dispersible polyurethane composition according to claim 1, wherein the epoxysilane derivative is represented by the following general formula (1) or (2). Embedded image (Wherein R, X, and n are the same as those in the general formula (I);
Represents an alkylene group having 1 to 4 carbon atoms)