JP2007326985A - Silylated urethane-based aqueous composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a silylated urethane-based aqueous composition having excellent water resistance and heat resistance and exhibiting excellent adhesiveness, adhesivity, coating film properties and storage stability at an excellent level. <P>SOLUTION: The silylated urethane-based aqueous composition comprises a water-dispersible silylated urethane-based resin. The water-dispersible silylated urethane-based resin is a water-dispersible silylated urethane-based resin having a constitution in which at least one alkoxysilyl group is introduced as a side chain into a molecule by an alkoxysilane compound containing at least two secondary amino groups. An alkoxysilane compound containing at least two secondary amino groups in a form in which a secondary amino group containing a group containing a secondary amino group is bonded through or not through a bifunctional organic group to the silicon atom of an alkoxysilyl group is preferably used as the alkoxysilane compound containing at least two secondary amino groups. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a silylated urethane-based aqueous composition, and more specifically, a silylated urethane-based aqueous solution containing a water-dispersible silylated urethane-based resin having a structure in which an alkoxysilyl group is introduced into a side chain. Relates to the composition.

  Conventionally, many proposals have been made regarding a one-component cross-linked urethane emulsion obtained by making a silylated urethane resin into which a hydrolyzable silyl group such as an alkoxysilyl group is introduced as an aqueous solution. Among these proposals, Many proposals have been made on techniques for introducing hydrolyzable silyl groups at the ends (see Patent Documents 1 to 5). In such a one-component crosslinked urethane emulsion, the hydrolyzable silyl group is modified to protect the hydrolyzable silyl group in order to enhance the storage stability of the silylated urethane resin after water dispersion. Those that have been used are particularly useful. However, when the silylated urethane resin has a configuration in which a hydrolyzable silyl group is introduced at the end of the urethane resin, the amount of the hydrolyzable silyl group that can be introduced into one molecule is introduced. Is 2 or less (1 or 2), so it is contained in the silylated urethane aqueous composition in order to improve the water resistance, solvent resistance and heat resistance of the cured product of the silylated urethane resin. Increasing the amount of hydrolyzable silyl groups inevitably reduces the molecular weight (weight average molecular weight, etc.) of the urethane-based resin, improving adhesion when bonding, and adhesion (coating film) when coating It is difficult to improve the physical properties of the film, such as the adhesion properties of the film and the hardness characteristics of the film.

  In addition, a method of introducing a hydrolyzable silyl group into a side chain instead of a terminal has been proposed (see Patent Document 6). Thus, in the silylated urethane resin in which the hydrolyzable silyl group is introduced into the side chain, the hydrolyzable silyl group is introduced into the side chain instead of the terminal, so the molecular weight of the silylated urethane resin Even if it is not reduced, it is considered possible to increase the amount of the hydrolyzable silyl group introduced. In addition, in such silylated urethane resins in which a hydrolyzable silyl group is introduced into such a side chain, a further hydrolyzable silyl group or a functional group other than the hydrolyzable silyl group is introduced at the terminal. It is also possible to give various functions to the silylated urethane resin, and to give a new function due to a synergistic effect with the silyl crosslinking.

JP 2004-300402 A JP 2004-43554 A JP 2003-105053 A JP 2003-96406 A JP 2003-48946 A Japanese Patent Application Laid-Open No. 2004-217743

  However, in Japanese Patent Application Laid-Open No. 2004-217943, when preparing a silylated urethane resin in which a hydrolyzable silyl group is introduced into a side chain, a silane coupling agent (isocyanate) having at least one free isocyanate group is prepared. When the amount of alkoxysilyl groups introduced is increased, the silylated urethane resin in which a hydrolyzable silyl group is introduced into the side chain is practically used. It would be extremely difficult to prepare. In addition, in the case of using an alkoxysilane compound having a polyfunctional isocyanate group used in Example 3 in JP-A No. 2004-217743, gelation occurs further. It seems that it is more difficult to use an alkoxysilane compound having a polyfunctional isocyanate group. Moreover, the obtained silylated urethane resin has low storage stability in water and high cost.

  In addition, when introducing an alkoxysilyl group as a hydrolyzable silyl group into a silylated urethane-based resin, an alkoxysilane compound having an amino group or the like is used. When an alkoxysilane compound having two amino groups containing at least a primary amino group (unsubstituted amino group) is used as the alkoxysilane compound having such an amino group, the reactivity of the primary amino group is high. It is difficult to add during the synthesis of the urethane prepolymer, and even if it can be added by controlling the synthesis conditions of the urethane prepolymer, the addition amount is very small, and the cured product of the silylated urethane resin It is extremely difficult to improve water resistance and heat resistance to excellent levels.

  Therefore, in the conventional silylated urethane resin in which an alkoxysilyl group is introduced into the side chain, the introduction amount of the alkoxysilyl group is substantially limited, and the silylated urethane containing the water-dispersible silylated urethane resin is included. For water-based aqueous compositions, water resistance, solvent resistance and heat resistance (especially water resistance and / or heat resistance) are further improved, as well as adhesion, adhesion, and film physical properties (such as film hardness characteristics). It was difficult to improve. In particular, it has been required to improve the adhesion. In addition, it is difficult to ensure storage stability in water at an excellent level.

Accordingly, an object of the present invention is to provide a silylated urethane-based aqueous composition capable of exhibiting adhesion at an excellent level.
Another object of the present invention is a silylated urethane-based aqueous composition that is excellent in water resistance and / or heat resistance and can exhibit adhesiveness, adhesion, film properties, or storage stability at an excellent level. To provide things.

  As a result of intensive studies to solve the above problems, the present inventors have found that when a water-dispersible silylated urethane-based resin is prepared, when a specific alkoxysilane compound is used, the alkoxysilyl group is converted to water resistance and heat resistance. Can be introduced into water-dispersible silylated urethane resins in an introduction amount that can sufficiently improve the water resistance, and water-dispersible silylated urethane resins are adhesive, adhesive, film properties, and storage stability. It was found that the property can be exhibited at an excellent level. The present invention has been completed based on these findings.

  That is, the present invention relates to a silylated urethane-based aqueous composition containing a water-dispersible silylated urethane-based resin, wherein the water-dispersible silylated urethane-based resin contains at least two secondary amino groups. A water-dispersible silylated urethane resin having a constitution in which at least one alkoxysilyl group is introduced as a side chain in a molecule by a silane compound. .

  As the alkoxysilane compound containing at least two secondary amino groups, a secondary amino group having a secondary amino group-containing group may or may not pass through a divalent organic group. An alkoxysilane compound containing at least two secondary amino groups in a form bonded to a silicon atom of an alkoxysilyl group can be preferably used. Among these, a primary amino group and a secondary amino group can be used. Each of which is obtained by a reaction between an alkoxysilane compound containing at least one and a compound having a carbon-carbon double bond or a compound having an isocyanate group, and containing at least two secondary amino groups Is preferred. The compound having a carbon-carbon double bond is preferably an α, β-unsaturated carboxylic acid compound, and particularly an unsaturated aliphatic carboxylic acid alkyl having 1 to 20 carbon atoms in the alkyl ester moiety. Esters can be suitably used.

  Moreover, as a water-dispersible silylated urethane resin having a structure in which at least one alkoxysilyl group is introduced as a side chain in the molecule, an alkoxysilane compound containing at least two secondary amino groups, An alkoxysilyl group obtained by reacting a compound containing no anionic group and containing a plurality of isocyanate-reactive groups, a compound containing an anionic group and a plurality of isocyanate-reactive groups, and a polyisocyanate compound is side-chained. The water dispersible urethane prepolymer (A) is preferably used.

  According to the silylated urethane-based aqueous composition of the present invention, the adhesiveness can be exhibited at an excellent level because it has the above configuration. In addition to being excellent in water resistance and / or heat resistance, it is possible to exhibit adhesiveness, adhesion, film properties, or storage stability at an excellent level.

  The silylated urethane-based aqueous composition of the present invention may be referred to as an alkoxysilane compound containing at least two secondary amino groups (monosubstituted amino groups) (“secondary amino group-containing alkoxysilane compound”). ) Contains a water-dispersible silylated urethane resin having a structure in which at least one alkoxysilyl group (monoalkoxysilyl group, dialkoxysilyl group, trialkoxysilyl group, etc.) is introduced as a side chain in the molecule. ing. In addition, water dispersible silylated urethane type resin can be used individually or in combination of 2 or more types.

[Alkoxysilane compound containing a plurality of secondary amino groups]
Thus, in the water-dispersible silylated urethane resin, the secondary amino group-containing alkoxysilane compound is used when introducing an alkoxysilyl group as a side chain into the molecule. The secondary amino group-containing alkoxysilane compound is an alkoxysilane compound containing at least two secondary amino groups in the molecule (inside the molecule), and at least two (two or more) second alkoxy groups. An alkoxysilyl group (monoalkoxysilyl group, dialkoxysilyl group, trialkoxy) in which a primary amino group and at least one (1, 2, or 3) alkoxy group are bonded to a silicon atom (Si) Silyl group). In the alkoxysilane compound containing a plurality of secondary amino groups, at least two secondary amino groups may be each independently bonded to the silicon atom of the alkoxysilyl group, but at least one secondary amino group is present. It is preferably bonded to the silicon atom of the alkoxysilyl group in the form of a secondary amino group having a containing group (sometimes referred to as “secondary amino-containing group”). At this time, the secondary amino group bonded to the silicon atom of the alkoxysilyl group may be bonded to the silicon atom of the alkoxysilyl group via a divalent organic group, and the divalent organic group may be bonded via the divalent organic group. Alternatively, it may be bonded to the silicon atom of the alkoxysilyl group. Therefore, as the secondary amino group-containing alkoxysilane compound, the secondary amino group having a secondary amino group is bonded to the silicon atom of the alkoxysilyl group with or without a divalent organic group. A secondary amino group-containing alkoxysilane compound in a bonded form is preferred.

  The secondary amino group is a mono-substituted amino group, specifically, an amino group having a structure in which only one hydrogen atom is bonded to a nitrogen atom [ie, a hydrogen atom and a group other than a hydrogen atom. And a substituent that is bonded to a nitrogen atom]. The substituent bonded to the nitrogen atom in the secondary amino group is not particularly limited and can be appropriately selected from various organic groups. For example, among the at least two secondary amino groups in the secondary amino group-containing alkoxysilane compound, the substituent related to at least one secondary amino group is a secondary amino group-containing group as described above. It may be.

  The number of amino groups contained in the secondary amino-containing group is not particularly limited as long as it contains at least one secondary amino group. As the secondary amino-containing group, when two or more secondary amino groups are contained, the secondary amino group may be another secondary amino group with or without a divalent organic group. It preferably has a form bonded to a group.

  Furthermore, as the secondary amino group having a secondary amino-containing group, the secondary amino group in the secondary amino-containing group is not a divalent organic group, but a secondary amino group (secondary amino group). A secondary amino group that is not a secondary amino-containing group), but the secondary amino group in the secondary amino-containing group is bonded via a divalent organic group. In addition, it preferably has a form bonded to a secondary amino group.

  Therefore, in the present invention, the secondary amino group having a secondary amino-containing group preferably has a form in which all secondary amino groups are arranged in a straight chain. The secondary amino groups are preferably arranged in a linear form in such a manner that each secondary amino group is bonded to another secondary amino group via a divalent organic group. Of course, if the secondary amino group having a secondary amino-containing group has three or more secondary amino groups, the secondary amino groups are not all linearly arranged, Alternatively, it may have a form that is linearly arranged. Specifically, as the secondary amino group having a secondary amino-containing group, for example, when the secondary amino group has a form in which two secondary amino groups are linearly arranged, N- ( Mono-substituted amino-2valent organic group) -amino group is preferable, and in the case where three secondary amino groups are arranged in a straight chain, N- [N ′-(mono Substituted amino-2valent organic group) -amino-2valent organic group] -amino group is preferred.

  The divalent organic group is not particularly limited and can be appropriately selected from known divalent organic groups. Examples of the divalent organic group include carbon atoms, oxygen atoms, hydrogen atoms, nitrogen atoms, and sulfur atoms. Examples thereof include divalent organic groups composed of various atoms. More specifically, as the divalent organic group, for example, a divalent hydrocarbon group constituted only by a hydrocarbon group such as an alkylene group, an arylene group, an alkylene-arylene group, an alkylene-arylene-alkylene group; Hydrocarbon groups such as alkylene-oxy-alkylene groups, alkylene-carbonyl-oxy-alkylene groups, alkylene-oxy-carbonyl-alkylene groups, alkylene-poly (oxyalkylene) groups, alkylene-imino groups, alkylene-imino-alkylene groups And various divalent groups composed of various combinations of oxy groups, carbonyl-oxy groups, oxy-carbonyl groups, carbonyl groups, imino groups, amide bond-containing groups, and the like. As the divalent organic group, a divalent organic group having about 1 to 20 carbon atoms (such as a divalent hydrocarbon group) can be suitably used. In such a divalent organic group, examples of the alkylene group include a methylene group, an ethylene group, a trimethylene group, a propylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, a heptamethylene group, and an octamethylene group. Examples of the arylene group include a phenylene group.

  Further, among at least two secondary amino groups in the alkoxysilane compound containing a plurality of secondary amino groups, at least one secondary amino group (for example, a plurality of secondary amino groups are arranged in a straight chain) The secondary amino group on the terminal side is an organic compound capable of reacting with the primary amino group (“primary amino group reaction”). Or a secondary amino group formed by the reaction. That is, as the secondary amino group, the nitrogen in the secondary amino group when the secondary amino group is formed by reacting the primary amino group with the primary amino group-reactive organic compound. An organic group substituted with an atom (an organic group corresponding to the primary amino group-reactive organic compound) may be included as a substituent. Such a primary amino group-reactive organic compound is not particularly limited as long as it is an organic compound having reactivity with a primary amino group, but a compound having a carbon-carbon double bond ( A compound having an isocyanate group (sometimes referred to as an “isocyanate group-containing compound”) or a compound having an isocyanate group is preferred. Therefore, the secondary amino group preferably has an organic group corresponding to the carbon-carbon double bond-containing compound or an organic group corresponding to the isocyanate group-containing compound as a substituent.

  Therefore, the secondary amino group-containing alkoxysilane compound has a secondary amino group having a secondary amino-containing group, and the secondary amino group on the terminal side is a carbon-carbon double compound. A secondary amino group-containing alkoxysilane compound having an organic group corresponding to the bond-containing compound or an organic group corresponding to the isocyanate group-containing compound as a substituent is preferred.

  In the primary amino group-reactive organic compound, the carbon-carbon double bond-containing compound is preferably an organic compound having a vinyl group, such as an α, β-unsaturated carboxylic acid compound, an acrylonitrile compound, Maleimide compounds and the like can be mentioned. Moreover, as an isocyanate group containing compound, an isocyanate type compound etc. are mentioned, for example. The primary amino group-reactive organic compounds can be used alone or in combination of two or more.

  Examples of the α, β-unsaturated carboxylic acid compound include acrylic acid ester, methacrylic acid ester, crotonic acid ester, isocrotonic acid ester, 2-butenoic acid ester, 3-methyl-2-butenoic acid ester, 2- In addition to pentenoic acid ester, 2-octenoic acid ester and the like, unsaturated monovalent carboxylic acid ester such as cinnamic acid ester; maleic acid ester (mono or diester), fumaric acid ester (mono or diester), itaconic acid ester (mono or And esters of divalent unsaturated carboxylic acids (monoesters, diesters). In such unsaturated carboxylic acid ester (unsaturated monovalent carboxylic acid ester or unsaturated divalent carboxylic acid ester), the ester moiety may be methyl ester, ethyl ester, propyl ester, isopropyl ester, butyl ester, isobutyl. Ester, s-butyl ester, t-butyl ester, pentyl ester, isopentyl ester, hexyl ester, heptyl ester, octyl ester, 2-ethylhexyl ester, isooctyl ester, nonyl ester, isononyl ester, decyl ester, isodecyl ester , Undecyl ester, dodecyl ester (lauryl ester), tridecyl ester, tetradecyl ester, hexadecyl ester, octadecyl ester (stearyl ester), iso Esters with aliphatic hydrocarbons (alkyl esters, etc.) such as the tearyl ester, nonadecyl ester, eicosyl ester; cyclohexyl ester, isobornyl ester, bornyl ester, dicyclopentadienyl ester, dicyclopentanyl ester, Examples include esters with alicyclic hydrocarbons such as dicyclopentenyl esters and tricyclodecanyl esters (cycloalkyl esters and the like); esters with aromatic hydrocarbons such as phenyl esters and benzyl esters (aryl esters and the like). In addition, when it has two or more ester site | parts, each ester site | part may be the same and may differ.

In the present invention, an unsaturated aliphatic carboxylic acid alkyl ester is suitable as the α, β-unsaturated carboxylic acid compound. Examples of such unsaturated aliphatic carboxylic acid alkyl esters include unsaturated aliphatic carboxylic acid alkyl esters in which the alkyl group has 1 to 20 carbon atoms in the alkyl ester moiety (“unsaturated aliphatic carboxylic acid C _1-20 alkyl”). In some cases, an unsaturated aliphatic carboxylic acid alkyl ester having 1 to 18 carbon atoms of the alkyl group in the alkyl ester moiety can be preferably used.

  Examples of the α, β-unsaturated carboxylic acid compounds include acrylic acid esters and methacrylic acid esters (hereinafter sometimes referred to as “(meth) acrylic acid esters”) among the unsaturated carboxylic acid esters exemplified above. Maleic acid diesters can be preferably used. More specifically, as (meth) acrylic acid ester, for example, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, (meth) acrylic acid Heptyl, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, (meth) acrylic Isodecyl acid, undecyl (meth) acrylate, dodecyl (meth) acrylate, tridecyl (meth) acrylate, tetradecyl (meth) acrylate, hexadecyl (meth) acrylate, octadecyl (meth) acrylate, (meth) acrylic acid Isostearyl, nonadecyl (meth) acrylate, (meth) acryl An acid (meth) acrylic acid alkyl esters, such as eicosyl and the like. Examples of the maleic acid diester include dimethyl maleate, diethyl maleate, dibutyl maleate, dihexyl maleate, diheptyl maleate, dioctyl maleate, di (2-ethylhexyl) maleate, diisooctyl maleate, and dinonyl maleate. , Diisononyl maleate, didecyl maleate, diisodecyl maleate, diundecyl maleate, didodecyl maleate, ditridecyl maleate, ditetradecyl maleate, dihexadecyl maleate, dioctadecyl maleate, diisostearyl maleate, dinonadecyl maleate, maleic acid And maleic acid dialkyl esters such as dieicosyl.

  Examples of the acrylonitrile compound include acrylonitrile and methacrylonitrile. Furthermore, examples of the maleimide compound include N-phenylmaleimide, N-cyclohexylmaleimide, hydroxyphenylmonomaleimide, N-laurylmaleimide, diethylphenylmonomaleimide, N- (2-chlorophenyl) maleimide, and the like. Furthermore, examples of the isocyanate compound include ethyl isocyanate, n-hexyl isocyanate, n-decyl isocyanate, p-toluenesulfonyl isocyanate, benzyl isocyanate, 2-methoxyphenyl isocyanate, and the like.

  As the primary amino group-reactive organic compound, a carbon-carbon double bond-containing compound is suitable, and among these, α, β-unsaturated carboxylic acid compounds can be suitably used.

［式（１ａ）〜（１ｄ）において、Ｒ^1aは水素原子、炭化水素基又は「Ｃ（＝Ｏ）Ｚ」で示される基である。Ｒ^1bは水素原子又は炭化水素基である。Ｚは炭化水素−オキシ基を示す。Ｒ^1cは水素原子又は有機基である。Ｒ^1dは有機基である。］ Specifically, as the secondary amino group formed by the reaction of the primary amino group-reactive organic compound with the primary amino group, for example, the primary amino group-reactive organic compound is α, When it is a β-unsaturated carboxylic acid compound, examples thereof include those represented by the following formula (1a). When the primary amino group-reactive organic compound is a maleimide compound, the following formula (1b) In the case where the primary amino group-reactive organic compound is an acrylonitrile-based compound, examples include those represented by the following formula (1c), and the primary amino group-reactive organic compound: In the case where is an isocyanate compound, those represented by the following formula (1d) are exemplified.

[In the formulas (1a) to (1d), R ^1a is a hydrogen atom, a hydrocarbon group or a group represented by “C (═O) Z”. R ^1b is a hydrogen atom or a hydrocarbon group. Z represents a hydrocarbon-oxy group. R ^1c is a hydrogen atom or an organic group. R ^1d is an organic group. ]

In the formulas (1a) to (1d), examples of the hydrocarbon group according to R ^1a include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, and a cycloalkyl-alkyl group. Further, examples of the hydrocarbon group related to R ^1b include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, and the like, similarly to the hydrocarbon group related to R ^1a . In these hydrocarbon groups, examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a t-butyl group, a s-butyl group, an n-pentyl group, a hexyl group, Heptyl, octyl, 2-ethylhexyl, isooctyl, nonyl, isononyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, isostearyl And an alkyl group having about 1 to 20 carbon atoms such as a nonadecyl group and an eicosyl group. Examples of the cycloalkyl group include cycloalkyl groups having about 5 to 10 carbon atoms constituting the ring, such as a cyclopentyl group and a cyclohexyl group. Examples of the aryl group include a phenyl group and a naphthyl group. Examples of the aralkyl group include phenyl-C _1-6 alkyl groups such as benzyl group, phenethyl group, and phenylpropyl group. Examples of the cycloalkyl-alkyl group include cyclohexyl-methyl group and cyclohexyl-ethyl. And a cycloalkyl-C _1-6 alkyl group such as a group. The cycloalkyl group or aryl group has a substituent such as an alkyl group, an alkoxy group, an aryloxy group, a cycloalkyloxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, a cycloalkyloxycarbonyl group, and an acyl group. May be. In the present invention, the hydrocarbon group according to R ^1b is preferably a methyl group.

Examples of the hydrocarbon-oxy group as Z include an alkoxy group, an aryloxy group, a cycloalkyloxy group, an aralkyloxy group, and a cycloalkyloxy group. In the hydrocarbon-oxy group, examples of the alkoxy group include methoxy group, ethoxy group, isopropoxy group, butoxy group, isobutyloxy group, s-butyloxy group, t-butyloxy group, pentyloxy group, hexyloxy group, heptyl. Oxy group, octyloxy group, isooctyloxy group, 2-ethylhexyloxy group, nonyloxy group, isononyloxy group, decyloxy group, isodecyloxy group, undecyloxy group, dodecyloxy group, tridecyloxy group, tetradecyl Examples thereof include C _1-20 alkyl-oxy groups such as oxy group, pentadecyloxy group, hexadecyloxy group, heptadecyloxy group, octadecyloxy group, isostearyloxy group, nonadecyloxy group, and eicosyloxy group. Examples of the aryloxy group include a phenyloxy group and a naphthyloxy group. Examples of the cycloalkyloxy group include a cyclohexyloxy group. Examples of the aralkyloxy group include a benzyloxy group. Examples of the cycloalkyloxy group include a cyclohexyloxy group. As the hydrocarbon-oxy group as Z, an alkoxy group is preferred. In addition, when R ^1a is a group represented by “C (═O) Z”, the Z related to two “C (═O) Z” in the secondary amino group represented by (1a) is the same. May be different or different.

Examples of the organic group related to R ^1c include monovalent hydrocarbon groups composed only of hydrocarbon groups such as alkyl groups, aryl groups, cycloalkyl groups, and aralkyl groups; alkyl-oxy-alkyl groups, alkyl- Consists of various combinations of hydrocarbon groups such as carbonyl-oxy-alkyl groups, alkyl-oxy-carbonyl-alkyl groups, and other groups (oxy groups, carbonyl-oxy groups, oxy-carbonyl groups, carbonyl groups, etc.). And various monovalent groups. In the hydrocarbon group related to R ^1c , examples of the alkyl group, aryl group and cycloalkyl group include the alkyl group, aryl group and cycloalkyl group exemplified as the hydrocarbon group related to R ^1a above. The aryl group or cycloalkyl group has a substituent such as an alkyl group, an alkoxy group, an aryloxy group, a cycloalkyloxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, a cycloalkyloxycarbonyl group, and an acyl group. May be.

As the organic group related to R ^1d , similarly to the organic group related to R ^1c , for example, a monovalent hydrocarbon constituted only by a hydrocarbon group such as an alkyl group, an aryl group, a cycloalkyl group, and an aralkyl group Groups; hydrocarbon groups such as alkyl-oxy-alkyl groups, alkyl-carbonyl-oxy-alkyl groups, alkyl-oxy-carbonyl-alkyl groups, and other groups (oxy groups, carbonyl-oxy groups, oxy-carbonyl groups, carbonyl groups) And various monovalent groups constituted by various combinations with a group. In the hydrocarbon group related to R ^1d , examples of the alkyl group, aryl group, and cycloalkyl group include the alkyl group, aryl group, and cycloalkyl group exemplified as the hydrocarbon group related to R ^1a above. The aryl group or cycloalkyl group has a substituent such as an alkyl group, an alkoxy group, an aryloxy group, a cycloalkyloxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, a cycloalkyloxycarbonyl group, and an acyl group. May be.

Moreover, in the secondary amino group-containing alkoxysilane compound, the alkoxysilyl group usually has 1 to 3 alkoxy groups (preferably 2 or 3 alkoxy groups). When the alkoxysilyl group has 2 or 3 alkoxy groups, the 2 or 3 alkoxy groups may all be the same alkoxy group, or may be partially the same or all different alkoxy groups. Also good. As the alkoxy group in the alkoxysilyl group, for example, a C _1-4 alkoxy group such as methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, isobutyloxy group, s-butyloxy group, t-butyloxy group and the like is preferable. Can be used. As the alkoxy group, a methoxy group, an ethoxy group, and a propoxy group are more preferable, and a methoxy group and an ethoxy group are particularly preferable.

  Accordingly, as the alkoxysilyl group, when it is a monoalkoxysilyl group, for example, a monomethoxysilyl group, a monoethoxysilyl group, a monopropoxysilyl group, and the like can be mentioned, and when it is a dialkoxysilyl group, for example, a dimethoxysilyl group. A silyl group, a diethoxysilyl group, a dipropoxysilyl group, etc. are mentioned, Furthermore, when it is a trialkoxysilyl group, a trimethoxysilyl group, a triethoxysilyl group, a tripropoxysilyl group etc. are mentioned, for example.

［式（２）において、Ｒ¹、Ｒ²は、同一又は異なって、アルキル基を示す。Ｒ³はアルキレン基又はアリレン基を示し、Ｒ⁴はアルキレン基又はアリレン基を示す。なお、Ｒ³、Ｒ⁴は、同一であってもよく、異なっていてもよい。また、Ｒ⁵は水素原子又は「−Ｃ（＝Ｏ）ＯＲ⁷」で示される基である。Ｒ⁶は水素原子又はメチル基である。Ｒ⁷は炭化水素基である。ｎは１〜３の整数を示す。］ More specifically, as the secondary amino group-containing alkoxysilane compound, for example, in the case of having two secondary amino groups, a plurality of secondary amino groups represented by the following formula (2): A contained alkoxysilane compound can be preferably used.

[In the formula ^{(2), R 1, R} 2 are the same or different and are each an alkyl group. R ³ represents an alkylene group or an arylene group, and R ⁴ represents an alkylene group or an arylene group. R ³ and R ⁴ may be the same or different. R ⁵ is a hydrogen atom or a group represented by “—C (═O) OR ⁷ ”. R ⁶ is a hydrogen atom or a methyl group. R ⁷ is a hydrocarbon group. n shows the integer of 1-3. ]

In the formula (2), examples of the alkyl group represented by R ¹ include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a t-butyl group, an s-butyl group, an n-pentyl group, 1 to 20 carbon atoms such as hexyl, heptyl, octyl, 2-ethylhexyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl About an alkyl group (C _1-20 alkyl group) can be preferably used. As the alkyl group for R ¹ , an alkyl group having about 1 to 4 carbon atoms such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, and a t-butyl group is preferable.

The alkyl groups R ^2, may be used the same alkyl group and the alkyl group of R ^1, a methyl group and an ethyl group are preferable.

R ¹ and R ² may be the same or different.

Furthermore, as an alkylene group of R < ³ >, C1-C10 alkylene groups, such as a methylene group, ethylene group, trimethylene group, etc. are mentioned, for example, A C1-C3 alkylene group is suitable. Examples of the arylene group for R ³ include a phenylene group. In addition, as the alkylene group for R ^4, an alkylene group having 1 to 10 carbon atoms can be used as in the alkylene group for R ^{3, and} an alkylene group having 1 to 3 carbon atoms is preferable. Examples of the arylene group for R ⁴ include a phenylene group and the like, similarly to the arylene group for R ³ . In R ³ and R ⁴ , the alkylene group may have a side chain, and the arylene group may have a substituent. R ³ and R ⁴ are preferably both alkylene groups. R ³ and R ⁴ may be the same or different.

Furthermore, examples of the hydrocarbon group for R ⁷ include an alkyl group, a cycloalkyl group, an aryl group, and an aralkyl group (aralkyl group). As the hydrocarbon group for R ⁷ , an alkyl group is preferred. Examples of the alkyl group for R ⁷ include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, s-butyl, n-pentyl, hexyl, heptyl, and octyl. Group, 2-ethylhexyl group, isooctyl group, nonyl group, isononyl group, decyl group, isodecyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, isostearyl group, Examples thereof include an alkyl group having about 1 to 20 carbon atoms (C _1-20 alkyl group) such as a nonadecyl group and an eicosyl group. Examples of the cycloalkyl group represented by R ⁷ include a cyclopentyl group and a cyclohexyl group. Examples of the aryl group for R ⁷ include a phenyl group and a naphthyl group. Examples of the aralkyl group for R ⁷ include a benzyl group, a phenethyl group, and a phenylpropyl group.

When R ⁵ is “—C (═O) OR ⁷ ”, it is directly bonded to “—C (═O) OR ⁷ ” related to R ⁵ and the carbon atom to which R ⁶ is bonded. “—C (═O) OR ⁷ ” may be the same or different. When R ⁵ is “—C (═O) OR ⁷ ”, R ⁶ is preferably a hydrogen atom.

  Accordingly, as the secondary amino group-containing alkoxysilane compound represented by the formula (2), for example, N- {N ′-[2- (alkoxycarbonyl) -ethyl] -aminoalkyl} -aminoalkyl- Trialkoxysilane, N- {N '-[2- (alkoxycarbonyl) -2-methyl-ethyl] -aminoalkyl} -aminoalkyl-trialkoxysilane, N- {N'-[1,2-di (alkoxy) N- (monosubstituted aminoalkyl) -aminoalkyl-trialkoxysilanes such as carbonyl) -ethyl] -aminoalkyl} -aminoalkyl-trialkoxysilane; N- {N ′-[2- (alkoxycarbonyl) -ethyl] -Aminoalkyl} -aminoalkyl-dialkoxymonoalkylsilane, N- {N ′-[2- (alkoxycarboni ) -2-methyl-ethyl] -aminoalkyl} -aminoalkyl-dialkoxymonoalkylsilane, N- {N ′-[1,2-di (alkoxycarbonyl) -ethyl] -aminoalkyl} -aminoalkyl- N- (monosubstituted aminoalkyl) -aminoalkyl-dialkoxymonoalkylsilanes such as dialkoxymonoalkylsilane; N- {N ′-[2- (alkoxycarbonyl) -ethyl] -aminoalkyl} -aminoalkyl-mono Alkoxydialkylsilane, N- {N '-[2- (alkoxycarbonyl) -2-methyl-ethyl] -aminoalkyl} -aminoalkyl-monoalkoxydialkylsilane, N- {N'-[1,2-di ( Alkoxycarbonyl) -ethyl] -aminoalkyl} -aminoalkyl-monoalkoxy dial Rushiran etc. N- (monosubstituted aminoalkyl) - aminoalkyl - such as monoalkoxy dialkyl silane.

  More specifically, in N- (mono-substituted aminoalkyl) -aminoalkyl-trialkoxysilane, N- {N ′-[2- (alkoxycarbonyl) -ethyl] -aminoalkyl} -aminoalkyl-trialkoxysilane As, for example, N- {N ′-[2- (alkoxycarbonyl) -ethyl] -β-amino-ethyl} -γ-aminopropyl-trimethoxysilane, N- {N ′-[2- (alkoxycarbonyl) ) -Ethyl] -β-amino-ethyl} -γ-aminopropyl-triethoxysilane, N- {N ′-[2- (alkoxycarbonyl) -ethyl] -β-amino-ethyl} -γ-aminopropyl- Tripropoxysilane, N- {N ′-[2- (alkoxycarbonyl) -ethyl] -β-amino-ethyl} -γ-aminopropyl-triiso Ropokishishiran, N- {N'- [2- (alkoxycarbonyl) - ethyl]-.beta.-amino - ethyl}-.gamma.-aminopropyl - such tributoxysilane silane.

  N- {N ′-[2- (alkoxycarbonyl) -2-methyl-ethyl] -aminoalkyl} -aminoalkyl-trialkoxysilane includes N- {N ′-[2- (alkoxycarbonyl) -Ethyl] -aminoalkyl} -aminoalkyl-trialkoxysilanes corresponding to those exemplified.

  Furthermore, as N- {N ′-[1,2-di (alkoxycarbonyl) -ethyl] -aminoalkyl} -aminoalkyl-trialkoxysilane, for example, N- {N ′-[1,2-di ( Alkoxycarbonyl) -ethyl] -β-amino-ethyl} -γ-aminopropyl-trimethoxysilane, N- {N ′-[1,2-di (alkoxycarbonyl) -ethyl] -β-amino-ethyl}- γ-aminopropyl-triethoxysilane, N- {N ′-[1,2-di (alkoxycarbonyl) -ethyl] -β-amino-ethyl} -γ-aminopropyl-tripropoxysilane, N- {N ′ -[1,2-di (alkoxycarbonyl) -ethyl] -β-amino-ethyl} -γ-aminopropyl-triisopropoxysilane, N- {N ′-[1,2-di (alkoxycal Bonyl) -ethyl] -β-amino-ethyl} -γ-aminopropyl-tributoxysilane and the like.

In addition, “alkoxycarbonyl” group in “2- (alkoxycarbonyl) -ethyl” group in N- {N ′-[2- (alkoxycarbonyl) -ethyl] -aminoalkyl} -aminoalkyl-trialkoxysilane, N -"Nalkoxy" in the "2- (alkoxycarbonyl) -2-methyl-ethyl" group in-{N '-[2- (alkoxycarbonyl) -2-methyl-ethyl] -aminoalkyl} -aminoalkyl-trialkoxysilane A “carbonyl” group or a “1,2-di (alkoxycarbonyl) -ethyl” group in N- {N ′-[1,2-di (alkoxycarbonyl) -ethyl] -aminoalkyl} -aminoalkyl-trialkoxysilane Examples of the “alkoxycarbonyl” group include a methoxycarbonyl group and ethoxycarbonyl group. Group, isopropoxycarbonyl group, butoxycarbonyl group, isobutyloxycarbonyl group, s-butyloxycarbonyl group, t-butyloxycarbonyl group, pentyloxycarbonyl group, hexyloxycarbonyl group, heptyloxycarbonyl group, octyloxycarbonyl group, Isooctyloxycarbonyl group, 2-ethylhexyloxycarbonyl group, nonyloxycarbonyl group, isononyloxycarbonyl group, decyloxycarbonyl group, isodecyloxycarbonyl group, undecyloxycarbonyl group, dodecyloxycarbonyl group, tridecyloxycarbonyl group Group, tetradecyloxycarbonyl group, pentadecyloxycarbonyl group, hexadecyloxycarbonyl group, heptadecyloxycarbonyl group, octadecyl group Oxy - - oxycarbonyl group, isostearyl oxycarbonyl group, nonadecyl oxycarbonyl group, C _1-20 alkyl, such as eicosyl oxycarbonyl group such as a carbonyl group.

  N- {N '-[2- (alkoxycarbonyl) -ethyl] -aminoalkyl} -aminoalkyl-dialkoxymonoalkylsilane in N- (monosubstituted aminoalkyl) -aminoalkyl-dialkoxymonoalkylsilane For example, N- {N ′-[2- (alkoxycarbonyl) -ethyl] -β-amino-ethyl} -γ-aminopropyl-methyldimethoxysilane, N- {N ′-[2- (alkoxycarbonyl)- Ethyl] -β-amino-ethyl} -γ-aminopropyl-methyldiethoxysilane, N- {N ′-[2- (alkoxycarbonyl) -ethyl] -β-amino-ethyl} -γ-aminopropyl-ethyl Dimethoxysilane, N- {N ′-[2- (alkoxycarbonyl) -ethyl] -β-amino-ethyl} -γ-aminopro Le - such as ethyl diethoxy silane.

  N- {N ′-[2- (alkoxycarbonyl) -2-methyl-ethyl] -aminoalkyl} -aminoalkyl-dialkoxymonoalkylsilane includes N- {N ′-[2- (alkoxy And the like corresponding to those exemplified as carbonyl) -ethyl] -aminoalkyl} -aminoalkyl-dialkoxymonoalkylsilane.

  Furthermore, as N- {N ′-[1,2-di (alkoxycarbonyl) -ethyl] -aminoalkyl} -aminoalkyl-dialkoxymonoalkylsilane, for example, N- {N ′-[1,2- Di (alkoxycarbonyl) -ethyl] -β-amino-ethyl} -γ-aminopropyl-methyldimethoxysilane, N- {N ′-[1,2-di (alkoxycarbonyl) -ethyl] -β-amino-ethyl } -Γ-aminopropyl-methyldiethoxysilane, N- {N ′-[1,2-di (alkoxycarbonyl) -ethyl] -β-amino-ethyl} -γ-aminopropyl-ethyldimethoxysilane, N— {N ′-[1,2-di (alkoxycarbonyl) -ethyl] -β-amino-ethyl} -γ-aminopropyl-ethyldiethoxysilane and the like.

The “alkoxycarbonyl” group in the “2- (alkoxycarbonyl) -ethyl” group in N- {N ′-[2- (alkoxycarbonyl) -ethyl] -aminoalkyl} -aminoalkyl-dialkoxymonoalkylsilane N- {N ′-[2- (alkoxycarbonyl) -2-methyl-ethyl] -aminoalkyl} -aminoalkyl-dialkoxymonoalkylsilane in “2- (alkoxycarbonyl) -2-methyl-ethyl” group Or “1,2-di (alkoxy) in N- {N ′-[1,2-di (alkoxycarbonyl) -ethyl] -aminoalkyl} -aminoalkyl-dialkoxymonoalkylsilane The “alkoxycarbonyl” group in the “carbonyl) -ethyl” group includes N- (monosubstituted Noarukiru) - aminoalkyl - is the same as in the case of trialkoxysilane, C _1-20 alkyl - oxy -, carbonyl groups and the like.

  In N- (monosubstituted aminoalkyl) -aminoalkyl-monoalkoxydialkylsilane, N- {N ′-[2- (alkoxycarbonyl) -ethyl] -aminoalkyl} -aminoalkyl-monoalkoxydialkylsilane, N- { N ′-[2- (alkoxycarbonyl) -2-methyl-ethyl] -aminoalkyl} -aminoalkyl-monoalkoxydialkylsilane, N- {N ′-[1,2-di (alkoxycarbonyl) -ethyl] Examples of -aminoalkyl} -aminoalkyl-monoalkoxydialkylsilane include those corresponding to the case of the N- (monosubstituted aminoalkyl) -aminoalkyl-dialkoxymonoalkylsilane.

  In the present invention, the alkoxysilane compound containing a plurality of secondary amino groups has two or more secondary amino groups, and therefore can also function as a chain extender.

[Water dispersible silylated urethane resin]
In the water-dispersible silylated urethane resin contained in the silylated urethane-based aqueous composition, at least one alkoxysilyl group is introduced as a side chain in the molecule by the secondary amino group-containing alkoxysilane compound. Therefore, one or more alkoxysilyl groups may be introduced into the molecule, and in particular, three or more alkoxysilyl groups may be introduced. That is, regardless of the amount of alkoxysilyl group introduced in the silylated urethane-based aqueous composition, regardless of the amount introduced, the molecular weight (weight average molecular weight) of the water-dispersible silylated urethane-based resin is not affected. (Specifically, even if the molecular weight of the water-dispersible silylated urethane resin is not reduced), a water-dispersible silylated urethane resin in which an alkoxysilyl group is introduced in an appropriate amount in the molecule is prepared. be able to.

  In the water dispersible silylated urethane resin, the amount of the alkoxysilyl group introduced as a side chain in the molecule is not particularly limited, and as described above, the molecular weight (weight average) of the water dispersible silylated urethane resin. The molecular weight can be set as appropriate regardless of the molecular weight, and can be appropriately selected according to various required properties (water resistance, solvent resistance, heat resistance, etc.). Specifically, the amount of alkoxysilyl group introduced as a side chain in the molecule in the water-dispersible silylated urethane resin may be, for example, one or more per molecule, and preferably in one molecule. 2 or more (more preferably 3 or more in one molecule). The upper limit of the amount of the alkoxysilyl group introduced as a side chain in the molecule in the water-dispersible silylated urethane resin is not particularly limited, but may be, for example, 200 or less per molecule, preferably 100 or less per molecule (more preferably 50 or less per molecule). In the water-dispersible silylated urethane resin, the value of the amount of alkoxysilyl group introduced as a side chain in the molecule is usually an average value, a calculated value, or a theoretical value.

  In addition, the weight average molecular weight of the water-dispersible silylated urethane resin is not particularly limited, and is appropriately determined regardless of the amount of alkoxysilyl group introduced as a side chain in the molecule of the water-dispersible silylated urethane resin. It can be set and can be appropriately selected according to the film properties, hardness, viscosity and the like of the water-dispersible silylated urethane resin. Specifically, the weight average molecular weight of the water-dispersible silylated urethane resin can be appropriately selected from the range of, for example, 2000 to 1,000,000 (preferably 3000 to 500,000, more preferably 5000 to 200,000). it can. The weight-average molecular weight of the water-dispersible silylated urethane resin is determined by amine-crosslinking isocyanate groups in water based on the ratio (mass%) of isocyanate groups in the prepolymer before water dispersion (of course, This is a value calculated by how many times the prepolymer has been chain extended.

  Thus, in the present invention, the molecular weight (weight average molecular weight, etc.) of the water-dispersible silylated urethane resin and the amount of alkoxysilyl groups introduced as side chains in the molecule of the water-dispersible silylated urethane resin ( That is, it is possible to control independently (separately) the introduction amount of alkoxysilyl groups contained in the silylated urethane-based aqueous composition. Therefore, even if the molecular weight of the water-dispersible silylated urethane-based resin is not increased or decreased, the amount of alkoxysilyl groups contained in the silylated urethane-based aqueous composition is increased or decreased even in a constant state (particularly increased). Can). In addition, the molecular weight of the water dispersible silylated urethane resin is increased or decreased even in a constant state without increasing or decreasing the amount of alkoxysilyl groups contained in the silylated urethane aqueous composition (especially increased). Can).

  Furthermore, since the alkoxysilyl group is introduced into the side chain of the water-dispersible silylated urethane resin, various functional groups other than the alkoxysilyl group are introduced at the end of the water-dispersible silylated urethane resin. May be. That is, in the present invention, the water-dispersible silylated urethane resin in which an alkoxysilyl group is introduced into the side chain is not limited at the end, and the desired properties (adhesion, adhesion, film properties, storage stability) , Fast curing, crosslinkability, pigment dispersibility, etc.) may be exhibited or may have a functional group at the end of the main chain. Therefore, the terminal of the water-dispersible silylated urethane resin in which the alkoxysilyl group is introduced into the side chain can be controlled so as to impart the desired characteristics. High degree of freedom. Specifically, for example, the water-dispersible silylated urethane resin has the same terminal as the terminal group in a normal urethane resin (a urethane resin having no special functional group such as an alkoxysilyl group). By using the above group (isocyanate group or the like), the same adhesiveness or adhesiveness as that of a normal urethane resin can be exhibited. In addition, for example, a water-dispersible silylated urethane resin has a terminal functional group (isocyanate group, etc.) having reactivity, and is chain-extended using a chain extender, whereby the molecular weight (weight average molecular weight) Etc.) and the physical properties of the film such as the hardness characteristics of the film (particularly, the hardness characteristics of the film at a high temperature) can be further improved. Further, by using an amine chain extender as the chain extender, the quick curability of the water-dispersible silylated urethane resin can be enhanced. Moreover, the water-dispersible silylated urethane resin has excellent storage stability.

  Thus, in the present invention, the water-dispersible silylated urethane resin having an alkoxysilyl group introduced into the side chain undergoes a crosslinking reaction by crosslinking with an alkoxysilyl group on the side chain or crosslinking with a functional group at the end. In addition, each cross-link can be controlled independently (separately). Therefore, as in the conventional case, in a water-dispersible silylated urethane resin having an alkoxysilyl group at the terminal, when crosslinking with a chain extender is performed, the amount of the alkoxysilyl group at the terminal is reduced to reduce isocyanate. However, in the water dispersible silylated urethane resin in which an alkoxysilyl group is introduced in the side chain in the present invention, the alkoxysilyl group is introduced in the side chain. Such restrictions do not occur.

  Accordingly, the water-dispersible silylated urethane resin can exhibit adhesion at an excellent level. In particular, the water-dispersible silylated urethane resin can exhibit excellent adhesion even to a surface that has been subjected to a surface treatment such as a corona discharge treatment.

  In addition, the water-dispersible silylated urethane resin has excellent water resistance and / or heat resistance, and can exhibit adhesiveness, adhesiveness, film properties, or storage stability at an excellent level. That is, the water-dispersible silylated urethane resin can improve adhesiveness, adhesion, film properties, or storage stability, and can exhibit excellent water resistance and / or heat resistance. .

  In addition, the water-dispersible silylated urethane resin has a silanol group and / or a siloxane bond in water, in which the alkoxysilyl group in the side chain is partially or entirely hydrolyzed by water. When the group undergoes a condensation reaction, curing (crosslinking) occurs to exhibit adhesiveness. This curing (crosslinking) reaction proceeds due to a decrease in water, and can proceed even if water is present to some extent. Therefore, the water-dispersible silylated urethane resin having a configuration in which at least one alkoxysilyl group is introduced as a side chain in the molecule by the secondary amino group-containing alkoxysilane compound, Cohesive force can be expressed.

  In the present invention, it is important that the water-dispersible silylated urethane resin has at least a urethane bond site from the viewpoint of the urethane resin. Therefore, in the water dispersible silylated urethane resin, at least a polyisocyanate compound and an isocyanate reactive compound having reactivity with the isocyanate compound are used as monomer components.

  Moreover, it is important that the water dispersible silylated urethane resin has water solubility or water dispersibility from the viewpoint of water dispersibility. The water-dispersible silylated urethane resin has a hydrophilic group in its molecule (for example, a carboxyl group or a salt thereof, a sulfo group or a salt thereof, a hydroxyl group, an amino group or a salt thereof, a group containing an ether bond, etc. ) Is introduced, water solubility or water dispersibility can be exhibited. Therefore, in the water-dispersible silylated urethane resin, an isocyanate-reactive compound having an anionic group such as a diol component containing a carboxyl group may be used as the monomer component.

  Therefore, the water-dispersible silylated urethane resin has at least a urethane bond site, an anionic group (such as a carboxyl group) in the molecule, and an alkoxysilyl group in the side chain. And water dispersible silylated urethane resins. In such a water-dispersible silylated urethane resin having an anionic group, the monomer component is a secondary amino group-containing alkoxysilane compound [“secondary amino group-containing alkoxysilane compound (A1)]. And a compound that is free of an anionic group and contains a plurality of isocyanate-reactive groups [sometimes referred to as an “anionic group-free isocyanate-reactive compound (A2)”], anionic A compound containing a group and a plurality of isocyanate-reactive groups [sometimes referred to as “anionic group-containing isocyanate-reactive compound (A3)”] and polyisocyanate compound [sometimes referred to as “polyisocyanate compound (A4)”. ] Is preferably used. That is, as the water-dispersible silylated urethane resin, the secondary amino group-containing alkoxysilane compound (A1), the anionic group-free isocyanate-reactive compound (A2), and the anionic group-containing isocyanate-reactive compound Water dispersible urethane prepolymer (A) having an alkoxysilyl group in the side chain, obtained by reacting (A3) with the polyisocyanate compound (A4) [“alkoxysilyl group side chain-containing water dispersible urethane prepolymer (A) may be referred to suitably ”.

  In the present invention, in the water-dispersible silylated urethane resin, a chain extender [may be referred to as “chain extender (A5)”] may be further used. By using the chain extender (A5) (especially amine chain extender), the physical properties of the film can be improved.

[Anionic group-free isocyanate-reactive compound (A2)]
An anionic group-free isocyanate-reactive compound (A2) (a compound that does not contain an anionic group and contains a plurality of isocyanate-reactive groups) has no anionic group in the molecule and If it is a compound which has at least 2 isocyanate reactive group, there will be no restriction | limiting in particular. The anionic group-free isocyanate-reactive compound (A2) can be used alone or in combination of two or more. In the anionic group-free isocyanate-reactive compound (A2), the isocyanate-reactive group is not particularly limited as long as it is a group having reactivity with an isocyanate group. For example, a hydroxyl group, a primary amino group (unsubstituted) Amino group), secondary amino group (mono-substituted amino group), mercapto group and the like. In addition, only 1 type may be sufficient as an isocyanate reactive group, and 2 or more types may be combined. In the present invention, the isocyanate-reactive group is preferably a hydroxyl group, a primary amino group or a secondary amino group, and particularly preferably a hydroxyl group. Accordingly, examples of the anionic group-free isocyanate-reactive compound (A2) include an anionic group-free polyol compound, an anionic group-free polyamine compound, and an anionic group-free polythiol compound (preferably an anionic group-free polythiol compound). Containing polyol compounds and anionic group-free polyamine compounds, particularly anionic group-free polyol compounds).

  In the anionic group-free isocyanate-reactive compound (A2), examples of the anionic group-free polyol compound include polyhydric alcohol, polyether polyol, polyvinyl ether polyol, polyester polyol, polycarbonate polyol, polyolefin polyol, polyacrylic polyol, and castor. Examples include oil.

  In the anionic group-free polyol compound, the polyhydric alcohol includes, for example, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, trimethylene glycol, 1,4-tetramethylenediol (1,4-butanediol), 1 , 3-tetramethylenediol, 2-methyl-1,3-trimethylenediol, 1,5-pentamethylenediol, neopentyl glycol, 1,6-hexamethylenediol, 3-methyl-1,5-pentamethylenediol 2,4-diethyl-1,5-pentamethylenediol, glycerin, trimethylolpropane, trimethylolethane, cyclohexanediols (such as 1,4-cyclohexanediol), bisphenols (such as bisphenol A), sugar alcohols Call compounds (such as xylitol or sorbitol) and the like.

  Examples of the polyether polyol include polyalkylene glycols such as polyethylene glycol, polypropylene glycol, and polytetramethylene glycol, and a plurality of alkylene oxides as monomer components such as an ethylene oxide-propylene oxide copolymer (alkylene oxide-others). Alkylene oxide) copolymer and the like.

  Examples of the polyester polyol include a condensation polymerization product of a polyhydric alcohol and a polycarboxylic acid; a ring-opening polymerization product of a cyclic ester (lactone); a reaction with three components of a polyhydric alcohol, a polyhydric carboxylic acid, and a cyclic ester. Things can be used. In the condensation polymerization product of a polyhydric alcohol and a polycarboxylic acid, the polyhydric alcohols exemplified above can be used as the polyhydric alcohol. On the other hand, examples of polycarboxylic acids include aliphatic dicarboxylic acids such as malonic acid, maleic acid, succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, and dodecanedioic acid; 1,4-cyclohexane Examples thereof include alicyclic dicarboxylic acids such as dicarboxylic acid; aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, orthophthalic acid, 2,6-naphthalenedicarboxylic acid, paraphenylene dicarboxylic acid and trimellitic acid. In the ring-opening polymer of cyclic ester, examples of the cyclic ester include propiolactone, β-methyl-δ-valerolactone, and ε-caprolactone. In the reaction product of the three types of components, those exemplified above can be used as the polyhydric alcohol, polyvalent carboxylic acid, and cyclic ester.

  Examples of the polycarbonate polyol include a reaction product of a polyhydric alcohol and phosgene; a ring-opening polymerization product of a cyclic carbonate (such as alkylene carbonate). Specifically, in the reaction product of the polyhydric alcohol and phosgene, the polyhydric alcohol exemplified above can be used as the polyhydric alcohol. In the ring-opening polymer of cyclic carbonate, examples of the alkylene carbonate include ethylene carbonate, trimethylene carbonate, tetramethylene carbonate, hexamethylene carbonate, and the like. In addition, the polycarbonate polyol should just be a compound which has a carbonate bond in a molecule | numerator, and the terminal is a hydroxyl group, and may have an ester bond with a carbonate bond.

  The polyolefin polyol is a polyol having an olefin as a component of the skeleton (or main chain) of the polymer or copolymer and having at least two hydroxyl groups in the molecule (particularly at the terminal). The olefin may be an olefin having a carbon-carbon double bond at the terminal (for example, an α-olefin such as ethylene or propylene), or an olefin having a carbon-carbon double bond at a position other than the terminal. (For example, isobutene and the like) and diene (for example, butadiene, isoprene and the like) may be used.

The polyacrylic polyol is a polyol having (meth) acrylate as a component of the polymer (or copolymer) skeleton (or main chain) and having at least two hydroxyl groups in the molecule (particularly at the terminal). (Meth) acrylate includes (meth) acrylic acid alkyl ester [for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, (meth) acrylic acid C _1-20 alkyl (meth) acrylates such as hexyl, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, octadecyl (meth) acrylate Ester etc.] are preferably used.

  In addition, in polyolefin polyol and polyacryl polyol, in order to introduce a hydroxyl group into the molecule, an α, β-unsaturated compound having a hydroxyl group [for example, (meth) as a copolymer component of olefin or (meth) acrylate 2-hydroxyethyl acrylate, hydroxyalkyl (meth) acrylate such as 3-hydroxypropyl (meth) acrylate, etc.] can be used.

  In addition, as the anionic group-free polyol compound, a polyol compound having a tertiary amino group in the molecule (sometimes referred to as “tertiary amino group-containing polyol compound”) can also be used. Such a tertiary amino group-containing polyol compound is not particularly limited as long as it is a compound containing at least one tertiary amino group in the molecule and having at least two hydroxyl groups in the molecule. In the tertiary amino group-containing polyol compound, as the tertiary amino group (disubstituted amino group), a hydrocarbon group (for example, an alkyl group such as a methyl group, an ethyl group, a propyl group, an n-butyl group; a phenyl group; A tertiary amino group may be formed by having a substituent such as an aryl group such as a cycloalkyl group such as a cyclohexyl group. The hydrocarbon group further has another substituent (for example, an alkoxy group, an aryloxy group, a cycloalkyloxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, a cycloalkyloxycarbonyl group, an acyl group, etc.). Also good. The number of tertiary amino groups in the molecule in the tertiary amino group-containing polyol is not particularly limited, and can be selected, for example, from the range of 1 to 6, preferably 1 to 3 (more preferably 1 Or 2, particularly 1). Thus, the tertiary amino group-containing polyol compound may have a plurality of tertiary amino groups in the molecule, but it is particularly preferable to have only one tertiary amino group. In addition, when it has a some tertiary amino group, the tertiary amino group may be only 1 type, and may be combined 2 or more types.

  Further, the number of hydroxyl groups in the molecule in the tertiary amino group-containing polyol compound is not particularly limited as long as it is at least two, but for example, it is selected from the range of 1 to 6 (preferably 1 to 3). In particular, 2 is preferable. In the tertiary amino group-containing polyol compound, the hydroxyl group may be directly bonded to the nitrogen atom of the tertiary amino group, but is preferably bonded via a divalent group. Examples of such a divalent group include a divalent hydrocarbon group composed only of a hydrocarbon group such as an alkylene group, an arylene group, an alkylene-arylene group, and an alkylene-arylene-alkylene group; an oxy-alkylene group Hydrocarbon groups such as alkylene-oxy-alkylene group, alkylene-carbonyl-oxy-alkylene group, alkylene-oxy-carbonyl-alkylene group, alkylene-poly (oxyalkylene) group [poly (alkyleneoxy) -alkylene group] Examples include various divalent groups constituted by various combinations with other groups (oxy group, carbonyl-oxy group, etc.).

  The tertiary amino group-containing polyol compound has a form in which the tertiary amino group is bonded to various organic groups. The organic group to which the tertiary amino group is bonded is not particularly limited, but a hydrocarbon group is preferable. Examples of such hydrocarbon groups include aliphatic hydrocarbon groups (for example, alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, pentyl, and hexyl groups), alicyclic carbon Examples thereof include a hydrogen group (for example, a cycloalkyl group such as a cyclohexyl group) and an aromatic hydrocarbon group (for example, an aryl group such as a phenyl group). The hydrocarbon group may have one or more substituents. Examples of the substituent include other hydrocarbon groups, isocyanate-reactive groups (for example, hydroxyl groups, primary amino groups). Secondary amino groups, mercapto groups, etc.) and non-isocyanate reactive groups (eg tertiary amino groups, alkoxy groups, aryloxy groups, cycloalkyloxy groups, alkoxycarbonyl groups, aryloxycarbonyl groups, cycloalkyl) Oxycarbonyl group, acyl group, etc.).

  Specifically, as the tertiary amino group-containing polyol compound, for example, N, N-bis (hydroxymethyl) -N-methylamine, N, N-bis (2-hydroxyethyl) -N-methylamine, N, N-bis (3-hydroxypropyl) -N-methylamine, N, N-bis (2-hydroxypropyl) -N-methylamine, N, N-bis (4-hydroxybutyl) -N-methylamine N, N-bis (hydroxymethyl) -N-ethylamine, N, N-bis (2-hydroxyethyl) -N-ethylamine, N, N-bis (3-hydroxypropyl) -N-ethylamine, N, N -Bis (2-hydroxypropyl) -N-ethylamine, N, N-bis (4-hydroxybutyl) -N-ethylamine, N, N-bis (2-hydroxyethyl) -N- N, N-bis (hydroxyalkyl) -N-, such as propylamine, N, N-bis (2-hydroxyethyl) -N-isopropylamine, N, N-bis (2-hydroxyethyl) -Nn-butylamine N, N-bis [hydroxymethyl-poly (oxymethylene)]-N-methylamine, N, N-bis [2-hydroxyethyl-poly (oxyethylene)]-N-methylamine, N, N -Bis [3-hydroxypropyl-poly (oxypropylene)]-N-methylamine, N, N-bis [2-hydroxypropyl-poly (oxyisopropylene)]-N-methylamine, N, N-bis [ 4-hydroxybutyl-poly (oxybutylene)]-N-methylamine, N, N-bis [hydroxymethyl-poly (oxymethylene)]-N- Tylamine, N, N-bis [2-hydroxyethyl-poly (oxyethylene)]-N-ethylamine, N, N-bis [3-hydroxypropyl-poly (oxypropylene)]-N-ethylamine, N, N- Bis [2-hydroxypropyl-poly (oxyisopropylene)]-N-ethylamine, N, N-bis [4-hydroxybutyl-poly (oxybutylene)]-N-ethylamine, N, N-bis [2-hydroxy Ethyl-poly (oxyethylene)]-N-propylamine, N, N-bis [2-hydroxyethyl-poly (oxyethylene)]-N-isopropylamine, N, N-bis [2-hydroxyethyl-poly ( N, N-bis [hydroxyalkyl-poly (oxyalkylene)]-N-a, such as oxyethylene)]-Nn-butylamine N, N-bis (hydroxy-organic group) -N-alkylamine such as alkylamine, N, N-bis (hydroxymethyl) -N-phenylamine, N, N-bis (2-hydroxyethyl) -N- Phenylamine, N, N-bis (3-hydroxypropyl) -N-phenylamine, N, N-bis (2-hydroxypropyl) -N-phenylamine, N, N-bis (4-hydroxybutyl) -N N, N-bis (hydroxyalkyl) -N-arylamines such as phenylamine; N, N-bis [hydroxymethyl-poly (oxymethylene)]-N-phenylamine, N, N-bis [2-hydroxy Ethyl-poly (oxyethylene)]-N-phenylamine, N, N-bis [3-hydroxypropyl-poly (oxypropylene)]-N-phenylamino N, N-bis [2-hydroxypropyl-poly (oxyisopropylene)]-N-phenylamine, N, N-bis [4-hydroxybutyl-poly (oxybutylene)]-N-phenylamine, etc. , N-bis [hydroxyalkyl-poly (oxyalkylene)]-N-arylamines and other N, N-bis (hydroxy-organic groups) -N-arylamines; corresponding N, N-bis (hydroxy-) Organic group) -N-cycloalkylamine and the like.

  Examples of the tertiary amino group-containing polyol compound include N, N, N-tris (hydroxymethyl) amine, N, N, N-tris (2-hydroxyethyl) amine, N, N, N-tris. N, N, N-tris (hydroxyalkyl) such as (3-hydroxypropyl) amine, N, N, N-tris (2-hydroxypropyl) amine, N, N, N-tris (4-hydroxybutyl) amine N, N, N-tris [hydroxymethyl-poly (oxymethylene)] amine, N, N, N-tris [2-hydroxyethyl-poly (oxyethylene)] amine, N, N, N-tris [ 3-hydroxypropyl-poly (oxypropylene)] amine, N, N, N-tris [2-hydroxypropyl-poly (oxyisopropylene)] amine, N, N, N, N-tris (hydroxy-organic) such as N, N, N-tris [hydroxyalkyl-poly (oxyalkylene)] amine such as N, N-tris [4-hydroxybutyl-poly (oxybutylene)] amine Group) amine and the like can also be used. Furthermore, examples of the tertiary amino group-containing polyol compound include N, N, N ′, N′-tetra (hydroxymethyl) ethylenediamine, N, N, N ′, N′-tetra (2-hydroxyethyl), and the like. Ethylenediamine, N, N, N ', N'-tetra (3-hydroxypropyl) ethylenediamine, N, N, N', N'-tetra (2-hydroxypropyl) ethylenediamine, N, N, N ', N'- N, N, N ′, N′-tetra (hydroxy-organic group) alkylenediamine such as N, N, N ′, N′-tetra (hydroxy-alkyl) alkylenediamine such as tetra (4-hydroxybutyl) ethylenediamine Can also be used.

  In the anionic group-free isocyanate-reactive compound (A2), as the anionic group-free polyol compound, polyhydric alcohol, tertiary amino group-containing polyol, polyether polyol, polyester polyol, polycarbonate polyol are preferably used. In particular, polyether polyol (particularly, polytetramethylene glycol) can be preferably used.

  The anionic group-free polyamine compound or the anionic group-free polythiol compound as the anionic group-free isocyanate-reactive compound (A2) corresponds to, for example, the anionic group-free polyol compound exemplified above. Anionic group-free polyamine compounds, anionic group-free polythiol compounds, and the like can be mentioned.

  Specifically, examples of the anionic group-free polyamine compound include aliphatic polyamines, alicyclic polyamines, aromatic polyamines, araliphatic polyamines, hydrazine and derivatives thereof. Examples of the aliphatic polyamine include ethylenediamine, 1,3-trimethylenediamine, 1,4-tetramethylenediamine, 1,3-pentamethylenediamine, 1,5-pentamethylenediamine, and 1,6-hexamethylenediamine. 1,2-propylenediamine, 1,2-butylenediamine, 2,3-butylenediamine, 1,3-butylenediamine, 2-methyl-1,5-pentamethylenediamine, 3-methyl-1,5-penta In addition to aliphatic diamines such as methylenediamine, 2,4,4-trimethyl-1,6-hexamethylenediamine, 2,2,4-trimethyl-1,6-hexamethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylene Examples include pentamine and pentaethylenehexamine.

  Examples of the alicyclic polyamine include 1,3-cyclopentanediamine, 1,4-cyclohexanediamine, 1,3-cyclohexanediamine, 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane, -Amino-1-methyl-4-aminomethylcyclohexane, 1-amino-1-methyl-3-aminomethylcyclohexane, 4,4'-methylenebis (cyclohexylamine), 4,4'-methylenebis (3-methyl-cyclohexyl) Amine), methyl-2,3-cyclohexanediamine, methyl-2,4-cyclohexanediamine, methyl-2,6-cyclohexanediamine, 1,3-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) Cyclohexane, isophoronediamine, norbornanediamine, etc. And alicyclic diamines.

  Aromatic polyamines include m-phenylenediamine, p-phenylenediamine, 2,4-tolylenediamine, 2,6-tolylenediamine, naphthylene-1,4-diamine, naphthylene-1,5-diamine, 4, 4'-diphenyldiamine, 4,4'-diphenylmethanediamine, 2,4'-diphenylmethanediamine, 4,4'-diphenyletherdiamine, 2-nitrodiphenyl-4,4'-diamine, 2,2'-diphenyl Fragrances such as propane-4,4'-diamine, 3,3'-dimethyldiphenylmethane-4,4'-diamine, 4,4'-diphenylpropanediamine, 3,3'-dimethoxydiphenyl-4,4'-diamine Group diamine and the like.

  Examples of the araliphatic polyamine include 1,3-xylylenediamine, 1,4-xylylenediamine, α, α, α ′, α′-tetramethyl-1,3-xylylenediamine, α, α, α ′, α′-tetramethyl-1,4-xylylenediamine, ω, ω′-diamino-1,4-diethylbenzene, 1,3-bis (1-amino-1-methylethyl) benzene, 1,4 And aromatic aliphatic diamines such as -bis (1-amino-1-methylethyl) benzene and 1,3-bis (α, α-dimethylaminomethyl) benzene.

  Examples of hydrazine and derivatives thereof include hydrazine and dihydrazide compounds. Examples of the dihydrazide compounds include aliphatic dicarboxylic acid dihydrazides such as carbodihydrazide (carbohydrazide), oxalic acid dihydrazide, malonic acid dihydrazide, succinic acid dihydrazide, glutaric acid dihydrazide, adipic acid dihydrazide; isophthalic acid dihydrazide, diphthalide Aromatic dicarboxylic acid dihydrazides such as alicyclic dicarboxylic acid dihydrazides such as 1,4-cyclohexanedicarboxylic acid dihydrazide.

  In the present invention, the anionic group-free isocyanate-reactive compound (A2) includes an anionic group-free isocyanate-reactive compound having a number average molecular weight of 500 or more and an anionic group-free compound having a number average molecular weight of less than 500. You may use it in combination with a contained isocyanate-reactive compound.

[Anionic group-containing isocyanate-reactive compound (A3)]
The anionic group-containing isocyanate-reactive compound (A3) (compound containing an anionic group and a plurality of isocyanate-reactive groups) has at least one anionic group in the molecule, and at least in the molecule. If it is a compound which has two isocyanate reactive groups, it will not restrict | limit in particular. The anionic group-containing isocyanate-reactive compound (A3) can be used alone or in combination of two or more. In the anionic group-containing isocyanate-reactive compound (A3), as the anionic group, a carboxyl group or a sulfo group can be preferably used, and among them, the carboxyl group is most suitable. In the anionic group-containing isocyanate-reactive compound (A3), the isocyanate-reactive group is not particularly limited as long as it is a group having reactivity with an isocyanate group. For example, a hydroxyl group, a primary amino group (nothing) Substituted amino group), secondary amino group (mono-substituted amino group), mercapto group and the like. In addition, only 1 type may be sufficient as an anionic group and an isocyanate reactive group, and 2 or more types may be combined together. In the present invention, the isocyanate-reactive group is preferably a hydroxyl group, a primary amino group or a secondary amino group, and particularly preferably a hydroxyl group. Accordingly, examples of the anionic group-containing isocyanate-reactive compound (A3) include an anionic group-containing polyol compound, an anionic group-containing polyamine compound, and an anionic group-containing polythiol compound (preferably an anionic group-containing polyol compound and an anion). For example, an anionic group-containing polyamine compound, particularly an anionic group-containing polyol compound).

Examples of the anionic group-containing polyol compound as the anionic group-containing isocyanate-reactive compound (A3) include a carboxyl group in the anionic group-free polyol compound as the anionic group-free isocyanate-reactive compound (A2). Examples thereof include an introduced carboxyl group-containing polyol compound. In the present invention, the anionic group-containing isocyanate-reactive compound (A3) is preferably a low molecular weight polyol compound having an anionic group, and in particular, a polyhydroxycarboxylic acid represented by the following formula (3) is preferably used. be able to.
(HO) _X L (COOH) _Y (3)
(However, in Formula (3), L shows a C1-C12 hydrocarbon site | part. X is an integer greater than or equal to 2, Y is an integer greater than or equal to 1.)

  In the formula (3), the hydrocarbon moiety of L is preferably an aliphatic hydrocarbon moiety, and may be either linear or branched. X and Y may be the same or different. Two or more hydroxyl groups may be bonded to the same carbon atom or may be bonded to different carbon atoms. Furthermore, when Y is 2 or more, two or more carboxyl groups may be bonded to the same carbon atom or may be bonded to different carbon atoms.

  As such a polyhydroxycarboxylic acid, dimethylolalkanoic acid (particularly 2,2-dimethylolalkanoic acid) is particularly suitable. Examples of the dimethylol alkanoic acid include 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid, 2,2-dimethylolpentanoic acid, 2,2-dimethylolhexanoic acid, 2,2-dimethylol. Examples include methylol heptanoic acid, 2,2-dimethylol octanoic acid, 2,2-dimethylol nonanoic acid, and 2,2-dimethylol decanoic acid.

  Examples of the anionic group-containing polyamine compound or the anionic group-containing polythiol compound as the anionic group-containing isocyanate-reactive compound (A3) include an anionic group-containing polyamine compound corresponding to the anionic group-containing polyol compound ( A polyaminecarboxylic acid corresponding to the polyhydroxycarboxylic acid represented by the formula (3)) or an anionic group-containing polythiol compound (such as a polythiolcarboxylic acid corresponding to the polyhydroxycarboxylic acid represented by the formula (3)). Etc.

[Polyisocyanate compound (A4)]
The polyisocyanate compound (A4) (polyisocyanate compound) is not particularly limited as long as it is a compound having at least two isocyanate groups in the molecule. A polyisocyanate compound (A4) can be used individually or in combination of 2 or more types.

  Examples of the polyisocyanate compound (A4) include various polyisocyanate compounds such as aliphatic polyisocyanate, alicyclic polyisocyanate, aromatic polyisocyanate, and araliphatic polyisocyanate.

  Examples of the aliphatic polyisocyanate include 1,3-trimethylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,3-pentamethylene diisocyanate, 1,5-pentamethylene diisocyanate, 1,6-hexa. Methylene diisocyanate, 1,2-propylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, 2-methyl-1,5-pentamethylene diisocyanate, 3-methyl -1,5-pentamethylene diisocyanate, 2,4,4-trimethyl-1,6-hexamethylene diisocyanate, 2,2,4-trimethyl-1,6-hexamethylene diisocyanate, 2,6-diisocyanate methyl caproate Lysine diiso Ane - and aliphatic diisocyanates such as bets and the like.

  Examples of the alicyclic polyisocyanate include 1,3-cyclopentane diisocyanate, 1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate, 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate, 4,4. '-Methylenebis (cyclohexyl isocyanate), methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, 1,3-bis (isocyanate methyl) cyclohexane, 1,4-bis (isocyanate methyl) cyclohexane, isophorone diisocyanate And alicyclic diisocyanates such as norbornane diisocyanate.

  Examples of aromatic polyisocyanates include m-phenylene diisocyanate, p-phenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, and naphthylene. 1,4-diisocyanate, naphthylene-1,5-diisocyanate, 4,4'-diphenyl diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane Isocyanate, 4,4'-diphenyl ether diisocyanate, 2-nitrodiphenyl-4,4'-diisocyanate, 2,2'-diphenylpropane-4,4'-diisocyanate, 3, 3'-dimethyldiphenylmethane-4,4'-diisocyanate, 4,4'-diphenylpropane diisocyanate, 3,3'-dimethoxydiphenyl-4, And aromatic diisocyanates such as 4'-diisocyanate.

  Examples of the araliphatic polyisocyanate include 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, ω, ω′-diisocyanate-1,4-diethylbenzene, 1,3-bis. Aroaliphatic diisocyanates such as (1-isocyanate-1-methylethyl) benzene, 1,4-bis (1-isocyanate-1-methylethyl) benzene, 1,3-bis (α, α-dimethylisocyanatomethyl) benzene Etc.

  Examples of the polyisocyanate compound (A4) include 1,6-hexamethylene diisocyanate, 4,4′-methylenebis (cyclohexyl isocyanate), 1,3-bis (isocyanatemethyl) cyclohexane, 1,4-bis (isocyanate). Methyl) cyclohexane, isophorone diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 1,3-xylylene diisocyanate 1,4-xylylene diisocyanate, norbornane diisocyanate, and 1,3-bis (α, α-dimethylisocyanatomethyl) benzene can be suitably used. In addition, if aliphatic polyisocyanate, alicyclic polyisocyanate, or araliphatic polyisocyanate is used as the polyisocyanate compound (A4), a resin with little discoloration can be obtained.

  In the present invention, the polyisocyanate compound (A4) is a dimer or trimer based on the above exemplified aliphatic polyisocyanate, alicyclic polyisocyanate, aromatic polyisocyanate, or araliphatic polyisocyanate. , Reaction products or polymers (eg diphenylmethane diisocyanate dimers and trimers, reaction products of trimethylolpropane and tolylene diisocyanate, reaction products of trimethylolpropane and hexamethylene diisocyanate, polymethylene Polyphenyl isocyanate, polyether polyisocyanate, polyester polyisocyanate, etc.) can also be used.

  In the present invention, a diisothiocyanate compound (for example, phenyl diisothiocyanate) can be used in combination with the polyisocyanate compound (A4).

[Chain extender (A5)]
The chain extender (A5) (chain extender) is not particularly limited and can be appropriately selected from known chain extenders (amine chain extender, polyol chain extender, etc.). A chain extender can be preferably used. A chain extender (A5) can be used individually or in combination of 2 or more types.

  In the chain extender (A5), the amine chain extender includes an amino group other than a tertiary amino group (disubstituted amino group) [primary amino group (unsubstituted amino group), An amine compound having one tertiary amino group (mono-substituted amino group, etc.) may be used, but a polyamine having a plurality of amino groups other than tertiary amino groups in the molecule can be suitably used. The number of amino groups (functional amino groups) other than the tertiary amino group in the polyamine molecule is not particularly limited as long as it is at least two. For example, 2 to 6 (preferably 2 to 4, More preferably, it can select from the range of 2-3).

  Specifically, as the amine chain extender, for example, the number average molecular weight exemplified as the anionic group-free polyamine compound in the section of the anionic group-free isocyanate-reactive compound (A2) is less than 500. These anionic group-free polyamine compounds (aliphatic polyamines, alicyclic polyamines, aromatic polyamines, araliphatic polyamines, hydrazine and derivatives thereof) can be appropriately selected and used. Examples of amine chain extenders include ethylenediamine, 1,3-pentamethylenediamine, 1,6-hexamethylenediamine, diethylenetriamine, triethylenetetramine, 4,4′-methylenebis (cyclohexylamine), 4,4′-methylenebis ( 3-methyl-cyclohexylamine), 1,3-bis (aminomethyl) cyclohexane, isophoronediamine, norbornanediamine, 1,3-xylylenediamine, and other aliphatic, alicyclic and araliphatic polyamines, hydrazine, carbo Hydrazine such as dihydrazide and derivatives thereof can be preferably used.

  Examples of the polyol chain extender include an anionic group having a number average molecular weight of less than 500 exemplified as an anionic group-free polyol compound in the section of an anionic group-free isocyanate-reactive compound (A2). Non-group-containing polyol compound (polyhydric alcohol, polyether polyol having a number average molecular weight of less than 500, polyester polyol having a number average molecular weight of less than 500, polycarbonate polyol having a number average molecular weight of less than 500, a number average molecular weight of less than 500 Polyolefin polyol, polyacryl polyol having a number average molecular weight of less than 500, tertiary amino group-containing polyol compound having a number average molecular weight of less than 500, and the like.

[Alkoxysilyl group side chain-containing water dispersible urethane prepolymer (A)]
In the present invention, as the water dispersible silylated urethane resin, an alkoxysilyl group side chain-containing water dispersible urethane prepolymer (A) can be suitably used. As described above, the alkoxysilyl group side chain-containing water-dispersible urethane prepolymer (A) includes the secondary amino group-containing alkoxysilane compound (A1) and the anionic group-free isocyanate-reactive compound (A2). Is a reaction product of an anionic group-containing isocyanate-reactive compound (A3), a polyisocyanate compound (A4), and, if necessary, a chain extender (A5). It is a urethane polymer having at least an alkoxysilyl group derived from the multiple-containing alkoxysilane compound (A1) and an anionic group derived from the anionic group-containing isocyanate-reactive compound (A3) in the molecule. Furthermore, the alkoxysilyl group side chain-containing water-dispersible urethane prepolymer (A) comprises an isocyanate group derived from the polyisocyanate compound (A4) and an amino group of the amine chain extender as the chain extender (A5). If necessary, it can have a urea binding site by reaction.

  Examples of the water-dispersible urethane prepolymer (A) containing an alkoxysilyl group include an anionic group-free isocyanate-reactive compound (A2), an anionic group-containing isocyanate-reactive compound (A3), and a polyisocyanate compound (A4). The anionic group-containing urethane prepolymer obtained by the above reaction and the secondary amino group-containing alkoxysilane compound (A1) are chain-extended by the reaction of the secondary amino group-containing alkoxysilane compound (A1). It may be an anionic group-containing urethane prepolymer introduced with a silyl group (sometimes referred to as “alkoxysilyl group side chain-introduced anionic group-containing urethane prepolymer”), and the alkoxysilyl group side chain-introduced anionic property The group-containing urethane prepolymer is further reacted with a chain extender (A5) , By reacting the remaining functional groups (such as isocyanate groups) in the alkoxysilyl group side chain-introduced anionic group-containing urethane prepolymer with functional groups (such as amino groups) of the chain extender (A5), It may be a chain-extended alkoxysilyl group side chain-introduced anionic group-containing urethane prepolymer.

  The method for preparing the alkoxysilyl group side chain-containing water-dispersible urethane prepolymer (A) is not particularly limited. The alkoxysilyl group side chain-containing water-dispersible urethane prepolymer (A) includes an anionic group-free isocyanate-reactive compound (A2), an anionic group-containing isocyanate-reactive compound (A3), a polyisocyanate compound ( A4) is reacted to obtain an anionic group-containing urethane prepolymer as a reaction product, and then the anionic group-containing urethane prepolymer is reacted with a secondary amino group-containing alkoxysilane compound (A1). If necessary, it can be further prepared by obtaining an alkoxysilyl group side chain-introduced anionic group-containing urethane prepolymer as a reaction product by further reacting with a chain extender (A5).

  The anionic group-containing urethane prepolymer is a reaction product of an anionic group-free isocyanate-reactive compound (A2), an anionic group-containing isocyanate-reactive compound (A3), and a polyisocyanate compound (A4). The reaction can be carried out according to a known or commonly used method for preparing a urethane prepolymer by reacting a polyol compound and a polyisocyanate compound. For example, an anionic group-free isocyanate-reactive compound (A2), Examples include a method in which the anionic group-containing isocyanate-reactive compound (A3) and the polyisocyanate compound (A4) are mixed and heated as necessary. The anionic group-containing urethane prepolymer preferably has an isocyanate group at the end.

  When mixing or reacting the anionic group-free isocyanate-reactive compound (A2), the anionic group-containing isocyanate-reactive compound (A3), and the polyisocyanate compound (A4), a polymerization catalyst is used to accelerate the reaction. be able to. Moreover, reaction or mixing can be performed in a solvent. In preparing the anionic group-containing urethane prepolymer, the polyisocyanate compound (A4) is added to a mixture of the anionic group-free isocyanate-reactive compound (A2) and the anionic group-containing isocyanate-reactive compound (A3). In addition, it is preferable to prepare an anionic group-containing urethane prepolymer by further adding a polymerization catalyst and reacting as necessary.

  In addition, the reaction between the anionic group-containing urethane prepolymer and the secondary amino group-containing alkoxysilane compound (A1) can be carried out by mixing both and heating as necessary. By reacting such an anionic group-containing urethane prepolymer with a secondary amino group-containing alkoxysilane compound (A1), an isocyanate group at the terminal of the anionic group-containing urethane prepolymer and a secondary amino group are obtained. The secondary amino group of the multiple-containing alkoxysilane compound (A1) reacts, and the anionic group-containing urethane prepolymer becomes chain-extended by the secondary amino group-containing alkoxysilane compound (A1). An alkoxysilyl group-side chain-introduced anionic group-containing urethane prepolymer having an alkoxysilyl group introduced into the chain [that is, an alkoxysilyl group-side chain-containing water-dispersible urethane prepolymer (A)] can be prepared. In this mixing or reaction, a polymerization catalyst can be used as described above. Moreover, a solvent can be used in the said mixing or reaction. In preparing the alkoxysilyl group side chain-introduced anionic group-containing urethane prepolymer, the reaction mixture obtained by the preparation of the anionic group-containing urethane prepolymer was added to the secondary amino group-containing alkoxysilane compound (A1). ) Is preferably reacted to prepare an alkoxysilyl group side chain-introduced anionic group-containing urethane prepolymer.

  As said polymerization catalyst, the well-known thru | or usual polymerization catalyst (curing catalyst) used when making a polyol compound and a polyisocyanate compound react can be used, for example. More specifically, examples of the polymerization catalyst include organic tin compounds, metal complexes, basic compounds such as amine compounds, and organic phosphoric acid compounds. Examples of the organic tin compound include dibutyltin dilaurate, dibutyltin malate, dibutyltin phthalate, stannous octylate, dibutyltin methoxide, dibutyltin diacetylacetate, dibutyltin diversate, and the like. Examples of metal complexes include titanate compounds such as tetrabutyl titanate, tetraisopropyl titanate, and triethanolamine titanate; carboxylate metal salts such as lead octylate, lead naphthenate, nickel naphthenate, and cobalt naphthenate; aluminum acetylacetate Examples thereof include metal acetylacetonate complexes such as narate complexes and vanadium acetylacetonate complexes. Furthermore, basic compounds such as amine compounds include, for example, aminosilanes such as γ-aminopropyltrimethoxysilane and γ-aminopropyltriethoxysilane; quaternary ammonium salts such as tetramethylammonium chloride and benzalkonium chloride. Linear or cyclic containing a plurality of nitrogen atoms, such as Sankyo Air Products' trade name “DABCO” series and “DABCO BL” series, 1,8-diazabicyclo [5.4.0] undec-7-ene; Tertiary amines or quaternary ammonium salts are included. Furthermore, examples of the organic phosphoric acid compound include monomethyl phosphoric acid, di-n-butyl phosphoric acid, and triphenyl phosphate.

  Further, the reaction between the alkoxysilyl group side chain-introduced anionic group-containing urethane prepolymer and the chain extender (A5) can be carried out by mixing both and heating as necessary. By this reaction, the remaining functional group (such as a terminal isocyanate group) in the alkoxysilyl group side chain-introduced anionic group-containing urethane prepolymer and the reactive group (such as an amino group) of the chain extender (A5) ), The alkoxysilyl group-side chain-introduced anionic group-containing urethane prepolymer is chain-extended by the chain extender (A5), and further chain-extended alkoxysilyl group-side chain-introduced anionic group-containing urethane A prepolymer [that is, an alkoxysilyl group side chain-containing water-dispersible urethane prepolymer (A)] can be prepared. In the mixing or reaction, a polymerization catalyst can be added in the same manner as described above. As a polymerization catalyst, the well-known thru | or usual polymerization catalyst (curing catalyst) used when making a polyol compound and a polyisocyanate compound react can be used, for example.

  In particular, the mixing or reaction of the alkoxysilyl group side chain-introduced anionic group-containing urethane prepolymer and the chain extender (A5) is performed by the alkoxysilyl group side chain-introduced anionic group-containing urethane prepolymer or a reaction mixture thereof ( It may be before, during or after dispersion in water (which may contain a basic compound), but is preferably during or after dispersion. That is, when the alkoxysilyl group side chain-introduced anionic group-containing urethane prepolymer is dispersed in water, the chain extender (A5) is added with water, or after being dispersed in water, the chain extender (A5) It is preferable that the alkoxysilyl group side chain-introduced anionic group-containing urethane prepolymer is reacted with the chain extender (A5). Specifically, when the chain extender (A5) is used, the reaction is performed by adding the secondary amino group-containing alkoxysilane compound (A1) to the reaction mixture obtained by preparing the anionic group-containing urethane prepolymer. To prepare an alkoxysilyl group side chain-introduced anionic group-containing urethane prepolymer, and then add a chain extender (A5) together with water to obtain an alkoxysilyl group side-chain-introduced anionic group-containing urethane prepolymer. When dispersed in water, the alkoxysilyl group side chain-introduced anionic group-containing urethane prepolymer is chain-extended with a chain extender (A5), and the chain-extended alkoxysilyl group side chain-introduced anionic group-containing urethane prepolymer Is preferably prepared.

  In the alkoxysilyl group side chain-containing water-dispersible urethane prepolymer (A), the ratio of each component is not particularly limited. Specifically, for example, the ratio of the polyisocyanate compound (A4) to the anionic group-free isocyanate-reactive compound (A2) and the anionic group-containing isocyanate-reactive compound (A3) is the polyisocyanate compound (A4). ) Is an isocyanate-reactive group (NCO / NCO-reactive group) (equivalent ratio) in the isocyanate group / anionic group-free isocyanate-reactive compound (A2) and the anionic group-containing isocyanate-reactive compound (A3). It can be selected from a range that is 2.0 or less (preferably 1.02 to 1.5, more preferably 1.05 to 1.4). When the ratio of NCO / NCO reactive groups exceeds 2.0 (equivalent ratio), unreacted monomer components remain, so that it becomes difficult to control the reaction (crosslinking reaction) during extension or dispersion. The sex will be reduced. On the other hand, when the ratio of NCO / NCO reactive groups is 1 or less, it becomes difficult to obtain a urethane prepolymer having an isocyanate group at the end.

  Alternatively, the polyisocyanate compound (A4) has an isocyanate group content in the anionic group-containing urethane prepolymer of 0.1 to 20% by mass (preferably 0.2 to 15% by mass, more preferably 0.3%). -10 mass%).

  The anionic group-containing isocyanate-reactive compound (A3) has an anionic group content of 0.1 meq / g or more (for example, 0) in the alkoxysilyl group side chain-containing water-dispersible urethane prepolymer (A). .2 to 0.8 meq / g, preferably 0.2 to 0.7 meq / g). When there is too much content of this anionic group, while the viscosity of silylated urethane type aqueous composition will become high and workability | operativity will fall, the water resistance after hardening will also fall. On the other hand, when the content of the anionic group is too small (for example, less than 0.1 meq / g), the dispersion stability of the resin component in the silylated urethane-based aqueous composition is lowered and the tack force is reduced. descend.

  In the secondary amino group-containing alkoxysilane compound (A1), the content of silicon atoms in the alkoxysilyl group side chain-containing water-dispersible urethane prepolymer (A) is, for example, 0.01 meq / g or more. It may be used at a high rate, and is preferably used at a rate of 0.02 meq / g or more (more preferably a rate of 0.05 meq / g or more).

  Accordingly, in the water-dispersible silylated urethane resin [alkoxysilyl group side chain-containing water-dispersible urethane prepolymer (A), etc.], the alkoxysilyl group (monoalkoxysilyl group, dialkoxy) introduced as a side chain in the molecule. As described above, the number of silyl groups or trialkoxysilyl groups can be appropriately set from one or more ranges in one molecule. Thus, since the water dispersible silylated urethane resin contains an alkoxysilyl group as a side chain, it can contain three or more in one molecule. Of course, the water dispersible silylated urethane resin may contain 1 to 2 alkoxysilyl groups in one molecule.

  The chain extender (A5) is used in an anionic group-containing urethane prepolymer and an alkoxysilyl group side chain-introduced anionic group obtained by the reaction of a secondary amino group-containing alkoxysilane compound (A1). It is preferable to react with a functional group (such as a terminal isocyanate group) in the urethane prepolymer in an equivalent amount in a stoichiometric manner, but during or after water dispersion of the alkoxysilyl group side chain-containing water-dispersible urethane prepolymer (A). When the chain extender (A5) is added, the reaction between the chain extender (A5) and water is considered depending on the reaction apparatus and stirring conditions, and 0.5 to 1 equivalent of the functional group (isocyanate group, etc.) You may select from the range of 1.0 equivalent.

[Basic compounds]
In the present invention, the water dispersible silylated urethane resin is a water dispersible silylated urethane resin having an anionic group in the molecule (referred to as “anionic group-containing water dispersible silylated urethane resin”). [For example, when it is an alkoxysilyl group side chain-containing water-dispersible urethane prepolymer (A) (that is, an alkoxysilyl group side chain-introduced anionic group-containing urethane prepolymer)], silylated urethane In the aqueous system composition, a basic compound may be contained. By using a basic compound, an anionic group-containing water-dispersible silylated urethane resin (for example, an alkoxysilyl group side chain-introduced anionic group-containing urethane prepolymer, etc.) is converted into a salt form to be water-soluble or water-dispersible. Can be.

  The basic compound may be a basic inorganic compound or a basic organic compound. A basic compound can be used individually or in combination of 2 or more types. Examples of the basic inorganic compound include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; alkali metal carbonates such as sodium carbonate and potassium carbonate; alkali metal hydrogen carbonates such as sodium hydrogen carbonate and potassium hydrogen carbonate ; Alkali metal compounds such as alkali metal acetates such as sodium acetate and potassium acetate; alkaline earth metal hydroxides such as magnesium hydroxide; alkaline earth metal compounds such as alkaline earth metal carbonates such as magnesium carbonate; In addition, ammonia can be preferably used.

  On the other hand, as the basic organic compound, for example, amine compounds such as aliphatic amines, aromatic amines and basic nitrogen-containing heterocyclic compounds can be suitably used. Examples of the aliphatic amine include trialkylamines such as trimethylamine, triethylamine, tripropylamine, triisopropylamine, tributylamine, triisobutylamine, tris-butylamine, tri-t-butylamine, tripentylamine, and trihexylamine; Dialkylamines such as dimethylamine, diethylamine, and dibutylamine; monoalkylamines such as methylamine, ethylamine, and butylamine; trimethanolamine, triethanolamine, tripropanolamine, triisopropanolamine, tributanolamine, tripentanolamine, Trialcoholamines such as isopentanolamine and trihexanolamine; dialcohols such as dimethanolamine and diethanolamine Triethanolamine; methanol amine, other such monoalcohols amines such as ethanolamine, ethylenediamine, diethylenetriamine and the like. Aromatic amines include, for example, N, N-dimethylaniline. Examples of basic nitrogen-containing heterocyclic compounds include cyclic amines such as morpholine, piperidine, and pyrrolidine, as well as pyridine, α-picoline, β-picoline, γ-picoline, quinoline, N-methylmorpholine, and the like.

  As the basic compound, ammonia and amine compounds (tertiary amine compounds such as trialkylamine and trialcoholamine) can be suitably used.

[water]
In the silylated urethane-based aqueous composition of the present invention, water (for example, tap water, ion exchange water, pure water, etc.) is used.

[Silylated urethane-based aqueous composition]
As described above, the silylated urethane-based aqueous composition of the present invention contains a water-dispersible silylated urethane-based resin and, of course, also contains water. In the silylated urethane-based aqueous composition of the present invention, the water-dispersible silylated urethane-based resin is an anionic group-containing water-dispersible silylated urethane-based resin (for example, an alkoxysilyl group side chain-introduced anionic group-containing urethane). In the case of a (prepolymer), the anionic group-containing water-dispersible silylated urethane resin may have a salt form. Therefore, as described above, a substance (for example, a basic compound or an acid) for forming a salt is used for a water-dispersible silylated urethane resin such as an anionic group-containing water-dispersible silylated urethane resin. It may be done.

  The water dispersible silylated urethane resin may react with water. Examples of the reaction between the water-dispersible silylated urethane resin and water include a hydrolysis reaction in which the side-chain alkoxysilyl group in the water-dispersible silylated urethane resin is hydrolyzed by water. That is, by reaction of water-dispersible silylated urethane resin with water, the side-chain alkoxysilyl groups in the water-dispersible silylated urethane resin partially or entirely become silanol groups and / or siloxane bonds. It may be. The silanol group means a group composed of a silicon atom having at least one hydroxyl group, and may have a substituent such as an alkoxy group.

  Accordingly, when the water-dispersible silylated urethane resin is an anionic group-containing water-dispersible silylated urethane resin, the silylated urethane-based aqueous composition is an anion in the anionic group-containing water-dispersible silylated urethane resin. The neutral group is neutralized with a basic compound to form a salt of an anionic group, and the side-chain alkoxysilyl group is partially or entirely hydrolyzed with water to form a silanol group and / or a siloxane bond. An aqueous silanolated urethane-based resin may be included.

  In addition, the basic compound as a water dispersing agent may be used after preparing an anionic group-containing water-dispersible silylated urethane resin, and an anionic group-containing water-dispersible silylated urethane resin is prepared. May be used in advance. The amount of the basic compound used is selected from the range of about 50 to 120 mol% (preferably 80 to 110 mol%) with respect to the anionic group in the anionic group-containing water-dispersible silylated urethane resin. Can do.

  Water may be used after preparing a water-dispersible silylated urethane resin (such as an anionic group-containing water-dispersible silylated urethane resin), and prepares a water-dispersible silylated urethane resin. It may be used in advance. The amount of water used can be selected from a range of about 65 to 900 parts by mass (preferably 100 to 400 parts by mass) with respect to 100 parts by mass of the water dispersible silylated urethane resin.

  In addition, in the silylated urethane type aqueous composition of this invention, although it does not restrict | limit especially as a resin part, For example, it can select from the range of about 10-60 mass% (preferably 20-50 mass%).

  The silylated urethane-based aqueous composition of the present invention is preferably a completely aqueous silylated urethane-based composition that does not contain any organic solvent. For adjusting viscosity, ketones, lower alcohols, etc. The hydrophilic organic solvent (water-soluble organic solvent) may be included.

  Examples of the silylated urethane-based aqueous composition include wettability-modified hydrophilic solvents (for example, surfactants such as N-methyl-2-pyrrolidone and polyoxyethylene alkyl ether, sodium alginate, mucopolysaccharide, Sodium acrylate, etc.), fillers (for example, calcium carbonate, fumed silica, clay, talc, various balloons, noble silica, kaolin, aluminum silicate, etc.), plasticizers (for example, phthalic acid esters such as dioctyl phthalate, dibutyl phthalate) Class: aliphatic carboxylic acid esters such as dioctyl adipate and dibutyl sebacate), anti-aging agents, UV absorbers, antioxidants, heat stabilizers, colorants (pigments and dyes), fungicides, wettability Agents, viscosity improvers, fragrances, various tackifiers (eg, stabilized rosin Stealth, polymerized rosin ester, terpene phenol, emulsion tackifiers such as petroleum resins, etc.), coupling agents (titanate coupling agents, aluminum coupling agents, etc.), photocuring catalysts, emulsifiers, surfactants, emulsions, etc. Latex, crosslinking agent (eg, isocyanate crosslinking agent, epoxy crosslinking agent, carbodiimide crosslinking agent, aziridine crosslinking agent, polyethyleneimine crosslinking agent, melamine crosslinking agent, colloidal silica, etc.), humectant, antifoaming agent, etc. The various additives or components, solvents, and the like may be included.

  Further, in the silylated urethane-based aqueous composition, together with the water-dispersible silylated urethane-based resin having a structure in which at least one alkoxysilyl group is introduced as a side chain in the molecule, the water-dispersible silyl Water-soluble or water-dispersible polymers other than fluorinated urethane resins (for example, silylated urethane-based resins having an alkoxysilyl group at the terminal and water-soluble or water-dispersible, and alkoxysilyl groups at the terminal or side chain) And a water-soluble or water-dispersible polyurethane-based polymer, polyvinyl pyrrolidone, etc.).

[Water-based adhesives, etc.]
The silylated urethane-based aqueous composition of the present invention can be used as a water-based adhesive or a water-based coating agent (water-based paint or the like), and can be particularly preferably used as a water-based adhesive. The silylated urethane-based aqueous composition can be used as a binder, laminate, sealer, primer, sizing agent, sealing material and the like in addition to the aqueous adhesive and the aqueous coating agent. That is, various treatment agents such as an aqueous adhesive and an aqueous coating agent contain the silylated urethane-based aqueous composition.

  The water-based adhesive or water-based coating agent containing the silylated urethane-based aqueous composition is water having a structure in which the silylated urethane-based aqueous composition has at least one alkoxysilyl group introduced as a side chain in the molecule. Because it contains a dispersible silylated urethane resin, it is possible to improve adhesiveness, adhesion, film properties, or storage stability and to exhibit excellent water resistance and / or heat resistance. Can do.

  Moreover, in the water-dispersible silylated urethane resin [particularly, the alkoxysilyl group side chain-containing water-dispersible urethane prepolymer (A)], the alkoxysilyl group introduced as a side chain in the molecule is partly in water. It can exist stably in the state which hydrolyzed by water or entirely by the water, and became the silanol group and / or the siloxane bond. Therefore, the aqueous adhesive containing the silylated urethane-based aqueous composition of the present invention, the aqueous coating agent, and the like are one-component treatment agents such as a one-component aqueous adhesive and a one-component aqueous coating agent. can do.

  Since these water-based adhesives and water-based coating agents are water-based types (especially, they may be completely water-free without any organic solvent), they are excellent in handling and workability. High safety for the environment.

  In addition, since the alkoxysilyl group of the water dispersible silylated urethane resin [particularly, alkoxysilyl group side chain-containing water dispersible urethane prepolymer (A)] is in the form of a silanol group or the like, the silylated urethane series Aqueous adhesives (particularly aqueous contact adhesives) and aqueous coating agents containing aqueous compositions are good not only for porous materials such as paper, but also for nonporous materials such as metals and glass. Adhesiveness and adhesion can be expressed. That is, various base materials can be used as the base material (adhered body, coated body, etc.) to which the water-based adhesive or the water-based coating agent can be applied, as shown in specific examples below. In addition, as a base material at the time of bonding together by adhesion | attachment, the base materials which consist of the same raw material may be sufficient, and the base material which consists of a different raw material may be sufficient. The substrates may be used alone or in combination of two or more.

  The substrate may be, for example, a porous material or a non-porous material. More specifically, examples of the material of the adherend include wood materials such as wood, plywood, chipboard, particle board and hard board; inorganic materials such as slate board, quartz board, mortar and tile; melamine resin makeup Plastic materials such as plates, bakelite plates, polystyrene foam, various plastic films or molded articles (for example, polyvinyl chloride films or molded articles, polyester films or molded articles, polystyrene films or molded articles, polyolefin films or molded articles, etc.) Rubber materials such as natural rubber, synthetic rubber and silicon rubber; paper materials such as corrugated paper, paperboard and kraft paper, and hard-to-bond paper such as processed paper (for example, surface-treated processed paper such as moisture-proof paper) Material, glass material, metal material (eg iron, aluminum, stainless steel, copper ), Leather materials, fabrics, etc. fibrous material such as nonwoven fabric and the like.

  Thus, the aqueous adhesive or aqueous coating agent containing the silylated urethane-based aqueous composition of the present invention can be applied to substrates made of a wide range of materials. It can also be used for adhesion between porous materials.

  The method for bonding the adherends using an aqueous adhesive containing a silylated urethane-based aqueous composition is not particularly limited. For example, after applying to the adherends, the adherends are pasted immediately. Various methods such as a bonding method and a contact bonding method for adhering adherends to each other in a state where water is retained and adhesiveness is developed after a predetermined time has elapsed after being applied to the adherends. Can be adopted. In the present invention, as a contact bonding method, as defined in JIS K 6800, it is applied to the bonding surfaces of both adherends in the two adherends to be bonded, and a predetermined time elapses. Not only the method of adhering and adhering two adherends in a state where the water is retained and the adhesiveness is expressed, but also adhering one of the adherends to the two adherends to be bonded together A method is also included in which two adherends are bonded and adhered to each other in a state where water is retained and adhesiveness is developed after a predetermined time has elapsed. That is, in the present invention, the contact adhesion is a state where the adhesive is applied to at least one of the adherends to be bonded and retains water after a predetermined time and also exhibits adhesiveness. This means that the two adherends are bonded and bonded together.

  EXAMPLES Hereinafter, although an Example demonstrates this invention more concretely, this invention is not limited by these Examples. In the following, “part” means “part by mass” and “%” means “% by mass” unless otherwise specified.

(Preparation example of alkoxysilane compound (A1) containing a plurality of secondary amino groups)
(1) Trade name “KBM603” [manufactured by Shin-Etsu Chemical Co., Ltd., N-β (aminoethyl) -γ-aminopropyltrimethoxysilane]: 222.4 parts, 2-ethylhexyl acrylate: 184.3 parts Used in proportions, mixed and reacted at 50 ° C. for 28 days to give 2-ethylhexyl to the primary amino group (unsubstituted amino group) in N-β (aminoethyl) -γ-aminopropyltrimethoxysilane. A reaction mixture containing a secondary amino group-containing alkoxysilane compound (A1) having an acrylate addition form [sometimes referred to as “silylating agent (A)”] was obtained.
(2) Trade name “KBM603” [manufactured by Shin-Etsu Chemical Co., Ltd., N-β (aminoethyl) -γ-aminopropyltrimethoxysilane]: 222.4 parts, ratio of isostearyl acrylate: 324.6 parts And mixed, and reacted at 50 ° C. for 28 days. Isostearyl acrylate is converted to the primary amino group (unsubstituted amino group) in N-β (aminoethyl) -γ-aminopropyltrimethoxysilane. A reaction mixture containing a secondary amino group-containing alkoxysilane compound (A1) having an added form (sometimes referred to as “silylating agent (B)”) was obtained.
(3) Trade name “KBM603” [manufactured by Shin-Etsu Chemical Co., Ltd., N-β (aminoethyl) -γ-aminopropyltrimethoxysilane]: 222.4 parts, but in a ratio of butyl acrylate: 128.2 parts. Used, mixed and reacted at 50 ° C. for 28 days, and butyl acrylate was added to the primary amino group (unsubstituted amino group) in N-β (aminoethyl) -γ-aminopropyltrimethoxysilane A reaction mixture containing a secondary amino group-containing alkoxysilane compound (A1) having the formula [sometimes referred to as “silylating agent (C)”] was obtained.
(4) Product name “KBM603” [manufactured by Shin-Etsu Chemical Co., Ltd., N-β (aminoethyl) -γ-aminopropyltrimethoxysilane]: 222.4 parts, methyl acrylate: 86.1 parts Used, mixed, and reacted at 50 ° C. for 28 days to add methyl acrylate to the primary amino group (unsubstituted amino group) in N-β (aminoethyl) -γ-aminopropyltrimethoxysilane. A reaction mixture containing a secondary amino group-containing alkoxysilane compound (A1) having a form [sometimes referred to as “silylating agent (D)”] was obtained.
(5) Trade name “KBM602” [manufactured by Shin-Etsu Chemical Co., Ltd., N-β (aminoethyl) -γ-aminopropylmethyldimethoxysilane]: 206.4 parts, but in a ratio of butyl acrylate: 128.2 parts. Used, mixed and reacted at 50 ° C. for 28 days to add butyl acrylate to the primary amino group (unsubstituted amino group) in N-β (aminoethyl) -γ-aminopropylmethyldimethoxysilane. A reaction mixture containing a secondary amino group-containing alkoxysilane compound (A1) having a form [sometimes referred to as “silylating agent (E)”] was obtained.

(Alkoxysilane compound containing secondary amino group and primary amino group)
(1) Product name “KBM603” [manufactured by Shin-Etsu Chemical Co., Ltd., N-β (aminoethyl) -γ-aminopropyltrimethoxysilane; sometimes referred to as “silylating agent (F)”]

(Preparation example of alkoxysilane compound containing a single secondary amino group)
(1) Trade name “KBE903” [manufactured by Shin-Etsu Chemical Co., Ltd., γ-aminopropyltriethoxysilane]: 221.4 parts, mixed with lauryl acrylate: 240.4 parts, mixed at 50 ° C. Reaction mixture containing an alkoxysilane compound having a form in which lauryl acrylate is added to a primary amino group in γ-aminopropyltriethoxysilane [“silylating agent (G)” May be referred to as].
(2) Trade name “KBE903” [manufactured by Shin-Etsu Chemical Co., Ltd., γ-aminopropyltriethoxysilane]: 221.4 parts with respect to isostearyl acrylate: 324.6 parts, mixed, and 50 The reaction mixture containing an alkoxysilane compound having a form in which isostearyl acrylate is added to a primary amino group in γ-aminopropyltriethoxysilane after reacting at 28 ° C. for 28 days [“silylating agent (H ) ”.
(3) Trade name “KBM603” [manufactured by Shin-Etsu Chemical Co., Ltd., N-β (aminoethyl) -γ-aminopropyltrimethoxysilane]: 222.4 parts, 2-ethylhexyl acrylate: 368.6 parts The primary amino group (unsubstituted amino group) and secondary amino group in N-β (aminoethyl) -γ-aminopropyltrimethoxysilane were reacted at 50 ° C. for 28 days. A reaction mixture containing an alkoxysilane compound having a form in which 2-ethylhexyl acrylate was added to the group [may be referred to as “silylating agent (I)”] was obtained.
(4) Proportion of trade name “KBM603” [manufactured by Shin-Etsu Chemical Co., Ltd., N-β (aminoethyl) -γ-aminopropyltrimethoxysilane]: 222.4 parts, ratio of isostearyl acrylate: 649.1 parts The primary amino group (unsubstituted amino group) and the secondary amino group in N-β (aminoethyl) -γ-aminopropyltrimethoxysilane were mixed and reacted at 50 ° C. for 28 days. In addition, a reaction mixture containing an alkoxysilane compound having a form to which isostearyl acrylate was added [may be referred to as “silylating agent (J)”] was obtained.

[Anionic group-free isocyanate-reactive compound (A2)]
(1) Trade name “PTMG2000” (manufactured by Mitsubishi Chemical Corporation, polytetramethylene ether glycol, number average molecular weight: 2000, hydroxyl value: 58.2 mg-KOH / g; sometimes referred to as “PTMG2000”)
(2) Product name “NS2400” (manufactured by Asahi Denka Kogyo Co., Ltd., polyester diol, number average molecular weight: 2000, hydroxyl value: 56.2 mg-KOH / g; sometimes referred to as “NS2400”)
(3) Trade name “Byron 220” (manufactured by Toyobo Co., Ltd., polyester diol, number average molecular weight: 2000, hydroxyl value: 50 mg-KOH / g; sometimes referred to as “Byron 220”)
(4) Product name “T4672” (manufactured by Asahi Kasei Chemicals Corporation, polycarbonate diol, number average molecular weight: 2000, hydroxyl value: 54.3 mg-KOH / g; sometimes referred to as “T4672”)
(5) 1,4-butanediol (hydroxyl value: 1245.3 mg-KOH / g; sometimes referred to as “1,4-BD”)
(6) 1,6-hexanediol (hydroxyl value: 949.5 mg-KOH / g; sometimes referred to as “1,6-HD”)

[Anionic group-containing isocyanate-reactive compound (A3)]
(1) 2,2-dimethylolpropionic acid (hydroxyl value: 832.0 mg-KOH / g; sometimes referred to as “DMPA”)

[Polyisocyanate compound (A4)]
(1) Isophorone diisocyanate [isocyanate content (NCO content): 37.8%; may be referred to as “IPDI”]

[Chain extender (A5)]
(1) Isophoronediamine (sometimes referred to as “IPDA”)

[Basic compounds]
(1) Triethylamine

[Secondary amino group-containing compound]
(1) Di-n-butylamine (sometimes referred to as “dibutylamine”)

[water]
(1) Ion exchange water (deionized water)

[catalyst]
(1) Dibutyltin dilaurate

Example 1
In a four-necked flask equipped with a nitrogen inlet tube, a thermometer, a condenser and a stirrer, PTMG2000: 80 parts, DMPA: 14.6 parts, IPDI: 120.1 parts, 1,4-BD: 18.7 parts, And methyl ethyl ketone (MEK): 200 parts, dibutyltin dilaurate diluted to 5% with MEK as a catalyst: 0.01 part, and reacted at a temperature of 80 to 85 ° C. in a nitrogen stream for 5 hours to obtain residual isocyanate A reaction mixture containing 6.6% anionic group-containing isocyanate group-terminated urethane prepolymer was obtained.

  Next, after cooling to 60 ° C., the total amount of the reaction mixture containing the anionic group-containing isocyanate group-terminated urethane prepolymer is added with a silylating agent (A): 47.4, which is a secondary amino group-containing alkoxysilane compound. After mixing and mixing the parts, the reaction is carried out at a temperature of 70 ° C. under a nitrogen stream for 1.5 hours, and contains an alkoxysilyl group side chain-containing water-dispersible urethane prepolymer having a residual isocyanate group of 2.0%. A reaction mixture was obtained.

  Next, after cooling the total amount of the reaction mixture containing the alkoxysilyl group side chain-containing water-dispersible urethane prepolymer to 40 ° C., triethylamine: 11.09 parts is blended, and dibutylamine: 3.48 in advance under high-speed stirring. Part and IPDA: 7.34 parts dissolved in ion-exchanged water: 845 parts was added to obtain a dispersion. After MEK was distilled off from this dispersion at 40 to 45 ° C. under reduced pressure, the solid content was adjusted to 25.1% by mass with ion-exchanged water, and the viscosity (23 ° C .; BM viscometer, rotor: No. 1, the number of rotations: 30 rpm) was 145 mPa · s, and a urethane-based aqueous composition having a silyl group in the side chain was obtained.

  The urethane-based aqueous composition was stored at room temperature for 60 days and at 50 ° C. for 30 days, respectively, but neither gelation nor separation occurred, and the viscosity was within ± 30% of the initial viscosity, It showed good storage stability. In addition, the urethane-based aqueous composition after storage was evaluated for water resistance, solvent resistance and adhesion in accordance with the following evaluation method. The initial urethane-based aqueous composition (urethane-based aqueous composition before storage) ) Was maintained.

(Example 2)
In a four-necked flask equipped with a nitrogen inlet tube, a thermometer, a condenser and a stirrer, PTMG2000: 80 parts, DMPA: 14.6 parts, IPDI: 120.1 parts, 1,4-BD: 18.7 parts, And methyl ethyl ketone (MEK): 200 parts, dibutyltin dilaurate diluted to 5% with MEK as a catalyst: 0.01 part, and reacted at a temperature of 80 to 85 ° C. in a nitrogen stream for 5 hours to obtain residual isocyanate A reaction mixture containing 6.6% anionic group-containing isocyanate group-terminated urethane prepolymer was obtained.

  Next, after cooling to 60 ° C., 62 parts of silylating agent (B), which is a secondary amino group-containing alkoxysilane compound, is added to the total amount of the reaction mixture containing the anionic group-containing isocyanate group-terminated urethane prepolymer. After mixing and mixing, the reaction mixture is reacted at a temperature of 70 ° C. under a nitrogen stream for 1.5 hours, and contains a water-dispersible urethane prepolymer containing an alkoxysilyl group side chain containing 2.0% of the remaining isocyanate groups. Got.

  Next, after cooling the total amount of the reaction mixture containing the alkoxysilyl group side chain-containing water-dispersible urethane prepolymer to 40 ° C., 11.02 parts of triethylamine is blended, and dibutylamine: 3.64 in advance under high-speed stirring. Part and IPDA: 7.67 parts dissolved in ion exchange water: 710 parts was added to obtain a dispersion. After MEK was distilled off at 40 to 45 ° C. under reduced pressure, the solid content was adjusted to 29.5% by mass with ion-exchanged water, and the viscosity (23 ° C .; BM type viscometer, rotor: No. 1, the number of rotations: 30 rpm) was 55 mPa · s, and a urethane-based aqueous composition having a silyl group in the side chain was obtained.

  The urethane-based aqueous composition was stored in the same manner as in Example 1 for 60 days at room temperature and 30 days at 50 ° C., but neither gelation nor separation occurred. It was within ± 30% of the value and showed good storage stability. Moreover, when the water-based urethane composition after storage was evaluated for water resistance, solvent resistance and adhesion in the same manner as in Example 1, the performance equivalent to that of the initial urethane-based aqueous composition was maintained.

(Example 3)
In a four-necked flask equipped with a nitrogen inlet tube, a thermometer, a condenser and a stirrer, PTMG2000: 80 parts, DMPA: 14.6 parts, IPDI: 120.1 parts, 1,4-BD: 24.3 parts, And 200 parts of methyl ethyl ketone (MEK), dibutyltin dilaurate diluted to 5% with MEK as a catalyst: 0.01 part, reacted at 80 to 85 ° C. in a nitrogen stream for 6 hours to obtain residual isocyanate A reaction mixture containing 4.3% anionic group-containing isocyanate group-terminated urethane prepolymer was obtained.

  Next, after cooling to 60 ° C., 24 parts of silylating agent (A), which is a secondary amino group-containing alkoxysilane compound, is added to the total amount of the reaction mixture containing the anionic group-containing isocyanate group-terminated urethane prepolymer. After mixing and mixing, the reaction mixture is reacted at a temperature of 70 ° C. under a nitrogen stream for 1.5 hours, and contains a water-dispersible urethane prepolymer containing an alkoxysilyl group side chain containing 2.0% of the remaining isocyanate groups. Got.

  Next, after cooling the total amount of the reaction mixture containing the alkoxysilyl group side chain-containing water-dispersible urethane prepolymer to 40 ° C., 11.02 parts of triethylamine was added, and dibutylamine: 3.23 was previously added under high-speed stirring. Part and IPDA: 6.81 parts dissolved in ion-exchanged water: 755 parts were added to obtain a dispersion. After the MEK was distilled off from this dispersion at 40 to 45 ° C. under reduced pressure, the solid content was adjusted to 26.0 mass% with ion-exchanged water, and the viscosity (23 ° C .; BM viscometer, rotor: No. 1, the number of rotations: 30 rpm) was 155 mPa · s, and a urethane-based aqueous composition having a silyl group in the side chain was obtained.

  The urethane-based aqueous composition was stored in the same manner as in Example 1 for 60 days at room temperature and 30 days at 50 ° C., but neither gelation nor separation occurred. It was within ± 30% of the value and showed good storage stability. Moreover, when the water-based urethane composition after storage was evaluated for water resistance, solvent resistance and adhesion in the same manner as in Example 1, the performance equivalent to that of the initial urethane-based aqueous composition was maintained.

Example 4
In a four-necked flask equipped with a nitrogen inlet tube, a thermometer, a condenser and a stirrer, PTMG2000: 80 parts, DMPA: 14.6 parts, IPDI: 120.1 parts, 1,4-BD: 27.8 parts, And methyl ethyl ketone (MEK): 200 parts, dibutyltin dilaurate diluted to 5% with MEK as a catalyst: 0.01 part, and reacted at a temperature of 80 to 85 ° C. in a nitrogen stream for 8 hours to obtain residual isocyanate A reaction mixture containing an anionic group-containing isocyanate group-terminated urethane prepolymer having a group of 2.9% was obtained.

  Next, after cooling to 60 ° C., 9 parts of silylating agent (A), which is a secondary amino group-containing alkoxysilane compound, is added to the total amount of the reaction mixture containing the anionic group-containing isocyanate group-terminated urethane prepolymer. After mixing and mixing, the reaction mixture is reacted at a temperature of 70 ° C. under a nitrogen stream for 1.5 hours, and contains a water-dispersible urethane prepolymer containing an alkoxysilyl group side chain containing 2.0% of the remaining isocyanate groups. Got.

  Next, after cooling the total amount of the reaction mixture containing the alkoxysilyl group side chain-containing water-dispersible urethane prepolymer to 40 ° C., triethylamine: 11.02 parts were blended, and dibutylamine: 3.13 in advance under high-speed stirring. Part and IPDA: 6.60 parts dissolved in ion-exchanged water: 750 parts was added to obtain a dispersion. After MEK was distilled off at 40 to 45 ° C. under reduced pressure, the dispersion was adjusted to 25.2% by mass with ion-exchanged water, and the viscosity (23 ° C .; BM viscometer, rotor: No. 1, the number of rotations: 30 rpm) was 175 mPa · s, and a urethane-based aqueous composition having a silyl group in the side chain was obtained.

  The urethane-based aqueous composition was stored in the same manner as in Example 1 for 60 days at room temperature and 30 days at 50 ° C., but neither gelation nor separation occurred. It was within ± 30% of the value and showed good storage stability. Moreover, when the water-based urethane composition after storage was evaluated for water resistance, solvent resistance and adhesion in the same manner as in Example 1, the performance equivalent to that of the initial urethane-based aqueous composition was maintained.

(Example 5)
In a four-necked flask equipped with a nitrogen inlet tube, a thermometer, a condenser and a stirrer, PTMG2000: 80 parts, DMPA: 14.6 parts, IPDI: 120.1 parts, 1,4-BD: 18.7 parts, And methyl ethyl ketone (MEK): 200 parts, dibutyltin dilaurate diluted to 5% with MEK as a catalyst: 0.01 part, and reacted at a temperature of 80 to 85 ° C. in a nitrogen stream for 5 hours to obtain residual isocyanate A reaction mixture containing 6.6% anionic group-containing isocyanate group-terminated urethane prepolymer was obtained.

  Next, after cooling to 60 ° C., the total amount of the reaction mixture containing the anionic group-containing isocyanate group-terminated urethane prepolymer is added to the silylating agent (A): 47.4, which is a secondary amino group-containing alkoxysilane compound. After mixing and mixing the parts, the mixture is reacted at a temperature of 70 ° C. under a nitrogen stream for 1.5 hours, and contains an alkoxysilyl group side chain-containing water-dispersible urethane prepolymer having a residual isocyanate group of 2.0%. A reaction mixture was obtained.

  Next, after cooling the total amount of the reaction mixture containing the alkoxysilyl group side chain-containing water-dispersible urethane prepolymer to 40 ° C., 11.02 parts of triethylamine was added, and dibutylamine: 0.35 in advance under high-speed stirring. Part and IPDA: 9.35 parts dissolved in ion-exchanged water: 705 parts were added to obtain a dispersion. After the MEK was distilled off from this dispersion at 40 to 45 ° C. under reduced pressure, the solid content was adjusted to 28.8 mass% with ion-exchanged water, and the viscosity (23 ° C .; BM viscometer, rotor: No. 2, the rotation speed: 30 rpm) was 225 mPa · s, and a urethane-based aqueous composition having a silyl group in the side chain was obtained.

  The urethane-based aqueous composition was stored in the same manner as in Example 1 for 60 days at room temperature and 30 days at 50 ° C., but neither gelation nor separation occurred. It was within ± 30% of the value and showed good storage stability. Moreover, when the water-based urethane composition after storage was evaluated for water resistance, solvent resistance and adhesion in the same manner as in Example 1, the performance equivalent to that of the initial urethane-based aqueous composition was maintained.

(Example 6)
NS2400: 80 parts, DMPA: 14.6 parts, IPDI: 119.9 parts, 1,6-HD: 24.3 parts, in a four-necked flask equipped with a nitrogen inlet tube, thermometer, condenser and stirrer, And methyl ethyl ketone (MEK): 200 parts, dibutyltin dilaurate diluted to 5% with MEK as a catalyst: 0.01 part, and reacted at a temperature of 80 to 85 ° C. in a nitrogen stream for 5 hours to obtain residual isocyanate A reaction mixture containing 6.5% anionic group-containing isocyanate group-terminated urethane prepolymer was obtained.

  Next, after cooling to 60 ° C., the total amount of the reaction mixture containing the anionic group-containing isocyanate group-terminated urethane prepolymer is added to the silylating agent (A): 47.4, which is a secondary amino group-containing alkoxysilane compound. After mixing and mixing the parts, the mixture is reacted at a temperature of 70 ° C. under a nitrogen stream for 1.5 hours, and contains an alkoxysilyl group side chain-containing water-dispersible urethane prepolymer having a residual isocyanate group of 2.0%. A reaction mixture was obtained.

  Next, after cooling the total amount of the reaction mixture containing the alkoxysilyl group side chain-containing water-dispersible urethane prepolymer to 40 ° C., triethylamine: 11.02 parts are blended, and dibutylamine: 3.60 in advance under high-speed stirring. Part and IPDA: 7.58 parts dissolved in ion-exchanged water: 600 parts were added to obtain a dispersion. After MEK was distilled off at 40 to 45 ° C. under reduced pressure, the dispersion was adjusted to 32.3% by mass with ion-exchanged water, and the viscosity (23 ° C .; BM viscometer, rotor: No. 1, the rotation speed: 30 rpm) was 110 mPa · s, and a urethane-based aqueous composition having a silyl group in the side chain was obtained.

  The urethane-based aqueous composition was stored in the same manner as in Example 1 for 60 days at room temperature and 30 days at 50 ° C., but neither gelation nor separation occurred. It was within ± 30% of the value and showed good storage stability. Moreover, when the water-based urethane composition after storage was evaluated for water resistance, solvent resistance and adhesion in the same manner as in Example 1, the performance equivalent to that of the initial urethane-based aqueous composition was maintained.

(Example 7)
In a four-necked flask equipped with a nitrogen inlet tube, a thermometer, a condenser and a stirrer, T4672: 80 parts, DMPA: 14.6 parts, IPDI: 119.5 parts, 1,4-BD: 18.7 parts, And methyl ethyl ketone (MEK): 200 parts, dibutyltin dilaurate diluted to 5% with MEK as a catalyst: 0.01 part, and reacted at a temperature of 80 to 85 ° C. in a nitrogen stream for 5 hours to obtain residual isocyanate A reaction mixture containing 6.6% anionic group-containing isocyanate group-terminated urethane prepolymer was obtained.

  Next, after cooling to 60 ° C., the total amount of the reaction mixture containing the anionic group-containing isocyanate group-terminated urethane prepolymer is added to the silylating agent (A): 47.4, which is a secondary amino group-containing alkoxysilane compound. After mixing and mixing the parts, the mixture is reacted at a temperature of 70 ° C. under a nitrogen stream for 1.5 hours, and contains an alkoxysilyl group side chain-containing water-dispersible urethane prepolymer having a residual isocyanate group of 2.0%. A reaction mixture was obtained.

  Next, after cooling the total amount of the reaction mixture containing the alkoxysilyl group side chain-containing water-dispersible urethane prepolymer to 40 ° C., triethylamine: 11.02 parts were blended, and dibutylamine: 3.48 in advance under high-speed stirring. Part and IPDA: 7.32 parts dissolved in ion exchange water: 700 parts was added to obtain an aqueous dispersion. After the MEK was distilled off from this dispersion at 40 to 45 ° C. under reduced pressure, the solid content was adjusted to 28.7 mass% with ion-exchanged water, and the viscosity (23 ° C .; BM viscometer, rotor: No. 1, the number of rotations: 30 rpm) was 60 mPa · s, and a urethane-based aqueous composition having a silyl group in the side chain was obtained.

  The urethane-based aqueous composition was stored in the same manner as in Example 1 for 60 days at room temperature and 30 days at 50 ° C., but neither gelation nor separation occurred. It was within ± 30% of the value and showed good storage stability. Moreover, when the water-based urethane composition after storage was evaluated for water resistance, solvent resistance and adhesion in the same manner as in Example 1, the performance equivalent to that of the initial urethane-based aqueous composition was maintained.

(Example 8)
In a four-necked flask equipped with a nitrogen inlet tube, a thermometer, a condenser and a stirrer, PTMG2000: 80 parts, DMPA: 14.6 parts, IPDI: 120.1 parts, 1,4-BD: 18.7 parts, And methyl ethyl ketone (MEK): 200 parts, dibutyltin dilaurate diluted to 5% with MEK as a catalyst: 0.01 part, and reacted at a temperature of 80 to 85 ° C. in a nitrogen stream for 5 hours to obtain residual isocyanate A reaction mixture containing 6.6% anionic group-containing isocyanate group-terminated urethane prepolymer was obtained.

  Next, after cooling to 60 ° C., the total amount of the reaction mixture containing the anionic group-containing isocyanate group-terminated urethane prepolymer is added to the silylating agent (A): 47.4, which is a secondary amino group-containing alkoxysilane compound. After mixing and mixing the parts, the mixture is reacted at a temperature of 70 ° C. under a nitrogen stream for 1.5 hours, and contains an alkoxysilyl group side chain-containing water-dispersible urethane prepolymer having a residual isocyanate group of 2.0%. A reaction mixture was obtained.

  Next, after cooling the total amount of the reaction mixture containing the alkoxysilyl group side chain-containing water-dispersible urethane prepolymer to 40 ° C., triethylamine: 11.02 parts were added, and dibutylamine: 17.36 in advance under high-speed stirring. An aqueous solution in which parts were dissolved in 850 parts of ion-exchanged water was added to obtain a dispersion. After MEK was distilled off at 40 to 45 ° C. under reduced pressure, the dispersion was adjusted to 24.2% by mass with ion-exchanged water, and the viscosity (23 ° C .; BM viscometer, rotor: No. 1, the number of rotations: 30 rpm) was 155 mPa · s, and a urethane-based aqueous composition having a silyl group in the side chain was obtained.

  The urethane-based aqueous composition was stored in the same manner as in Example 1 for 60 days at room temperature and 30 days at 50 ° C., but neither gelation nor separation occurred. It was within ± 30% of the value and showed good storage stability. Moreover, when the water-based urethane composition after storage was evaluated for water resistance, solvent resistance and adhesion in the same manner as in Example 1, the performance equivalent to that of the initial urethane-based aqueous composition was maintained.

Example 9
In a four-necked flask equipped with a nitrogen inlet tube, a thermometer, a condenser and a stirrer, PTMG2000: 75 parts, Byron 220: 75 parts, DMPA: 22.7 parts, IPDI: 89.8 parts, and methyl ethyl ketone (MEK) : 200 parts, dibutyltin dilaurate diluted to 5% with MEK as a catalyst: 0.01 part was mixed and reacted at a temperature of 80 to 85 ° C. in a nitrogen stream for 6 hours. % Of an anionic group-containing isocyanate group-terminated urethane prepolymer was obtained.

  Next, after cooling to 60 ° C., the total amount of the reaction mixture containing the anionic group-containing isocyanate group-terminated urethane prepolymer is added to a silylating agent (A): 33.7 which is a secondary amino group-containing alkoxysilane compound. After mixing and mixing the parts, the mixture is reacted at a temperature of 70 ° C. under a nitrogen stream for 1.5 hours, and contains an alkoxysilyl group side chain-containing water-dispersible urethane prepolymer having a residual isocyanate group of 2.0%. A reaction mixture was obtained.

  Next, after cooling to 60 ° C., the silylating agent (F), which is an alkoxysilane compound containing a single secondary amino group, is added to the total amount of the reaction mixture containing the anionic group-containing isocyanate group-terminated urethane prepolymer: 84 After mixing and mixing 0.000 parts, the reaction mixture is reacted at a temperature of 70 ° C. under a nitrogen stream for 1.5 hours, and contains a water-dispersible urethane containing alkoxysilyl groups in the side chain and terminal. Got.

  Next, after cooling the total amount of the reaction mixture containing the water-dispersible urethane containing the alkoxysilyl group at the side chain and terminal to 40 ° C., 17.13 parts of triethylamine was blended, and ion exchange was performed under high-speed stirring. Water: 600 parts were added to obtain a dispersion. After the MEK was distilled off from this dispersion at 40 to 45 ° C. under reduced pressure, the solid content was adjusted to 38.1% with ion-exchanged water, and the viscosity (23 ° C .; BM viscometer, rotor: No. 1 , Rotation speed: 30 rpm) was 50 mPa · s, and a urethane-based aqueous composition having a silyl group in the side chain (side chain and terminal) was obtained.

  The urethane-based aqueous composition was stored in the same manner as in Example 1 for 60 days at room temperature and 30 days at 50 ° C., but neither gelation nor separation occurred. It was within ± 30% of the value and showed good storage stability. Moreover, when the water-based urethane composition after storage was evaluated for water resistance, solvent resistance and adhesion in the same manner as in Example 1, the performance equivalent to that of the initial urethane-based aqueous composition was maintained.

(Example 10)
In a four-necked flask equipped with a nitrogen inlet tube, a thermometer, a condenser and a stirrer, PTMG2000: 80 parts, DMPA: 14.6 parts, IPDI: 120.1 parts, 1,4-BD: 18.7 parts, And methyl ethyl ketone (MEK): 200 parts, dibutyltin dilaurate diluted to 5% with MEK as a catalyst: 0.01 part, and reacted at a temperature of 80 to 85 ° C. in a nitrogen stream for 5 hours to obtain residual isocyanate A reaction mixture containing 6.6% anionic group-containing isocyanate group-terminated urethane prepolymer was obtained.

  Next, after cooling to 60 ° C., the total amount of the reaction mixture containing the anionic group-containing isocyanate group-terminated urethane prepolymer is added to a silylating agent (C): 41.4 which is a secondary amino group-containing alkoxysilane compound. After mixing and mixing the parts, the mixture is reacted at a temperature of 70 ° C. under a nitrogen stream for 1.5 hours, and contains an alkoxysilyl group side chain-containing water-dispersible urethane prepolymer having a residual isocyanate group of 2.0%. A reaction mixture was obtained.

  Next, after cooling the total amount of the reaction mixture containing the alkoxysilyl group side chain-containing water-dispersible urethane prepolymer to 40 ° C., 11.02 parts of triethylamine was blended, and dibutylamine: 3.39 in advance under high-speed stirring. Part and IPDA: 7.15 parts dissolved in ion-exchanged water: 650 parts was added to obtain a dispersion. After MEK was distilled off at 40 to 45 ° C. under reduced pressure, the dispersion was adjusted to 30.1% by mass with ion-exchanged water, and the viscosity (23 ° C .; BM viscometer, rotor: No. 1, the number of rotations: 30 rpm) was 70 mPa · s, and a urethane-based aqueous composition having a silyl group in the side chain was obtained.

  The urethane-based aqueous composition was stored in the same manner as in Example 1 for 60 days at room temperature and 30 days at 50 ° C., but neither gelation nor separation occurred. It was within ± 30% of the value and showed good storage stability. Moreover, when the water-based urethane composition after storage was evaluated for water resistance, solvent resistance and adhesion in the same manner as in Example 1, the performance equivalent to that of the initial urethane-based aqueous composition was maintained.

(Example 11)
In a four-necked flask equipped with a nitrogen inlet tube, a thermometer, a condenser and a stirrer, PTMG2000: 80 parts, DMPA: 14.6 parts, IPDI: 120.1 parts, 1,4-BD: 18.7 parts, And methyl ethyl ketone (MEK): 200 parts, dibutyltin dilaurate diluted to 5% with MEK as a catalyst: 0.01 part, and reacted at a temperature of 80 to 85 ° C. in a nitrogen stream for 5 hours to obtain residual isocyanate A reaction mixture containing 6.6% anionic group-containing isocyanate group-terminated urethane prepolymer was obtained.

  Next, after cooling to 60 ° C., the total amount of the reaction mixture containing the anionic group-containing isocyanate group-terminated urethane prepolymer is changed to a silylating agent (D): 36.8, which is a secondary amino group-containing alkoxysilane compound. After mixing and mixing the parts, the mixture is reacted at a temperature of 70 ° C. under a nitrogen stream for 1.5 hours, and contains an alkoxysilyl group side chain-containing water-dispersible urethane prepolymer having a residual isocyanate group of 2.0%. A reaction mixture was obtained.

  Next, after cooling the total amount of the reaction mixture containing the alkoxysilyl group side chain-containing water-dispersible urethane prepolymer to 40 ° C., 11.02 parts of triethylamine was blended, and dibutylamine: 3.33 was previously added under high-speed stirring. Part and IPDA: 7.02 parts dissolved in ion-exchanged water: 550 parts were added to obtain a dispersion. After MEK was distilled off at 40 to 45 ° C. under reduced pressure, the solid content was adjusted to 33.3% by mass with ion-exchanged water, and the viscosity (23 ° C .; BM viscometer, rotor: No. 1, the number of rotations: 30 rpm) was 30 mPa · s, and a urethane-based aqueous composition having a silyl group in the side chain was obtained.

  The urethane-based aqueous composition was stored in the same manner as in Example 1 for 60 days at room temperature and 30 days at 50 ° C., but neither gelation nor separation occurred. It was within ± 30% of the value and showed good storage stability. Moreover, when the water-based urethane composition after storage was evaluated for water resistance, solvent resistance and adhesion in the same manner as in Example 1, the performance equivalent to that of the initial urethane-based aqueous composition was maintained.

(Example 12)
In a four-necked flask equipped with a nitrogen inlet tube, a thermometer, a condenser and a stirrer, PTMG2000: 80 parts, DMPA: 14.6 parts, IPDI: 120.1 parts, 1,4-BD: 18.7 parts, And methyl ethyl ketone (MEK): 200 parts, dibutyltin dilaurate diluted to 5% with MEK as a catalyst: 0.01 part, and reacted at a temperature of 80 to 85 ° C. in a nitrogen stream for 5 hours to obtain residual isocyanate A reaction mixture containing 6.6% anionic group-containing isocyanate group-terminated urethane prepolymer was obtained.

  Next, after cooling to 60 ° C., the total amount of the reaction mixture containing the anionic group-containing isocyanate group-terminated urethane prepolymer is changed to a silylating agent (E) that is a secondary amino group-containing alkoxysilane compound: 39.7 After mixing and mixing the parts, the mixture is reacted at a temperature of 70 ° C. under a nitrogen stream for 1.5 hours, and contains an alkoxysilyl group side chain-containing water-dispersible urethane prepolymer having a residual isocyanate group of 2.0%. A reaction mixture was obtained.

  Next, the total amount of the reaction mixture containing the alkoxysilyl group side chain-containing water-dispersible urethane prepolymer is cooled to 40 ° C., and then mixed with 11.02 parts of triethylamine and preliminarily mixed with dibutylamine: 3.36 under high-speed stirring. Part and IPDA: 7.09 parts dissolved in ion exchange water: 560 parts was added to obtain a dispersion. After MEK was distilled off at 40 to 45 ° C. under reduced pressure, the solid content was adjusted to 33.3% by mass with ion-exchanged water, and the viscosity (23 ° C .; BM viscometer, rotor: No. 1, the number of rotations: 30 rpm) was 55 mPa · s, and a urethane-based aqueous composition having a silyl group in the side chain was obtained.

  The urethane-based aqueous composition was stored in the same manner as in Example 1 for 60 days at room temperature and 30 days at 50 ° C., but neither gelation nor separation occurred. It was within ± 30% of the value and showed good storage stability. Moreover, when the water-based urethane composition after storage was evaluated for water resistance, solvent resistance and adhesion in the same manner as in Example 1, the performance equivalent to that of the initial urethane-based aqueous composition was maintained.

(Comparative Example 1)
In a four-necked flask equipped with a nitrogen inlet tube, a thermometer, a condenser and a stirrer, PTMG2000: 80 parts, DMPA: 14.6 parts, IPDI: 120.1 parts, 1,4-BD: 30 parts, and methyl ethyl ketone (MEK): 200 parts, dibutyltin dilaurate diluted to 5% with MEK as a catalyst: 0.01 part was blended and reacted at a temperature of 80 to 85 ° C. in a nitrogen stream for 9 hours. A reaction mixture containing 2.0% of an anionic group-containing isocyanate group-terminated urethane prepolymer was obtained.

  Next, after cooling to 60 ° C., the silylating agent (H), which is an alkoxysilane compound containing a single secondary amino group, is added to the total amount of the reaction mixture containing the anionic group-containing isocyanate group-terminated urethane prepolymer: 63 After mixing and mixing 62 parts, the reaction was carried out at a temperature of 70 ° C. under a nitrogen stream for 1.5 hours to obtain a reaction mixture containing a water-dispersible urethane containing an alkoxysilyl group at the end. .

  Next, after cooling the total amount of the reaction mixture containing the water-dispersible urethane containing an alkoxysilyl group at the terminal to 40 ° C., 11.02 parts of triethylamine is blended, and ion-exchanged water: 1045 with high-speed stirring. Part was added to obtain a dispersion. After the MEK was distilled off at 40 to 45 ° C. under reduced pressure, the dispersion was adjusted to 22.6% by mass with ion-exchanged water, and the viscosity (23 ° C .; BM viscometer, rotor: No. 1, the number of rotations: 30 rpm) was 95 mPa · s, and a urethane-based aqueous composition having a silyl group at the terminal was obtained.

(Comparative Example 2)
To a four-necked flask equipped with a nitrogen inlet tube, a thermometer, a condenser and a stirrer, PTMG2000: 80 parts, DMPA: 22 parts, IPDI: 120.1 parts, 1,4-BD: 25 parts, and methyl ethyl ketone (MEK ): 200 parts, dibutyltin dilaurate diluted to 5% with MEK as a catalyst: 0.01 part was mixed and reacted at a temperature of 80 to 85 ° C. for 9 hours under a nitrogen stream. A reaction mixture containing 0% anionic group-containing isocyanate group-terminated urethane prepolymer was obtained.

  Next, after cooling to 60 ° C., the silylating agent (G), which is an alkoxysilane compound containing a single secondary amino group, in the total amount of the reaction mixture containing the anionic group-containing isocyanate group-terminated urethane prepolymer: 54 After mixing 38 parts, the reaction was carried out at 70 ° C. under a nitrogen stream for 1.5 hours to obtain a reaction mixture containing a water-dispersible urethane containing an alkoxysilyl group at the end. .

  Next, after cooling the total amount of the reaction mixture containing the water-dispersible urethane containing an alkoxysilyl group at the end to 40 ° C., triethylamine: 16.60 parts were added, and ion-exchanged water: 870 parts were added. A dispersion was obtained. After MEK was distilled off at 40 to 45 ° C. under reduced pressure, the dispersion was adjusted to 25.4% by mass with ion-exchanged water, and the viscosity (23 ° C .; BM viscometer, rotor: No. 2, the rotation speed: 30 rpm) was 900 mPa · s, and an aqueous urethane-based composition having a silyl group at the terminal was obtained.

(Comparative Example 3)
In a four-necked flask equipped with a nitrogen inlet tube, a thermometer, a condenser and a stirrer, PTMG2000: 80 parts, DMPA: 14.6 parts, IPDI: 120.1 parts, 1,4-BD: 30 parts, and methyl ethyl ketone (MEK): 200 parts, dibutyltin dilaurate diluted to 5% with MEK as a catalyst: 0.01 part was blended and reacted at a temperature of 80 to 85 ° C. in a nitrogen stream for 9 hours. A reaction mixture containing 2.0% of an anionic group-containing isocyanate group-terminated urethane prepolymer was obtained.

  Next, after cooling to 60 ° C., the silylating agent (I), which is an alkoxysilane compound containing a single secondary amino group, in the total amount of the reaction mixture containing the anionic group-containing isocyanate group-terminated urethane prepolymer: 68 After mixing 80 parts, the mixture was reacted at 70 ° C. under a nitrogen stream for 1.5 hours to obtain a reaction mixture containing a water-dispersible urethane containing an alkoxysilyl group at the end. .

  Next, after cooling the total amount of the reaction mixture containing the water-dispersible urethane containing an alkoxysilyl group at the terminal to 40 ° C., 11.02 parts of triethylamine is blended, and ion-exchanged water: 1025 with high-speed stirring. Part was added to obtain a dispersion. After the MEK was distilled off at 40 to 45 ° C. under reduced pressure, the solid content was adjusted to 23.2% by mass with ion-exchanged water, and the viscosity (23 ° C .; BM viscometer, rotor: No. 2, the rotation speed: 30 rpm) was 320 mPa · s, and a urethane-based aqueous composition having a silyl group at the terminal was obtained.

(Comparative Example 4)
In a four-necked flask equipped with a nitrogen inlet tube, a thermometer, a condenser and a stirrer, PTMG2000: 80 parts, DMPA: 14.6 parts, IPDI: 120.1 parts, 1,4-BD: 30 parts, and methyl ethyl ketone (MEK): 200 parts, dibutyltin dilaurate diluted to 5% with MEK as a catalyst: 0.01 part was blended and reacted at a temperature of 80 to 85 ° C. in a nitrogen stream for 9 hours. A reaction mixture containing 2.0% of an anionic group-containing isocyanate group-terminated urethane prepolymer was obtained.

  Next, after cooling to 60 ° C., the silylating agent (I), which is an alkoxysilane compound containing a single secondary amino group, in the total amount of the reaction mixture containing the anionic group-containing isocyanate group-terminated urethane prepolymer: 13 After mixing and mixing .76 parts, the reaction was carried out at a temperature of 70 ° C. under a nitrogen stream for 1.5 hours to obtain a reaction mixture containing a water-dispersible urethane containing an alkoxysilyl group at the end. .

  Next, after cooling the whole reaction mixture containing the water-dispersible urethane containing the alkoxysilyl group at the terminal to 40 ° C., triethylamine is mixed with 11.02 parts, and IPDA: 6. An aqueous solution obtained by dissolving 35 parts in ion-exchanged water: 820 parts was added to obtain a dispersion. After MEK was distilled off at 40 to 45 ° C. under reduced pressure, the dispersion was adjusted to 24.2% by mass with ion-exchanged water, and the viscosity (23 ° C .; BM viscometer, rotor: No. 2, the number of revolutions: 30 rpm) was 330 mPa · s, and a urethane-based aqueous composition having a silyl group at the terminal was obtained.

(Comparative Example 5)
In a four-necked flask equipped with a nitrogen inlet tube, a thermometer, a condenser and a stirrer, PTMG2000: 80 parts, DMPA: 14.6 parts, IPDI: 120.1 parts, 1,4-BD: 30 parts, and methyl ethyl ketone (MEK): 200 parts, dibutyltin dilaurate diluted to 5% with MEK as a catalyst: 0.01 part was blended and reacted at a temperature of 80 to 85 ° C. in a nitrogen stream for 9 hours. A reaction mixture containing 2.0% of an anionic group-containing isocyanate group-terminated urethane prepolymer was obtained.

  Next, after cooling to 60 ° C., the silylating agent (J): 101, which is an alkoxysilane compound containing a single secondary amino group in the total amount of the reaction mixture containing the anionic group-containing isocyanate group-terminated urethane prepolymer. After mixing and mixing .55 parts, the reaction was carried out at a temperature of 70 ° C. under a nitrogen stream for 1.5 hours to obtain a reaction mixture containing a water-dispersible urethane containing an alkoxysilyl group at the end. .

  Next, after cooling the total amount of the reaction mixture containing the water-dispersible urethane containing an alkoxysilyl group at the terminal to 40 ° C., 11.02 parts of triethylamine is blended, and ion-exchanged water: 1460 with high-speed stirring. Part was added to obtain a dispersion. After the MEK was distilled off at 40 to 45 ° C. under reduced pressure, the solid content was adjusted to 19.1% by mass with ion-exchanged water, and the viscosity (23 ° C .; BM viscometer, rotor: No. 2, the rotation speed: 30 rpm) was 620 mPa · s, and a urethane-based aqueous composition having a silyl group at the terminal was obtained.

(Comparative Example 6)
In a four-necked flask equipped with a nitrogen inlet tube, a thermometer, a condenser and a stirrer, PTMG2000: 80 parts, DMPA: 14.6 parts, IPDI: 120.1 parts, 1,4-BD: 30 parts, and methyl ethyl ketone (MEK): 200 parts, dibutyltin dilaurate diluted to 5% with MEK as a catalyst: 0.01 part was blended and reacted at a temperature of 80 to 85 ° C. in a nitrogen stream for 9 hours. A reaction mixture containing 2.0% of an anionic group-containing isocyanate group-terminated urethane prepolymer was obtained.

  Next, after cooling the total amount of the reaction mixture containing the anionic group-containing isocyanate group-terminated urethane prepolymer to 40 ° C., triethylamine: 11.02 parts were blended, and dibutylamine: 3.01 parts in advance under high-speed stirring. An aqueous solution prepared by dissolving 6.35 parts of IPDA in 670 parts of ion-exchanged water was added to obtain a dispersion. After MEK was distilled off at 40 to 45 ° C. under reduced pressure, the solid content was adjusted to 26.8% by mass with ion-exchanged water, and the viscosity (23 ° C .; BM viscometer, rotor: No. 1, the number of rotations: 30 rpm) was 130 mPa · s, and a urethane-based aqueous composition having no silyl group was obtained.

(Comparative Example 7)
In a four-necked flask equipped with a nitrogen inlet tube, a thermometer, a condenser and a stirrer, PTMG2000: 80 parts, DMPA: 14.6 parts, IPDI: 120.1 parts, 1,4-BD: 30 parts, and methyl ethyl ketone (MEK): 200 parts, dibutyltin dilaurate diluted to 5% with MEK as a catalyst: 0.01 part was blended and reacted at a temperature of 80 to 85 ° C. in a nitrogen stream for 9 hours. A reaction mixture containing 2.0% of an anionic group-containing isocyanate group-terminated urethane prepolymer was obtained.

  Next, after cooling the total amount of the reaction mixture containing the anionic group-containing isocyanate group-terminated urethane prepolymer to 40 ° C., triethylamine: 11.02 parts were blended, and dibutylamine: 15.07 parts in advance under high-speed stirring. Ion exchange water: An aqueous solution dissolved in 725 parts was added to obtain a dispersion. After MEK was distilled off at 40 to 45 ° C. under reduced pressure, the solid content was adjusted to 24.6% by mass with ion-exchanged water, and the viscosity (23 ° C .; BM viscometer, rotor: No. 2, the rotation speed: 30 rpm) was 440 mPa · s, and a urethane-based aqueous composition having no silyl group was obtained.

(Comparative Example 8)
In a four-necked flask equipped with a nitrogen inlet tube, a thermometer, a condenser and a stirrer, PTMG2000: 80 parts, DMPA: 14.6 parts, IPDI: 120.1 parts, 1,4-BD: 28.9 parts, And methyl ethyl ketone (MEK): 200 parts, dibutyltin dilaurate diluted to 5% with MEK as a catalyst: 0.01 part, and reacted at a temperature of 80 to 85 ° C. in a nitrogen stream for 8 hours to obtain residual isocyanate A reaction mixture containing 2.4% anionic group-containing isocyanate group-terminated urethane prepolymer was obtained.

  Next, after cooling to 60 ° C., the silylating agent which is an alkoxysilane compound containing a secondary amino group and a primary amino group in the total amount of the reaction mixture containing the anionic group-containing isocyanate group-terminated urethane prepolymer (F): After 2.6 parts were mixed and mixed, when the reaction was attempted at a temperature of 70 ° C. under a nitrogen stream, the system gelled and the reaction could not be continued. .

(Comparative Example 9)
In a four-necked flask equipped with a nitrogen inlet tube, a thermometer, a condenser and a stirrer, PTMG2000: 80 parts, DMPA: 14.6 parts, IPDI: 120.1 parts, 1,4-BD: 18.7 parts, And methyl ethyl ketone (MEK): 200 parts, dibutyltin dilaurate diluted to 5% with MEK as a catalyst: 0.01 part, and reacted at a temperature of 80 to 85 ° C. in a nitrogen stream for 5 hours to obtain residual isocyanate A reaction mixture containing 6.6% anionic group-containing isocyanate group-terminated urethane prepolymer was obtained.

  Next, after cooling to 60 ° C., the silylating agent which is an alkoxysilane compound containing a secondary amino group and a primary amino group in the total amount of the reaction mixture containing the anionic group-containing isocyanate group-terminated urethane prepolymer (F): 27 parts were mixed and mixed, and then the reaction was attempted at a temperature of 70 ° C. under a nitrogen stream. As a result, the system gelled and the reaction could not be continued.

  In addition, about the urethane type aqueous composition obtained by Examples 1-12 and Comparative Examples 1-9, the data about a composition and a physical property were shown to Tables 1-3. In Tables 1 to 3, “COOH content (meq / g)” indicates the content (meq / g) of carboxyl groups (COOH) in the resin unit mass in the urethane-based aqueous composition. The “silyl group content (meq / g)” indicates the number of moles (meq / g) of silicon atoms (Si) contained in the resin unit mass in the urethane-based aqueous composition. The “silyl group amount (number / molecule)” indicates the average number (number / molecule) of silyl groups (trimethoxysilyl group or methyldimethoxysilyl group) in one molecule of the urethane polymer.

(Evaluation)
About the urethane type aqueous composition obtained by Examples 1-12 and Comparative Examples 1-7, by the following evaluation method (The evaluation method of water resistance, the evaluation method of solvent resistance, the evaluation method of adhesiveness), water resistance The solvent resistance and adhesion were evaluated. The evaluation results are shown in Tables 1 to 3.

(Water resistance evaluation method)
For the corona discharge-treated surface of the trade name “EMBLET” (manufactured by Unitika; polyethylene terephthalate film; brand S, thickness 25 μm), obtained using Examples 1-12 and Comparative Examples 1-7 using a baker type applicator. Each urethane-based aqueous composition was applied so that the coating amount after drying was 10 g / m ² , dried at 120 ° C. for 100 seconds, and coated with a urethane-based aqueous composition on one surface of the polyethylene terephthalate film. Formed. The film having this film was immersed in warm water at 50 ° C. or 70 ° C. for 24 hours, and then the state of the film was visually observed. The water resistance of the urethane-based aqueous composition was determined according to the following water resistance evaluation criteria. Evaluated.
Evaluation criteria for water resistance ○: The film remains transparent and no change.
X: The film is whitened.

(Solvent resistance evaluation method)
For the corona discharge-treated surface of the trade name “EMBLET” (manufactured by Unitika; polyethylene terephthalate film; brand S, thickness 25 μm), obtained using Examples 1-12 and Comparative Examples 1-7 using a baker type applicator. Each urethane-based aqueous composition was applied so that the coating amount after drying was 10 g / m ² , dried at 120 ° C. for 100 seconds, and coated with a urethane-based aqueous composition on one surface of the polyethylene terephthalate film. Formed. The film having this film was immersed in tetrahydrofuran (THF) at 23 ° C. for 24 hours, and then the state of the film was visually observed, and the urethane-based aqueous composition was evaluated according to the following evaluation criteria for solvent resistance. The solvent resistance was evaluated.
Evaluation criteria for solvent resistance ○: The film is not dissolved and the original state is maintained.
X: The film is dissolved.

(Adhesion evaluation method)
For the corona discharge-treated surface of the trade name “EMBLET” (manufactured by Unitika; polyethylene terephthalate film; brand S, thickness 25 μm), obtained using Examples 1-12 and Comparative Examples 1-7 using a baker type applicator. Each urethane-based aqueous composition was applied so that the coating amount after drying was 10 g / m ² , dried at 120 ° C. for 100 seconds, and coated with a urethane-based aqueous composition on one surface of the polyethylene terephthalate film. Formed. The film having this film is cut into the surface on which the film is formed with a cutter so as to form a grid of 1 cm × 1 cm and 1 mm intervals, and an adhesive tape (trade name “4051P-18” is applied from above. (Made by Nichiban Co., Ltd.), and after 10 reciprocations with a 1 kg roller, the adhesive tape was peeled off at a pulling speed of 200 mm / s and a peeling angle of 180 °, and a 180 ° peeling test was performed. It observed visually and evaluated the adhesiveness about a urethane type aqueous composition with the following evaluation criteria of adhesiveness.
Evaluation Criteria for Adhesion A: A portion torn in the polyethylene terephthalate film is generated.
○: The polyethylene terephthalate film is elongated by peeling, and the polyethylene terephthalate film is white.
(Triangle | delta): The cohesive failure of the urethane type aqueous composition layer which has formed the membrane | film | coat has arisen.
X: Peeling occurs at the interface between the polyethylene terephthalate film and the coating.

(Example 13)
In a four-necked flask equipped with a nitrogen inlet tube, a thermometer, a condenser and a stirrer, PTMG2000: 80 parts, DMPA: 14.6 parts, IPDI: 120.1 parts, 1,4-BD: 18.7 parts, And methyl ethyl ketone (MEK): 200 parts, dibutyltin dilaurate diluted to 5% with MEK as a catalyst: 0.01 part, and reacted at a temperature of 80 to 85 ° C. in a nitrogen stream for 5 hours to obtain residual isocyanate A reaction mixture containing 6.6% anionic group-containing isocyanate group-terminated urethane prepolymer was obtained.

Next, after cooling to 60 ° C., the reaction product containing the anionic group-containing isocyanate group-terminated urethane prepolymer is added to the total amount of secondary amino group-containing alkoxysilane compound as a trade name “X-12-5283” [ Manufactured by Shin-Etsu Chemical Co., Ltd .; Structural formula: (CH ₃ O) ₃ Si (CH ₂ ) ₃ NH (CH ₂ ) ₂ NH (CH ₂ ) ₃ Si (OCH ₃ ) ₃ ]: 44.9 parts are mixed and mixed Then, the reaction was carried out at a temperature of 70 ° C. under a nitrogen stream for 1.5 hours to obtain a reaction mixture containing an alkoxysilyl group side chain-containing water-dispersible urethane prepolymer having a residual isocyanate group of 2.0%.

  Next, after cooling the total amount of the reaction mixture containing the alkoxysilyl group side chain-containing water-dispersible urethane prepolymer to 40 ° C., triethylamine: 11.02 parts are blended, and dibutylamine: 3.47 in advance under high-speed stirring. Part and IPDA: 7.25 parts dissolved in ion-exchanged water: 710 parts was added to obtain a dispersion. After the MEK was distilled off at 40 to 45 ° C. under reduced pressure, the solid content was adjusted to 28.6% by mass with ion-exchanged water, and the viscosity (23 ° C .; BM viscometer, rotor: No. 1, the number of rotations: 30 rpm) was 10 mPa · s, and a urethane-based aqueous composition having a silyl group in the side chain was obtained.

  The urethane-based aqueous composition having a silyl group in the side chain was evaluated for adhesion by the above-described adhesion evaluation method. As a result, “O: polyethylene terephthalate film stretched by peeling, polyethylene terephthalate film” Is white. "

  In addition, about the urethane type aqueous composition which has a silyl group in the side chain which concerns on Example 13, the content rate (meq / g) [COOH] of the carboxyl group (COOH) in the resin unit mass in a urethane type aqueous composition Content (meq / g)] was 0.38 (meq / g). Moreover, the number of moles (meq / g) [silyl group content (meq / g)] of silicon atom (Si) in the resin unit mass in the urethane-based aqueous composition is 0.81 (meq / g). there were. Further, the average number of silyl groups (trimethoxysilyl group) in one molecule of alkoxysilyl group side chain-containing water-dispersible urethane prepolymer (number / molecule) [the amount of silyl groups (number / molecule)] is 17 8 (pieces / molecule).

(Example 14)
In a four-necked flask equipped with a nitrogen inlet tube, a thermometer, a condenser and a stirrer, PTMG2000: 80 parts, DMPA: 13.9 parts, IPDI: 120.1 parts, 1,4-BD: 25.2 parts, And 200 parts of methyl ethyl ketone (MEK), dibutyltin dilaurate diluted to 5% with MEK as a catalyst: 0.01 part, reacted at 80 to 85 ° C. in a nitrogen stream for 6 hours to obtain residual isocyanate A reaction mixture containing 4.1% anionic group-containing isocyanate group-terminated urethane prepolymer was obtained.

Next, after cooling to 60 ° C., the reaction product containing the anionic group-containing isocyanate group-terminated urethane prepolymer is added to the total amount of secondary amino group-containing alkoxysilane compound as a trade name “X-12-5283” [ Manufactured by Shin-Etsu Chemical Co., Ltd .; Structural formula: (CH ₃ O) ₃ Si (CH ₂ ) ₃ NH (CH ₂ ) ₂ NH (CH ₂ ) ₃ Si (OCH ₃ ) ₃ ]: After 21 parts are mixed and mixed The reaction was performed at a temperature of 70 ° C. under a nitrogen stream for 1.5 hours to obtain a reaction mixture containing an alkoxysilyl group side chain-containing water-dispersible urethane prepolymer having a residual isocyanate group of 2.0%.

  Next, after cooling the total amount of the reaction mixture containing the alkoxysilyl group side chain-containing water-dispersible urethane prepolymer to 40 ° C., 10.49 parts of triethylamine is blended, and dibutylamine: 3.21 in advance under high-speed stirring. Part and IPDA: 6.76 parts dissolved in ion-exchanged water: 725 parts were added to obtain a dispersion. After MEK was distilled off at 40 to 45 ° C. under reduced pressure, the dispersion was adjusted to 26.7% by mass with ion-exchanged water, and the viscosity (23 ° C .; BM type viscometer, rotor: No. 2, the rotation speed: 30 rpm) was 300 mPa · s, and a urethane-based aqueous composition having a silyl group in the side chain was obtained.

  With respect to the urethane-based aqueous composition having a silyl group in the side chain, the adhesiveness was evaluated by the above-described adhesiveness evaluation method. As a result, “◎: a portion torn in the polyethylene terephthalate film was generated”. Evaluation results were obtained.

  In addition, about the urethane type aqueous composition which has a silyl group in the side chain which concerns on Example 14, the content rate (meq / g) of the carboxyl group (COOH) in the unit mass per resin in a urethane type aqueous composition [ COOH content (meq / g)] was 0.38 (meq / g). Moreover, the number of moles (meq / g) [silyl group content (meq / g)] of silicon atoms (Si) in the resin unit mass in the urethane-based aqueous composition is 0.41 (meq / g). there were. Furthermore, the average number of silyl (trimethoxysilyl groups) in one molecule of alkoxysilyl group side chain-containing water-dispersible urethane prepolymer (number of molecules / molecule) [the amount of silyl groups (number of molecules / molecule)] is 8. 9 (pieces / molecule).

(Evaluation of elastic properties)
The urethane-based aqueous composition having a silyl group at the side chain or terminal according to Example 1 and Comparative Example 1 (that is, the silylated urethane-based aqueous composition according to Example 1 has a silyl group in the side chain. Measurement of the following elastic characteristics of the urethane-based aqueous composition, and the silylated urethane-based aqueous composition according to Comparative Example 1 is a urethane-based aqueous composition having a silyl group at the terminal) According to the method, the data on the elastic modulus of the urethane-based aqueous composition having a silyl group at the side chain or terminal [dynamic storage elastic modulus (E ′), dynamic loss elastic modulus (E ″), loss tangent (tan δ) )] Was measured, a graph as shown in Fig. 1 was obtained, where the graph (data) indicated by "solid line" is data relating to Example 1, and the graph (data) indicated by "+". ) Is related to Comparative Example 1 Data. In addition, the graphs indicated by the “solid line” and “+” located in the upper stage on the left end side (low temperature side) of the graph relate to the dynamic storage elastic modulus (E ′), and are located in the middle stage on the left end side of the graph. The graphs indicated by “solid lines” and “+” are related to the loss tangent (tan δ), and the graphs indicated by “solid lines” and “+” located at the lower stage on the left end side of the graph are the dynamic loss elasticity. Further, in the graph shown in FIG. 1, the horizontal axis (X axis) is temperature (Temp .; ° C.), while the vertical axis (Y axis) is dynamic storage elasticity. Regarding the rate (E ′) (Pa), dynamic loss elastic modulus (E ″) (Pa), and loss tangent (tan δ), the left scale of the two scales located on the left side of the graph is the loss tangent ( tan δ) scale (range 0.0001-2.8000; common logarithm table) Among the two scales located on the left side of the graph, the scale on the right side is the scale (3.0 × 10 ^{6 to} 6.0 ×) of the dynamic storage elastic modulus (E ′) (Pa). 10 ⁹ range; logarithmic display), and the scale on the right side of the graph is the dynamic loss modulus (E ″) (Pa) (1.0 × 10 ^{3 to} 1.4 × 10 ¹⁴ range; Logarithmic display).

(Measurement method of elastic properties)
Product name “EMBLET” (manufactured by Unitika; polyethylene terephthalate film; brand S, thickness: 25 μm) on a glass plate (10 cm × 10 cm, thickness: 0.1 cm), with the corona discharge treatment surface positioned on the glass plate side (Ie, in a form in which the untreated surface of the corona discharge is located on the outer surface side), “TM tape W1” (made by Konishi, double-sided tape, thickness) on the end of the polyethylene terephthalate film bonded to the glass plate : 1.15 mm) was affixed twice to form a frame. And, in this frame, each urethane-based aqueous composition was poured so that the thickness of the dried film was 0.5 mm, dried at 95 ° C. for 3 hours, and further dried at 70 ° C. for 1 week, A film of the urethane-based aqueous composition was formed on the untreated corona discharge surface of the polyethylene terephthalate film. Next, the film | membrane of the urethane type aqueous composition was cut out by the size (thickness: 0.5 mm) of 40 mm x 10 mm. Then, the viscoelasticity measurement of the cut-out film | membrane was performed using the brand name "DMS6100" (made by SII nanotechnology company) which is a viscoelasticity measurement apparatus of a film | membrane (measuring condition; temperature increase rate: 2 degree-C / min, Frequency: 1 Hz, distance between chucks: 20 mm, strain amplitude: 10 μm, minimum tension / compression force: 100 mN, tension / compression force gain: 1.5), data on elastic modulus [dynamic storage elastic modulus (E ′), dynamic Loss elastic modulus (E ″), loss tangent (tan δ)].

From the graph shown in FIG. 1, the urethane-based aqueous composition having a silyl group in the side chain according to Example 1 is more than the urethane-based aqueous composition having a silyl group at the terminal according to Comparative Example 1. However, the temperature at which the dynamic storage elastic modulus (E ′) begins to decrease as the temperature rises is higher (the “solid line” and “ Graph indicated by “+”). In other words, any temperature in the temperature range where the dynamic storage elastic modulus (E ′) of the urethane-based aqueous composition having a silyl group at the terminal according to Comparative Example 1 is rapidly decreased (for example, The value of the dynamic storage elastic modulus related to the temperature in the urethane-based aqueous composition having a silyl group in the side chain according to Example 1 is larger than the value of the dynamic storage elastic modulus related to 100 ° C). It has become. Therefore, the urethane-based aqueous composition having a silyl group in the side chain according to Example 1 can effectively maintain the film properties even at high temperatures, and has a dynamic storage elastic modulus (E ′ ) 10 ⁶ rubbery plateau portion of the order of Pa ¹⁰⁶ Pa following flow fields in temperature is high to migrate high heat creep temperature, it can be confirmed that the excellent film properties.

  Thus, it is possible to effectively control the heat resistance of the urethane-based aqueous composition having a silyl group by using a secondary amino group-containing alkoxysilane compound as a silylating agent. Was confirmed.

  Furthermore, the urethane-based aqueous composition having a silyl group according to the examples has a very good storage stability even if it has a large number of alkoxysilyl groups because the curing reaction proceeds due to a decrease in water. is there.

  Accordingly, a silylated urethane-based aqueous composition having excellent adhesion was obtained. In particular, a silylated urethane-based aqueous composition having excellent adhesion, adhesion, film properties and storage stability as well as water resistance and heat resistance was obtained.

FIG. 1 is a diagram showing a graph of data relating to elastic modulus obtained when the elastic characteristics of a urethane-based aqueous composition were evaluated in Examples.

Claims (6)

  A water-dispersed silylated urethane-based composition containing a water-dispersible silylated urethane-based resin, wherein the water-dispersible silylated urethane-based resin is at least 1 by an alkoxysilane compound containing at least two secondary amino groups. A silylated urethane-based aqueous composition, which is a water-dispersible silylated urethane-based resin having a structure in which two alkoxysilyl groups are introduced as side chains in the molecule.   An alkoxysilane compound containing at least two secondary amino groups has a secondary amino group having a secondary amino group-containing alkoxy group with or without a divalent organic group. The silylated urethane-based aqueous composition according to claim 1, which is an alkoxysilane compound containing at least two secondary amino groups in a form bonded to a silicon atom of a silyl group.   An alkoxysilane compound containing at least two secondary amino groups, an alkoxysilane compound containing at least one primary amino group and a secondary amino group, respectively, and a compound having a carbon-carbon double bond The silylated urethane-based aqueous composition according to claim 1 or 2, which is an alkoxysilane compound containing at least two secondary amino groups, which is obtained by a reaction with a compound having an isocyanate group.   The silylated urethane-based aqueous composition according to claim 3, wherein the compound having a carbon-carbon double bond is an α, β-unsaturated carboxylic acid compound.   The silylated urethane-based aqueous composition according to claim 4, wherein the α, β-unsaturated carboxylic acid compound is an unsaturated aliphatic carboxylic acid alkyl ester having 1 to 20 carbon atoms in the alkyl group at the alkyl ester moiety.   The water-dispersible silylated urethane resin having a structure in which at least one alkoxysilyl group is introduced as a side chain in the molecule is an alkoxysilane compound containing at least two secondary amino groups, an anionic group Non-containing compound containing a plurality of isocyanate-reactive groups, an anionic group, a compound containing a plurality of isocyanate-reactive groups, and water obtained by reacting a polyisocyanate compound with an alkoxysilyl group in the side chain It is a dispersible urethane prepolymer (A), The silylated urethane type aqueous composition as described in any one of Claims 1-5.

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