CN1788030A - Silanized polyurethane water-based composition, and water-based encapsulation adhesive and water-based contact adhesive - Google Patents

Abstract

The aqueous silylated polyurethane composition is highly safe, and can be used as an aqueous adhesive which requires a short time to exhibit excellent adhesion and has excellent initial adhesion. The aqueous silylated polyurethane composition is characterized by containing the following component , component (B) and component (C): an alkoxysilyl-terminated polyurethane prepolymer containing an anionic group and a tertiary amino group obtained by reacting a polyol compound containing no anionic group (a1), a polyol compound containing an anionic group (a2), a compound containing a tertiary amino group and an isocyanate-reactive group (A3), a polyisocyanate compound (a4), an alkoxysilane compound containing an isocyanate-reactive group (a5), and an amine chain extender (a6), (B) a basic compound, and (C) water.

Description

Silanized polyurethane-based water-based composition, and water-based encapsulation adhesive and water-based contact adhesive

technical field

The present invention relates to a silylated polyurethane water-based composition, a water-based encapsulating adhesive, and a water-based contact adhesive. More specifically, it relates to high safety and a short time required to express excellent adhesion , a silylated polyurethane-based aqueous composition, an aqueous encapsulating adhesive, and an aqueous contact adhesive that exhibit excellent initial adhesiveness and productivity equivalent to that of solvent-based adhesives.

Background technique

Conventionally, solvent-type polyurethane resin-based adhesives excellent in initial adhesiveness and cohesive force have been mainly used as adhesives for encapsulation. However, in recent years, there has been a demand for highly safe adhesives from the viewpoint of environmental issues, disease-causing housing issues, and the like. Therefore, although various water-based adhesives have been proposed so far as adhesives for encapsulation, the current situation is that not only does it take a long time to express adhesiveness, but also the adhesive force is insufficient. In fact, especially in industrial Not available yet.

On the other hand, as a resin composition for water-based adhesives, as described in JP-A-2003-48946, the present inventors have developed a silylated polyurethane-based water-based composition containing A polymer having an alkoxysilyl group at the end in addition to an anionic group (an anionic group-containing alkoxysilyl-terminated polymer). In this silylated polyurethane-based water-based composition, since an alkoxysilyl-terminated polymer containing anionic groups is used, the time to achieve adhesion and the adhesive force are better than conventional water-based adhesives. Although it has been improved, it cannot be said to be sufficient when compared with solvent-based adhesives, so it can be said that the range of use is limited. Thus, there is still room for improvement in the time to develop adhesion and the adhesive force, and the development of a water-based adhesive that has excellent adhesive force and further shortens the time to develop adhesive force is desired.

Contents of the invention

The object of the present invention is to provide a silylated polyurethane-based water-based composition, a water-based encapsulation adhesive, and a water-based contact-type adhesive that are highly safe, exhibit excellent adhesion in a short time, and have excellent initial adhesion. glue.

Another object of the present invention is to provide a silylated polyurethane-based aqueous composition, an aqueous encapsulation adhesive, and an aqueous contact adhesive that can exhibit productivity equivalent to that of a solvent-based adhesive.

As a result of intensive research by the present inventors to solve the above-mentioned problems, it has been found that a specific silylated polyurethane-based aqueous composition requires a short time to exhibit excellent adhesive force, has excellent initial adhesiveness, and is highly safe because it is water-based. Furthermore, when used as an adhesive for encapsulation, the same productivity as when using a solvent-based adhesive can be exhibited, and the present invention has been completed.

That is, the present invention relates to a silylated polyurethane-based aqueous composition containing the following (A) component, (B) component, and (C) component.

(A) polyol compound (A1) not containing anionic group, polyol compound (A2) containing anionic group, compound (A3) containing tertiary amino group and isocyanate reactive group, polyisocyanate compound ( A4), the alkoxysilane compound (A5) containing the isocyanate reactive group, and the alkoxysilyl terminal polyurethane prepolymerization containing the anionic group and the tertiary amino group obtained by the reaction of the amine chain extender (A6) thing

(B) Basic compound

(C) water

In the silylated polyurethane water-based composition of the present invention, the alkoxysilyl-terminated polyurethane prepolymer (A) containing anionic groups and tertiary amino groups may also be obtained by An anionic group-containing polyol compound (A2) containing an anionic group-containing polyol compound (A2), a compound (A3) containing a tertiary amino group and an isocyanate reactive group (A3), and a polyisocyanate compound (A4) obtained by reacting an alcohol compound (A1) The polyurethane prepolymer with tertiary amino group is reacted with the alkoxysilane compound (A5) containing isocyanate reactive group, and the isocyanate group at the end of the above-mentioned polyurethane prepolymer containing anionic group and tertiary amino group is partially alkylated. The polyurethane prepolymer containing alkoxysilylated anionic groups and tertiary amino groups obtained by oxysilylization, and then passed through the amine chain extender (A6) to make the above-mentioned alkoxysilane containing terminal parts The isocyanate group remaining in the polyurethane prepolymer of the anionic group and tertiary amino group, the anionic group containing alkoxysilanization and the chain extended reaction with the amino group of the above-mentioned amine chain extender (A6) Tertiary amino polyurethane prepolymer.

As such a silylated polyurethane-based aqueous composition, it is preferable that the anionic group in the polyurethane prepolymer (A) containing an alkoxysilyl terminal containing an anionic group and a tertiary amino group is replaced by a basic compound (B). Aqueous silylated polyurethane prepolymer composition in which neutralized terminal alkoxysilyl groups are hydrolyzed by water (C).

In the present invention, as the anionic group-containing polyol compound (A2), the anionic group is preferably a carboxyl group, and dimethylolalkanoic acid can be preferably used.

As the compound (A3) containing a tertiary amino group and an isocyanate-reactive group, preferably a tertiary amine compound containing a plurality of isocyanate-reactive groups, more preferably N, N-bis(hydroxyl-organic group)-N- Alkylamines.

In addition, in the present invention, as the alkoxysilane compound (A5) containing an isocyanate-reactive group, an alkoxysilane compound containing a secondary amino group obtained by reacting an alkoxysilane compound containing at least a primary amino group with an unsaturated carboxylic acid ester is preferable. The oxysilane compound is more preferably an alkoxysilane compound containing a secondary amino group obtained by reacting an alkoxysilane compound containing a primary amino group and a secondary amino group with an unsaturated carboxylic acid ester.

In the alkoxysilyl-terminated polyurethane prepolymer (A) containing an anionic group and a tertiary amino group, the content as the anionic group is preferably 0.4 meq/g or more, and the content as the tertiary amino group is preferably 0.4 meq/g or more. Preferably it is 0.15 meq/g or more. As a ratio of the said anionic group and a tertiary amino group, it is preferable that a tertiary amino group/anionic group (molar ratio)=0.2-1.

In addition, as the ratio of the tertiary amino group and the alkoxysilyl group in the alkoxysilyl-terminated polyurethane prepolymer (A) containing an anionic group and a tertiary amino group, a tertiary amino group/alkoxysilyl group ( Molar ratio)=1.0～5.5.

In addition, the present invention includes a water-based sealing adhesive or a water-based contact adhesive characterized by containing the above-mentioned silylated polyurethane-based aqueous composition.

A brief description of the drawings

Fig. 1 is a schematic cross-sectional view showing the cross-sectional shape of MDF bonded with a polyolefin sheet by a sealing machine.

Fig. 2 is a schematic cross-sectional view showing the cross-sectional shape of MDF bonded with a polyolefin sheet by a sealing machine.

Fig. 3 is a schematic cross-sectional view showing the cross-sectional shape of MDF bonded with a polyolefin sheet by a sealing machine.

4 is a schematic cross-sectional view showing a state where a polyolefin sheet is bonded to MDF with the cross-sectional shape shown in FIG. 1 by a sealing machine.

5 is a schematic cross-sectional view showing a state where a polyolefin sheet is bonded to MDF with the cross-sectional shape shown in FIG. 2 by a sealing machine.

6 is a schematic cross-sectional view showing a state where a polyolefin sheet is bonded to MDF with the cross-sectional shape shown in FIG. 3 by a sealing machine.

Best way to implement the invention

In the silylated polyurethane aqueous composition of the present invention, the alkoxysilyl-terminated polyurethane prepolymer (A) containing an anionic group and a tertiary amino group passes through the polyol compound (A1) not containing an anionic group , polyol compound (A2) containing anionic group, compound (A3) containing tertiary amino group and isocyanate-reactive group, polyisocyanate compound (A4), alkoxysilane compound (A5) containing isocyanate-reactive group ), and an amine chain extender (A6) to react.

[Polyol compound (A1) not containing anionic group]

Polyol compounds (A1) not containing anionic groups (hereinafter sometimes referred to as "polyols (A1)"), as long as they do not have anionic groups in the molecule and have at least 2 hydroxyl groups in the molecule, there is no special restrictions. The polyol (A1) can be used alone or in combination of two or more.

Examples of the polyol (A1) include polyols, polyether polyols, polyester polyols, polycarbonate polyols, polyolefin polyols, polyacrylic polyols, and castor oil.

In the polyol (A1), the polyol includes, for example, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, trimethylene glycol, 1,4-tetramethylene glycol, 1,3- Tetramethylene glycol, 2-methyl-1,3-trimethylene glycol, 1,5-pentamethylene glycol, neopentyl glycol, 1,6-hexamethylene glycol, 3 -Methyl-1,5-pentamethylene glycol, 2,4-diethyl-1,5-pentamethylene glycol, glycerin, trimethylolpropane, trimethylolethane, cyclo Hexylene glycols (1,4-cyclohexanediol, etc.), bisphenols (bisphenol A, etc.), sugar alcohols (xylitol, sorbitol, etc.), and the like.

Examples of polyether polyols include polyalkylene glycols such as polyethylene glycol, polypropylene glycol, and polytetramethylene glycol, and other ethylene oxide-propylene oxide copolymers. Copolymers containing a plurality of alkylene oxides (alkylene oxide-other alkylene oxides) as monomer components, etc.

As the polyester polyol, for example, polycondensate of polyhydric alcohol and polycarboxylic acid; ring-opening polymer of cyclic ester (lactone); reaction of three components of polyhydric alcohol, polycarboxylic acid, and cyclic ester can be used. things etc. In the polycondensate of a polyhydric alcohol and a polyvalent carboxylic acid, the polyhydric alcohols exemplified above can be used as the polyhydric alcohol. On the other hand, examples of the polyvalent carboxylic acid include malonic acid, maleic acid, succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, and dodecanedioic acid. Aliphatic dicarboxylic acids; alicyclic dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid; terephthalic acid, isophthalic acid, phthalic acid, 2,6-naphthalene dicarboxylic acid, terephthalic acid Aromatic dicarboxylic acids such as carboxylic acid and trimellitic acid, etc. In addition, in the ring-opening polymer of cyclic ester, examples of the cyclic ester include propiolactone, β-methyl-δ-valerolactone, and ε-caprolactone. Among the reactants produced from the three components, those exemplified above can be used as the polyhydric alcohol, polycarboxylic acid, and cyclic ester.

Examples of polycarbonate polyols include reactants of polyols and phosgene; ring-opened polymers of cyclic carbonates (such as alkylene carbonates); and the like. Specifically, among the reactants of polyhydric alcohol and phosgene, the polyhydric alcohols exemplified above can be used as the polyhydric alcohol. In addition, in the ring-opening polymer of cyclic carbonate, examples of the alkylene carbonate include ethylene carbonate, trimethylene carbonate, tetramethylene carbonate, hexamethylene carbonate, etc. . In addition, the polycarbonate polyol may be a compound having a carbonate bond in the molecule and a hydroxyl group at the end, or may have both a carbonate bond and an ester bond.

Polyolefin polyols are polyols that use olefins as the backbone (or main chain) component of polymers or copolymers and contain at least two hydroxyl groups in the molecule (especially at the end). The above-mentioned olefin may be an olefin having a carbon-carbon double bond at the terminal (for example, α-olefins such as ethylene and propylene, etc.), and may also be an olefin having a carbon-carbon double bond at a position other than the terminal (for example, isobutylene, etc. ), can also be diolefins (eg, butadiene, isoprene, etc.).

Polyacrylic polyols are polyols that use (meth)acrylate as the backbone (or main chain) of polymers or copolymers and contain at least two hydroxyl groups in the molecule. As the (meth)acrylate, it is preferable to use an alkyl (meth)acrylate [for example, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate ester, hexyl (meth)acrylate, octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, decyl (meth)acrylate, dodecyl (meth)acrylate, (meth)acrylate base) octadecyl acrylate, etc. (meth)acrylic acid C _1-20 alkyl esters, etc.].

In addition, in polyolefin polyols or polyacrylic polyols, in order to introduce hydroxyl groups into molecules, α,β-unsaturated compounds having hydroxyl groups [for example, 2-Hydroxyethyl (meth)acrylate, 3-Hydroxypropyl (meth)acrylate, etc. (Hydroxyalkyl)acrylate, etc.]

As polyol (A1), polyether polyol, polyester polyol, polycarbonate polyol can be preferably used.

[Anionic group-containing polyol compound (A2)]

Anionic group-containing polyol compound (A2) (hereinafter sometimes referred to as polyol (A2)), as long as it has at least one anionic group and at least two hydroxyl groups in the molecule, there is no special restrictions. In the polyol (A2), it is preferable to use a carboxyl group or a sulfo group as an anionic group, and among them, a carboxyl group is most preferable. A polyol (A2) can be used individually or in combination of 2 or more types.

As the polyol (A2), for example, a carboxyl group-containing polyol obtained by introducing a carboxyl group into the polyol shown in the item of polyol (A1) above, etc. may be mentioned. In the present invention, the polyol (A2) is preferably a low-molecular-weight polyol having an anionic group, and in particular, a polyhydroxycarboxylic acid represented by the following formula (1) can be preferably used.

(HO) _X L(COOH) _Y (1)

(Here, in formula (1), L represents a hydrocarbon moiety having 1 to 12 carbon atoms. X is an integer of 2 or more, and Y is an integer of 1 or more.)

In the above formula (1), the hydrocarbon moiety of L is preferably an aliphatic hydrocarbon moiety, either in a linear or branched form. In addition, X and Y may be the same or different. Two or more hydroxyl groups can be combined on the same carbon atom or on different carbon atoms. In addition, when Y is 2 or more, two or more carboxyl groups can be combined on the same carbon atom. Carbon atoms can be bonded to different carbon atoms.

As such a polyhydroxycarboxylic acid, dimethylolalkanoic acid (especially 2,2-dimethylolalkanoic acid) is especially preferable. Examples of dimethylolalkanoic acid include 2,2-dimethylolpropionic acid, 2,2-dimethylolbutyric acid, 2,2-dimethylolvaleric acid, 2,2 - Dimethylol hexanoic acid, 2,2-dimethylol heptanoic acid, 2,2-dimethylol caprylic acid, 2,2-dimethylol nonanoic acid, 2,2-dimethylol decanoic acid wait.

[Compound (A3) containing a tertiary amino group and an isocyanate-reactive group]

A compound (A3) containing a tertiary amino group and an isocyanate-reactive gene (hereinafter sometimes referred to as "a tertiary amino group-containing isocyanate-reactive compound (A3)") as long as it contains at least one tertiary amino group and at least one isocyanate in its molecule The compound of the reactive group is not particularly limited. The isocyanate-reactive compound (A3) containing a tertiary amino group may be used individually or in combination of 2 or more types.

In the isocyanate-reactive compound (A3) containing a tertiary amino group, as a tertiary amino group (disubstituted amino group), it can also be obtained by having a hydrocarbon group (such as an aryl group such as a phenyl group; an alkyl group such as a methyl group, an ethyl group, a propyl group, or a butyl group) ; Cycloalkyl such as cyclohexyl, etc.) and other substituents form tertiary amino groups. The hydrocarbon group may also have other substituents (for example, alkoxy, aryloxy, cycloalkoxy, alkoxycarbonyl, aryloxycarbonyl, cycloalkoxycarbonyl, acyl, etc.).

The number of tertiary amino groups in the molecule of the isocyanate-reactive compound (A3) containing tertiary amino groups is not particularly limited, and can be selected from, for example, 1 to 6, preferably 1 to 3 (more preferably 1 or 2, particularly preferably 1). Thus, the tertiary amino group-containing isocyanate-reactive compound (A3) 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 there are a plurality of tertiary amino groups, only one kind of tertiary amino group may be used, or two or more kinds may be combined.

In addition, in the isocyanate-reactive compound (A3) containing a tertiary amino group, the isocyanate-reactive group is not particularly limited as long as it is a group reactive to isocyanate groups, and examples thereof include hydroxyl groups, primary Amino or secondary amino, mercapto, etc., preferably hydroxyl, primary or secondary amino, particularly preferably hydroxyl. The molecule of the tertiary amino group-containing isocyanate-reactive compound (A3) may have only one isocyanate-reactive group or may have a plurality of them. In this way, the number of isocyanate-reactive groups in the molecule of the isocyanate-reactive compound (A3) containing a tertiary amino group is not particularly limited as long as it is at least one, but it can range from, for example, 1 to 6 (preferably 1 to 3 ) range selection, particularly preferably 2. In addition, when having a plurality of isocyanate-reactive groups, only one type of isocyanate-reactive groups may be used, or two or more types may be combined.

In the tertiary amino group-containing isocyanate-reactive compound (A3), the isocyanate-reactive group may be directly bonded to the nitrogen atom of the tertiary amino group, but is preferably bonded via a divalent group. As such a divalent group, for example, an alkylene group, an alkenylene group (arilen group), an alkylene-alkenylene group, an alkylene-alkenylene group-alkylene group, etc., which are composed only of hydrocarbon groups Divalent hydrocarbon group; oxy-alkylene, alkylene-oxy-alkylene, alkylene-carbonyl-oxy-alkylene, alkylene-oxygen-carbonyl-alkylene, alkylene-poly( Various divalent groups formed by various combinations of hydrocarbon groups and other groups (oxy, carbonyl-oxy, etc.) such as oxyalkylene) group [poly(oxyalkylene)-alkylene], etc.

The tertiary amino group-containing isocyanate-reactive compound (A3) has a form in which a tertiary amino group is bonded to various organic groups. The organic group bonded as the tertiary amino group is not particularly limited, but is preferably a hydrocarbon group. Such hydrocarbon groups include, for example, aliphatic hydrocarbon groups (for example, alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, pentyl, hexyl, etc.), alicyclic hydrocarbon groups (for example, cycloalkyl such as cyclohexyl, etc.), aromatic hydrocarbon groups (for example, aryl such as phenyl, etc.), and the like. The hydrocarbon group may also have one or two or more substituents. As the substituent, for example, other hydrocarbon groups, isocyanate-reactive groups (for example, hydroxyl, primary amino, secondary amino, mercapto, etc.) ), non-isocyanate reactive groups (eg, tertiary amino, alkoxy, aryloxy, cycloalkoxy, alkoxycarbonyl, aryloxycarbonyl, cycloalkoxycarbonyl, acyl, etc.), etc.

Therefore, as the isocyanate-reactive compound (A3) containing a tertiary amino group, a tertiary amine compound containing a plurality of isocyanate-reactive groups can be used. Such a tertiary amine compound containing a plurality of isocyanate-reactive groups is not particularly limited as long as it is a tertiary amine compound containing a plurality of isocyanate-reactive groups, but examples thereof include, for example, Tertiary in the form of bonding one organic group containing an isocyanate-reactive group (organic group containing an isocyanate-reactive group) and two organic groups containing a hydrocarbon group (organic group containing a hydrocarbon group) Amine compound [tertiary amine compound (A3-1) containing an organic group containing one isocyanate-reactive group], while bonding two organic groups containing an isocyanate-reactive group to one nitrogen atom , a tertiary amine compound in the form of one organic group containing a hydrocarbon group [tertiary amine compound (A3-2) containing an organic group containing two isocyanate-reactive groups], bonded to one nitrogen atom Tertiary amine compound in the form of three organic groups containing isocyanate-reactive groups [tertiary amine compound (A3-3) containing three organic groups containing isocyanate-reactive groups], in 1 A tertiary amine compound in the form of two tertiary amino groups containing isocyanate-reactive groups bonded to each other directly or through a divalent group [having two organic groups containing two isocyanate-reactive groups] The tertiary amine compound of the tertiary amino group (A3-4)] and the like.

Specifically, as the tertiary amine compound (A3-1) containing an organic group containing one isocyanate-reactive group, the "tertiary amine containing an organic group containing one hydroxyl group" in which the isocyanate-reactive group is a hydroxyl group In the case of "like compounds", for example, N-hydroxymethyl-N, N-dimethylamine, N-(2-hydroxyethyl)-N, N-dimethylamine, N-(3-hydroxypropyl base)-N,N-dimethylamine, N-(2-hydroxypropyl)-N,N-dimethylamine, N-(4-hydroxybutyl)-N,N-dimethylamine, N-hydroxy Methyl-N, N-diethylamine, N-(2-hydroxyethyl)-N,N-diethylamine, N-(3-hydroxypropyl)-N,N-diethylamine, N-( 2-hydroxypropyl)-N,N-diethylamine, N-(4-hydroxybutyl)-N,N-diethylamine, N-(2-hydroxyethyl)-N,N-dipropylamine, N-(2-hydroxyethyl)-N,N-diisopropylamine, N-(2-hydroxyethyl)-N,N-di-n-butylamine, etc. N-hydroxyalkyl-N,N-dialkyl Amine; N-[hydroxymethyl-poly(oxymethylene)]-N,N-dimethylamine, N-[2-hydroxyethyl-poly(oxyethylene)]-N,N-dimethylamine Amine, N-[3-hydroxypropyl-poly(oxypropylene)]-N,N-dimethylamine, N-[2-hydroxypropyl-poly(oxypropylene)]-N,N -Dimethylamine, N-[4-hydroxybutyl-poly(oxybutylene)]-N,N-dimethylamine, N-[hydroxymethyl-poly(oxymethylene)]-N,N- Diethylamine, N-[2-hydroxyethyl-poly(oxyethylene)]-N,N-diethylamine, N-[3-hydroxypropyl-poly(oxypropylene)]-N, N-diethylamine, N-[2-hydroxypropyl-poly(isopropylene oxide)]-N,N-diethylamine, N-[4-hydroxybutyl-poly(oxybutylene)]- N,N-diethylamine, N-[2-hydroxyethyl-poly(oxyethylene)]-N,N-dipropylamine, N-[2-hydroxyethyl-poly(oxyethylene)] -N,N-diisopropylamine, N-[2-hydroxyethyl-poly(oxyethylene)]-N,N-di-n-butylamine, etc. N-[hydroxyalkyl-poly(oxyalkylene) ]-N, N-dialkylamine, etc. N-(hydroxyl-organic group)-N,N-dialkylamine, or N-methylol-N,N-diphenylamine, N-(2-hydroxy Ethyl)-N, N-diphenylamine, N-(3-hydroxypropyl)-N,N-diphenylamine, N-(2-hydroxypropyl)-N,N-diphenylamine, N-(4- N-hydroxyalkyl-N,N-diarylamine such as hydroxybutyl)-N,N-diphenylamine; N-[hydroxymethyl-poly(oxymethylene)]-N,N-diphenylamine, N-[2-hydroxyethyl-poly(oxyethylene)]-N,N-diphenylamine, N-[3-hydroxypropyl-poly(oxypropylene)-N,N-diphenylamine, N -[2-hydroxypropyl-poly(isopropylene oxide)-N,N-diphenylamine, N-[4-hydroxybutyl-poly(oxybutylene)-N,N-diphenylamine, etc. -[hydroxyalkyl-poly(oxyalkylene)]-N,N-diarylamines and other N,N-bis(hydroxyl-organic groups)]-N,N-diarylamines; corresponding to their N-(hydroxy-organic group)-N,N-dicycloalkylamine and the like.

In addition, as the tertiary amine compound (A3-1) containing an organic group containing one isocyanate-reactive group, in the case where the isocyanate-reactive group is an amino group (primary or secondary amino group) In the case of "tertiary amine compound with an organic group containing a secondary amino group", for example, tertiary amine compounds corresponding to those exemplified above as "tertiary amine compound containing an organic group containing one hydroxyl group".

As a tertiary amine compound (A3-2) containing an organic group containing two isocyanate-reactive groups, a "tertiary amine compound containing an organic group containing two hydroxyl groups" in which the isocyanate-reactive group is a hydroxyl group When, 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-propylamine , N, N-bis(2-hydroxyethyl)-N-isopropylamine, N,N-bis(2-hydroxyethyl)-N-n-butylamine, etc. N,N-bis(hydroxyalkyl)-N -Alkylamine; 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(oxypropylene) )]-N-methylamine, N,N-bis[4-hydroxybutyl-poly(oxybutylene)]-N-methylamine, N,N-bis[hydroxymethyl-poly(oxymethylene) ]-N-ethylamine, N,N-bis[2-hydroxyethyl-poly(oxyethylene)]-N-ethylamine, N,N-bis[3-hydroxypropyl-poly(oxypropylene) base)]-N-ethylamine, N,N-bis[2-hydroxypropyl-poly(isopropylidene oxide)]-N-ethylamine, N,N-bis[4-hydroxybutyl-poly( Butylene oxide)]-N-ethylamine, N,N-bis[2-hydroxyethyl-poly(oxyethylene)]-N-propylamine, N,N-bis[2-hydroxyethyl-poly( Oxyethylene)]-N-isopropylamine, N,N-bis[2-hydroxyethyl-poly(oxyethylene)]-N-n-butylamine, etc. N,N-bis[hydroxyalkyl-poly (Oxyalkylene)]-N-alkylamines such as N,N-bis(hydroxyl-organic group)-N-alkylamine, or N,N-bis(hydroxymethyl)-N-aniline, N , N-bis(2-hydroxyethyl)-N-aniline, N,N-bis(3-hydroxypropyl)-N-aniline, N,N-bis(2-hydroxypropyl)-N-aniline, N,N-bis(4-hydroxybutyl)-N-aniline and other N,N-bis(hydroxyalkyl)-N-arylamines; N,N-bis[hydroxymethyl-poly(oxymethylene )]-N-aniline, N,N-bis[2-hydroxyethyl-poly(oxyethylene)]-N-aniline, N,N-bis[3-hydroxypropyl-poly(oxypropylene) )]-N-aniline, N,N-bis[2-hydroxypropyl-poly(isopropylidene oxide)]-N-aniline, N,N-bis[4-hydroxybutyl-poly(oxybutylene )]-N-aniline, etc. N,N-bis[hydroxyalkyl-poly(oxyalkylene)1-N-arylamine, etc. ; Corresponding to their N, N-bis(hydroxyl-organic group)-N-cycloalkylamine and the like.

In addition, as the tertiary amine compound (A3-2) containing an organic group containing 2 isocyanate-reactive groups, in the case where the isocyanate-reactive group is an amino group (primary or secondary amino group) In the case of "tertiary amine compounds with organic groups containing secondary amino groups", for example, tertiary amine compounds corresponding to those exemplified above as "tertiary amine compounds containing organic groups containing two hydroxyl groups".

As a tertiary amine compound (A3-3) containing an organic group containing 3 isocyanate-reactive groups, a "tertiary amine compound containing an organic group containing 3 hydroxyl groups" in which the isocyanate-reactive group is a hydroxyl group When, for example, N,N,N-tris(hydroxymethyl)amine, N,N,N-tris(2-hydroxyethyl)amine, N,N,N-tris(3-hydroxypropyl) N,N,N-tris(2-hydroxypropyl)amine, N,N,N-tris(4-hydroxybutyl)amine, etc. N,N,N-tris(hydroxyalkyl)-N -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(oxypropylene)]amine, N, N,N-tris[4-hydroxybutyl-poly(oxybutylene)]amine, etc. N,N,N-tris[hydroxyalkyl-poly(oxyalkylene)]amine, etc. N,N,N-tris (Hydroxy-organic) amines, etc.

In addition, as the tertiary amine compound (A3-3) containing an organic group containing 3 isocyanate-reactive groups, in the case where the isocyanate-reactive group is an amino group (primary or secondary amino group) In the case of tertiary amine compounds with organic groups of secondary amino groups", for example, tertiary amine compounds corresponding to the above-mentioned "tertiary amine compounds containing organic groups containing three hydroxyl groups" .

As a tertiary amine compound (A3-4) having two tertiary amino groups containing an organic group containing two isocyanate-reactive groups, in the case where the isocyanate-reactive group is a hydroxyl group, "having two organic groups containing two hydroxyl groups As for the tertiary amine compound of the tertiary amino group of the organic group", for example, N, N, N', N'-tetrakis (hydroxymethyl) ethylenediamine, N, N, N', N '-Tetrakis(2-hydroxyethyl)ethylenediamine, N,N,N',N'-tetrakis(3-hydroxypropyl)ethylenediamine, N,N,N',N'- N, N, N', N'-tetra( Hydroxy-alkyl)alkylenediamine, etc. N,N,N',N'-tetrakis(hydroxy-organo)alkylenediamine, etc.

In addition, as a tertiary amine compound (A3-4) having two tertiary amino groups containing an organic group containing two isocyanate-reactive groups, in the " In the case of tertiary amine compounds having two tertiary amino groups containing organic groups containing two primary or secondary amino groups", for example, the above-mentioned "tertiary amino compounds having two organic groups containing two hydroxyl groups" Amino tertiary amine compounds" exemplified substances corresponding to tertiary amine compounds.

[polyisocyanate compound (A4)]

The polyisocyanate compound (A4) (hereinafter, may be referred to as "polyisocyanate (A4)") is not particularly limited as long as it has at least two isocyanate groups in the molecule. The polyisocyanate (A4) includes, for example, aliphatic polyisocyanate, alicyclic polyisocyanate, aromatic polyisocyanate, araliphatic polyisocyanate, and the like. Polyisocyanate (A4) can be used individually or in combination of 2 or more types.

Examples of aliphatic polyisocyanates include 1,3-trimethylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,3-pentamethylene diisocyanate, 1,5-pentamethylene Methyl diisocyanate, 1,6-hexamethylene diisocyanate, 1,2-propylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate Diisocyanate, 2-methyl-1,5-pentamethylene diisocyanate, 3-methyl-1,5-pentamethylene diisocyanate, 2,4,4-trimethyl-1,6-hexa Aliphatic diisocyanates such as methylene diisocyanate, 2,2,4-trimethyl-1,6-hexamethylene diisocyanate, 2,6-diisocyanate methyl caproate, lysine diisocyanate, and the like.

Examples of alicyclic polyisocyanates include 1,3-cyclopentane diisocyanate, 1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate, 3-isocyanate methyl -3,3,5-trimethylcyclohexyl isocyanate, 4,4'-methylene bis(cyclohexyl isocyanate), methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane Hexane diisocyanate, 1,3-bis(isocyanatomethyl)cyclohexane, 1,4-bis(isocyanatomethyl)cyclohexane, isophorone diisocyanate, norbornane diisocyanate, etc. Alicyclic diisocyanate, etc.

Examples of the aromatic polyisocyanate include m-phenylene diisocyanate, p-phenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, naphthylene-1, 4-diisocyanate, naphthylene-1,5-diisocyanate, 4,4'-diphenyl diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate , 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-4,4'-diisocyanate, etc. Aromatic diisocyanates, etc.

Examples of araliphatic polyisocyanates include 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, ω,ω′-diisocyanate-1,4-diethyl Benzene, 1,3-bis(1-isocyanate-1-methylethyl)benzene, 1,4-bis(1-isocyanate-1-methylethyl)benzene, 1,3-bis(α,α- Araliphatic diisocyanates such as dimethylisocyanate (methyl)benzene, etc.

As the polyisocyanate (A4), 1,6-hexamethylene diisocyanate, 4,4'-methylene bis(cyclohexyl isocyanate), 1,3-bis(isocyanatomethyl)cyclohexane, 1,4-bis(isocyanatomethyl)cyclohexane, isophorone diisocyanate, 2,4-toluylene diisocyanate, 2,6-toluylene diisocyanate, 4,4'-diphenylmethane diisocyanate , 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, norbornane diisocyanate, 1,3-bis(α,α-dimethylisocyanatomethyl)benzene. In addition, when an aliphatic polyisocyanate, an alicyclic polyisocyanate, or an araliphatic polyisocyanate is used as the polyisocyanate (A4), a resin with little discoloration can be obtained.

In addition, in the present invention, dimers or trimers obtained from the aliphatic polyisocyanates, alicyclic polyisocyanates, aromatic polyisocyanates, and araliphatic polyisocyanates exemplified above can also be used as the polyisocyanate (A4). , reaction products or polymers (such as dimers or trimers of diphenylmethane diisocyanate, reaction products of trimethylolpropane and tolylene diisocyanate, trimethylolpropane and hexamethylene diisocyanate reaction product of isocyanate, polymethylene polyphenylisocyanate, polyether polyisocyanate, polyester polyisocyanate, etc.) and the like.

Moreover, in this invention, a diisothiocyanate compound (for example, phenyl diisothiocyanate etc.) can be used together with a polyisocyanate (A4).

[Alkoxysilane compound (A5) containing an isocyanate-reactive group]

As an isocyanate-reactive group-containing alkoxysilane compound (A5) (hereinafter, sometimes referred to as "isocyanate-reactive group-containing alkoxysilane (A5)"), as long as it has at least one isocyanate-reactive There is no particular limitation if there is at least one alkoxysilane compound in the molecule. The isocyanate-reactive group-containing alkoxysilanes (A5) can be used alone or in combination of two or more.

The isocyanate-reactive group is not particularly limited as long as it is a group reactive to isocyanate groups. For example, primary amino groups, secondary amino groups, mercapto groups, isocyanate groups, hydroxyl groups, etc., preferably primary or secondary amino groups, Mercapto. In addition, the isocyanate-reactive group may be used alone or in combination of two or more.

In the present invention, as the alkoxysilane (A5) containing the isocyanate-reactive group, the alkoxysilane compound (A5-1) containing the primary or secondary amino group, the alkoxysilane compound (A5-1) containing the mercapto group can be preferably used -2).

In addition, the alkoxysilane compound (A5-1) containing a primary or secondary amino group (hereinafter sometimes referred to as "amino group-containing alkoxysilane (A5-1)") has at least one primary or secondary amino group in the molecule. Amino groups and silane compounds having at least one alkoxy group in the molecule are not particularly limited. Therefore, the amino group-containing alkoxysilane (A5-1) may contain one or more tertiary amino groups as the amino group. In addition, as the mercapto group-containing alkoxysilane compound (A5-2), (hereinafter sometimes referred to as "mercapto group-containing alkoxysilane (A5-2)"), as long as it has at least one mercapto group in the molecule, and the molecule The silane compound having at least one alkoxy group in it is not particularly limited.

Among the alkoxysilanes (A5) containing isocyanate-reactive groups, as alkoxy groups, for example, methoxy, ethoxy, propoxy, isopropoxy, butoxy, iso C _1-4 alkoxy groups such as butoxy, sec-butoxy and tert-butoxy. More preferable alkoxy groups include methoxy, ethoxy and propoxy (especially methoxy and ethoxy). Such alkoxy groups are usually bonded to the silicon atom of the isocyanate-reactive group-containing alkoxysilane (A5), and the number thereof is usually 1 to 3 (preferably 2 or 3). In addition, alkoxy groups may be used alone or in combination of two or more. That is, the same alkoxy group may be bonded to the silicon atom of the isocyanate-reactive group-containing alkoxysilane (A5), or two or more different alkoxy groups may be bonded in combination.

In addition, when the isocyanate-reactive group is an amino group, the secondary amino group or the tertiary amino group can be obtained by having a hydrocarbon group (for example, an aryl group such as phenyl; an alkyl group such as methyl, ethyl, propyl, or butyl; a cycloalkyl group such as cyclohexyl, etc. ) and other substituents can form secondary or tertiary amino groups. In addition, this hydrocarbon group may have other substituents (eg, alkoxy, aryloxy, cycloalkoxy, alkoxycarbonyl, aryloxycarbonyl, cycloalkoxycarbonyl, acyl, etc.).

In addition, although an isocyanate-reactive group (primary amino group, secondary amino group, mercapto group, etc.) may be directly bonded to a silicon atom, it is preferably bonded via a divalent group. Examples of such divalent groups include divalent hydrocarbon groups composed only of hydrocarbon groups such as alkylene groups, alkenylene groups, alkylene-alkenylene groups, and alkylene-alkenylene-alkylene groups. ; Alkylene-oxygen-alkylene, alkylene-carbonyl-oxygen-alkylene, alkylene-oxygen-carbonyl-alkylene, alkylene-poly(oxyalkylene) group, etc. through hydrocarbon group Various divalent groups formed by various combinations with other groups (oxy, carbonyl-oxy, etc.).

Therefore, for example, when the isocyanate-reactive group-containing alkoxysilane (A5) is an amino group-containing alkoxysilane (A5-1), it may contain an amino group in the form of an aminoalkyl group. Such aminoalkyl groups include, for example, amino- _{C1 ～3} alkyl groups, or their secondary amino groups (amino-C _1～3 alkyl groups with 1 hydrocarbon group as substituent, etc.) or tertiary amino groups (amino C _1～3 alkyl groups with 2 hydrocarbon groups as substituents) etc. In addition, a substituent such as a substituted hydrocarbon group may have an amino group on a nitrogen atom in a secondary or tertiary amino group. That is, it may be in the form of, for example, N-aminoalkyl-aminoalkyl, N-[N-(aminoalkyl)aminoalkyl]aminoalkyl. In addition, it may have a primary amino group and a secondary amino group at the same time. The number of primary or secondary amino groups is not particularly limited, but is usually 1 or 2.

More specifically, when the isocyanate-reactive group-containing alkoxysilane (A5) is, for example, an amino-group-containing alkoxysilane (A5-1), the isocyanate-reactive group represented by the following formula (2a) As an isocyanate-reactive group represented by the following formula (2b), an amino group-containing alkoxysilane having only a primary amino group can be preferably used, and an amino group-containing alkoxysilane having a primary amino group and a secondary amino group can be preferably used , As the isocyanate-reactive group represented by the following formula (2c), amino group-containing alkoxysilanes having only secondary amino groups, or mercapto-containing alkoxysilanes (A5-2) can be preferably used as As the isocyanate-reactive group represented by the following formula (2d), a mercapto-group-containing alkoxysilane having only a mercapto group can be preferably used.

(In formulas (2a) to (2d), R ¹ and R ² are the same or different, representing an alkyl group, R ³ and R ⁴ representing an alkylene group, R ⁵ representing an aryl group, an alkyl group or a cycloalkyl group. In addition , m is an integer of 1 to 3. In addition, the alkylene groups of R ³ and R ⁴ in formula (2b) may be the same or different.)

In the above-mentioned formulas (2a) to (2d), as the alkyl group of ^R1 , for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl and other groups having 1 carbon atoms are preferred. ~4 or so alkyl groups. In addition, as the alkyl group of ^R2 , the same alkyl group as the alkyl group of ^R1 can be used, but methyl or ethyl is preferable. The alkylene group for ^R3 is preferably an alkylene group having about 1 to 3 carbon atoms, such as methylene group, ethylene group, and trimethylene group. In addition, as the alkylene group for R ⁴ , an alkylene group having about 1 to 3 carbon atoms is used in the same manner as the alkylene group for R ³ described above. In addition, in ^R5 , it is preferable to use a phenyl group as an aryl group, and it is preferable to use a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, etc., having 1 to 2 carbon atoms as an alkyl group. As an alkyl group of about 4, a cyclohexyl group is preferably used as the cycloalkyl group. In addition, m is an integer of 1-3.

More specifically, as the isocyanate-reactive group represented by the above formula (2a), as the amino group-containing alkoxysilane having only primary amino groups, for example, aminomethyltrimethoxysilane, aminomethyl Triethoxysilane, β-aminoethyltrimethoxysilane, β-aminoethyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ -Aminoalkyltrialkoxysilanes such as aminopropyltripropoxysilane, γ-aminopropyltriisopropoxysilane, γ-aminopropyltributoxysilane, etc.; Methoxysilane, β-aminoethylmethyldiethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, γ-aminopropylmethyl (Aminoalkyl)alkyldialkoxysilanes such as dipropoxysilane, or aminoalkyldialkyl (mono)alkoxysilanes corresponding to them.

As the isocyanate-reactive group represented by the above formula (2b), examples of amino group-containing alkoxysilanes having primary and secondary amino groups include N-β(aminoethyl)-γ-aminopropyl Trimethoxysilane, N-β(aminoethyl)-γ-aminopropyltriethoxysilane, etc. N-(aminoalkyl)aminoalkyltrialkoxysilane; N-β(aminoethyl)- γ-aminopropylmethyldimethoxysilane, N-β(aminoethyl)-γ-aminopropylmethyldiethoxysilane, etc. N-(aminoalkyl)aminoalkylalkyldialkoxy base silane, etc.

In addition, as the isocyanate-reactive group represented by the above-mentioned formula (2c), examples of the amino group-containing alkoxysilane having only secondary amino groups include N-phenyl-β-aminoethyltrimethoxysilane , N-phenyl-β-aminoethyltriethoxysilane, etc. N-phenyl-β-aminoethyltrialkoxysilane; N-phenyl-γ-aminopropyltrimethoxysilane, N- Phenyl-γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltripropoxysilane, N-phenyl-γ-aminopropyltributoxysilane, etc. N-phenyl -γ-aminopropyltrialkoxysilane, or their corresponding N-phenylaminoalkyl (mono- or di)alkyl (di- or mono)alkoxysilane, in addition, can also be mentioned, with the above-mentioned The substituent of the secondary amino group of the phenyl group is the corresponding N-alkylaminoalkyltrialkoxysilane of the amino-containing alkoxysilane (for example, N-methyl-3-aminopropyltrimethoxysilane, N-ethyl-3-aminopropyltrimethoxysilane, N-n-propyl-3-aminopropyltrimethoxysilane, N-n-butyl-aminomethyltrimethoxysilane, N-n-butyl -2-aminoethyltrimethoxysilane, N-n-butyl-3-aminopropyltrimethoxysilane, N-n-butyl-3-aminopropyltriethoxysilane, N-n-butyl- 3-aminopropyltripropoxysilane, etc.) or N-alkylaminoalkyl (mono- or di)alkyl (di- or mono)alkoxysilane, etc.

In the present invention, as the amino group-containing alkoxysilane (A5-1), trade names "KBM6063", trade names "X-12-869", trade names "KBM576", trade names "X-12 -565", product name "X-12-580", product name "X-12-5263", product name "X-12-666", product name "KBM6123", product name "X-12-575", Product name "X-12-577", product name "X-12-563B", product name "X-12-730", product name "X-12-562", product name "X-12-5202", Trade name "X-12-5204", trade name "KBE9703" (the above are manufactured by Shin-Etsu Chemical Co., Ltd.), and the like. Therefore, as an amino group-containing alkoxysilane (A5-1), N-(5-aminopentyl)-γ-aminopropyltrimethoxysilane, N-β[N-β(aminoethyl) Base) aminoethyl]-γ-aminopropyltrimethoxysilane, 1,2-bis(γ-trimethoxysilyl-propylamino)ethane, bis(γ-trimethoxysilyl- Propyl)amine, N-β(aminoethyl)-β(4-aminomethylphenyl)ethyltrimethoxysilane and their corresponding hydrocarbon groups (alkyl or alkylene, etc.) with different numbers of carbon atoms Alkoxysilane compounds, etc., or alkoxysilane compounds with primary or secondary amino groups and other groups (styrene-type unsaturated groups, olefin-type unsaturated groups, carboxyl groups, etc.), primary or secondary An alkoxysilane compound having a salt form (hydrochloride, etc.) with a secondary amino group, and an alkoxysilane compound having a plurality of alkoxysilyl groups having a primary or secondary amino group.

In addition, as the isocyanate-reactive group represented by the above formula (2d), examples of mercapto-containing alkoxysilanes include mercaptomethyltrimethoxysilane, mercaptomethyltriethoxysilane, β- Mercaptoethyltrimethoxysilane, β-mercaptoethyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropyltripropoxysilane , γ-mercaptopropyltriisopropoxysilane, γ-mercaptopropyltributoxysilane and other mercaptoalkyltrialkoxysilanes; β-mercaptoethylmethyldimethoxysilane, β-mercaptoethyl Methyldiethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, γ-mercaptopropylmethyldipropoxysilane, etc. (mercapto Alkyl)alkyldialkoxysilanes or their corresponding mercaptoalkyldialkyl (mono)alkoxysilanes and the like.

In the present invention, as the alkoxysilane (A5) containing an isocyanate-reactive group, an amino group-containing alkoxysilane (A5-1) can be preferably used from the viewpoints of easiness of reaction and ease of commercial availability. . In the amino group-containing alkoxysilane (A5-1), as the isocyanate-reactive group, as the amino group-containing alkoxysilane having at least a primary amino group, for example, N-β(aminoethyl)-γ -Aminopropyltrimethoxysilane, N-β(aminoethyl)-γ-aminopropyltriethoxysilane, N-β(aminoethyl)-γ-aminopropylmethyldimethoxysilane , γ-aminopropyltrimethoxysilane. In addition, as the isocyanate-reactive group, as an amino group-containing alkoxysilane having only a secondary amino group, for example, N-phenyl-γ-aminopropyltrimethoxysilane, N-n-butyl-3- Aminopropyltrimethoxysilane.

Furthermore, as an amino group-containing alkoxysilane (A5-1), it may also be an alkoxysilane compound ( Hereinafter, sometimes referred to as "alkoxysilane containing primary amino group"), and an alkoxysilane compound containing at least a secondary amino group as an isocyanate-reactive group obtained by reacting with an unsaturated carboxylic acid ester (A5-3) (hereinafter , sometimes referred to as "ester-transformed amino-containing alkoxysilane (A5-4)". As an ester-transformed amino-containing alkoxysilane (A5-4), it is preferable to use at least a primary amino-containing alkoxysilane compound And the alkoxysilane compound containing the secondary amino group obtained by reacting with the unsaturated carboxylic acid ester (A5-3), it is particularly preferable to use the alkoxysilane compound containing the primary amino group and the secondary amino group and the unsaturated carboxylic acid ester ( A5-3) The secondary amino group-containing alkoxysilane compound obtained by the reaction.

Among the alkoxysilanes (A5-4) containing such an ester converted to an amino group, as the unsaturated carboxylic acid ester (A5-3), as long as it is at least one of the carboxylic acid groups (carboxyl groups) of the unsaturated carboxylic acid ( All) are preferably compounds in the form of esters, and are not particularly limited. As unsaturated carboxylic acid ester (A5-3), unsaturated monocarboxylic acid ester may be sufficient, and unsaturated polyhydric carboxylic acid ester (for example, unsaturated dicarboxylic acid ester etc.) may be sufficient. The unsaturated carboxylic acid esters (A5-3) can be used alone or in combination of two or more.

As the unsaturated carboxylic acid ester (A5-3), a compound in which a carboxyl group or its ester (eg, alkoxycarbonyl, cycloalkoxycarbonyl, aryloxycarbonyl, etc.) is directly bonded to a carbon atom forming a carbon-carbon double bond is preferable. Such compounds include, for example, acrylate, methacrylate, crotonate, methacrylate, 2-butenoate, 3-methyl-2-butenoate, 2-pentacrylate Enenoate, 2-octenoate, etc., and unsaturated monocarboxylic acid esters such as cinnamate; maleate (mono or diester), fumarate (mono or diester), itaconic acid Unsaturated dicarboxylic acid esters such as acid esters (mono- or diesters), etc.

Among the unsaturated carboxylic acid esters (A5-3), the ester moieties include methyl ester, ethyl ester, propyl ester, isopropyl ester, butyl ester, isobutyl ester, sec-butyl ester, tert-butyl ester, pentyl ester, Esters, Isopentyl, Hexyl, Heptyl, Octyl, 2-Ethylhexyl, Nonyl, Decyl, Isodecyl, Undecyl, Dodecyl, Tridecyl, Tetradecyl Esters (alkyl esters, etc.) derived from aliphatic hydrocarbons such as esters, cetyl esters, and stearyl esters; Esters derived from alicyclic hydrocarbons (cyclohydrocarbyl esters, etc.) such as cyclopentyl esters, dicyclopentenyl esters, and tricyclodecenyl esters; esters derived from aromatic hydrocarbons such as phenyl esters and benzyl esters (aryl esters, etc.), etc. . In addition, when having a plurality of ester moieties, the respective ester moieties may be the same or different.

As the unsaturated carboxylic acid ester (A5-3), among the unsaturated carboxylic acid esters exemplified above, acrylate, methacrylate (they may be collectively referred to as "(meth)acrylate" below), methacrylate, etc. are preferably used. Toric acid diester. More specifically, examples of (meth)acrylates include methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, hexyl (meth)acrylate , Octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, dodecyl (meth)acrylate, octadecyl (meth)acrylate, etc. Alkyl (meth)acrylates, etc. . In addition, maleic acid diesters include, for example, dimethyl maleate, diethyl maleate, dibutyl maleate, dihexyl maleate, dioctyl maleate, maleic acid Dialkyl maleates such as di(2-ethylhexyl) ester, di(dodecyl) maleate, dioctadecyl maleate, and the like.

More specifically, as an alkoxysilane compound containing at least a secondary amino group as an isocyanate-reactive group obtained by reacting an alkoxysilane containing a primary amino group with an unsaturated carboxylic acid ester (A5-3) [ester-transformed amino group-containing The alkoxysilane (A5-4)] can be mentioned, the carbon atom at the β position in the carbon-carbon double bond of the unsaturated carboxylate (A5-3) is at least bonded in the alkoxysilane containing the primary amino group Compounds on the nitrogen atom of the amino group, etc. That is, the ester-converted amino group-containing alkoxysilane (A5-4) is the unsaturated bond (carbon -carbon double bond) is a compound obtained by Michael addition reaction. The reaction can be performed in the presence or absence of a solvent. In addition, heating or pressure may be applied during the reaction.

Specifically, as the ester-transformed amino group-containing alkoxysilane (A5-4), for example, a primary amino group-containing alkoxysilane having only a primary amino group as an isocyanate-reactive group represented by the above formula (2a) When an alkoxysilane compound, an unsaturated carboxylic acid ester (A5-3) is an unsaturated carboxylic acid ester represented by following formula (3), it can be represented by following formula (4).

(In formula (3), R ⁶ and R ⁸ are the same or different, representing a hydrogen atom or an alkyl group. ^{R 7} represents an alkyl group, an aryl group or a cycloalkyl group. ^{R 9} represents a hydrogen atom, an alkyl group, an aryl group, an alkyl group Oxycarbonyl, aryloxycarbonyl, cycloalkoxycarbonyl)

(In formula (4), R ¹ to R ³ , R ⁶ to R ⁹ and m are the same as defined above.)

In addition, as the ester-transformed amino group-containing alkoxysilane (A5-4), for example, a primary amino group-containing alkoxysilane has a primary amino group and a secondary amino group as an isocyanate-reactive group represented by the above formula (2b). When the alkoxysilane compound of the unsaturated carboxylic acid ester (A5-3) is an unsaturated carboxylic acid ester represented by the above formula (3), it can be represented by the following formula (5a) or the following formula (5b).

(In (5a) and (5b), R ¹ to R ⁴ , R ⁶ to R ⁹ and m are the same as defined above.)

In the above formulas (3), (4), (5a) and (5b), R ¹ to R ⁴ and m are the same as above. Specifically, as the alkyl group of ^R1 , for example, an alkyl group having about 1 to 4 carbon atoms such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, and tert-butyl is preferable. In addition, as the alkyl group of ^R2 , the same alkyl group as the alkyl group of ^R1 can be used, but methyl or ethyl is preferable. The alkylene group for ^R3 is preferably an alkylene group having about 1 to 3 carbon atoms, such as methylene group, ethylene group, and trimethylene group. In addition, as the alkylene group for R ⁴ , an alkylene group having about 1 to 3 carbon atoms can be used in the same manner as the alkylene group for R ³ described above. In addition, m is an integer of 1-3.

In addition, examples of the alkyl group for R ⁶ include alkyl groups having about 1 to 2 carbon atoms, such as methyl groups and ethyl groups, and the like. Examples of the alkyl group for ^R include, for example, methyl, ethyl, propyl, butyl, isobutyl, tert-butyl, hexyl, octyl, 2-ethylhexyl, etc., having 1 to 20 carbon atoms. Alkylate left and right. In addition, examples of the aryl group for ^R7 include phenyl, and examples of the cycloalkyl group for ^R7 include cyclohexyl groups and the like. Examples of the alkyl group for R ⁸ include, for example, alkyl groups having about 1 to 6 carbon atoms such as methyl, ethyl, propyl, butyl, isobutyl, tert-butyl, and hexyl. In addition, as the alkyl group of R ⁹ , for example, an alkyl group having about 1 to 2 carbon atoms such as a methyl group and an ethyl group, etc. may be mentioned. Examples of the aryl group for ^R9 include phenyl. In addition, in the alkoxycarbonyl group, aryloxycarbonyl group ^, and cycloalkoxycarbonyl group of ^R9 , it is preferable to use the alkyl, aryl, ring alkyl.

In the present invention, as the amino group-containing alkoxysilane (A5), preferably an alkoxysilane compound containing at least a secondary amino group [especially represented by the above formula (4), the above formula (5a) or the above formula (5b) Ester-transformed alkoxysilanes (A5-4)]

[Amine chain extender (A6)]

The amine chain extender (A6) may be an amine compound having one amino group (primary amino group or secondary amino group, etc.) of polyamines. The number of amino groups (functional amino groups) other than tertiary amino groups in the molecule of such a polyamine is not particularly limited as long as it is at least 2, but it can be from, for example, 2 to 6 (preferably 2 to 4, more preferably 2 to 3). ) range selection. The amine chain extender (A6) includes, for example, aliphatic polyamines, alicyclic polyamines, aromatic polyamines, araliphatic polyamines, hydrazine, derivatives thereof, and the like. Amine chain extenders (A6) can be used alone or in combination of two or more.

Specifically, among the amine chain extenders (A6), examples of aliphatic polyamines include ethylenediamine, 1,3-trimethylenediamine, 1,4-tetramethylenediamine, Amine, 1,3-pentamethylenediamine, 1,5-pentamethylenediamine, 1,6-hexamethylenediamine, 1,2-propylenediamine, 1,2-butylene diamine, 2,3-butylenediamine, 1,3-butylenediamine, 2-methyl-1,5-pentamethylenediamine, 3-methyl-1,5-pentamethylene Aliphatic diamines such as 2,4,4-trimethyl-1,6-hexamethylenediamine, 2,2,4-trimethyl-1,6-hexamethylenediamine , and diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, etc.

Examples of alicyclic polyamines include 1,3-cyclopentanediamine, 1,4-cyclohexanediamine, 1,3-cyclohexanediamine, 1-amino-3-amino Methyl-3,5,5-trimethylcyclohexane, 1-amino-1-methyl-4-aminomethylcyclohexane, 1-amino-1-methyl-3-aminomethylcyclohexane Alkane, 4,4'-methylenebis(cyclohexylamine), 4,4'-methylenebis(3-methyl-cyclohexylamine), methyl-2,3-cyclohexanediamine, Methyl-2,4-cyclohexanediamine, methyl-2,6-cyclohexanediamine, 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl) Alicyclic diamines such as cyclohexane, isophoronediamine, norbornanediamine, and the like.

Examples of aromatic polyamines include m-phenylenediamine, p-phenylenediamine, 2,4-toluenediamine, 2,6-toluenediamine, naphthylene-1,4-diamine, Naphthyl-1,5-diamine, 4,4'-diphenyldiamine, 4,4'-diphenylmethanediamine, 2,4'-diphenylmethanediamine, 4,4'- Diphenyl ether diamine, 2-nitrodiphenyl-4,4'-diamine, 2,2'-diphenylpropane-4,4'-diamine, 3,3'-dimethyldiphenyl Aromatic diamines such as methoxymethane-4,4'-diamine, 4,4'-diphenylpropanediamine, 3,3'-dimethoxydiphenyl-4,4'-diamine, and the like.

As araliphatic polyamines, for example, 1,3-xylylenediamine, 1,4-xylylenediamine, α,α,α′,α′-tetramethyl-1 , 3-xylylenediamine, α,α,α′,α′-tetramethyl-1,4-xylylenediamine, ω,ω′-diamine-1,4-diethyl Benzene, 1,3-bis(1-amino-1-methylethyl)benzene, 1,4-bis(1-amino-1-methylethyl)benzene, 1,3-bis(α,α- Araliphatic diamines such as dimethylaminomethyl)benzene and the like.

Hydrazine and derivatives thereof include, for example, hydrazine, dihydrazine compounds, and the like. Dihydrazine compounds contain, for example, aliphatic dihydrazine dihydrazine oxalate, dihydrazine malonate, dihydrazine succinate, dihydrazine glutarate, dihydrazine adipate, etc. Acid dihydrazines; isophthalic acid dihydrazines, terephthalic acid dihydrazines and other aromatic dicarboxylic acid dihydrazines; 1,4-cyclohexanedicarboxylic acid dihydrazines and other alicyclic dicarboxylic acid dihydrazines class etc.

As the amine chain extender (A6), ethylenediamine, 1,3-pentamethylenediamine, 1,6-hexamethylenediamine, diethylenetriamine, triethylenediamine, Tetramine, 4,4'-methylenebis(cyclohexylamine), 4,4'-methylenebis(3-methyl-cyclohexylamine), 1,3-bis(aminomethyl)cyclo Hexane, isophoronediamine, norbornanediamine, 1,3-xylylenediamine and other aliphatic, alicyclic and araliphatic polyamines or hydrazine, carbodihydrazine and other hydrazines and their derivatives things.

[Alkoxysilyl-terminated polyurethane prepolymer (A) containing anionic group and tertiary amino group]

The alkoxysilyl-terminated polyurethane prepolymer (A) containing an anionic group and a tertiary amino group is, as described above, a polyol (A1), a polyol (A2), an isocyanate-reactive compound containing a tertiary amino group ( The reaction product of A3), polyisocyanate (A4), alkoxysilane (A5) containing isocyanate-reactive groups, and amine chain extender (A6) is an anion derived from polyol (A2) in the molecule Reactive group, and the tertiary amino group derived from the isocyanate reactive compound (A3) containing the tertiary amino group in the molecule, and the alkoxysilyl group derived from the alkoxysilane (A5) containing the isocyanate reactive group at the end of the main chain, And a polyurethane prepolymer having a urea bond site obtained by reacting the isocyanate group of the polyisocyanate (A4) with the amine group of the amine chain extender (A6). In addition, the alkoxysilyl-terminated polyurethane prepolymer (A) containing an anionic group and a tertiary amino group, if necessary, has the disadvantages derived from the alkoxysilane (A5) containing an isocyanate reactive group. A side chain [ester group (group having an ester bond)] of a saturated carboxylic acid ester.

The alkoxysilyl-terminated polyurethane prepolymer (A) containing anionic groups and tertiary amino groups can also be, for example, prepared from polyol (A1), polyol (A2), isocyanate containing tertiary amino groups The reaction of the polyurethane prepolymer containing anionic groups and tertiary amino groups obtained by the reaction of the reactive compound (A3) and the polyisocyanate (A4) with the reaction of the alkoxysilane (A5) containing the isocyanate reactive group makes the above Anionic group and tertiary amino group-containing polyurethane obtained by partially alkoxysilylation of terminal isocyanate group of polyurethane prepolymer containing anionic group and tertiary amino group In the prepolymer, the isocyanate group remaining in the polyurethane prepolymer containing an anionic group and a tertiary amino group containing the alkoxy silylation of the above-mentioned terminal part is further combined with the above-mentioned amines by using an amine chain extender (A6). An alkoxysilylated polyurethane prepolymer containing an anionic group and a tertiary amino group in which the amino group of the chain extender (A6) reacts to extend the chain.

More specifically, the polyurethane prepolymer containing an anionic group and a tertiary amino group is a reaction product of a polyol (A1), a polyol (A2), an isocyanate-reactive compound (A3) containing a tertiary amino group, and a polyisocyanate (A4). The product, this reaction can be carried out by a known or commonly used method of preparing a polyurethane prepolymer by reacting a polyol compound and a polyisocyanate compound. As a polyurethane prepolymer containing an anionic group and a tertiary amino group, it is preferable that the terminal is an isocyanate group.

In addition, when mixing or reacting polyol (A1), polyol (A2), tertiary amino group-containing isocyanate-reactive compound (A3), and polyisocyanate (A4), a polymerization catalyst may be used to accelerate the reaction. Alternatively, the reaction or mixing can be performed in a solvent.

Moreover, the reaction of the polyurethane prepolymer containing an anionic group and a tertiary amino group, and the alkoxysilane (A5) containing an isocyanate reactive group can be performed by mixing both, and heating as needed. Through the reaction of such polyurethane prepolymer containing anionic group and tertiary amino group and alkoxysilane (A5) containing isocyanate reactive group, the polyurethane prepolymer containing above-mentioned anionic group and tertiary amino group can be made The isocyanate group at the terminal is alkoxysilylated to prepare an alkoxysilylated anionic group-containing polyurethane prepolymer containing a terminal portion. In addition, when performing this mixing or reaction, a polymerization catalyst may be used as described above. In addition, a solvent may be used during the above-mentioned mixing or reaction.

As the above-mentioned polymerization catalyst, for example, known or commonly used polymerization catalysts (curing catalysts) used in the reaction of polyol compounds and polyisocyanate compounds can be used. More specifically, examples of the polymerization catalyst include organic tin compounds, metal complexes, basic compounds such as amine compounds, organic phosphoric acid compounds, and the like. Organotin compounds include, for example, dibutyltin dilaurate, dibutyltin maleate, dibutyltin phthalate, stannous octoate, dibutyltin methanol, dibutyltin diacetoacetate, basate Dibutyltin, etc. In addition, examples of metal complexes include titanate compounds such as tetrabutyl titanate, tetraisopropyl titanate, and triethanolamine titanate; Carboxylic acid metal salts such as cobalt alkanoate; acetylacetonate metal complexes such as aluminum acetylacetonate complexes, acetylacetonate vanadium complexes, etc. In addition, basic compounds such as amine compounds include, for example, silanes such as γ-aminopropyltrimethoxysilane and γ-aminopropyltriethoxysilane; tetramethylammonium chloride, benzalkonium chloride, etc. Quaternary ammonium salts; Sankyo Electronics Co., Ltd.'s trade name "DABCO" series or "DABCOBL" series, containing multiple nitrogen atoms such as 1,8-diazabicyclo[5.4.0]undecene-7-ene Linear or cyclic tertiary amine or quaternary ammonium salt, etc. Moreover, as an organic phosphoric acid compound, monomethyl phosphate, di-n-butyl phosphate, triphenyl phosphate, etc. are mentioned.

In addition, the reaction of the polyurethane prepolymer containing an anionic group and tertiary amino group containing an alkoxysilanized terminal part and the amine chain extender (A6) can be carried out by mixing the two and heating if necessary. . Through this reaction, the terminal isocyanate group remaining in the polyurethane prepolymer containing an anionic group and a tertiary amino group whose terminal part is alkoxysilanized reacts with the amino group of the above-mentioned amine chain extender (A6), and the above-mentioned An alkoxysilanized polyurethane prepolymer containing anionic groups and tertiary amino groups is chain-extended to prepare a polyurethane prepolymer containing alkoxysilanized anionic groups and tertiary amino groups. Alkoxysilyl-terminated polyurethane prepolymer (A) with group and tertiary amino group. When performing this mixing or reaction, a polymerization catalyst may be added in the same manner as above. As the polymerization catalyst, for example, known or commonly used catalysts (curing catalysts) used when polyol compounds and polyisocyanate compounds are reacted can be used.

In particular, the mixing or reaction of the polyurethane prepolymer containing anionic groups and tertiary amino groups and the amine chain extender (A6) with the above-mentioned alkoxysilanized terminal part can be performed on the alkoxysilanized terminal part The polyurethane prepolymer containing anionic groups and tertiary amino groups or its reaction mixture [may also contain a basic compound (B)] is carried out at any time before, during or after dispersing into water (C), but preferably after dispersing After neutralizing or dispersing. That is, it is preferable to add an amine chain extender (A6) to the water simultaneously when dispersing the polyurethane prepolymer containing an anionic group and a tertiary amino group whose terminal part is alkoxysilanized in water (C), or to disperse The amine chain extender (A6) was added and mixed in water, and the polyurethane prepolymer containing an anionic group and a tertiary amino group and the amine chain extender (A6) were reacted with the above-mentioned alkoxysilanized terminal portion.

In this way, an alkoxysilyl-terminated polyurethane prepolymer (A) containing an anionic group and a tertiary amino group can be prepared. In addition, it is not necessary to consider the mixing order of the components when performing these mixings. However, in order to efficiently obtain an alkoxysilyl-terminated polyurethane prepolymer (A) containing an anionic group and a tertiary amino group, it is preferable to firstly prepare polyol (A1), polyol (A2), and tertiary amino group-containing Add polyisocyanate (A4) to the mixture of isocyanate-reactive compound (A3), if necessary, add polymerization catalyst for reaction, prepare polyurethane prepolymer containing anionic group and tertiary amino group, add to the reaction mixture Alkoxysilane (A5) containing an isocyanate-reactive group is reacted to prepare a polyurethane prepolymer containing an anionic group and a tertiary amino group with an alkoxysilanized terminal part, and then the amine is extended Chain agent (A6) and water (C) are added at the same time, and the polyurethane prepolymer containing anionic group and tertiary amino group with alkoxysilanized terminal part is dispersed in water. At this time, alkoxysilanized terminal part The polyurethane prepolymer containing an anionic group and a tertiary amino group is chain-extended with an amine chain extender (A6), and a polyurethane prepolymer containing an alkoxysilanized anionic group and a tertiary amino group is prepared.

In the alkoxysilyl-terminated polyurethane prepolymer (A) containing an anionic group and a tertiary amino group, a polyol (A1), a polyol (A2), a tertiary amino group-containing isocyanate-reactive compound (A3) The ratio of each component of polyisocyanate (A4), alkoxysilane (A5) containing isocyanate-reactive groups, and amine chain extender (A6) is not particularly limited. For example, as the ratio of polyisocyanate (A4), polyol (A1), polyol (A2) and isocyanate-reactive compound (A3) containing tertiary amino groups, it can be obtained from the ratio of isocyanate group/polyol (A1) in polyisocyanate (A4) ), polyol (A2) and tertiary amino group-containing isocyanate-reactive compound (A3) containing hydroxyl-containing isocyanate-reactive groups (NCO/NCO-reactive groups) (equivalent ratio) is greater than 1 but is 2.0 or less (preferably 1.02 to 1.5, more preferably 1.05 to 1.4) range selection. When the ratio of this NCO/NCO reactive group is too large (for example, when it exceeds 2.0 (equivalent ratio)), it will become difficult to control the reaction (crosslinking reaction) at the time of chain extension, and dispersibility will fall. On the other hand, when the ratio of the NCO/NCO reactive group is too small (for example, when it is 1.0 or less (equivalent ratio)), the chain extension and the introduction of the silyl group cannot be sufficiently performed, and not only the time until the viscosity is extended, but also Furthermore, the physical properties are also lowered.

Alternatively, the polyisocyanate (A4) may have an isocyanate group content of 0.3 to 7.0% by mass (preferably 0.4 to 4.0% by mass, more preferably 0.5 to 3.0% by mass) in the polyurethane prepolymer containing an anionic group and a tertiary amino group. The ratio of mass %) contains. When the content of isocyanate groups is too large (for example, when it exceeds 7.0% by mass), it becomes difficult to control the reaction (crosslinking reaction) at the time of chain extension, and the dispersibility decreases. On the other hand, when the content of isocyanate groups is too small (for example, less than 0.3% by mass), the reaction time becomes very long, chain extension and silyl group introduction cannot proceed sufficiently, water resistance decreases, and the curing rate also becomes slow.

The polyol (A2) preferably has an anionic group content of 0.4 meq/g or more in the alkoxysilyl-terminated polyurethane prepolymer (A) containing an anionic group and a tertiary amino group. (eg, 0.4 to 0.7 meq/g, preferably 0.4 to 0.6 meq/g) is contained. When the content of the anionic group is too large, the viscosity of the silylated polyurethane water-based composition becomes high, resulting in a decrease in handleability, and at the same time, the water resistance after curing decreases. On the other hand, when the content of the anionic group is too small (for example, less than 0.4 meq/g), the dispersion stability of the resin component in the silylated polyurethane-based aqueous composition decreases and the adhesive force decreases.

The isocyanate-reactive compound (A3) containing a tertiary amino group is preferably an alkoxysilyl-terminated polyurethane prepolymer (A) containing an anionic group and a tertiary amino group. The content of the tertiary amino group is 0.15meq/g or 0.15meq /g or more (for example, 0.15 to 0.8 meq/g, preferably 0.15 to 0.6 meq/g). When the content of the tertiary amino group is too large, the viscosity of the alkoxysilyl-terminated polyurethane prepolymer (A) or the silylated polyurethane aqueous composition containing an anionic group and a tertiary amino group becomes high and the handleability decreases. On the other hand, when the content of the tertiary amino group is too small (for example, less than 0.15 meq/g), the adhesive force of the alkoxysilyl-terminated polyurethane prepolymer (A) containing an anionic group and a tertiary amino group decreases, The time required for the expression of the adhesive force becomes longer, and the initial adhesiveness decreases.

The alkoxysilane (A5) containing an isocyanate-reactive group is preferably an alkoxysilyl-terminated polyurethane prepolymer (A) containing an anionic group and a tertiary amino group. The silicon atom content in the polyurethane prepolymer (A) is, for example, 0.05 to 0.4 It is contained in a ratio of meq/g (preferably 0.05 to 0.3 meq/g). When the silicon content is too large (for example, when it exceeds 0.4 meq/g), since the molecular weight of the prepolymer decreases, the adhesive force decreases, and the time required to express the adhesive force tends to be longer. On the other hand, if it is too small (for example, when it is less than 0.05meq/g), due to the excessive molecular weight of the prepolymer, the physical properties of the film when viscous is exhibited will become hard, and the wettability will deteriorate. On the contrary, the adhesive force will decrease, and there will be , and the viscosity retention time becomes shorter. By controlling the silicon content (molecular weight of the prepolymer) it is possible to control the cohesion, the time to exhibit tack, and the tack retention time.

Moreover, when using an unsaturated carboxylic acid ester (A5-3), the usage-amount is preferable that the amino group containing alkoxysilane (A5-4) which was ester-transformed has at least one secondary amino group remaining. For example, it can be selected from the range of about 0.8 to 2 mol with respect to 1 mol of the primary amino group or the secondary amino group in the primary amino group-containing alkoxysilane. In addition, the unsaturated carboxylic acid ester (A5-3) can be reacted and used under conditions where at least a secondary amino group remains.

The amount of the amine chain extender (A6) preferably corresponds to the end portion obtained by the reaction of the polyurethane prepolymer containing anionic groups and tertiary amino groups and the alkoxysilane (A5) containing isocyanate reactive groups The amount of the terminal isocyanate group (the terminal isocyanate group remaining without carrying out alkoxysilylation) in the polyurethane prepolymer containing anionic group and tertiary amino group of alkoxysilanization can also be obtained from, for example , is selected in the range of 0.5 to 1.0 equivalents with respect to 1 equivalent of the isocyanate group.

In the present invention, the alkoxysilyl-terminated polyurethane prepolymer (A) containing anionic groups and tertiary amino groups, the ratio of anionic groups and tertiary amino groups contained in the molecule is preferably tertiary amino groups/anionic Group (molar ratio) = 0.2 to 1 (preferably 0.3 to 0.9). The ratio of the anionic group and the tertiary amino group in the alkoxysilyl-terminated polyurethane prepolymer (A) containing an anionic group and a tertiary amino group is tertiary amino group/anionic group (molar ratio)=0.2～ When 1, the time required to express the adhesive force can be effectively shortened, and the adhesive force can be improved.

In addition, in the polyurethane prepolymer (A) containing an anionic group and an alkoxysilyl group terminated with a tertiary amino group, the ratio of the tertiary amino group to the alkoxysilyl group contained in the molecule is preferably tertiary amino group/alkoxy group Silyl group (molar ratio) = 1.0 to 5.5 (preferably 1.5 to 5.5, more preferably 1.6 to 4.0). By adjusting the ratio of the tertiary amino group and the alkoxysilyl group in the polyurethane prepolymer (A) containing an anionic group and an alkoxysilyl group terminated with a tertiary amino group to tertiary amino group/alkoxysilyl group (Molar ratio) = 1.0 to 5.5 (by adjusting the molecular weight of the polymer and the interaction between polymer molecules), the time required to express the adhesive force can be effectively shortened, and the initial adhesiveness can be improved.

Thus, in the present invention, by controlling the ratio of the anionic group and the tertiary amino group contained in the molecule of the alkoxysilyl-terminated polyurethane prepolymer (A) containing the anionic group and the tertiary amino group, or the ratio of the tertiary amino group The ratio of amino group and alkoxysilyl group (especially the ratio of anionic group, tertiary amino group and alkoxysilyl group) can be adjusted when the water is slightly volatile. The effect is sharply improved. In addition, silanols condense with each other and gel quickly. Compared with conventional water-based adhesives, the time to develop viscosity can be greatly shortened, and excellent adhesion can also be exhibited. That is, excellent performance is exhibited by the synergistic effect of an anionic group, a tertiary amino group, and a silyl group.

[Basic compound (B)]

The basic compound (B) may be a basic inorganic compound or a basic organic compound. The basic compound (B) can be used individually or in combination of 2 or more types. As the basic inorganic compound, preferably used, for example, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; alkali metal carbonates such as sodium carbonate and potassium carbonate; alkali metal bicarbonates such as sodium bicarbonate and potassium bicarbonate Alkali metal compounds such as alkali metal acetates such as sodium acetate and potassium acetate, or alkaline earth metal hydroxides such as magnesium hydroxide; alkaline earth metal compounds such as alkaline earth metal carbonates such as magnesium carbonate, and ammonia.

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 are preferably used. Examples of the aliphatic amine include. For example, trimethylamine, triethylamine, tripropylamine, triisopropylamine, tributylamine, triisobutylamine, tri-sec-butylamine, tri-tert-butylamine, tripentylamine, trihexylamine and other trialkylamines; dimethylamine, Dialkylamines such as diethylamine and dibutylamine; monoalkylamines such as methylamine, ethylamine and butylamine; trimethanolamine, triethanolamine, tripropanolamine, triisopropanolamine, tributanolamine, Triolamines such as tripentanolamine, triisopentanolamine, and trihexanolamine; diolamines such as dimethanolamine and diethanolamine; monoolamines such as methanolamine and ethanolamine, and ethylenediamine, diethylene Triamine etc. Aromatic amines include, for example, N,N-dimethylaniline and the like. Examples of basic nitrogen-containing heterocyclic compounds include cyclic amines such as morpholine, piperidine, and pyrrolidine, and pyridine, α-picoline, β-picoline, γ-picoline, and quinoline. , N-methylmorpholine, etc.

In the present invention, ammonia or an amine compound is preferably used as the basic compound (B). Among the amine compounds, tertiary amine compounds such as trialkylamines and triolamines are preferable.

[Water (C)]

In the present invention, tap water, ion-exchanged water, pure water, or the like can be used as water (C).

[Silylated polyurethane water-based composition]

The silylated polyurethane aqueous composition of the present invention comprises an alkoxysilyl-terminated polyurethane prepolymer (A) containing an anionic group and a tertiary amino group, a basic compound (B), and water (C). . Specifically, the silylated polyurethane water-based composition may be a mixture of an alkoxysilyl-terminated polyurethane prepolymer (A) containing anionic groups and tertiary amino groups, a basic compound (B) and water (C). , may also be a reaction product comprising reacting an alkoxysilyl-terminated polyurethane prepolymer (A) containing an anionic group and a tertiary amino group, a basic compound (B) and water (C) by the mixture. The reaction composition of the object. Examples of the reaction between an alkoxysilyl-terminated polyurethane prepolymer (A) containing an anionic group and a tertiary amino group and a basic compound (B) include alkoxy groups containing an anionic group and a tertiary amino group. The neutralization reaction in which the anionic group in the silyl-terminated polyurethane prepolymer (A) is partially or completely neutralized by the basic compound (B). That is, through the reaction of the alkoxysilyl-terminated polyurethane prepolymer (A) containing an anionic group and a tertiary amino group and the basic compound (B), the alkoxymethyl group containing an anionic group and a tertiary amino group The anionic group in the silyl group-terminated polyurethane prepolymer (A) becomes a salt.

On the other hand, examples of the reaction between an alkoxysilyl-terminated polyurethane prepolymer (A) containing an anionic group and a tertiary amino group and water (C) include alkane containing an anionic group and a tertiary amino group. A hydrolysis reaction in which the terminal alkoxysilyl group in the oxysilyl-terminated polyurethane prepolymer (A) is hydrolyzed by water. That is, by reacting the polyurethane prepolymer (A) terminated with an alkoxysilyl group containing an anionic group and a tertiary amino group and water (C), the alkoxysilyl group containing an anionic group and a tertiary amino group A part or all of the terminal alkoxysilyl groups in the terminal polyurethane prepolymer (A) are silanol groups and/or siloxane bonds. That is, at least one alkoxy group in the terminal alkoxysilyl group in the alkoxysilyl-terminated polyurethane prepolymer (A) containing an anionic group and a tertiary amino group is subjected to water (C) effect on the hydrolysis reaction. In addition, a silanol group refers to a group containing a silicon atom having at least one hydroxyl group, and may have a substituent such as an alkoxy group.

Therefore, as the reaction product of the above-mentioned alkoxysilyl-terminated polyurethane prepolymer (A) containing an anionic group and a tertiary amino group, the basic compound (B) and water (C) react, there may be mentioned, The anionic group in the alkoxysilyl-terminated polyurethane prepolymer (A) containing an anionic group and a tertiary amino group is neutralized by a basic compound (B) to become a salt of an anionic group, and the terminal Aqueous silylated polyurethane prepolymers in which alkoxysilyl groups are partially or fully hydrolyzed by water to form silanol groups and/or siloxane linkages. That is, in the present invention, an aqueous silylated polyurethane-based composition containing the aforementioned aqueous silylated polyurethane prepolymer is preferable as the silylated polyurethane-based aqueous composition.

In this way, in the present invention, the silylated polyurethane aqueous composition can be an alkoxysilyl-terminated polyurethane prepolymer (A) containing an anionic group and a tertiary amino group, and a basic compound (B), and Water (C) is mixed for preparation, and the order of mixing is not particularly limited. As the silylated polyurethane water-based polymer of the present invention, a basic compound (B) and water (C) are blended into an alkoxysilyl-terminated polyurethane prepolymer (A) containing an anionic group and a tertiary amino group. , It is preferable to prepare an aqueous solution or an aqueous dispersion by promoting a reaction such as a neutralization reaction or a hydrolysis reaction by performing vigorous stirring or the like.

In addition, in the present invention, the basic compound (B) or water (C) may be used in advance when preparing the alkoxysilyl-terminated polyurethane prepolymer (A) containing an anionic group and a tertiary amino group. Specifically, for example, reaction products of polyol (A1), polyol (A2), tertiary amino group-containing isocyanate-reactive compound (A3) and polyisocyanate (A4) and isocyanate-reactive group-containing alkoxy When the silane (A5) is reacted, the above reaction can be performed in the presence of the basic compound (B) by adding the basic compound (B).

In the present invention, the basic compound (B) can be used not only when the polyurethane prepolymer containing anionic groups and tertiary amino groups reacts with the alkoxysilane (A5) containing isocyanate reactive groups, but also when preparing It can be used at any time during the process of the polyurethane prepolymer (A) terminated with the alkoxysilyl group of the neutral group and the tertiary amino group or the silylated polyurethane-based aqueous composition. Specifically, the basic compound (B) can be reacted with a polyol (A1), a polyol (A2), an isocyanate-reactive compound (A3) containing a tertiary amino group, and a polyisocyanate (A4) to prepare a Amino polyurethane prepolymers, or polyurethane prepolymers containing anionic groups and tertiary amino groups react with alkoxysilanes (A5) containing isocyanate reactive groups to prepare alkane containing anionic groups and tertiary amino groups. At any time or after the reaction, such as during the oxysilyl-terminated polyurethane prepolymer (A), the alkoxysilyl-terminated polyurethane prepolymer (A) containing an anionic group and a tertiary amino group It is used when dispersing in water (C).

In addition, water (C), for example, is the reaction product of polyol (A1), polyol (A2), tertiary amino group-containing isocyanate-reactive compound (A3) and polyisocyanate (A4) and isocyanate-reactive group-containing The polyurethane prepolymer containing anionic groups and tertiary amino groups obtained by the reaction of the alkoxysilane (A5) at the end part, and further, after reacting with the amine chain extender (A6) and extending the chain By adding water (C) before or during the dispersion of the anionic group-containing and tertiary amino group-containing polyurethane prepolymer having an alkoxysilanized terminal portion in water or after dispersion, the above chain extension reaction can be performed.

In the present invention, the amount of the basic compound (B) to be used can be as low as the anionic group in the alkoxysilyl-terminated polyurethane prepolymer (A) containing an anionic group and a tertiary amino group. It is selected from the range of about 50 to 120 mol % (preferably 80 to 110 mol %).

In addition, in the present invention, the amount of water (C) used may range from 65 to 100 parts by mass of the alkoxysilyl-terminated polyurethane prepolymer (A) containing an anionic group and a tertiary amino group. It is selected within the range of about 900 parts by mass (preferably 100 to 400 parts by mass).

In the present invention, the hydroxyl value (OHV) of the silylated polyurethane water-based composition is not particularly limited, and may range from, for example, about 60 to 400 mg-KOH/g (preferably 80 to 350 mg-KOH/g). range selection. In addition, the resin portion is not particularly limited, but can be selected from a range of about 10 to 60% by mass (preferably 20 to 50% by mass), for example.

In addition, in the present invention, the silylated polyurethane aqueous composition may be in the form of a completely aqueous silylated polyurethane aqueous composition that does not contain an organic solvent at all. In addition, the silylated polyurethane aqueous composition may contain hydrophilic organic solvents (water-soluble organic solvents) such as ketones and lower alcohols in order to adjust the viscosity of its aqueous solution or aqueous dispersion. These organic solvents can be used alone or in combination of two or more. Specifically, ketones include acetone and the like. In addition, examples of lower alcohols include monohydric alcohols such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol, sec-butanol, tert-butanol, pentanol, and hexanol; Polyols such as alcohol, propylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, glycerin, etc. In addition, as a water-soluble organic solvent, propylene carbonate; dimethyl carbonate; trimethyl phosphate; diether, diester or diallyl ether of polyethylene oxide; Diacetates; 1,3-dioxolane; N-methyl-2-pyrrolidone, etc. The usage-amount of such an organic solvent can be suitably selected according to the magnitude|size of the viscosity etc. which are adjusted, For example, with respect to 100 mass parts of polyurethane prepolymers (A) of the alkoxysilyl group terminal containing an anionic group and a tertiary amino group , can be selected from the range of about 0 to 100 parts by mass (preferably 0 to 50 parts by mass).

In addition, the silylated polyurethane-based aqueous composition may also contain a wettability-modified hydrophilic solvent. Examples of the wettability-modified hydrophilic solvent include surfactants such as N-methyl-2-pyrrolidone and polyethylene oxide alkyl ether, sodium alginate, mucopolysaccharides, sodium acrylate, etc. wait.

In the present invention, the silylated polyurethane water-based composition may also contain fillers, plasticizers, anti-aging agents, ultraviolet absorbers, antioxidants, heat stabilizers, colorants (pigments or dyes, etc.), anti-mildew agent, wetting accelerator, viscosity improver, perfume, various tackifiers (emulsification tackifier, etc.), coupling agent (titanate coupling agent, aluminum coupling agent, etc.), photocuring catalyst, emulsifier, surface Various additives or components such as active agents, latex or latex, cross-linking agents, humectants, defoamers, solvents, etc. For example, examples of fillers include calcium carbonate or calcium carbonate treated in various ways, fumed silica, clay, talc, various microspheres, neutral silica, kaolin, silicic acid aluminum etc. In addition, plasticizers include phthalates such as dioctyl phthalate and dibutyl phthalate; aliphatic carboxylic acid esters such as dioctyl adipate and dibutyl sebacate, and the like. Examples of the tackifier include emulsified tackifiers such as stabilized rosin esters, polymerized rosin esters, terpene phenols, and petroleum resins. As the crosslinking agent, isocyanate crosslinking agent, epoxy crosslinking agent, carbodiimide crosslinking agent, aziridine crosslinking agent, polyethyleneimine crosslinking agent, melamine crosslinking agent, etc. agent, colloidal silicon dioxide, etc. In addition, as the solvent, as long as it is a silylated polyurethane with an alkoxysilyl-terminated polyurethane prepolymer (A) containing an anionic group and a tertiary amino group (A), a basic compound (B) and water (C), There are no particular limitations on the substance having good compatibility with the aqueous composition, and any solvent can be used.

[Water-based adhesives, etc.]

The above-mentioned silylated polyurethane water-based composition can be used as a water-based adhesive or a water-based coating agent (water-based paint, etc.), especially, preferably as a water-based adhesive (especially a water-based encapsulation adhesive or a water-based contact adhesive) Adhesive) use. In addition, the silylated polyurethane water-based composition can be used not only as a water-based adhesive or a water-based coating agent, but also as an adhesive, a lamination material, a sealing primer, a primer, a sizing agent, a sealing material, and the like. That is, various processing agents such as aqueous adhesives and aqueous coating agents contain the aforementioned silylated polyurethane-based aqueous composition.

Water-based adhesives or water-based coating agents containing silylated polyurethane-based aqueous compositions have excellent initial adhesion (initial adhesiveness, initial adhesion, etc.) . Specifically, since the silylated polyurethane-based aqueous composition can be used as the polymer component, an alkoxysilyl-terminated polyurethane prepolymer (A) containing an anionic group and a tertiary amino group can be used, so it can be expressed in a short time. Excellent adhesion, excellent initial adhesion or initial adhesion. The reason is not certain, but it is considered to be because, when the alkoxysilyl-terminated polyurethane prepolymer (A) containing anionic group and tertiary amino group (A) is cured, even if the water in the silylated polyurethane aqueous composition Although there is almost no reduction, the interaction between anionic groups and tertiary amino groups also occurs in the molecule or between molecules, so that the molecular weight increases sharply on the surface.

In addition, if the ratio of the alkoxysilyl group in the alkoxysilyl-terminated polyurethane prepolymer (A) containing an anionic group and a tertiary amino group is an appropriate ratio to the ratio of the tertiary amino group, it can be Well-balanced and effective expression of the adhesion due to the molecular weight of the polyurethane prepolymer (A) itself containing an anionic group and alkoxysilyl-terminated tertiary amino group and the adhesion due to the interaction related to the tertiary amino group Because of this, the time required to exhibit excellent adhesion can be greatly shortened, and the initial adhesion can be effectively improved.

Furthermore, in the aqueous silylated polyurethane composition of the present invention, excellent adhesive force can be rapidly expressed even in a state of water retention. This is because water is only slightly volatilized, and appropriate adhesion (increased viscosity) is exhibited by interaction with tertiary amines, and by adjusting the alkoxysilyl terminal containing anionic groups and tertiary amino groups, If the molecular weight of the polyurethane prepolymer (A) is an appropriate molecular weight (average molecular weight), the optimum adhesive force can be imparted, and even if the moisture is kept as it is, the crosslinking reaction will proceed, thereby excellent adhesion Strength can be manifested quickly.

In addition, since the amine chain extender (A6) was used as the chain extender, the curing speed was also increased.

In particular, since the above-mentioned silylated polyurethane aqueous composition comprises an alkoxysilyl-terminated polyurethane prepolymer (A) containing an anionic group and a tertiary amino group, a basic compound (B) and water (C), The silanol groups of aqueous silylated polyurethane prepolymers are very stable, even in water. The reason for this has not been determined, but it is considered that the stability is improved because a large number of water molecules in the system protect the silanol groups, inhibit or prevent the condensation reaction between the silanol groups. In addition, it is also considered that the silanol group is bonded to the nitrogen derived from the secondary or tertiary amino group of the amino group-containing alkoxysilane (A5-1) which is the isocyanate-reactive group-containing alkoxysilane compound (A5). The substituents on the atoms (for example, long-chain substituents from unsaturated carboxylic acid ester (A5-3) or its ester moiety, etc.) protect and inhibit or prevent the condensation reaction between silanol groups, and the stability is further improved.

Therefore, an aqueous adhesive or aqueous coating agent containing a silylated polyurethane-based aqueous composition can be used as a one-component treatment agent such as a one-component aqueous adhesive or a one-component aqueous coating agent.

In addition, the silylated polyurethane-based aqueous composition cures rapidly under conditions where the water in the system dries down due to evaporation or volatilization (for example, when coating on an open surface or on a porous material, etc.). Moreover, the curing rate of the curing has little dependence on the drying rate of water, and especially when the silylated polyurethane-based aqueous composition is used as an aqueous adhesive or an aqueous coating agent (aqueous paint, etc.), the aqueous adhesive Or the dependence of the curing speed of the water-based coating agent on the drying speed of water is smaller than that of conventional water-based adhesives or water-based coating agents. This is because, after the silylated polyurethane-based aqueous composition is coated, when the evaporation of water in the aqueous composition decreases, the silanol groups in the aqueous silylated polyurethane prepolymer in the aqueous composition cause a condensation reaction, thereby Curing (crosslinking) occurs. That is, it is considered that the condensation reaction of the silanol groups in the aqueous silylated polyurethane prepolymer in the aqueous composition is mainly involved in curing.

In addition, the crosslinking reaction proceeds due to the reduction of water, and this crosslinking reaction proceeds even in the presence of water to some extent, and cohesive force can be exhibited even if the water content is kept as it is.

Furthermore, since the alkoxysilyl-terminated polyurethane prepolymer (A) containing an anionic group and a tertiary amino group (A) is chain-extended by an amine chain extender (A6), it has a urea bond in the molecule, and the cohesion very high.

Therefore, the silylated polyurethane water-based composition of the present invention requires a short time to exhibit excellent adhesion, excellent initial adhesion (initial adhesion, etc.), and at the same time, has an extremely fast curing speed and has a unique fast curing property. .

In addition, it is considered that the faster the curing rate and the higher the initial adhesiveness, the ion centers (salts of anionic groups such as carboxylates) introduced into the molecules of the water-based silylated polyurethane prepolymer due to water-based Catalysts play a role in promoting the condensation reaction between silanol groups.

In this way, no matter whether the above-mentioned silylated polyurethane water-based composition is water-based or not, the curing speed is very fast, and it can show excellent adhesion and initial adhesion (initial adhesion or initial adhesion, etc.) in a short period of time. ) is excellent. Therefore, when the silylated polyurethane aqueous composition is used as various processing agents such as aqueous adhesives (adhesives for aqueous encapsulation, etc.), productivity equivalent to that of solvent-based adhesives can be exhibited. Specifically, when using a silylated polyurethane-based aqueous composition as an adhesive for aqueous encapsulation, the adhesive for aqueous encapsulation is coated on a plastic sheet, and the coated surface is bonded to a porous plate (such as , on substrates such as laminated boards, particleboards, MDF, etc., and because it can exhibit excellent adhesion in a short time at this time and exhibit excellent initial adhesion, it is compatible with the use of solvents It has the same productivity as the adhesive for encapsulation, and the encapsulation of the base material can be performed with a sheet made of plastic. Moreover, since the initial bonding strength is high, even if the surface of the substrate has unevenness, there will be no gap between the plastic sheet and the substrate, and the plastic sheet can be quickly bonded with excellent adhesion. on the substrate.

In particular, an aqueous adhesive containing a silylated polyurethane aqueous composition has excellent storage stability and can be prepared as an aqueous one-component adhesive. Therefore, by using the aqueous encapsulation adhesive as a one-component type, it is possible to remarkably improve the operability at the time of encapsulation operation, and from this point of view, it is possible to further improve productivity. That is, conventional encapsulation adhesives mainly use solution-type two-component adhesives. During encapsulation, the main agent and the two components of the curing agent must be mixed. However, in the present invention, by making an aqueous one- The liquid-type adhesive for encapsulation can omit the mixing process of mixing the main ingredient and the curing agent.

In addition, as an adhesive for encapsulation (for example, an adhesive for water-based encapsulation, etc.), it means that a sheet made of plastic is bonded to a base material through an adhesive layer, thereby encapsulating with a sheet made of plastic. Adhesives used for sealing substrates. When encapsulating the base material with a plastic sheet, it is usually used to apply the encapsulating adhesive on the plastic sheet, and then stick the encapsulating adhesive-applied surface of the plastic sheet to the base material. The above method, but the encapsulation method of the base material of the sheet made of plastic is not particularly limited. In such encapsulation, the industry can use a cloth wrapping machine, a molding machine, a curved surface bonding machine, a film pressure (vacuum film press, etc.), encapsulating machines using soft rolls, encapsulating machines called four-sided laminators, etc., various encapsulating machines are commercially available.

As the above-mentioned base material, for example, a base material made of a porous material can be preferably used, and a porous wooden material such as a laminated board, a particle board, and a wooden board such as MDF (porous wooden material) is particularly preferable. The shape of the substrate is not particularly limited, and may be, for example, a substrate having unevenness on the surface, or a plate-like substrate with a flat surface.

In addition, there are no particular limitations on the sheet made of the above-mentioned plastic, for example, a sheet made of polyester such as a sheet made of polyethylene terephthalate; a sheet made of polyvinyl chloride; a sheet made of polyethylene, a polyethylene terephthalate sheet, etc. Sheets made of polyolefins such as acrylic sheets may be sheets made of other resins. The size and thickness of the sheet made of plastic are not particularly limited and can be selected appropriately.

Since the silylated polyurethane aqueous composition of the present invention can be used as a configuration having contact adhesiveness, it can also be used as an aqueous contact adhesive. In this way, when the silylated polyurethane aqueous composition is used as a water-based contact adhesive, since the water-based contact adhesive has high initial bonding strength, it is not necessary to pre-press when bonding adherends together. · Pressing can shorten the time required for bonding, and the bonding workability is good, and multiple adherends can be easily bonded. In particular, it is extremely advantageous in that it is excellent in initial adhesive strength even if it is completely water-based that does not contain any organic solvent.

In addition, in the silylated polyurethane water-based composition, the alkoxysilyl-terminated polyurethane prepolymer (A) containing anionic groups and tertiary amino groups may also be a polymer with a relatively low molecular weight, for example, the number average The molecular weight can be selected from the range of about 3000 to 50000 (preferably 10000 to 30000). Also, after curing, siloxane bonds can be formed to become higher molecular weight polymers.

In this way, the silylated polyurethane water-based composition can be used as a water-based adhesive or a water-based coating agent (especially a water-based adhesive). Type adhesives are used.

In particular, since it is an aqueous type (particularly, it may be completely aqueous without any organic solvent), it is excellent in handling and operability, and is highly safe to humans and the environment.

In addition, since the alkoxysilyl-terminated polyurethane prepolymer (A) containing an anionic group and a tertiary amino group has a silanol group, a water-based adhesive (especially a water-based adhesive) containing a silylated polyurethane water-based composition Contact adhesives) or water-based coating agents exhibit good adhesion or adhesion not only to porous materials such as paper but also to non-porous materials such as metal and glass. That is, as the base material (adhered body, coated body, etc.) to which the above-mentioned aqueous adhesive or aqueous coating agent can be applied, various base materials can be used as shown in the following specific examples.

The base material may be, for example, either a porous material or a non-porous material. More specifically, as the material of the adherend, for example, wooden materials such as wood, laminated boards, wood chip boards, particleboards, and hard fiberboards; Inorganic materials such as tiles; melamine resin decorative boards, phenolic resin boards, expanded polystyrene, various plastic films or molded products (for example, polyvinyl chloride-based films or molded products, polyester-based films or molded products, polystyrene Plastic materials such as vinyl film or molded product, polyolefin film or molded product, etc.); rubber materials such as natural rubber, synthetic rubber, silicone rubber, etc.; Hard-to-adhesive paper materials such as surface-treated processed paper such as moisture-proof paper, glass materials, metal materials (such as iron, aluminum, stainless steel, copper, etc.), leather materials, fiber materials such as cloth and non-woven fabrics, etc.

In this way, the aqueous adhesive or coating agent containing the silylated polyurethane aqueous composition can be applied to substrates containing a wide range of materials, and can be used to bond porous materials especially by contact bonding.

The substrates used for bonding by adhesion may be substrates containing the same material or substrates containing different materials. The substrates may be used alone or in combination of two or more.

In addition, there is no particular limitation on the method of attaching the adherend using a water-based adhesive containing a silylated polyurethane water-based composition. For example, directly coating the adherend Various methods such as the method of bonding the adherends together, or the contact bonding method of attaching the adherends to each other in a state where adhesiveness is exhibited after a predetermined time has elapsed after coating on the adherends . In addition, in the present invention, as the contact bonding method, it includes not only coating on the bonding surface of two adherends among the two adherends as stipulated in JIS K 6800, and passing a predetermined time , a method of laminating and bonding two adherends in a state exhibiting adhesiveness, further comprising coating on the bonding surface of any one of the bonded two adherends In this method, after a predetermined period of time, two adherends are laminated and bonded in a state where adhesiveness is exhibited. That is, in the present invention, the so-called contact adhesion refers to coating on at least one of the bonding surfaces of the adherends to be bonded, and after a predetermined period of time, in a state where adhesiveness is exhibited Lay the two adherends together and bond them.

As mentioned above, since the silylated polyurethane water-based composition of the present invention has the above-mentioned constitution, it is highly safe, and in addition, it takes a short time to exhibit excellent adhesive force, and the initial adhesiveness is excellent. Same productivity when using solvent-based adhesives. Therefore, the aforementioned silylated polyurethane-based aqueous composition is useful as an aqueous encapsulation adhesive or an aqueous contact adhesive.

Example

Hereinafter, the present invention will be described more specifically by way of examples, but the present invention is not limited by these examples. In addition, below, unless otherwise specified, "part" means "mass part", and "%" means "mass %". Materials used in Examples and Comparative Examples are as follows.

[Polyol compound (A1) not containing anionic group]

(1) Trade name "PTMG2000" [manufactured by Mitsubishi Chemical Corporation, polytetramethylene ether glycol, number average molecular weight: 2000, hydroxyl value: 57.4 mg-KOH/g; sometimes called "polyol (A1-a) "]

(2) Trade name "NS2471" [manufactured by Asahi Denka Co., Ltd., polyester diol, number average molecular weight: 2000, hydroxyl value: 56.1 mg-KOH/g; sometimes called "polyol (A1-b)"]

(3) 1,4-Butanediol [sometimes called "polyol (A1-c)"]

[Anionic group-containing polyol compound (A2)]

(1) 2,2-Dimethylolpropionic acid [hydroxyl value: 837.3 mg-KOH/g; sometimes called "polyol (A2-a)"]

(2) 2,2-Dihydroxymethylbutanoic acid [hydroxyl value: 754.0 mg-KOH/g; sometimes called "polyol (A2-b)"]

[Compound (A3) containing a tertiary amino group and an isocyanate-reactive group]

(1) N-methyl-diethanolamine [N,N-bis(2-hydroxyethyl)-N-methylamine; hydroxyl value: 941.6mg-KOH/g; sometimes called "polyol (A3-a) "]

(2) N-n-butyl-diethanolamine [N, N-bis(2-hydroxyethyl)-N-n-butylamine; hydroxyl value: 695.9mg-KOH/g; sometimes called "polyol (A3- b)”]

(3) N, N-bis[2-hydroxyethyl-poly(oxyethylene-propylene oxide)]-N-ethylamine [so-called [amine polyol]; number average molecular weight: 2000, hydroxyl value: 55.7mg- KOH/g; sometimes called "Polyol (A3-c)"]

[polyisocyanate compound (A4)]

(1) Isocyanate diisocyanate [isocyanate content (NCO content): 37.8%, IPDI; sometimes called "polyisocyanate (A4-a)"]

[Alkoxysilane compound (A5) containing an isocyanate-reactive group]

(1) Product name "KBM903" [made by Shin-Etsu Chemical Co., Ltd., γ-aminopropyltrimethoxysilane; sometimes called "amino group-containing alkoxysilane (A5-a)"]

(2) Product name "KBM573" [Shin-Etsu Chemical Co., Ltd., N-phenyl-γ-aminopropyltrimethoxysilane; sometimes called "amino group-containing alkoxysilane (A5-b)"]

(3) For the product name "KBM602" [Shin-Etsu Chemical Co., Ltd., N-β(aminoethyl)-γ-aminopropylmethyldimethoxysilane]: 1 mole, using 2-ethylhexyl acrylic acid Esters: 2 moles, mixed, and reacted at 50°C for 7 days to obtain a reaction product [sometimes called "amino group-containing alkoxysilane (A5-c)"]

(4) For the product name "KBM602" [Shin-Etsu Chemical Co., Ltd., N-β(aminoethyl)-γ-aminopropylmethyldimethoxysilane]: 1 mole, n-butyl acrylate used: 2 Molar ratio, mixed, and reacted at 50°C for 7 days to obtain a reaction product [sometimes called "amino group-containing alkoxysilane (A5-d)"]

(5) To the product name "KBM903" [Shin-Etsu Chemical Co., Ltd., γ-aminopropyltrimethoxysilane]: 1 mole, 2-ethylhexyl acrylate: 2 moles, mixed, and heated at 50°C The reaction was carried out for 7 days to obtain a reaction product [sometimes called "amino group-containing alkoxysilane (A5-e)"]

[chain extender]

(1) Isophoronediamine [amine chain extender; sometimes called "chain extender (A6-a)"]

(2) Ethylenediamine [amine chain extender; sometimes called "chain extender (A6-b)"]

[Basic compound (B)]

(1) Triethylamine

[Water (C)]

(1) Ion exchanged water (deionized water)

(Example 1)

Mix polyol (A1-a): 150 parts, polyol (A2-b): 20 parts, polyol (A3-a) in a 4-neck flask equipped with a nitrogen inlet tube, thermometer, condenser, and stirring device : 8 parts, polyisocyanate (A4-a): 75.2 parts and methyl ethyl ketone (MEK): 100 parts, carried out the reaction for 6 hours at a temperature of 80 to 85° C. under a nitrogen stream to obtain a carboxyl group-containing and Reaction mixture of isocyanate-terminated polyurethane prepolymers with tertiary amino groups.

Next, in the total amount of the reaction mixture of the isocyanate group-terminated polyurethane prepolymer containing carboxyl groups and tertiary amino groups, 6.5 parts of alkoxysilanes (A5-a) containing amino groups: The reaction was carried out under temperature and nitrogen flow for 1 hour to obtain a reaction mixture containing isocyanate groups containing carboxyl groups and tertiary amino groups and alkoxysilyl-terminated polyurethane prepolymers.

Furthermore, after cooling the reaction mixture containing isocyanate groups containing carboxyl groups and tertiary amino groups and alkoxysilyl-terminated polyurethane prepolymers to 40°C, add triethylamine: 13.6 parts, and add in advance under high-speed stirring Chain extender (A6-a): 5.7 parts of aqueous solutions were dissolved in 496 g of deionized water to obtain a dispersion. MEK was distilled off from this dispersion liquid at 45-50 degreeC under reduced pressure, and the silylated polyurethane type aqueous composition which adjusted the solid content to 36% with deionized water was obtained.

(Examples 2-13)

Except having made the composition shown in Table 1 or 2, it carried out similarly to Example 1, and obtained the silylated polyurethane type aqueous composition which concerns on Examples 2-13, respectively.

(Comparative Examples 1-2, 6)

Except having made the composition shown in Table 3, it carried out similarly to Example 1, and obtained the silylated polyurethane type water-based composition or polyurethane type water-based composition concerning Comparative Examples 1-2, 6, respectively.

(comparative example 3)

Except having the composition shown in Table 3, it carried out similarly to Example 1, and obtained the reaction mixture containing the isocyanate group-terminated polyurethane prepolymer containing a carboxyl group and a tertiary amino group with 2.0% of residual isocyanate groups. Next, in the total amount of the reaction mixture of the isocyanate group-terminated polyurethane prepolymer containing carboxyl groups and tertiary amino groups, 20.6 parts of alkoxysilane (A5-c) containing amino groups, 1,4- Butanediol: 3.0 parts After mixing, the reaction was carried out at a temperature of 80-85° C. under a nitrogen flow for 2 hours to obtain a reaction mixture containing an alkoxysilyl-terminated polyurethane prepolymer containing carboxyl and tertiary amino groups. In addition, after cooling the reaction mixture containing isocyanate groups containing carboxyl groups and tertiary amino groups and alkoxysilyl-terminated polyurethane prepolymers to 40°C, add triethylamine: 13.6 parts and mix them. Under high-speed stirring, add 507 parts of deionized water to obtain a dispersion. MEK was distilled off from this dispersion liquid at 45-50 degreeC under reduced pressure, and the silylated polyurethane type aqueous composition which adjusted the solid content to 36% with deionized water was obtained.

(Comparative Examples 4-5, 7)

Except having made the composition shown in Table 3, it carried out similarly to the comparative example 3, and obtained the silylated polyurethane type water-based composition or polyurethane type water-based composition concerning Comparative Examples 4-5, 7, respectively.

In addition, in Tables 1-3, "carboxyl group equivalent (meq/g)" shows the equivalent of the carboxyl group in 1g of the resin component in the silylated polyurethane-type aqueous composition or polyurethane-type aqueous composition:1g. "Tertiary amino group equivalent (meq/g)" shows the equivalent of the tertiary amino group in 1 g of the resin component in a silylated polyurethane type aqueous composition or a polyurethane type aqueous composition. "Tertiary N/COOH (equivalent ratio)" represents the ratio of the equivalent weight of a tertiary amino group and the equivalent weight of a carboxyl group in 1 g of the silylated polyurethane aqueous composition or the resin component in a polyurethane aqueous composition.

Moreover, "silicon equivalent (meq/g)" shows the equivalent of the silicon atom in 1 g of the resin component in a silylated polyurethane-type aqueous composition or a polyurethane-type aqueous composition. "Tertiary N/Si (equivalent ratio)" represents the ratio of the equivalent weight of the tertiary amino group and the equivalent weight of a silicon atom in 1 g of the silylated polyurethane aqueous composition or the resin component in the polyurethane aqueous composition.

Table 1 Example 1 2 3 4 5 6 7 Polyol (A1-a) 150 150 150 150 150 150 Polyol (A1-b) 150 Polyol (A1-c) Polyol (A2-a) 20 20 Polyol (A2-b) 20 20 20 20 20 Polyol (A3-a) 8 8 8 8 8 8 8 Polyol (A3-b) Polyol (A3-c) Polyisocyanate (A4-a) 75.2 75.2 75.2 75.2 75.2 78.7 78.3 Amino-containing alkoxysilane (A5-a) 6.5 Amino-containing alkoxysilanes (A5-b) 9.2 Amino-containing alkoxysilane (A5-c) 20.8 Amino-containing alkoxysilanes (A5-d) 16.7 Amino-containing alkoxysilane (A5-e) 13.2 13.3 13.3 Chain extender (A6-a) 5.7 5.7 5.7 5.7 5.7 5.8 5.8 Chain extender (A6-b) Triethylamine 13.6 13.6 13.6 13.6 13.6 15.1 15.1 Deionized water 496 501 522 514 508 517 516 total 775 782.7 815.3 803.2 793.7 807.9 806.5 Carboxyl equivalent (meq/g) 0.51 0.50 0.48 0.49 0.50 0.54 0.54 Tertiary Amino(meq/g) 0.25. 0.25 0.24 0.24 0.25 0.24 0.24 Tertiary N/COOH group (equivalent ratio) 0.50 0.50 0.50 0.50 0.50 0.45 0.45 Si equivalent (meq/g) 0.14 0.13 0.13 0.13 0.13 0.13 0.13 Tertiary N/Si (equivalent ratio) 1.86 1.86 1.86 1.86 1.86 1.83 1.83 initial adhesion leave for 10 seconds x x x x x x x Leave for 15 seconds △ △ △ △ △ △ △ leave for 20 seconds ○ ○ ○ ○ ○ ○ ○ Leave for 25 seconds ○ ○ ○ ○ ○ ○ ○ leave for 30 seconds ○ ○ ○ ○ ○ ○ ○ Leave for 35 seconds ◎ ◎ ◎ ◎ ◎ ◎ ◎ leave for 40 seconds ×× ×× ×× ×× ×× ×× ×× Leave for 45 seconds Leave for 50 seconds Leave for 55 seconds Leave for 60 seconds Leave for 65 seconds Leave for 70 seconds

Table 2 Example 8 9 10 11 12 13 Polyol (A1-a) 150 100 150 150 150 150 Polyol (A1-b) Polyol (A1-c) 5 Polyol (A2-a) Polyol (A2-b) 25 25 25 25 20 20 Polyol (A3-a) 12 16 5 15 Polyol (A3-b) 12 Polyol (A3-c) 50 Polyisocyanate (A4-a) 85.3 80.3 91.5 99.6 69.2 89.4 Amino-containing alkoxysilane (A5-a) Amino-containing alkoxysilanes (A5-b) Amino-containing alkoxysilane (A5-c) 22.4 14.3 15.3 15.9 10.0 30.1 Amino-containing alkoxysilane (A5-d) Amino-containing alkoxysilane (A5-e) Chain extender (A6-a) 6.2 6.7 7.2 6.7 5.3 Chain extender (A6-b) 2.7 Triethylamine 17.1 17.1 17.1 17.1 13.6 13.6 Deionized water 565 530 565 573 488 575 total 883 828.4 883.1 899.3 762.5 898.4 Carboxyl equivalent (meq/g) 0.56 0.60 0.56 0.55 0.52 0.44 Tertiary Amino(meq/g) 0.25 0.09 0.33 0.43 0.16 0.41 Tertiary N/COOH group (equivalent ratio) 0.44 0.15 0.60 0.79 0.31 0.93 Si equivalent (meq/g) 0.13 0.09 0.09 0.09 0.07 0.17 Tertiary N/Si (equivalent ratio) 1.91 1.01 3.80 4.85 2.41 2.41 initial adhesion leave for 10 seconds x x x x x x Leave for 15 seconds ○ ○ ○ ○ ○ △ leave for 20 seconds ○ ○ ○ ◎ ○ ○ Leave for 25 seconds ○ ◎ ◎ ◎ ○ ○ leave for 30 seconds ◎ ◎ ◎ ×× ◎ ◎ Leave for 35 seconds ×× ×× ×× ×× ×× leave for 40 seconds Leave for 45 seconds Leave for 50 seconds Leave for 55 seconds Leave for 60 seconds Leave for 65 seconds Leave for 70 seconds

table 3 comparative example 1 2 3 4 5 6 7 Polyol (A1-a) 150 150 150 150 150 150 100 Polyol (A1-b) Polyol (A1-c) 6 6 6 5 Polyol (A2-a) Polyol (A2-b) 20 20 20 20 20 20 20 Polyol (A3-a) 6 6 6 Polyol (A3-b) Polyol (A3-c) 50 Polyisocyanate (A4-a) 75.0 75.0 75.0 71.2 71.2 71.2 72.2 Amino-containing alkoxysilane (A5-a) 6.4 Amino-containing alkoxysilane (A5-b) Amino-containing alkoxysilane (A5-c) 20.6 20.6 Amino-containing alkoxysilane (A5-d) 16.3 Amino-containing alkoxysilane (A5-e) 12.8 Chain extender (A6-a) 5.7 5.7 8.0 Chain extender (A6-b) 1,4-Butanediol 3.0 3.0 4.2 3.0 Triethylamine 13.6 13.6 13.6 13.6 13.6 13.6 13.6 Deionized water 492 517 507 493 464 478 486 total 768.7 807.9 795.2 773.1 729 746.8 762.6 Carboxyl equivalent (meq/g) 0.51 0.49 0.49 0.51 0.54 0.53 0.51 Tertiary Amino(meq/g) 0.00 0.00 0.00 0.19 0.20 0.20 0.10 Tertiary N/COOH group (equivalent ratio) 0.00 0.00 0.00 0.37 0.37 0.37 0.19 Si equivalent (meq/g) 0.14 0.13 0.13 0.13 0.00 0.00 0.13 Tertiary N/Si (equivalent ratio) 0.00 0.00 0.00 1.43 - - 0.71 initial adhesion leave for 10 seconds x x x x x x x Leave for 15 seconds x x x x x x x leave for 20 seconds x x x x x x x Leave for 25 seconds x x x x x x x leave for 30 seconds x x x △ x △ x Leave for 35 seconds △ △ △ △ △ △ △ leave for 40 seconds ×× ×× △ ○ ○ ×× ○ Leave for 45 seconds ○ ○ ○ ○ Leave for 50 seconds ○ ○ ○ ○ Leave for 55 seconds ○ ○ ○ ○ Leave for 60 seconds ○ ×× ×× ○ Leave for 65 seconds ×× ×× Leave for 70 seconds

(evaluate)

The initial adhesiveness of the silylated polyurethane aqueous composition, etc. was evaluated with respect to the silylated polyurethane aqueous composition or adhesive agent concerning Examples 1-13 and Comparative Examples 1-7 by the evaluation method of the following initial stage adhesiveness. In addition, the evaluation results were recorded in Tables 1-3 at the same time.

[Evaluation method of initial adhesion]

Apply the silylated polyurethane water-based composition or adhesive on a sheet made of olefin resin (coating amount: about 80 g/m ² ), and dry at 70°C for an arbitrary predetermined time (respectively, as listed in Tables 1 to 3). After the time indicated), the MDF (porous wooden material) was pasted on the coated surface, pressed with a hand roller, and the peeling adhesion strength (N/25mm) was measured immediately based on JIS K 6854-2, by the following Evaluation Criteria The initial adhesiveness was evaluated.

(evaluation criteria)

◎: Peel adhesive strength of 10 (N/25mm) or more

○: Peel adhesive strength is 7.5 (N/25mm) or more, less than 10 (N/25mm)

△: Peeling adhesive strength is 5 (N/25mm) or more, less than 7.5 (N/25mm)

×: Peeling adhesive strength is less than 5 (N/25mm)

××: Loss of tack, unable to bond

In addition, in the evaluation criteria of the above test (evaluation method of initial adhesion), "◎" indicates "excellent", "○" indicates "good", "△" indicates "pass", and "×" indicates "failure". ".

As can be clearly seen from Tables 1 to 3, the silylated polyurethane-based water-based compositions corresponding to Examples 1 to 13 of the present invention exhibit adhesive force 15 seconds after coating, and the time required to exhibit adhesive force is even water-based Also extremely short. Therefore, when using the silylated polyurethane water-based composition related to the examples, since it is water-based, it is highly safe, and even if it is water-based, it can be obtained in a short time to exhibit excellent adhesive force, and the initial Various treatment agents such as adhesives and coating agents with excellent adhesion.

In addition, for the silylated polyurethane water-based composition (or adhesive) related to Example 10, even if the weight loss (heating weight loss) when drying at 70°C for 20 seconds is about 20% by mass, it will appear at this time. Good adhesive, showing convergence (receiving まり). On the other hand, for the silylated polyurethane-based aqueous composition (or adhesive) according to Comparative Example 3, the weight loss (heat loss) when dried at 70° C. for 20 seconds was about 20 mass by weight as in Example 10. %, but at this time it was still in a wet state, showing no convergence at all. In this way, the silylated polyurethane water-based composition according to the examples has a small weight loss ratio due to evaporation of water, and also exhibits good adhesion at the initial stage of drying when it contains too much water, which has not been able to express adhesive force in the past. Adhesive force, the time required to express excellent adhesive force is short, and the initial stage adhesiveness is excellent.

In addition, apply the silylated polyurethane water-based composition (or adhesive) obtained in Example 3 on a slate, and make the coating amount about 300g/m ² , and place it under the conditions of 23°C and 55%RH After 5 minutes, when the cork floor tiles were pressed together with the stone slabs using a hand roller, shifting and floating (floating) could not be confirmed, showing good convergence.

Furthermore, the silylated polyurethane water-based composition (or adhesive) obtained in Example 3 is coated on each side of cork wood and gypsum board, and the coating amount is about 200g/m ² , at 23 After being left for 10 minutes under the conditions of °C and 55% RH, when the two were bonded together, no shifting or blooming was observed, showing good astringency.

Furthermore, the silylated polyurethane water-based composition (or adhesive) obtained in Example 3 is coated on each side of the decorative calcium silicate board and the gypsum board, and the coating amount is about 200g/m ² , After forced drying for 15 minutes, the two were pasted together and pulled and peeled off immediately, and the gypsum board was destroyed, showing good astringency.

Furthermore, the silylated polyurethane water-based composition obtained in Example 3 was used as an adhesive, and the product name of the device "Profile Laminator (Profair Ramine) PL-300CE" was used as an encapsulating machine. Manufactured by Marunaka Iron Works Co., Ltd.], a polyolefin sheet (thickness: 50 μm; surface treatment with a primer) printed with a wood grain pattern on the surface was bonded to Figures 1 to 3 under the following bonding conditions When the surface of MDF (length: 2.5m) with the cross-sectional shape shown is made into the forms shown in Fig. 4 to Fig. 6, the two-component solvent-based polyurethane At the same linear speed (approximately 15 m/min or more) as in the case of resin adhesives, the sheet can be bonded in a state of close contact along the shape of the MDF without cracking. Specifically, for example, in the MDF shown in FIG. 1, there is a portion A called a so-called "reverse radius portion". However, as shown in FIG. , can be fitted without problems. In addition, for the MDF shown in FIG. 2, as shown in FIG. 5, the place about 3 mm away from the corner is used as the end of the sheet, but even if it is a short bead width of about 3 mm, there is no gap on the sheet. Floating occurs and lamination can be performed without problems. In addition, in the MDF shown in FIG. 3, there is a part B which is a small convex part. However, as shown in FIG. fit.

(fitting conditions)

(1) In the case of MDF having the shape shown in Fig. 1

Coating amount: 80μm (wet thickness; 80g/m ² )

·Linear speed: 15m/min

·Temperature of drying oven: 60°C

(2) In the case of MDF having the shape shown in Fig. 2

Coating amount: 80μm (wet thickness; 80g/m ² )

·Linear speed: 18m/min

·Temperature of drying oven: 65°C

(3) In the case of MDF having the shape shown in Fig. 3

Coating amount: 80μm (wet thickness; 80g/m ² )

·Linear speed: 18m/min

·Temperature of drying oven: 65°C

1 to 3 are schematic cross-sectional views each showing a cross-sectional shape of MDF bonded with a polyolefin sheet by a sealing machine. FIGS. 4 to 6 are schematic cross-sectional views each showing a state where a polyolefin sheet is bonded to the MDF formed in the cross-section shown in FIGS. 1 to 3 by a sealing machine. In addition, in Fig. 4 to Fig. 6, for the convenience of explanation, there is a space between the polyolefin sheet and the MDF, but in fact the polyolefin sheet is closely attached to the MDF. In addition, in FIGS. 1-6, A is a reverse radius part, and B is a convex part.

In addition, when the heat-resistant creep test shown below was performed on the packaged processed product shown in FIG. 4 obtained by the above package bonding, the peeling length after 24 hours was 0 mm. Therefore, peeling did not occur at all even after 24 hours, and it was confirmed that it had favorable performance. That is, even with a one-component water-based adhesive, adhesive performance equivalent to conventionally used two-component solvent-based adhesives can be obtained.

[Heat resistance creep test]

On the encapsulated processed product shown in FIG. 4 obtained by the above-mentioned encapsulated bonding, cracks are made in the long direction with a width of 25 mm in advance, and then placed in an ambient atmosphere of 60 ° C. In the encapsulated processed product A static load of 500 gf/25 mm width (4.9 N/25 mm width) was applied at an angle of 90° to the longitudinal end of a 25 mm wide crack in the polyolefin sheet, and the peeling length after 24 hours was measured.

Industrial Applicability

As described above, the silylated polyurethane water-based composition of the present invention is highly safe, and the time required to express an excellent adhesive force is short, and the initial adhesiveness is high. In addition, it is possible to exhibit the same productivity as when using a solvent-based adhesive. Therefore, the silylated polyurethane aqueous composition of the present invention is extremely useful as an aqueous encapsulating adhesive or an aqueous contact adhesive.

Claims (15)

1. a silylated urethane waterborne compositions is characterized in that, said composition contains following (A) composition, (B) composition and (C) composition:

(A) do not contain the terminal polyurethane prepolymer of the alkoxysilyl that contains anionic property group and uncle's amino that the polyol compound (A1) of anionic property group, the polyol compound (A2) that contains the anionic property group, the compound (A3) that contains uncle's amino and isocyanate-reactive group, polyisocyanate compound (A4), the alkoxysilane compound containing trialkylsilyl group in molecular structure (A5) that contains isocyanate-reactive group and amine chain extender (A6) reaction obtain

(B) basic cpd

(C) water.

2. according to the silylated urethane waterborne compositions of claim 1 record, wherein, the terminal polyurethane prepolymer (A) of alkoxysilyl that contains anionic property group and uncle's amino, it is the polyurethane prepolymer that contains anionic property group and uncle's amino with the alkoxyl silicone alkanisation of terminal portions, further by amine chain extender (A6), make residual isocyanate group in the polyurethane prepolymer that contains anionic property group and uncle's amino of alkoxyl silicone alkanisation of above-mentioned end part, with the reaction of the amino of above-mentioned amine chain extender (A6) chain extension the polyurethane prepolymer that contains anionic property group and uncle's amino of alkoxyl silicone alkanisation, the polyurethane prepolymer that contains anionic property group and uncle's amino of the alkoxyl silicone alkanisation of described terminal portions, be by by the polyol compound that does not contain the anionic property group (A1), the polyol compound (A2) that contains the anionic property group, the compound (A3) that contains uncle's amino and isocyanate-reactive group, and the reaction of polyisocyanate compound (A4) and the polyurethane prepolymer that contains anionic property group and uncle's amino that obtains, with the reaction of the alkoxysilane compound containing trialkylsilyl group in molecular structure that contains isocyanate-reactive group (A5), the isocyanate group of the end of the polyurethane prepolymer that contains anionic property group and uncle's amino is obtained by alkoxyl silicone alkanisation partly.

3. according to claim 1 or the 2 silylated urethane waterborne compositions of putting down in writing, wherein, the silylated urethane waterborne compositions, be anionic property group in the polyurethane prepolymer (A) of the alkoxysilyl end by containing anionic property group and uncle's amino by basic cpd (B) neutralization, and the aqueous silane alcoholization polyurethane prepolymer compositions that obtained by water (C) hydrolysis of terminal alkoxysilyl.

4. according to the silylated urethane waterborne compositions of any record in the claim 1～3, wherein, the anionic property group that contains in the polyol compound (A2) of anionic property group is a carboxyl.

5. according to the silylated urethane waterborne compositions of any record in the claim 1～4, wherein, the polyol compound (A2) that contains the anionic property group is the dihydroxymethyl paraffinic acid.

6. according to the silylated urethane waterborne compositions of any record in the claim 1～5, wherein, containing uncle's compound (A3) amino and isocyanate-reactive group is the tertiary amine compounds that contains a plurality of isocyanate-reactive groups.

7. according to the silylated urethane waterborne compositions of any record in the claim 1～6, wherein, containing uncle's compound (A3) amino and isocyanate-reactive group is N, two (hydroxyl-organic group)-N-alkylamines of N-.

8. according to the silylated urethane waterborne compositions of any record in the claim 1～7, wherein, the alkoxysilane compound containing trialkylsilyl group in molecular structure (A5) that contains isocyanate-reactive group is the alkoxysilane compound containing trialkylsilyl group in molecular structure that contains secondary amino group that alkoxysilane compound containing trialkylsilyl group in molecular structure by containing primary amino at least and esters of unsaturated carboxylic acids reaction obtain.

9. according to the silylated urethane waterborne compositions of any record in the claim 1～8, wherein, the alkoxysilane compound containing trialkylsilyl group in molecular structure (A5) that contains isocyanate-reactive group is by containing the alkoxysilane compound containing trialkylsilyl group in molecular structure of primary amino and secondary amino group, reacting the alkoxysilane compound containing trialkylsilyl group in molecular structure that contains secondary amino group that obtains with esters of unsaturated carboxylic acids.

10. according to the silylated urethane waterborne compositions of any record in the claim 1～9, wherein, the content that contains the anionic property group in the terminal polyurethane prepolymer of alkoxysilyl (A) of anionic property group and uncle's amino is 0.4meq/g or more than the 0.4meq/g.

11. silylated urethane waterborne compositions according to any record in the claim 1～10, wherein, the content that contains the uncle's amino in the terminal polyurethane prepolymer of alkoxysilyl (A) of anionic property group and uncle's amino is 0.15meq/g or more than the 0.15meq/g.

12. silylated urethane waterborne compositions according to any record in the claim 1～11, wherein, containing the anionic property group in the terminal polyurethane prepolymer of alkoxysilyl (A) of anionic property group and uncle's amino and the ratio of uncle's amino is uncle's amino/anionic property group (mol ratio)=0.2～1.

13. silylated urethane waterborne compositions according to any record in the claim 1～12, wherein, the uncle's ratio amino and alkoxysilyl that contains in the terminal polyurethane prepolymer of alkoxysilyl (A) of anionic property group and uncle's amino is uncle's amino/alkoxysilyl (mol ratio)=1.0～5.5.

14. a water-based adhesives for wrapping is characterized in that, this caking agent contains the silylated urethane waterborne compositions of any record in the aforesaid right requirement 1～13.

15. a water-based contact adhesives is characterized in that, this caking agent contains the silylated urethane waterborne compositions of any record in the aforesaid right requirement 1～13.