JP4817630B2 - Urethane-based aqueous composition and aqueous adhesive - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an aqueous polyurethane composition and an aqueous adhesive having excellent initial adhesion strength and prolonged bondable period. <P>SOLUTION: The aqueous polyurethane composition contains (A) a water-dispersed polyurethane resin and (B) a compound having tert-amino group and an aromatic ring. The compound B having tert-amino group and aromatic ring is preferably N,N-bis(hydroxyalkyl)aniline or N,N-bis[hydroxy-mono or poly(alkylenoxy)-alkyl]aniline. The water-dispersed polyurethane resin A is preferably a water-dispersed silylated polyurethane resin. The aqueous adhesive contains the aqueous polyurethane composition. <P>COPYRIGHT: (C)2006,JPO&amp;NCIPI

Description

  The present invention relates to a urethane-based aqueous composition and an aqueous adhesive, and more specifically, a urethane-based aqueous composition capable of exhibiting excellent initial adhesive strength and a longer bonding time, and aqueous It relates to adhesives.

  As adhesives (especially adhesives for wrapping), solvent-based adhesives are still mainstream, but in recent years, from the viewpoint of environmental problems and the like, water-based adhesives have been studied by various companies. Examples of the aqueous adhesive include an aqueous adhesive having an ethylene-vinyl acetate polymer / urethane polymer, chloroprene latex and the like as a base polymer. However, these water-based adhesives require a longer time for the drying process than solvent-based adhesives, and problems such as difficulty in obtaining heat resistance and water resistance of the cured product have occurred. Furthermore, as in the case of solvent adhesives, the time required to develop an excellent tack force is shortened (that is, the initial adhesive strength is increased), and the time required to develop an excellent tack force is lengthened. It was extremely difficult (that is, to increase the possible bonding time). As described above, it is extremely difficult for the conventional water-based adhesive to exhibit the initial adhesive strength (tack force) and the bonding time (tack force holding time) at the same level as the solvent-based adhesive. There was also a problem.

  Then, in order to solve these problems, the water-based urethane adhesive which has a hydrolyzable silyl group which can exist stably in water is proposed (refer patent documents 1-2). In these water-based urethane adhesives, compared to normal or conventional water-based adhesives, the problem of time required for the drying process and the heat resistance and water resistance of the cured product are greatly improved, but the initial adhesion Regarding the strength and the bonding possible time, it cannot be said that it is sufficient yet, and there is a demand for an aqueous urethane adhesive having a high initial adhesive strength and an even longer bonding possible time.

JP 2003-48946 A JP 2003-96406 A

  Accordingly, an object of the present invention is to provide a urethane-based aqueous composition and an aqueous adhesive capable of exhibiting excellent initial adhesive strength and a longer bonding time.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have shortened the time required to develop an excellent tack force when using a water-dispersible polyurethane resin in combination with a specific compound. It was found that the initial adhesive strength can be expressed, and the time during which the tack force is expressed can be greatly lengthened, so that a very long bonding time can be expressed, and the present invention has been completed.

［式（１’）において、Ｒ¹ ’、Ｒ² ’は、同一又は異なって、ヒドロキシル基および／またはエーテル結合含有基を有するアルキル基である］ That is, the present invention
A urethane-based aqueous composition containing a water-dispersible polyurethane resin (A), further containing a compound (B ′ ) represented by the following formula (1 ′), an aqueous adhesive, an aqueous coating agent, A urethane-based aqueous composition characterized by being used for a binder, laminate, sealer, primer, sizing agent or sealing material .

[In the formula (1 ′ ), R ¹ ′ and R ² ′ are the same or different and are an alkyl group having a hydroxyl group and / or an ether bond-containing group ]

Examples of the compound (B ′ ) represented by the formula (1 ′) include N, N-bis (hydroxyalkyl) aniline, or N, N-bis [hydroxy-mono or poly (alkyleneoxy) -alkyl] aniline. Can be used.

In the present invention, the ratio of the compound (B ′ ) represented by the formula (1 ′) is 5 to 30 parts by mass with respect to 100 parts by mass (solid content) of the water-dispersible polyurethane resin (A). May be.

  The water-dispersible polyurethane resin (A) is preferably a water-dispersible silylated polyurethane resin, and further, an aqueous dispersion having an anionic group and a tertiary amino group in the molecule. A suitable silylated polyurethane-based resin is preferable.

［式（１）において、Ｒ ¹ 、Ｒ ² は、同一又は異なって、ヒドロキシル基および／または「−（Ｒ ³ −Ｏ） _n −」基（Ｒ ³ は２価の炭化水素基、ｎは１又は２以上の整数）を有していてもよいアルキル基である］
さらに、これらのウレタン系水性組成物を含有することを特徴とする水性接着剤、についても説明する。 In addition, the aqueous adhesive characterized by containing the said urethane type aqueous composition is contained in this invention.
In addition to the above invention, in this specification,
A urethane-based aqueous composition containing a water-dispersible polyurethane resin (A), further comprising a compound (B) containing a tertiary amino group and an aromatic ring The composition is also described.
Moreover, the said urethane type aqueous composition whose compound (B) containing a tertiary amino group and an aromatic ring is a compound represented by following formula (1) is also demonstrated.

[In the formula (1), R ^1, R ² are the same or different, a hydroxyl group and / or "- (R ³ -O) _n -" group (R ³ is a divalent hydrocarbon radical, n is 1 Or an alkyl group optionally having an integer of 2 or more]
Furthermore, the aqueous adhesive characterized by containing these urethane type aqueous compositions is also demonstrated.

  According to the urethane-based aqueous composition of the present invention, it is possible to exhibit excellent initial adhesive strength and a longer bonding time. Therefore, the urethane-based aqueous composition is useful as an aqueous adhesive.

[Tertiary amino group / aromatic ring-containing compound (B)]
In the urethane-based aqueous composition of the present invention, the water-dispersible polyurethane resin (A) is converted into a compound (B) containing a tertiary amino group and an aromatic ring [“tertiary amino group / aromatic ring-containing compound”. (B) "may be referred to] is important. Thus, by using a compound containing a tertiary amino group and an aromatic ring in one molecule, the action or effect of each group can be effectively and effectively exhibited. Such a tertiary amino group / aromatic ring-containing compound (B) has at least one tertiary amino group (disubstituted amino group) in one molecule and an aromatic ring (that is, an aromatic ring). If it is a compound which has at least 1 group hydrocarbon group), it will not restrict | limit. The tertiary amino group and the aromatic ring may be indirectly bonded through another group, but are preferably directly bonded. That is, it is preferable that the nitrogen atom constituting the tertiary amino group and the carbon atom constituting the aromatic ring are directly bonded.

  In addition, when the nitrogen atom which comprises a tertiary amino group, and the carbon atom which comprises an aromatic ring are couple | bonded indirectly through another group, a tertiary amino group and an aromatic ring The group located between them is not particularly limited, and may be any of known divalent organic groups [for example, divalent hydrocarbon groups such as alkylene groups (such as alkylene groups having 1 to 4 carbon atoms)]. It can be selected appropriately.

  In the tertiary amino group / aromatic ring-containing compound (B), when the carbon atom constituting the aromatic ring is directly bonded to the nitrogen atom constituting the tertiary amino group, the tertiary amino group is Although 1 to 3 aromatic hydrocarbon groups as an aromatic ring can be bonded to the constituting nitrogen atom, it is preferable that 1 or 2 (particularly 1) is bonded. Moreover, when the nitrogen atom which comprises a tertiary amino group is directly couple | bonded with the carbon atom which comprises an aromatic ring, 1-6 tertiary amino groups may couple | bond with an aromatic ring. Although it is possible, 1 to 3 (particularly one) are preferably bonded.

  The aromatic ring may be either a single ring or a condensed ring, but is preferably a single ring aromatic ring (particularly a benzene ring). Accordingly, a phenyl group can be suitably used as the aromatic hydrocarbon group as the aromatic ring. The aromatic hydrocarbon group such as a phenyl group may have one or more substituents (such as a hydrocarbon group such as an alkyl group) as long as the effects and actions of the present invention are not impaired.

［式（１）において、Ｒ¹、Ｒ²は、同一又は異なって、ヒドロキシル基および／または「−（Ｒ³−Ｏ）_n−」基（Ｒ³は２価の炭化水素基、ｎは１又は２以上の整数）を有していてもよいアルキル基である］ Specifically, as the tertiary amino group / aromatic ring-containing compound (B), a compound represented by the following formula (1) can be preferably used.

[In the formula (1), R ^1, R ² are the same or different, a hydroxyl group and / or "- (R ³ -O) _n -" group (R ³ is a divalent hydrocarbon radical, n is 1 Or an alkyl group optionally having an integer of 2 or more]

In the formula (1), R ¹ and R ² are each an alkyl group. Examples of the alkyl group include carbon such as methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, s-butyl group, t-butyl group, pentyl group, hexyl group, heptyl group and octyl group. Examples thereof include alkyl groups having 1 to 10 numbers. As the alkyl group for R ¹ and R ² , an alkyl group having 1 to 6 carbon atoms is preferable, and among them, an alkyl group having 1 to 4 carbon atoms (particularly, an ethyl group) is preferable. The alkyl groups of R ¹ and R ² may be the same alkyl group or different alkyl groups.

In addition, as the alkyl group in R ¹ and R ² , as a substituent, a hydroxyl group (—OH) or a “— (R ³ —O) _n —” group (R ³ is a divalent hydrocarbon group, n is 1 or an integer of 2 or more). The "- (R ³ -O) _n -" R ³ in the group (sometimes referred to as "ether bond-containing group") is a divalent hydrocarbon group (e.g., a divalent aliphatic hydrocarbon group) If it is, although it will not restrict | limit in particular, A bivalent aliphatic hydrocarbon group is suitable. Examples of the divalent aliphatic hydrocarbon group for R ³ include an alkylene group (for example, methylene group, ethylene group, trimethylene group, propylene group, tetramethylene group, 3-methyltrimethylene, 2,2-dimethylethylene, pentamethylene). Group, an alkylene group having 1 to 10 carbon atoms such as a hexamethylene group, etc.) can be preferably used. Among them, an alkylene group having 1 to 4 carbon atoms (particularly an ethylene group or a propylene group) is preferable. Although n will not be restrict | limited especially if it is an integer of 1 or 2 or more, the integer of 1-10 is suitable, and the integer of 1-6 (especially the integer of 1-4) is preferable among these.

In addition, when the alkyl group in R < ¹ >, R < ² > has an ether bond containing group, it is preferable that the terminal is a hydroxyl group.

As the alkyl group for R ¹ and R ² , an alkyl group having a hydroxyl group and / or an ether bond-containing group is preferable. Examples of such an alkyl group [ie, an alkyl group having a hydroxyl group and / or an ether bond-containing group] include a hydroxyalkyl group, a hydroxy-alkyleneoxy-alkyl group, a hydroxy-poly (alkyleneoxy) -alkyl group, and the like. Is mentioned.

  The phenyl group in the formula (1) (the phenyl group bonded to the nitrogen atom) is a substituent (for example, a hydrocarbon group such as an alkyl group) within the range not impairing the function or effect of the present invention. You may have.

Specifically, as the tertiary amino group / aromatic ring-containing compound (B) represented by the formula (1), when R ¹ and R ² are both the same or different alkyl groups, For example, N, N-dimethylaniline, N, N-diethylaniline, N, N-dipropylaniline, N, N-diisopropylaniline, N, N-din-butylaniline, N, N-diisobutylaniline, N, N, such as N-dis-butylaniline, N, N-di-t-butylaniline, N, N-dipentylaniline, N, N-dihexylaniline, N, N-diheptylaniline, N, N-dioctylaniline N-dialkylaniline; N-methyl-N-ethylaniline, N-methyl-N-propylaniline, N-methyl-N-isopropylaniline, N-methyl-Nn-butylaniline, -Methyl-N-isobutylaniline, N-methyl-Ns-butylaniline, N-methyl-Nt-butylaniline, N-ethyl-N-propylaniline, N-ethyl-N-isopropylaniline, N- N-alkyl-N-alkylanilines such as ethyl-Nn-butylaniline, N-ethyl-N-isobutylaniline, N-ethyl-Ns-butylaniline, N-ethyl-Nt-butylaniline, etc. Is mentioned.

Further, as the tertiary amino group / aromatic ring-containing compound (B) represented by the formula (1), when R ¹ and R ² are both the same or different hydroxyalkyl groups, R ¹ , R ² may be the same as or different from those exemplified above as the tertiary amino group / aromatic ring-containing compound (B) when they are the same or different alkyl groups. For example, when R ¹ and R ² are both the same hydroxyalkyl group, the tertiary amino group / aromatic ring-containing compound (B) represented by the formula (1) may be N, N— Bis (hydroxymethyl) aniline, N, N-bis (hydroxyethyl) aniline, N, N-bis (hydroxypropyl) aniline, N, N-bis (hydroxyisopropyl) aniline, N, N-bis (hydroxy n-butyl) N, N-bis (hydroxyalkyl) such as aniline, N, N-bis (hydroxyisobutyl) aniline, N, N-bis (hydroxys-butyl) aniline, N, N-bis (hydroxyt-butyl) aniline Examples include aniline.

Furthermore, as the tertiary amino group / aromatic ring-containing compound (B) represented by the formula (1), R ¹ and R ² are both the same or different hydroxy-mono or poly (alkyleneoxy). -When it is an alkyl group, R ¹ and R ² both correspond to those exemplified above as the tertiary amino group / aromatic ring-containing compound (B) when they are the same or different alkyl groups. Things. For example, when R ¹ and R ² are both the same hydroxy-mono or poly (alkyleneoxy) -alkyl group, the tertiary amino group / aromatic ring-containing compound represented by the formula (1) ( As B), N, N-bis [hydroxy-mono or poly (methyleneoxy) -methyl] aniline, N, N-bis [hydroxy-mono or poly (ethyleneoxy) -ethyl] aniline, N, N-bis [Hydroxy-mono or poly (trimethyleneoxy) -n-propyl] aniline, N, N-bis {2- [hydroxy-mono or poly (propyleneoxy)]-2-methylethyl] aniline, N, N-bis N, N-bis [hydroxy-mono or poly (alkyleneoxy) -alkyl such as [hydroxy-mono or poly (tetramethyleneoxy) -n-butyl] aniline Aniline, and the like. In N, N-bis [hydroxy-mono or poly (alkyleneoxy) -alkyl] aniline, when the number of alkyleneoxy units (repetition number) is 2 or more, the alkyleneoxy unit is only one kind. In addition, two or more kinds may be combined. Specifically, the tertiary amino group / aromatic ring-containing compound (B) is N, N-bis [hydroxy-mono or poly (propyleneoxy) -mono or poly (ethyleneoxy) -ethyl] aniline, N , N-bis {2- [hydroxy-mono or poly (ethyleneoxy) -mono or poly (propyleneoxy)]-2-methylethyl] aniline.

In the tertiary amino group / aromatic ring-containing compound (B) represented by the formula (1), R ¹ and / or R ² (particularly, R ¹ and R ² ) are a hydroxyl group or an ether bond. In the case of an alkyl group having a group, good hydrophilicity can be exhibited. Thus, when the tertiary amino group / aromatic ring-containing compound (B) has hydrophilicity, it can be dissolved when mixed with the urethane-based aqueous composition. Therefore, as the tertiary amino group / aromatic ring-containing compound (B), N, N-bis (hydroxyalkyl) aniline, N, N-bis [hydroxy-mono or poly (alkyleneoxy) -alkyl] aniline, etc. N, N-disubstituted aniline compounds [N, N-di (hydrophilic group) having an alkyl group (hydrophilic group-containing alkyl) containing a hydrophilic group (hydroxyl group, ether bond-containing group, etc.) Containing alkyl) aniline compounds] can be suitably used.

The tertiary amino group / aromatic ring-containing compound (B) can be prepared using a known production method. For example, the alkyl group represented by the formula (1) and the alkyl group of R ¹ and R ² has an alkyl group having a hydroxyl group or an ether bond-containing group (“— (R ³ —O) _n —” group). The tertiary amino group / aromatic ring-containing compound (B) as a group can be prepared by, for example, reacting a cyclic ether compound such as alkylene oxide with aniline at a predetermined ratio. Specifically, by reacting ethylene oxide with aniline, depending on the amount of ethylene oxide to be reacted, N, N-bis (hydroxyethyl) aniline, N, N-bis (hydroxyethyl-oxyethyl) aniline, N, N-bis [hydroxyethyl-poly (oxyethylene)] aniline and the like are obtained. In this reaction, the reaction conditions such as the reaction temperature are not particularly limited and can be appropriately selected from known or conventional reaction conditions. In the reaction, a known or commonly used catalyst or solvent can be appropriately selected and used.

  N, N-bis (hydroxyethyl-oxyethyl) aniline is equivalent to N, N-bis (hydroxy-ethyleneoxy-ethyl) aniline, and N, N-bis [hydroxyethyl-poly (oxyethylene)] Aniline is equivalent to N, N-bis [hydroxy-poly (ethyleneoxy) -ethyl] aniline. The same applies to other compounds.

[Water-dispersible polyurethane resin (A)]
The water dispersible polyurethane resin (A) can be appropriately selected from known polyurethane resins having at least a urethane bond site and having water solubility or water dispersibility. As for water-dispersible polyurethane-type resin (A), only 1 type may be used and 2 or more types may be used in combination. In the polyurethane resin, a hydrophilic group (for example, a carboxyl group or a salt thereof, a sulfo group or a salt thereof, a hydroxyl group, an amino group or a salt thereof, or a group containing an ether bond) is introduced into the molecule. Therefore, water solubility or water dispersibility can be exhibited. Thus, the polyurethane-type resin into which the hydrophilic group was introduce | transduced can be prepared by using the diol component etc. which have hydrophilic groups, such as a diol component containing a carboxyl group, as a monomer component, for example.

  In the present invention, a water-dispersible silylated polyurethane resin (A1) can be suitably used as the water-dispersible polyurethane resin (A). The water dispersible silylated polyurethane resin (A1) is composed of a urethane prepolymer (A1) containing an alkoxysilyl group (sometimes referred to as “water dispersible silylated polyurethane resin (A1)”). . In such a water dispersible silylated polyurethane resin (A1), in water, alkoxysilyl groups are partially or wholly hydrolyzed by water to form silanol groups and / or siloxane bonds. By causing a condensation reaction of the silanol group, curing (crosslinking) occurs, and adhesiveness can be exhibited. This curing (crosslinking) reaction proceeds due to a decrease in water, and can proceed even if water is present to some extent. For this reason, the water-dispersible silylated polyurethane resin (A1) can exhibit cohesive force even while retaining water.

  As such a water dispersible silylated polyurethane resin (A1), a polyurethane having at least a urethane bond site, an alkoxysilyl group, and water-soluble or water-dispersible. The resin is not particularly limited as long as it is a resin, but further, a water-dispersible silylated polyurethane resin having an anionic group (such as a carboxyl group) in the molecule [“anionic group-containing water-dispersible silylated polyurethane resin” (A1) ”may be preferably used. Examples of such an anionic group-containing water-dispersible silylated polyurethane resin (A1) include, for example, a compound that does not contain an anionic group and contains a plurality of isocyanate-reactive groups (A1-a), an anionic group, and An alkoxysilyl group-terminated urethane prepolymer obtained by reacting a compound (A1-b) containing a plurality of isocyanate-reactive groups, a polyisocyanate compound (A1-c) and an isocyanate-reactive group-containing alkoxysilane compound (A1-d) Can be suitably used.

  In particular, as an anionic group-containing water-dispersible silylated polyurethane resin (A1), as a monomer component, an anionic group-free compound containing a plurality of isocyanate-reactive groups (A1-a), an anionic group And a compound (A1-b) containing a plurality of isocyanate-reactive groups, a polyisocyanate compound (A1-c), and an isocyanate-reactive group-containing alkoxysilane compound (A1-d), as well as a tertiary amino group and an isocyanate. When the compound (A1-e) containing a reactive group is used, a further excellent initial adhesive strength can be exhibited. Accordingly, as the anionic group-containing water-dispersible silylated polyurethane resin (A1), a water-dispersible silylated polyurethane resin having an anionic group and a tertiary amino group in the molecule [“anionic property” Group and tertiary amino group-containing water dispersible silylated polyurethane resin (A1) ”. Such an anionic group and tertiary amino group-containing water-dispersible silylated polyurethane resin (A1) includes an anionic group-free compound (A1-a), an anion group and an anion group. Compound containing a reactive group and a plurality of isocyanate reactive groups (A1-b), a compound containing a tertiary amino group and an isocyanate reactive group (A1-e), a polyisocyanate compound (A1-c) and an isocyanate reaction An alkoxysilyl group-terminated urethane prepolymer obtained by the reaction of the functional group-containing alkoxysilane compound (A1-d) can be suitably used.

  The anionic group-containing water-dispersible silylated polyurethane resin (A1) [in particular, the anionic group and tertiary amino group-containing water-dispersible silylated polyurethane resin (A1)] is a chain extender (A1- f) may be used.

[Anionic group-free / multiple isocyanate-reactive group-containing compounds (A1-a)]
As the compound (A1-a) that does not contain an anionic group and contains a plurality of isocyanate-reactive groups (sometimes referred to as “isocyanate-reactive compound (A1-a)”), an anionic group is included in the molecule. The compound is not particularly limited as long as it is a compound that does not have and has at least two isocyanate-reactive groups in the molecule. The isocyanate-reactive compound (A1-a) can be used alone or in combination of two or more. In the isocyanate-reactive compound (A1-a), the isocyanate-reactive group is not particularly limited as long as it is a group reactive to an isocyanate group. For example, a hydroxyl group, a primary amino group (unsubstituted amino group) Secondary amino group (mono-substituted amino group), mercapto group and the like. In addition, only 1 type may be sufficient as an isocyanate reactive group, and 2 or more types may be combined. In the present invention, the isocyanate-reactive group is preferably a hydroxyl group, a primary amino group or a secondary amino group, and particularly preferably a hydroxyl group. Therefore, as the isocyanate-reactive compound (A1-a), for example, an anionic group-free polyol compound, an anionic group-free polyamine compound, an anionic group-free polythiol compound (preferably an anionic group-free polyol compound) Or an anionic group-free polyamine compound, particularly an anionic group-free polyol compound).

  In the isocyanate-reactive compound (A1-a), examples of the anionic group-free polyol compound include polyhydric alcohol, polyether polyol, polyvinyl ether polyol, polyester polyol, polycarbonate polyol, polyolefin polyol, polyacryl polyol, castor oil, and the like. Can be mentioned. As these anionic group-free polyol compounds, for example, in JP-A-2004-043554, the term “anionic group-free / multiple isocyanate-reactive group-containing compounds (A1-a)” is used. Anionic group-free polyol compound (A1-a) exemplified as anionic compound (A1-a) (polyhydric alcohol, polyether polyol, polyester polyol, polycarbonate polyol, polyolefin polyol) , Polyacryl polyol, castor oil, etc.).

  In the present invention, polyether polyol, polyvinyl ether polyol, polyester polyol, and polycarbonate polyol can be suitably used as the isocyanate-reactive compound (A1-a), and polyether polyol and polyester polyol are particularly preferable. Specifically, the polyether polyol as the isocyanate-reactive compound (A1-a) includes monomer components such as an ethylene oxide-propylene oxide copolymer in addition to a polyalkylene glycol such as polyethylene glycol, polypropylene glycol, and polytetramethylene glycol. (Alkylene oxide-other alkylene oxide) copolymers containing a plurality of alkylene oxides, and the like. Among them, polytetramethylene glycol is preferable. The polyester polyol includes, for example, a condensation polymer of a polyhydric alcohol and a polycarboxylic acid; a ring-opening polymer of a cyclic ester (lactone); a polyhydric alcohol, a polycarboxylic acid and a cyclic ester. Can be used. Examples of the polyhydric alcohol include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, trimethylene glycol, 1,4-tetramethylene diol, 1,3-tetramethylene diol, 2-methyl-1,3-trimethyl. Methylene diol, 1,5-pentamethylene diol, neopentyl glycol, 1,6-hexamethylene diol, 3-methyl-1,5-pentamethylene diol, 2,4-diethyl-1,5-pentamethylene diol, glycerin , Trimethylolpropane, trimethylolethane, cyclohexanediols (such as 1,4-cyclohexanediol), bisphenols (such as bisphenol A), and sugar alcohols (such as xylitol and sorbitol). Examples of the polyvalent carboxylic acid include aliphatic dicarboxylic acids such as malonic acid, maleic acid, succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, and dodecanedioic acid; 1,4-cyclohexanedicarboxylic acid Examples include alicyclic dicarboxylic acids such as acids; aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, orthophthalic acid, 2,6-naphthalenedicarboxylic acid, paraphenylene dicarboxylic acid, and trimellitic acid. Examples of the cyclic ester include propiolactone, β-methyl-δ-valerolactone, and ε-caprolactone.

  The anionic group-free polyamine compound or the anionic group-free polythiol compound as the isocyanate-reactive compound (A1-a) is, for example, an anionic group-free polyamine compound corresponding to the anionic group-free polyol compound. And anionic group-free polythiol compounds.

[Compound containing an anionic group and a plurality of isocyanate-reactive groups (A1-b)]
The compound (A1-b) containing an anionic group and a plurality of isocyanate-reactive groups (hereinafter sometimes referred to as “isocyanate-reactive compound (A1-b)”) includes at least one anionic group in the molecule. The compound is not particularly limited as long as it is a compound having a group and having at least two isocyanate-reactive groups in the molecule. The isocyanate-reactive compound (A1-b) can be used alone or in combination of two or more. In the isocyanate-reactive compound (A1-b), as the anionic group, a carboxyl group or a sulfo group can be preferably used, and among them, the carboxyl group is optimal. In the isocyanate-reactive compound (A1-b), the isocyanate-reactive group is not particularly limited as long as it is a group having reactivity with an isocyanate group. For example, a hydroxyl group, a primary amino group (unsubstituted amino group) Group), secondary amino group (mono-substituted amino group), mercapto group and the like. In addition, only 1 type may be sufficient as an anionic group and an isocyanate reactive group, and 2 or more types may be combined together. In the present invention, the isocyanate-reactive group is preferably a hydroxyl group, a primary amino group or a secondary amino group, and particularly preferably a hydroxyl group. Accordingly, examples of the isocyanate-reactive compound (A1-b) include an anionic group-containing polyol compound, an anionic group-containing polyamine compound, and an anionic group-containing polythiol compound (preferably an anionic group-containing polyol compound and an anionic group). Containing polyamine compounds, particularly anionic group-containing polyol compounds) and the like can be used.

Examples of the anionic group-containing polyol compound as the isocyanate-reactive compound (A1-b) include a carboxyl group in which a carboxyl group is introduced into the anionic group-free polyol compound as the isocyanate-reactive compound (A1-a). Examples thereof include a contained polyol compound. In the present invention, the isocyanate-reactive compound (A1-b) is preferably a low-molecular weight polyol compound having an anionic group. In JP-A-2004-043554, an anionic group containing a plurality of isocyanate-reactive groups is contained. Compound (A1-b)] is appropriately selected from the anionic group-containing polyol compounds exemplified as the anionic group-containing polyol compound (A1-b) as the isocyanate-reactive compound (A1-b). In particular, polyhydroxycarboxylic acid represented by the following formula (2) can be preferably used.
(HO) _X L (COOH) _Y (2)
(However, in Formula (2), L shows a C1-C12 hydrocarbon site | part. X is an integer greater than or equal to 2, Y is an integer greater than or equal to 1.)

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

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

  Examples of the anionic group-containing polyamine compound or the anionic group-containing polythiol compound as the isocyanate-reactive compound (A1-b) include an anionic group-containing polyamine compound (the above formula) corresponding to the anionic group-containing polyol compound. (Polyamine carboxylic acid corresponding to the polyhydroxycarboxylic acid represented by (2)) and an anionic group-containing polythiol compound (polythiolcarboxylic acid corresponding to the polyhydroxycarboxylic acid represented by the formula (2)), etc. Can be mentioned.

[Tertiary amino group and isocyanate-reactive group-containing compound (A1-e)]
The compound (A1-e) containing a tertiary amino group and an isocyanate-reactive group (hereinafter sometimes referred to as “isocyanate-reactive compound (A1-e)”) contains at least one tertiary group in the molecule. The compound is not particularly limited as long as it is a compound containing an amino group and having at least one isocyanate-reactive group in the molecule. The isocyanate-reactive compound (A1-e) can be used alone or in combination of two or more.

  In the isocyanate-reactive compound (A1-e), as the tertiary amino group (disubstituted amino group), a hydrocarbon group (for example, an aryl group such as a phenyl group; a methyl group, an ethyl group, a propyl group, a butyl group, etc.) And a tertiary amino group may be formed by having a substituent such as a cycloalkyl group such as a cyclohexyl group. The hydrocarbon group further has another substituent (for example, an alkoxy group, an aryloxy group, a cycloalkyloxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, a cycloalkyloxycarbonyl group, an acyl group, etc.). Also good. The number of tertiary amino groups in the molecule in the isocyanate-reactive compound (A1-e) is not particularly limited, and can be selected from the range of 1 to 6, for example, preferably 1 to 3 ( More preferably, it is 1 or 2, particularly 1). In addition, when it has a some tertiary amino group, the tertiary amino group may be only 1 type, and 2 or more types may be combined together.

  In the isocyanate-reactive compound (A1-e), the isocyanate-reactive group is not particularly limited as long as it is a group having reactivity with respect to the isocyanate group, and for example, a hydroxyl group, a primary amino group, or a secondary group. An amino group, a mercapto group, etc. are mentioned, A hydroxyl group, a primary amino group, or a secondary amino group is preferable, and especially a hydroxyl group is suitable. The number of isocyanate-reactive groups in the molecule in the isocyanate-reactive compound (A1-e) is not particularly limited as long as it is at least one. For example, it is selected from the range of 1 to 6 (preferably 1 to 3). 2 is particularly preferable. In addition, when it has several isocyanate reactive group, only 1 type may be sufficient as an isocyanate reactive group, and 2 or more types may be combined together.

  In the isocyanate-reactive compound (A1-e), 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. Examples of such a divalent group include a divalent hydrocarbon group composed only of a hydrocarbon group such as an alkylene group, an arylene group, an alkylene-arylene group, and an alkylene-arylene-alkylene group; an oxy-alkylene group Hydrocarbon groups such as alkylene-oxy-alkylene group, alkylene-carbonyl-oxy-alkylene group, alkylene-oxy-carbonyl-alkylene group, alkylene-poly (oxyalkylene) group [poly (alkyleneoxy) -alkyl group] Examples thereof include various divalent groups constituted by various combinations with other groups (oxy group, carbonyl-oxy group, etc.).

  The isocyanate-reactive compound (A1-e) has a form in which a tertiary amino group is bonded to various organic groups, and the organic group is preferably a hydrocarbon group. Examples of such hydrocarbon groups include aliphatic hydrocarbon groups (for example, alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, pentyl, and hexyl groups), alicyclic carbon Examples thereof include a hydrogen group (for example, a cycloalkyl group such as a cyclohexyl group) and an aromatic hydrocarbon group (for example, an aryl group such as a phenyl group). The hydrocarbon group may have one or more substituents. Examples of the substituent include other hydrocarbon groups, isocyanate-reactive groups (for example, hydroxyl groups, primary amino groups). Secondary amino groups, mercapto groups, etc.) and non-isocyanate reactive groups (eg tertiary amino groups, alkoxy groups, aryloxy groups, cycloalkyloxy groups, alkoxycarbonyl groups, aryloxycarbonyl groups, cycloalkyl) Oxycarbonyl group, acyl group, etc.).

  Therefore, as the isocyanate-reactive compound (A1-e), a tertiary amine compound containing an isocyanate-reactive group (particularly a hydroxyl group) can be used. As a tertiary amine compound containing an isocyanate-reactive group, for example, one organic group containing an isocyanate-reactive group (isocyanate-reactive group-containing organic group) is bonded to one nitrogen atom. , Tertiary amine compounds in which two organic groups containing hydrocarbon groups (hydrocarbon group-containing organic groups) are bonded [“isocyanate-reactive group-containing tertiary amine compounds (A1-e1) A tertiary amine system in which two isocyanate-reactive group-containing organic groups are bonded to one nitrogen atom and one hydrocarbon group-containing organic group is bonded to one nitrogen atom. Compound [sometimes referred to as “isocyanate-reactive group-containing tertiary amine compound (A1-e2)”] A compound having three isocyanate-reactive group-containing organic groups bonded to one nitrogen atom 3 Secondary amine compound [sometimes referred to as “isocyanate-reactive group-containing tertiary amine-based compound (A1-e3)”] Two isocyanate-reactive group-containing organic groups are bonded to one nitrogen atom. A tertiary amine compound in which tertiary amino groups are bonded directly or via a divalent group [referred to as “isocyanate-reactive group-containing tertiary amine compound (A1-e4)”. In some cases.

  Specifically, as the isocyanate-reactive group-containing tertiary amine compound (A1-e2), when the isocyanate-reactive group is a hydroxyl group, for example, N, N-bis (hydroxymethyl) -N-methyl Amine, 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-hydroxy) Til) -N-ethylamine, N, N-bis (2-hydroxyethyl) -N-propylamine, N, N-bis (2-hydroxyethyl) -N-isopropylamine, N, N-bis (2-hydroxy) N, N-bis (hydroxyalkyl) -N-alkylamines such as ethyl) -Nn-butylamine; N, N-bis [hydroxymethyl-poly (oxymethylene)]-N-methylamine, N, N- Bis [2-hydroxyethyl-poly (oxyethylene)]-N-methylamine, N, N-bis [3-hydroxypropyl-poly (oxypropylene)]-N-methylamine, N, N-bis [2- Hydroxypropyl-poly (oxyisopropylene)]-N-methylamine, N, N-bis [4-hydroxybutyl-poly (oxybutylene)]-N-methyla N, N-bis [hydroxymethyl-poly (oxymethylene)]-N-ethylamine, N, N-bis [2-hydroxyethyl-poly (oxyethylene)]-N-ethylamine, N, N-bis [ 3-hydroxypropyl-poly (oxypropylene)]-N-ethylamine, N, N-bis [2-hydroxypropyl-poly (oxyisopropylene)]-N-ethylamine, N, N-bis [4-hydroxybutyl- Poly (oxybutylene)]-N-ethylamine, N, N-bis [2-hydroxyethyl-poly (oxyethylene)]-N-propylamine, N, N-bis [2-hydroxyethyl-poly (oxyethylene) ] -N-isopropylamine, N, N-bis [2-hydroxyethyl-poly (oxyethylene)]-Nn-butylamine, etc. N, N-bis [hydroxyalkyl-poly (oxyalkylene)]-N-alkylamine and other N, N-bis (hydroxy-organic groups) -N-alkylamines and N, N-bis (hydroxymethyl)- N-phenylamine, N, N-bis (2-hydroxyethyl) -N-phenylamine, N, N-bis (3-hydroxypropyl) -N-phenylamine, N, N-bis (2-hydroxypropyl) N, N-bis (hydroxyalkyl) -N-arylamines such as N-phenylamine, N, N-bis (4-hydroxybutyl) -N-phenylamine; N, N-bis [hydroxymethyl-poly ( Oxymethylene)]-N-phenylamine, N, N-bis [2-hydroxyethyl-poly (oxyethylene)]-N-phenylamine, N, N-bis 3-hydroxypropyl-poly (oxypropylene)]-N-phenylamine, N, N-bis [2-hydroxypropyl-poly (oxyisopropylene)]-N-phenylamine, N, N-bis [4-hydroxy N, N-bis (hydroxy-organic group) -N such as N, N-bis [hydroxyalkyl-poly (oxyalkylene)]-N-arylamine such as butyl-poly (oxybutylene)]-N-phenylamine -Arylamine; N, N-bis (hydroxy-organic group) -N-cycloalkylamine and the like corresponding to these.

  Furthermore, as the isocyanate-reactive group-containing tertiary amine compound (A1-e3), when the isocyanate-reactive group is a hydroxyl group, for example, N, N, N-tris (hydroxymethyl) amine, N, N , N-tris (2-hydroxyethyl) amine, N, N, N-tris (3-hydroxypropyl) amine, N, N, N-tris (2-hydroxypropyl) amine, N, N, N-tris ( N, N, N-tris (hydroxyalkyl) amine such as 4-hydroxybutyl) amine; N, N, N-tris [hydroxymethyl-poly (oxymethylene)] amine, N, N, N-tris [2- Hydroxyethyl-poly (oxyethylene)] amine, N, N, N-tris [3-hydroxypropyl-poly (oxypropylene)] amine, N, N, N-to N, N, N-tris [hydroxyalkyl-poly, such as bis [2-hydroxypropyl-poly (oxyisopropylene)] amine, N, N, N-tris [4-hydroxybutyl-poly (oxybutylene)] amine (Oxyalkylene)] N, N, N-tris (hydroxy-organic group) amine such as amine.

  Furthermore, as the isocyanate-reactive group-containing tertiary amine compound (A1-e4), when the isocyanate-reactive group is a hydroxyl group, for example, N, N, N ′, N′-tetra (hydroxymethyl) Ethylenediamine, N, N, N ', N'-tetra (2-hydroxyethyl) ethylenediamine, N, N, N', N'-tetra (3-hydroxypropyl) ethylenediamine, N, N, N ', N'- N such as tetra (2-hydroxypropyl) ethylenediamine, N, N, N ′, N′-tetra (4-hydroxybutyl) ethylenediamine and the like, N, N, N ′, N′-tetra (hydroxy-alkyl) alkylenediamine and the like , N, N ′, N′-tetra (hydroxy-organic group) alkylenediamine and the like.

  In the isocyanate-reactive group-containing tertiary amine compound (A1-e1) to the isocyanate-reactive group-containing tertiary amine compound (A1-e4), the isocyanate-reactive group is an amino group (primary amino group). Or secondary amino group), the isocyanate-reactive group-containing tertiary amine compound (A1-e1) to the isocyanate-reactive group-containing third group in the case where the isocyanate-reactive group is a hydroxyl group, respectively. And tertiary amine compounds corresponding to the tertiary amine compounds (A1-e4).

[Polyisocyanate compound (A1-c)]
The polyisocyanate compound (A1-c) (hereinafter sometimes referred to as “polyisocyanate (A1-c)”) is not particularly limited as long as it is a compound having at least two isocyanate groups in the molecule. Polyisocyanate (A1-c) can be used alone or in combination of two or more.

  Examples of the polyisocyanate (A1-c) include various polyisocyanate compounds such as aliphatic polyisocyanate, alicyclic polyisocyanate, aromatic polyisocyanate, and araliphatic polyisocyanate. As these polyisocyanate compounds, polyisocyanate compounds (aliphatic compounds) exemplified as polyisocyanate compounds (A1-c) in the section of [Polyisocyanate compound (A1-c)] in JP-A No. 2004-043554. Polyisocyanate, alicyclic polyisocyanate, aromatic polyisocyanate, araliphatic polyisocyanate, and the like). In the present invention, the polyisocyanate (A1-c) is a dimer, trimer, reaction product or polymer (for example, diphenylmethane diisocyanate dimer, trimer, A reaction product of methylolpropane and tolylene diisocyanate, a reaction product of trimethylolpropane and hexamethylene diisocyanate, polymethylene polyphenyl isocyanate, polyether polyisocyanate, polyester polyisocyanate, etc.) can also be used.

  Examples of the polyisocyanate (A1-c) include 1,6-hexamethylene diisocyanate, 4,4′-methylenebis (cyclohexyl isocyanate), 1,3-bis (isocyanate methyl) cyclohexane, 1,4-bis ( Isocyanate methyl) cyclohexane, isophorone diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 1,3-xylylene diisocyanate -To, 1,4-xylylene diisocyanate, norbornane diisocyanate, and 1,3-bis (α, α-dimethylisocyanatomethyl) benzene can be suitably used.

[Isocyanate-reactive group-containing alkoxysilane compound (A1-d)]
Isocyanate-reactive group-containing alkoxysilane compound (A1-d) (hereinafter sometimes referred to as “isocyanate-reactive group-containing alkoxysilane (A1-d)”) includes at least one isocyanate-reactive group in the molecule. It is not particularly limited as long as it is a silane compound having at least one alkoxy group in the molecule. The isocyanate-reactive group-containing alkoxysilane (A1-d) can be used alone or in combination of two or more. In the isocyanate-reactive group-containing alkoxysilane (A1-d), the isocyanate-reactive group is not particularly limited as long as it is a group reactive to the isocyanate group. For example, a primary amino group, Secondary amino group, mercapto group, isocyanate group, hydroxyl group and the like can be mentioned, and primary or secondary amino group and mercapto group are preferable. In addition, only 1 type may be sufficient as an isocyanate reactive group, and 2 or more types may be combined.

  In the present invention, the isocyanate-reactive group-containing alkoxysilane (A1-d) is a primary or secondary amino group-containing alkoxysilane compound (A1-d1) (“amino group-containing alkoxysilane (A1-d1)”). And a mercapto group-containing alkoxysilane compound (A1-d2) (sometimes referred to as “mercapto group-containing alkoxysilane (A1-d2)”) can be preferably used.

In the isocyanate-reactive group-containing alkoxysilane (A1-d), examples of the alkoxy group include methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, isobutyloxy group, s-butyloxy group, and t-butyloxy group. C _1-4 alkoxy groups such as can be suitably used. More preferable alkoxy groups include a methoxy group, an ethoxy group, and a propoxy group (in particular, a methoxy group and an ethoxy group). Such an alkoxy group is usually bonded to a silicon atom of an isocyanate-reactive group-containing alkoxysilane (A1-d), and the number thereof is usually 1 to 3 (preferably 2 or 3). . The same alkoxy group may be bonded to the silicon atom of the isocyanate-reactive group-containing alkoxysilane (A1-d), or two or more different alkoxy groups may be combined and bonded.

  When the isocyanate-reactive group is an amino group, the secondary amino group or the tertiary amino group is a hydrocarbon group (for example, an aryl group such as a phenyl group; a methyl group, an ethyl group, a propyl group, a butyl group). A secondary amino group or a tertiary amino group may be formed by having a substituent such as an alkyl group such as a cycloalkyl group such as a cyclohexyl group. The hydrocarbon group further has another substituent (for example, an alkoxy group, an aryloxy group, a cycloalkyloxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, a cycloalkyloxycarbonyl group, an acyl group, etc.). It may be.

  Furthermore, an isocyanate-reactive group (a primary amino group, a secondary amino group, a mercapto group, etc.) may be directly bonded to a silicon atom, but is bonded via a divalent group. Is preferred. Examples of such a divalent group include a divalent hydrocarbon group composed only of a hydrocarbon group such as an alkylene group, an arylene group, an alkylene-arylene group, and an alkylene-arylene-alkylene group; Hydrocarbon groups such as alkylene groups, alkylene-carbonyl-oxy-alkylene groups, alkylene-oxy-carbonyl-alkylene groups, alkylene-poly (oxyalkylene) groups and other groups (oxy groups, carbonyl-oxy groups, etc.) Examples include various divalent groups constituted by various combinations.

Therefore, for example, when the isocyanate-reactive group-containing alkoxysilane (A1-d) is an amino group-containing alkoxysilane (A1-d1), it may contain an amino group as an aminoalkyl group. Examples of such aminoalkyl groups include amino-C ₁ such as aminomethyl group, 1-aminoethyl group, 2-aminoethyl group, 1-aminopropyl group, 2-aminopropyl group, and 3-aminopropyl group. _-3 alkyl group, a corresponding secondary amino group (such as an amino-C _1-3 alkyl group having one hydrocarbon group as a substituent) or a tertiary amino group (carbonized as a substituent) And an amino-C _1-3 alkyl group having two hydrogen groups). In addition, a substituent such as a hydrocarbon group substituted on a nitrogen atom in the secondary amino group or the tertiary amino group may further have an amino group. That is, for example, it may be in the form of an N-aminoalkyl-aminoalkyl group or an N- [N- (aminoalkyl) aminoalkyl] aminoalkyl group. In addition, you may have a secondary amino group with the primary amino group. The number of primary or secondary amino groups is not particularly limited, but is usually 1 or 2.

  In the isocyanate-reactive group-containing alkoxysilane (A1-d), examples of the amino group-containing alkoxysilane (A1-d1) and mercapto group-containing alkoxysilane (A1-d2) include, for example, JP-A-2004-043554, [ Amino group-containing alkoxysilanes exemplified as amino group-containing alkoxysilanes (A1-d1) and mercapto group-containing alkoxysilanes (A1-d2) in the section of isocyanate-reactive group-containing alkoxysilane compounds (A1-d)] A mercapto group-containing alkoxysilane (such as an amino group-containing alkoxysilane exemplified in formulas (2a) to (2c) or a mercapto group-containing alkoxysilane exemplified in formula (2d)) may be used as appropriate. it can.

  As the isocyanate-reactive group-containing alkoxysilane (A1-d), an amino group-containing alkoxysilane (A1-d1) can be suitably used. In the amino group-containing alkoxysilane (A1-d1), examples of the amino group-containing alkoxysilane having at least a primary amino group as an isocyanate-reactive group include N-β (aminoethyl) -γ-aminopropyltrimethoxysilane. N-β (aminoethyl) -γ-aminopropyltriethoxysilane, N-β (aminoethyl) -γ-aminopropylmethyldimethoxysilane, and γ-aminopropyltrimethoxysilane can be preferably used. Examples of the amino group-containing alkoxysilane having only a secondary amino group as an isocyanate-reactive group include N-phenyl-γ-aminopropyltrimethoxysilane and Nn-butyl-3-aminopropyltrimethoxysilane. Can be suitably used.

  In the present invention, as the amino group-containing alkoxysilane (A1-d1), at least a primary amino group (particularly, a primary amino group and a secondary amino group) as exemplified above is used as an isocyanate-reactive group. An isocyanate-reactive group containing at least a secondary amino group obtained by reacting an alkoxysilane compound (hereinafter sometimes referred to as “primary amino group-containing alkoxysilane”) with an unsaturated carboxylic acid ester. As an alkoxysilane compound (hereinafter sometimes referred to as “ester-modified amino group-containing alkoxysilane (A1-d3)”). As the ester-modified amino group-containing alkoxysilane (A1-d3), a secondary amino group-containing alkoxysilane compound obtained by a reaction between an alkoxysilane compound containing at least a primary amino group and an unsaturated carboxylic acid ester is used. In particular, a secondary amino group-containing alkoxysilane compound obtained by a reaction between an alkoxysilane compound containing a primary amino group and a secondary amino group and an unsaturated carboxylic acid ester is preferably used. Can do.

  In such an ester-modified amino group-containing alkoxysilane (A1-d3), as the unsaturated carboxylic acid ester, at least one (preferably all) of the carboxylic acid groups (carboxyl groups) of the unsaturated carboxylic acid are esters. The compound is not particularly limited as long as it is a compound in a form. The unsaturated carboxylic acid ester may be an unsaturated monovalent carboxylic acid ester or an unsaturated polyvalent carboxylic acid ester (for example, an unsaturated divalent carboxylic acid ester). Unsaturated carboxylic acid ester can be used individually or in combination of 2 or more types. Specific examples of the unsaturated carboxylic acid ester include, for example, the unsaturated carboxylic acid ester (A1-d3) in the section of [Isocyanate-reactive group-containing alkoxysilane compound (A1-d)] in JP-A No. 2004-043554. And unsaturated carboxylic acid esters exemplified as). In addition, as unsaturated carboxylic acid ester, acrylic acid ester, methacrylic acid ester (these may be named generically "(meth) acrylic acid ester"), and maleic acid diester can be used conveniently.

  Specific examples of the ester-modified amino group-containing alkoxysilane (A1-d3) are disclosed in JP-A No. 2004-043554, in the section [Isocyanate-reactive group-containing alkoxysilane compound (A1-d)]. Alkoxysilane compounds containing at least a secondary amino group as an isocyanate-reactive group exemplified as the containing alkoxysilane (A1-d4) (esters represented by formula (4), formula (5a), and formula (5b)) And a modified amino group-containing alkoxysilane (A1-d4) and the like.

  In the present invention, the amino group-containing alkoxysilane (A1-d1) is an alkoxysilane compound containing at least a secondary amino group [especially, in Japanese Patent Application Laid-Open No. 2004-043554, the formula (4), the formula An alkoxysilane compound (ester-modified alkoxysilane) containing at least a secondary amino group represented by (5a) or formula (5b) as an isocyanate-reactive group can be preferably used.

[Chain extender (A1-f)]
The chain extender (A1-f) is not particularly limited and can be appropriately selected from known chain extenders, but an amine chain extender can be preferably used. As the amine chain extender, for example, in JP-A-2004-043554, an isocyanate-reactive compound (A1) can be used in the section of [anionic group-free / multiple isocyanate-reactive group-containing compound (A1-a)]. -A) an anionic group-free polyamine compound (aliphatic polyamine, alicyclic polyamine, aromatic polyamine, araliphatic polyamine, having a number average molecular weight of less than 500 exemplified as the polyamine compound (A1-a2) Hydrazine and its derivatives) can be appropriately selected and used. Examples of amine chain extenders include ethylenediamine, 1,3-pentamethylenediamine, 1,6-hexamethylenediamine, diethylenetriamine, triethylenetetramine, 4,4′-methylenebis (cyclohexylamine), 4,4′-methylenebis ( 3-methyl-cyclohexylamine), 1,3-bis (aminomethyl) cyclohexane, isophoronediamine, norbornanediamine, 1,3-xylylenediamine, and other aliphatic, alicyclic and araliphatic polyamines, hydrazine, carbo Hydrazine such as dihydrazide and derivatives thereof can be preferably used.

[Anionic group-containing water-dispersible silylated polyurethane resin (A1)]
Anionic group-containing water-dispersible silylated polyurethane resins (A1) include, for example, isocyanate-reactive compounds (A1-a), isocyanate-reactive compounds (A1-b), polyisocyanates (A1-c) and isocyanate-reactive This is a reaction product of a group-containing alkoxysilane (A1-d) and, if necessary, an isocyanate-reactive compound (A1-e) or a chain extender (A1-f). In the molecule, an isocyanate-reactive compound (A1 It is a polymer having at least an anionic group derived from -b) and an alkoxysilyl group derived from an isocyanate-reactive group-containing alkoxysilane (A1-d) at the end of the main chain. Further, the anionic group-containing water-dispersible silylated polyurethane resin (A1) can be obtained, for example, from a side chain derived from an unsaturated carboxylic acid ester related to an isocyanate-reactive group-containing alkoxysilane (A1-d) [ester group (ester Group having a bond)], tertiary amino group derived from isocyanate-reactive compound (A1-e), isocyanate group derived from polyisocyanate (A1-c) and amine as chain extender (A1-f) It is a polymer that can have a urea binding site by reaction with an amino group of a chain extender, if necessary.

  Anionic group-containing water-dispersible silylated polyurethane resins (A1) include isocyanate-reactive compounds (A1-a), isocyanate-reactive compounds (A1-b), polyisocyanates (A1-c), and if necessary The anionic group-containing urethane prepolymer obtained by the reaction of the isocyanate-reactive compound (A1-e) and the isocyanate-reactive group-containing alkoxysilane (A1-d) The terminal partially alkoxysilylated anionic group-containing urethane prepolymer obtained by partially alkoxysilylating the terminal isocyanate group may be used, and the terminal partially alkoxysilylated anionic group-containing urethane prepolymer may be used. The terminal partial alkoxysilyl with a chain extender (A1-f) if necessary An alkoxysilylated anionic group-containing urethane obtained by reacting the remaining isocyanate group in the anionic group-containing urethane prepolymer with a functional group (such as an amino group) of the chain extender (A1-f). It may be a prepolymer.

  The method for preparing the anionic group-containing water-dispersible silylated polyurethane resin (A1) is not particularly limited. Examples of the anionic group-containing water-dispersible silylated polyurethane resin (A1) include a method for preparing an anionic group-containing alkoxysilyl group-terminated polymer (A1) exemplified in JP-A-2004-043554, JP-A-2003 Of an anionic group-containing alkoxysilyl group-terminated polymer (A) exemplified in JP-A-105053, an anionic group-containing alkoxysilyl group-terminated polymer (A) exemplified in JP-A-2003-105305 It can be prepared according to a preparation method such as a preparation method and a preparation method of an anionic group-containing alkoxysilyl group-terminated polymer (A) exemplified in JP-A-2003-105307.

  In the anionic group-containing water-dispersible silylated polyurethane resin (A1), the ratio of each component is not particularly limited. The proportion of each component in the anionic group-containing water-dispersible silylated polyurethane resin (A1) is, for example, each of the anionic group-containing alkoxysilyl group-terminated polymer (A1) exemplified in JP-A No. 2004-043554. Component ratio, proportion of each component of the anionic group-containing alkoxysilyl group-terminated polymer (A) exemplified in JP-A-2003-105053, anionic group-containing exemplified in JP-A-2003-105305 The proportion of each component of the alkoxysilyl group-terminated polymer (A) and the proportion of each component of the anionic group-containing alkoxysilyl group-terminated polymer (A) exemplified in JP-A-2003-105307 be able to. Although the isocyanate-reactive compound (A1-e) is not described in the conventional literature, it can be set so as to be included in the whole isocyanate-reactive compound to be reacted with the polyisocyanate compound. Specifically, when an isocyanate-reactive compound (A1-e) is used, a polyisocyanate (A1-c), an isocyanate-reactive compound (A1-a), an isocyanate-reactive compound (A1-b) and The ratio of the isocyanate reactive compound (A1-e) to the isocyanate group / isocyanate reactive compound (A1-a), isocyanate reactive compound (A1-b) and isocyanate reactive compound in the polyisocyanate (A1-c) Isocyanate-reactive groups (such as hydroxyl groups) (NCO / NCO-reactive groups) (equivalent ratio) in (A1-e) are greater than 1 and less than or equal to 2.0 (preferably 1.02-1.5, more preferably The range can be selected from 1.05 to 1.4). If the ratio of the NCO / NCO reactive group is too large (for example, exceeding 2.0 (equivalent ratio)), it becomes difficult to control the reaction (crosslinking reaction) at the time of extension, and the dispersibility is lowered. On the other hand, if the ratio of the NCO / NCO reactive group is too small (for example, 1 or less (equivalent ratio)), chain extension and silyl group introduction cannot be sufficiently performed, and the time until tack development is increased. In addition, the physical properties also deteriorate.

  Further, when an isocyanate-reactive compound (A1-e) is used (that is, an anionic group-containing water-dispersible silylated polyurethane resin (A1) is an anionic group and a tertiary amino group-containing water-dispersible silylated polyurethane resin) In the case of the resin (A1), the content of the tertiary amino group in the water-dispersible silylated polyurethane resin (A1) containing an anionic group and a tertiary amino group is 0.15 meq / g or more ( For example, by using the isocyanate-reactive compound (A1-e) at a rate of 0.15 to 0.8 meq / g, preferably 0.15 to 0.6 meq / g), The tack strength of the tertiary amino group-containing water-dispersible silylated polyurethane resin (A1) can be improved, the time required for developing the tack force can be shortened, and the initial adhesive strength can be effectively increased.

  Furthermore, when an isocyanate-reactive compound (A1-e) is used, an anionic group and a tertiary amino group-containing water-dispersible silylated polyurethane resin (A1) and an anionic group contained in the molecule The ratio with the tertiary amino group is such that the tertiary amino group / anionic group (molar ratio) = 0.2 to 1 (preferably 0.3 to 0.9), the anionic group and the primary amino group. The ratio of the tertiary amino group and alkoxysilyl group contained in the molecule of the tertiary amino group-containing water-dispersible silylated polyurethane resin (A1) is tertiary amino group / alkoxysilyl group (molar ratio) = By using the isocyanate-reactive compound (A1-e) in such a ratio that it is 1.0 to 5.5 (preferably 1.5 to 5.5, more preferably 1.6 to 4.0), Tack power is reduced by shortening the time required for tack power development. Increased, it is possible to increase the initial adhesive strength effectively.

  Thus, when the anionic group-containing water-dispersible silylated polyurethane resin (A1) is an anionic group and a tertiary amino group-containing water-dispersible silylated polyurethane resin (A1), The ratio of the anionic group and the tertiary amino group contained in the molecule of the tertiary amino group-containing water dispersible silylated polyurethane resin (A1), the ratio of the tertiary amino group and the alkoxysilyl group (particularly By controlling the ratio of anionic group, tertiary amino group and alkoxysilyl group), water dispersible silylated polyurethane resin (A1) containing anionic group and tertiary amino group is slightly scattered. As a result, the interaction between the anionic group and the tertiary amino group rapidly increases, and further, silanol groups condense and rapidly gel, which leads to the time until tack development. There can significantly reduce compared to conventional water-based adhesives can further exhibit excellent tackiness. That is, excellent performance is exhibited by the synergistic effect of the anionic group, tertiary amino group, and silyl group.

[Basic compounds]
In the present invention, when the water-dispersible polyurethane resin (A) has an anionic group in the molecule [for example, the water-dispersible polyurethane resin (A) is an anionic group-containing water-dispersible silylated In the case of the polyurethane resin (A1)], the urethane-based aqueous composition may contain a basic compound. By using a basic compound, a polymer having an anionic group in the molecule [for example, an anionic group-containing water-dispersible silylated polyurethane resin (A1), etc.] is converted into a salt form to make it water-soluble or water-dispersible. can do.

  The basic compound may be a basic inorganic compound or a basic organic compound. A basic compound can be used individually or in combination of 2 or more types. Examples of the basic compound include basic compounds (basic inorganic compounds and bases) exemplified as the basic compound (E) in the section of [Basic Compound (E)] in JP-A No. 2004-043554. Selected from organic compounds). As the basic compound, ammonia or an amine compound (in particular, a tertiary amine compound such as a trialkylamine or a trialcoholamine) can be preferably used.

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

[Urethane-based aqueous composition]
As described above, the urethane-based aqueous composition of the present invention contains the water-dispersible polyurethane-based resin (A) and the tertiary amino group / aromatic ring-containing compound (B). Of course, water is also contained in the urethane-based aqueous composition. The ratio of the water-dispersible polyurethane resin (A) and the tertiary amino group / aromatic ring-containing compound (B) is not particularly limited, but the tertiary amino group / aromatic ring-containing compound (B) is not limited. Can be appropriately selected from the range of 5 to 30 parts by mass (preferably 5 to 20 parts by mass) with respect to 100 parts by mass (solid content) of the water-dispersible polyurethane resin (A). When the proportion of the tertiary amino group / aromatic ring-containing compound (B) is less than 5 parts by mass with respect to 100 parts by mass (solid content) of the water-dispersible polyurethane resin (A), the bonding time is possible. On the other hand, when it exceeds 30 parts by mass, the cohesive force of the cured product or the coating is lowered.

  In the urethane-based aqueous composition of the present invention, the water-dispersible polyurethane resin (A) may have a salt form. Therefore, for the water-dispersible polyurethane resin (A), a substance for forming a salt (for example, a basic compound or an acid) may be used.

  When the water dispersible polyurethane resin (A) is a water dispersible silylated polyurethane resin (A1) (such as an anionic group-containing water dispersible silylated polyurethane resin (A1)), the water dispersible silyl The polyurethane-based resin (A1) may react with water. Examples of the reaction between the water-dispersible silylated polyurethane resin (A1) and water include a hydrolysis reaction in which the terminal alkoxysilyl group in the water-dispersible silylated polyurethane resin (A1) is hydrolyzed by water. . That is, the terminal alkoxysilyl group in the water-dispersible silylated polyurethane resin (A1) is partially or entirely silanol group and / or produced by the reaction between the water-dispersible silylated polyurethane resin (A1) and water. Or it is a siloxane bond. The silanol group means a group composed of a silicon atom having at least one hydroxyl group, and may have a substituent such as an alkoxy group.

  Accordingly, for example, when the water-dispersible polyurethane resin (A) is an anionic group-containing water-dispersible silylated polyurethane resin (A1), the urethane-based aqueous composition is an anionic group-containing water-dispersible silylated polyurethane. The anionic group in the resin (A1) is neutralized with a basic compound to form a salt of the anionic group, and the terminal alkoxysilyl group is partially or wholly hydrolyzed with water to produce a silanol group And / or an aqueous silanolated urethane prepolymer having a siloxane bond (sometimes referred to as “aqueous silanolated polyurethane resin”). That is, the urethane-based aqueous composition of the present invention contains an aqueous silanolated polyurethane-based resin as the water-dispersible polyurethane-based resin (A) and a tertiary amino group / aromatic ring-containing compound (B). May be.

  The basic compound as the water dispersing agent may be used after preparing the anionic group-containing water-dispersible silylated polyurethane resin (A1). It may be used in advance when preparing the resin (A1). As a usage-amount of a basic compound, it is from the range of about 50-120 mol% (preferably 80-110 mol%) with respect to the anionic group in an anionic group containing water-dispersible silylated polyurethane resin (A1). You can choose.

  Water is used after preparing a water-dispersible polyurethane resin (A) (water-dispersed silylated polyurethane resin (A1) such as an anionic group-containing water-dispersible silylated polyurethane resin (A1)). Or may be used in advance when preparing the water-dispersible polyurethane resin (A). As usage-amount of water, it can select from the range of about 65-900 mass parts (preferably 100-400 mass parts) with respect to 100 mass parts of water-dispersible polyurethane-type resin (A).

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

  The urethane-based aqueous composition of the present invention is preferably a completely aqueous urethane-based composition that does not contain any organic solvent. However, in order to adjust the viscosity, hydrophilic properties such as ketones and lower alcohols are used. An organic solvent (water-soluble organic solvent) may be included.

  Examples of the urethane-based aqueous composition include wettability-modified hydrophilic solvents (for example, surfactants such as N-methyl-2-pyrrolidone and polyoxyethylene alkyl ether, sodium alginate, mucopolysaccharide, acrylic acid). Sodium), fillers (for example, calcium carbonate, fumed silica, clay, talc, various balloons, noble silica, kaolin, aluminum silicate, etc.), plasticizers (for example, phthalates such as dioctyl phthalate, dibutyl phthalate); Aliphatic carboxylic acid esters such as dioctyl adipate and dibutyl sebacate), anti-aging agents, UV absorbers, antioxidants, heat stabilizers, colorants (such as pigments and dyes), fungicides, wetting accelerators, Viscosity improvers, fragrances, various tackifiers (eg, stabilized rosin esters Polymerized rosin ester, terpene phenol, emulsion tackifiers of petroleum resins, etc.), coupling agents (titanate coupling agents, aluminum coupling agents, etc.), photocuring catalysts, emulsifiers, surfactants, emulsions and latexes, Various crosslinking agents (eg, isocyanate crosslinking agents, epoxy crosslinking agents, carbodiimide crosslinking agents, aziridine crosslinking agents, polyethyleneimine crosslinking agents, melamine crosslinking agents, colloidal silica, etc.), moisturizing agents, antifoaming agents, etc. Additives or components, solvents and the like may be included.

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

  The water-based adhesive or water-based coating agent containing the urethane-based aqueous composition has the above-mentioned configuration because the urethane-based aqueous composition has the above configuration [that is, the water-dispersible polyurethane resin (A) and the third grade Since it is combined with the amino group / aromatic ring-containing compound (B)], the initial adhesive strength is high, the initial adhesiveness (initial adhesiveness, initial adhesiveness, etc.) is excellent, and bonding is possible. Time (open time) has been greatly extended. The reason for this is not clear, but in a compound containing no tertiary amino group and containing an aromatic ring, a compound containing no aromatic ring and containing a tertiary amino group, or a mixture thereof, Since such an effect is not exhibited, it can be said that the effect can be exhibited for the first time by using a compound having a tertiary amino group and an aromatic ring in the molecule.

  As described above, the water-based adhesive of the present invention has a wide and wide range of adherable conditions, and can exhibit an excellent adhesive effect stably. Specifically, since the bonding possible time is long, it is not necessary to bond the adherends immediately after applying the aqueous adhesive to a predetermined surface of the adherends. Further, since the initial adhesive strength is excellent, it is not necessary to perform temporary pressing and pressing when the adherends are bonded to each other, or the time required for the pressing can be shortened. Therefore, not only can adherends be easily and stably bonded, but even if there are a plurality of combinations (pairs) of adherends to be bonded, the bonding operation can be easily performed.

  By using an anionic group and tertiary amino group-containing water-dispersible silylated polyurethane resin (A1) as the water-dispersible polyurethane resin (A), even better tack force can be achieved in a short time. And even better initial adhesion and initial adhesion can be exhibited. Further, the curing rate can be increased by using an amine chain extender.

  In particular, when the water-dispersible polyurethane resin (A) is a silylated polyurethane resin (A1) [in particular, an anionic group-containing water-dispersible silylated polyurethane resin (A1)], the silylated polyurethane resin (A1) can exist stably even in water in a state where the terminal alkoxysilyl group is partially or entirely hydrolyzed by water to form a silanol group and / or a siloxane bond. Therefore, the aqueous adhesive containing the urethane-based aqueous composition of the present invention, the aqueous coating agent, and the like should be a one-component treatment agent such as a one-component aqueous adhesive or a one-component aqueous coating agent. Can do.

  Since these water-based adhesives and water-based coating agents are water-based types (especially they may be completely water-free without any organic solvent), they are easy to handle and work. High safety for the environment.

  When the water dispersible polyurethane resin (A) is a silylated polyurethane resin (A1) [in particular, an anionic group-containing water dispersible silylated polyurethane resin (A1)], the silylated polyurethane resin Since the alkoxysilyl group of (A1) is in the form of a silanol group or the like, an aqueous adhesive (particularly an aqueous contact adhesive) or an aqueous coating agent containing a urethane-based aqueous composition is used for paper, etc. Good adhesion and adhesion can be expressed not only for porous materials but also for non-porous materials such as metals and glass. That is, various base materials can be used as a base material (adhered body, coated body, etc.) to which the water-based adhesive or the water-based coating agent can be applied, as shown in specific examples below. In addition, as a base material at the time of bonding by adhesion | attachment, the base materials which consist of the same raw material may be sufficient, and the base material which consists of a different raw material may be sufficient. The substrates may be used alone or in combination of two or more.

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

  As described above, the aqueous adhesive or aqueous coating agent containing the urethane-based aqueous composition of the present invention can be applied to a substrate made of a wide range of materials, and particularly non-porous by contact adhesion. It can also be used for bonding between each other.

  The method for bonding the adherends using the aqueous adhesive containing the urethane-based aqueous composition is not particularly limited. For example, the method is a method in which the adherends are bonded together immediately after being applied to the adherends. Alternatively, various methods such as a contact bonding method in which adherends are bonded to each other in a state where adhesiveness is developed after a predetermined time has elapsed after application to the adherends can be employed. In the present invention, as a contact bonding method, as defined in JIS K 6800, it is applied to the adhesion surfaces of both adherends to be bonded together, and a predetermined time has elapsed, Not only a method of bonding and adhering two adherends in a state where adhesiveness is expressed, but also applying to the adherend surface of either one of the two adherends to be bonded together A method is also included in which two adherends are bonded and bonded together in a state where adhesiveness is developed over time. That is, in the present invention, the contact adhesion means that two adherends are applied to at least any one of the adherends to be bonded and adhesiveness is developed after a predetermined time has elapsed. Means that the two are bonded together.

  EXAMPLES Hereinafter, although an Example demonstrates this invention more concretely, this invention is not limited by these Examples. In the following, “part” means “part by mass” and “%” means “% by mass” unless otherwise specified. The materials used in the examples and comparative examples are as follows.

(Preparation Example 1 of Water Dispersible Polyurethane Resin Composition)
To a four-necked flask equipped with a nitrogen inlet tube, a thermometer, a condenser and a stirrer, a trade name “PTMG2000” (manufactured by Mitsubishi Chemical Corporation, polytetramethylene ether glycol, number average molecular weight: 2000, hydroxyl value: 57.4 mg− KOH / g; sometimes referred to as “polyol-1”: 150 parts 1,4-butanediol (sometimes referred to as “polyol-2”): 6 parts 2,2-dimethylolbutanoic acid ( Hydroxyl value: 754.0 mg-KOH / g; sometimes referred to as “polyol-3”): 20 parts, isophorone diisocyanate [isocyanate content (NCO content): 37.8%; sometimes referred to as “IPDI” Yes]: 75.0 parts and methyl ethyl ketone (MEK): 100 parts were mixed and reacted at a temperature of 80 to 85 ° C. under a nitrogen stream for 6 hours. Residual isocyanate group to obtain a reaction mixture containing 2.0% of the carboxyl group-containing isocyanate-terminated urethane prepolymer.

  Next, after cooling the reaction mixture containing this carboxyl group-containing isocyanate group-terminated urethane prepolymer to 40 ° C., 13.6 parts of triethylamine is blended, and isophoronediamine (“IPDA” is sometimes referred to in advance) under high-speed stirring. Yes): An aqueous solution in which 8.1 parts were dissolved in 409 g of deionized water was added to obtain a dispersion. After the MEK was distilled off from 45 to 50 ° C. under reduced pressure, the water-dispersible polyurethane resin composition (“polyurethane resin composition (1)”) whose solid content was adjusted to 38% with deionized water. May be called).

(Preparation Example 2 of Water Dispersible Polyurethane Resin Composition)
To a four-necked flask equipped with a nitrogen inlet tube, a thermometer, a condenser and a stirrer, a trade name “PTMG2000” (manufactured by Mitsubishi Chemical Corporation, polytetramethylene ether glycol, number average molecular weight: 2000, hydroxyl value: 57.4 mg− KOH / g; polyol-1): 150 parts, N-methyl-diethanolamine [N, N-bis (2-hydroxyethyl) -N-methylamine; hydroxyl value: 941.6 mg-KOH / g; ]: 6 parts, 2,2-dimethylolbutanoic acid (hydroxyl value: 754.0 mg-KOH / g; polyol-3): 20 parts, isophorone diisocyanate [isocyanate content (NCO content) : 37.8%; IPDI]: 71.2 parts and methyl ethyl ketone (MEK): 100 parts, 80-85 Of performed nitrogen stream for 6 hours at a temperature, the residual isocyanate group to obtain a reaction mixture containing 2.0% of the carboxyl group and a tertiary amino group-containing isocyanate-terminated urethane prepolymer.

  Next, the reaction mixture containing the carboxyl group and the tertiary amino group-containing isocyanate group-terminated urethane prepolymer was cooled to 40 ° C., and then mixed with 13.6 parts of triethylamine, and previously mixed with isophoronediamine (IPDA) under high-speed stirring. ): An aqueous solution in which 8.0 parts were dissolved in 403 g of deionized water was added to obtain a dispersion. After the MEK was distilled off from the dispersion at 45 to 50 ° C. under reduced pressure, the water-dispersible polyurethane resin composition (“polyurethane resin composition (2)”) whose solid content was adjusted to 38% with deionized water. May be called).

(Preparation Example 3 of Water Dispersible Polyurethane Resin Composition)
To a four-necked flask equipped with a nitrogen inlet tube, a thermometer, a condenser and a stirrer, a trade name “PTMG2000” (manufactured by Mitsubishi Chemical Corporation, polytetramethylene ether glycol, number average molecular weight: 2000, hydroxyl value: 57.4 mg− KOH / g; polyol-1): 150 parts, 1,4-butanediol (polyol-2): 6 parts, 2,2-dimethylolbutanoic acid (hydroxyl value: 754.0 mg-KOH / g; polyol-3) ): 20 parts, isophorone diisocyanate [isocyanate content (NCO content): 37.8%; IPDI]: 75.0 parts and methyl ethyl ketone (MEK): 100 parts, nitrogen stream at a temperature of 80 to 85 ° C. The reaction is continued for 6 hours, and the residual isocyanate group is 2.0% carboxyl group-containing isocyanate group-terminated urethane prepoly To obtain a reaction mixture containing over.

  In addition, the product name “KBM602” [manufactured by Shin-Etsu Chemical Co., Ltd., N-β (aminoethyl) -γ-aminopropylmethyldimethoxysilane]: 1 mol, 2-ethylhexyl acrylate: used in a ratio of 2 mol, mixed. And it was made to react at 50 degreeC for 7 days, and the amino group containing alkoxysilane was obtained.

  Next, after adding 16.6 parts of the amino group-containing alkoxysilane: 16.6 parts to the total reaction mixture of the carboxyl group-containing isocyanate group-terminated urethane prepolymer, the mixture is mixed at a temperature of 80 to 85 ° C. for 1 hour in a nitrogen stream. The reaction was carried out to obtain a reaction mixture containing an isocyanate group containing a carboxyl group and an alkoxysilyl group-terminated urethane prepolymer.

  Furthermore, after cooling the reaction mixture containing the isocyanate group containing the carboxyl group and the alkoxysilyl group-terminated urethane prepolymer to 40 ° C., 13.6 parts of triethylamine was blended, and isophoronediamine (IPDA) in advance under high-speed stirring. : An aqueous solution in which 5.7 parts were dissolved in 432 g of deionized water was added to obtain a dispersion. After the MEK was distilled off from 45 to 50 ° C. under reduced pressure, the water-dispersible polyurethane resin composition (“polyurethane resin composition (3)”) having a solid content adjusted to 38% with deionized water. May be called).

(Preparation Example 4 of Water Dispersible Polyurethane Resin Composition)
To a four-necked flask equipped with a nitrogen inlet tube, a thermometer, a condenser and a stirrer, a trade name “PTMG2000” (manufactured by Mitsubishi Chemical Corporation, polytetramethylene ether glycol, number average molecular weight: 2000, hydroxyl value: 57.4 mg− KOH / g; polyol-1): 150 parts, N-methyl-diethanolamine [N, N-bis (2-hydroxyethyl) -N-methylamine; hydroxyl value: 941.6 mg-KOH / g; polyol-4] : 8 parts 2,2-dimethylolbutanoic acid (hydroxyl value: 754.0 mg-KOH / g; polyol-3): 20 parts, isophorone diisocyanate [isocyanate content (NCO content): 37.8%; IPDI ]: 75.2 parts and methyl ethyl ketone (MEK): 100 parts are blended, and the temperature is 80 to 85 ° C. under a nitrogen stream. Performed between the reaction, the residual isocyanate group to obtain a reaction mixture containing 2.0% of the carboxyl group and a tertiary amino group-containing isocyanate-terminated urethane prepolymer.

  In addition, the product name “KBM602” [manufactured by Shin-Etsu Chemical Co., Ltd., N-β (aminoethyl) -γ-aminopropylmethyldimethoxysilane]: 1 mol, 2-ethylhexyl acrylate: used in a ratio of 2 mol, mixed. And it was made to react at 50 degreeC for 7 days, and the amino group containing alkoxysilane was obtained.

  Next, in the reaction mixture containing the carboxyl group and the tertiary amino group-containing isocyanate group-terminated urethane prepolymer, the amino group-containing alkoxysilane: 16.7 parts is mixed and mixed, and then the temperature is 80 to 85 ° C. The reaction mixture was reacted for 1 hour under a nitrogen stream to obtain a reaction mixture containing an isocyanate group containing a carboxyl group and a tertiary amino group and an alkoxysilyl group-terminated urethane prepolymer.

  Furthermore, after cooling the reaction mixture containing the isocyanate group containing the carboxyl group and the tertiary amino group and the alkoxysilyl group-terminated urethane prepolymer to 40 ° C., 13.6 parts of triethylamine was blended, An aqueous solution prepared by previously dissolving 5.7 parts of isophoronediamine (IPDA) in 436 g of deionized water was added to obtain a dispersion. After the MEK was distilled off from 45 to 50 ° C. under reduced pressure, the water-dispersible polyurethane resin composition (“polyurethane resin composition (4)”) having a solid content adjusted to 38% with deionized water. May be called).

  In addition, the water dispersible polyurethane resin composition obtained in Preparation Example 1 of the water dispersible polyurethane resin composition 1 to Preparation Example 4 of the water dispersible polyurethane resin composition has the composition shown in Table 1. Yes.

Example 1
As shown in Table 2, polyurethane resin composition (1) obtained in Preparation Example 1 of water-dispersible polyurethane resin composition (1): 100 parts, N, N-dihydroxyethylaniline: 3 parts Mixing at a ratio, a urethane-based aqueous composition was obtained.

(Examples 2 to 5)
As shown in Table 2, respectively, using the polyurethane-based resin composition (1) to the polyurethane-based resin composition (4) obtained by any of Preparation Examples 1 to 4 of the water-dispersible polyurethane-based resin composition , And N, N-dihydroxyethylaniline is used at a ratio of 6 parts to 100 parts of polyurethane resin composition of polyurethane resin composition (1) to polyurethane resin composition (4). By mixing, a urethane-based aqueous composition was obtained.

(Comparative Examples 1-4)
As the urethane-based aqueous composition, as shown in Table 2, respectively, the polyurethane-based resin composition (1) to the polyurethane-based resin obtained by any of Preparation Examples 1 to 4 of the water-dispersible polyurethane-based resin composition Only composition (4) was used.

(Comparative Example 5)
As shown in Table 2, polyurethane resin composition (1) obtained in Preparation Example 1 of water-dispersible polyurethane resin composition (1): 100 parts, N-methyl-diethanolamine: in a ratio of 6 parts By mixing, a urethane-based aqueous composition was obtained.

(Comparative Example 6)
As shown in Table 2, the polyurethane-based resin composition (1) obtained in Preparation Example 1 of the water-dispersible polyurethane-based resin composition (1): 100 parts is mixed with dibutyl phthalate: 6 parts. Thus, a urethane-based aqueous composition was obtained.

(Evaluation)
About the urethane type aqueous composition which concerns on Examples 1-5 and Comparative Examples 1-6, the initial stage adhesiveness of the urethane type aqueous composition was evaluated with the following initial adhesive evaluation method. The evaluation results are also shown in Table 2.

[Evaluation method of initial adhesiveness]
The urethane-based aqueous composition was applied to an olefin-based resin sheet (coating amount: about 80 g / m ² ), dried at 70 ° C. for any predetermined time (each time shown in Table 2), and then MDF (porous (Woody material) is pasted on the coated surface and pressure-bonded using a hot roll heated to 60 ° C., and the peel adhesion strength (N / 25 mm) is immediately measured according to JIS K 6854-2. The initial adhesiveness was evaluated according to the evaluation criteria.
(Evaluation criteria)
A: Peel adhesion strength is 10 (N / 25 mm) or more. O: Peel adhesion strength is 7.5 (N / 25 mm) or more and less than 10 (N / 25 mm). Δ: Peel adhesion strength is 5 ( N / 25 mm) or more and less than 7.5 (N / 25 mm) ×: The peel adhesion strength is less than 5 (N / 25 mm) XX: Tack-free and cannot be bonded together

  In the evaluation criteria of the above test (initial adhesion evaluation method), “◎” means “excellent”, “○” means “good”, and “△” means “good”. , “×” means “impossible”.

  As is clear from Table 2, the time required for the urethane-based aqueous compositions according to Examples 1 to 5 to develop tack force when compared with the corresponding urethane-based aqueous compositions according to Comparative Examples 1 to 4, respectively. And the initial adhesive strength at that time is increased. Furthermore, the time (tack holding time) in which the tack force is expressed is significantly increased, and the bonding possible time is greatly extended.

  In Comparative Example 5, a compound that does not have an aromatic ring and has a tertiary amino group (specifically, N-methyl-diethanolamine) is used. Compared to the case, the time required for the tack force to be developed has been shortened, and the bonding time has been extended, but the initial adhesive strength is low, and the adherends can be easily bonded together. Can not.

  Further, in Comparative Example 6, dibutyl phthalate having a function as a plasticizer is used, and compared with the case of Comparative Example 1, the time required for developing the tack force is longer. The bonding time has not been extended.

Claims (6)

A urethane-based aqueous composition containing a water-dispersible polyurethane resin (A), further containing a compound (B ′ ) represented by the following formula (1 ′), an aqueous adhesive, an aqueous coating agent, A urethane-based aqueous composition characterized by being used for a binder, laminate, sealer, primer, sizing agent or sealing material .

[In the formula (1 ′ ), R ¹ ′ and R ² ′ are the same or different and are an alkyl group having a hydroxyl group and / or an ether bond-containing group ] The compound (B ′ ) represented by the formula (1 ′) is N, N-bis (hydroxyalkyl) aniline, or N, N-bis [hydroxy-mono or poly (alkyleneoxy) -alkyl] aniline. The urethane-based aqueous composition according to claim 1 . The formula proportion of 'the compound represented by (B (1)') is, according to claim 1 or 2 water-dispersible polyurethane resin (A) 100 parts by mass of relative (solids) from 5 to 30 parts by weight The urethane-based aqueous composition described. The urethane-based aqueous composition according to any one of claims 1 to 3 , wherein the water-dispersible polyurethane resin (A) is a water-dispersible silylated polyurethane resin. The urethane-based aqueous composition according to claim 4 , wherein the water-dispersible polyurethane resin (A) is a water-dispersible silylated polyurethane resin having an anionic group and a tertiary amino group in the molecule. An aqueous adhesive comprising the urethane-based aqueous composition according to any one of claims 1 to 5 .