JP2003105053A - Anionic-group-containing, alkoxysilyl-terminated polymer or its salt or their alkoxysilyl-group-hydrolyzed polymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polymer which is useful as the adhesive component of a solid adhesive which is excellent in workability during application, settlement after lamination, adhesion to various adherends, and resistances to heat and water and is capable of contact adhesion. SOLUTION: The anionic-group-containing, alkoxysilyl-group-terminated polymer and its alkoxysilyl-group-hydrolyzed polymer are represented by formula (1): W-(-NH-CO-X)n [wherein W is a residue comprising a backbone of an anionic-group-containing polymer; and nitrogen atoms are derived from terminal isocyanate groups]. W has structural units represented by formula (2): -(-NH-CO- O-Y-O-CO-NH-Z-)-(wherein Y is a residue derived from a polyol compound; and Z is a residue derived from a polyisocyanate compound). X is an alkoxysilyl-containing group represented by formula (3).

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a polymer suitable as a polymer as an adhesive component of an aqueous solid adhesive, and an aqueous solid adhesive containing the polymer has good adhesiveness to various adherends, Moreover, it has excellent water resistance and heat resistance.

[0002]

2. Description of the Related Art Conventionally, as a water-based solid adhesive, for example, a stick-type adhesive containing a water-soluble polymer, a gelling agent and water as a main component has been excellent in ease of coating work and fit after bonding. Therefore, it is generally widely used. However, since the adhesive property of the water-soluble polymer itself is in a very limited range, it is actually used for adhering paper at present. Therefore, development of a stick-type adhesive capable of adhering to wood, various plastics, metals and the like is desired. In order to solve such a problem, a proposal has been made that an aqueous polyurethane dispersion is used as a stick-type adhesive as shown in Japanese Patent No. 2836957, but the adhesion to plastic is improved but the metal is used. Adhesion to glass and glass is insufficient. Further, since the aqueous polyurethane dispersion is a non-reactive polymer, it is substantially a linear polymer and is insufficient in heat resistance and water resistance. Furthermore, the aqueous polyurethane dispersion using an amine-based chain extender for imparting heat resistance and water resistance has a molecular weight of several hundreds of thousands, which results in an emulsion having a relatively large particle size and stick-type adhesion. It has the drawback that it is difficult to mold it into an agent.

[0003]

SUMMARY OF THE INVENTION Therefore, the object of the present invention is not only excellent in coating workability but also excellent in fittability after bonding, and good adhesiveness to various plastics, metals and glass, and after curing. Another object of the present invention is to provide a polymer useful as an adhesive component in a water-based solid adhesive having excellent heat resistance and water resistance. Another object of the present invention is to provide a polymer useful as an adhesive component in a water-based solid adhesive capable of further contact adhesion.

[0004]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that a specific alkoxylsilyl group-terminated polymer that cures by a condensation reaction with silanol groups as an adhesive component of an aqueous solid adhesive. When this is used, this water-based solid adhesive has excellent coating workability and good fit after bonding, and can exhibit excellent adhesiveness to various plastics, metals and glass, and The present invention has been completed by finding that the heat resistance and water resistance after curing are excellent and contact adhesion is possible.

That is, the present invention is an anionic group-containing alkoxysilyl group-terminated polymer represented by the following formula (1), a salt thereof, or an alkoxysilyl group-hydrolyzed polymer thereof.

[Chemical 9] [In the formula (1), W is a residue corresponding to the skeleton of the anionic group-containing polymer, and the nitrogen atom bonded to W is a nitrogen atom derived from the isocyanate group at the terminal of the anionic group-containing polymer. W has a structural unit represented by the following formula (2).

[Chemical 10] (In the formula (2), Y is a residue derived from the anionic group-free polyol compound (A1) having a number average molecular weight of 500 or more, and the anionic group-free polyol compound (A2) having a number average molecular weight of less than 500). Which is a residue derived from the anionic group-containing polyol compound (A3), and the oxygen atom bonded to Y has a number average molecular weight of 500 or more. An oxygen atom derived from the hydroxyl group of the compound (A1), the anionic group-free polyol compound (A2) or the anionic group-containing polyol compound (A3) having a number average molecular weight of less than 500. However, the number average as Y Residue derived from anionic group-free polyol compound (A1) having a molecular weight of 500 or more, and anionic group-free polyol compound having a number average molecular weight of less than 500 All of the residues derived from A2) and the anionic group-containing polyol compound (A3) are included, and Z is a residue derived from the polyisocyanate compound (A4). And the nitrogen atom on the opposite side to Z is a nitrogen atom derived from the isocyanate group of the polyisocyanate compound (A4).) X is the following formula (3), (4) or ( 5 shows an alkoxysilyl-containing group represented by 5).

[Chemical 11] (In the formula (3), R ¹ and R ² are the same or different,
It represents an alkyl group, and R ³ represents an alkylene group. Also,
R ⁴ and R ⁶ are the same or different and each represents a hydrogen atom or an alkyl group. R ⁵ is a hydrogen atom, an alkyl group, an aryl group,
An alkoxycarbonyl group, an aryloxycarbonyl group and a cycloalkyloxycarbonyl group are shown. R ⁷ represents an alkyl group, an aryl group or a cycloalkyl group.
m is an integer of 1 to 3. )

[Chemical 12] (In the formula (4), R ^{1 to} R ⁷ and m are the same as above. R ⁸
Represents an alkylene group, which may be the same as or different from the alkylene group for R ³ . )

[Chemical 13] (In the formula ^{(5), R 1 ~R 8} , m is the same.) In addition, n is an integer of 1-4. ]

In the present invention, as the anionic group-free polyol compound (A1) having a number average molecular weight of 500 or more,
A polyether polyol having a number average molecular weight of 500 or more,
A polyester polyol having a number average molecular weight of 500 or more,
At least one anionic group-free polyol compound selected from a polycarbonate polyol having a number average molecular weight of 500 or more, a polyolefin polyol having a number average molecular weight of 500 or more, and a polyacrylic polyol having a number average molecular weight of 500 or more can be used. . Further, as the anionic group-free polyol compound (A2) having a number average molecular weight of less than 500, a polyhydric alcohol, a polyether polyol having a number average molecular weight of less than 500, a polyester polyol having a number average molecular weight of less than 500, a number average molecular weight. Polycarbonate polyol having a ratio of less than 500,
At least one anionic group-free polyol compound selected from a polyolefin polyol having a number average molecular weight of less than 500 and a polyacrylic polyol having a number average molecular weight of less than 500 can be used. Furthermore, dimethylolalkanoic acid can be used as the anionic group-containing polyol compound (A3).

The anionic group-containing alkoxysilyl group-terminated polymer represented by the above formula (1) has a number average molecular weight of 5
00 or more anionic group-free polyol compound (A
1), an anionic group-free polyol compound (A2) having a number average molecular weight of less than 500, an anionic group-containing polymer which is a reaction product of an anionic group-containing polyol compound (A3) and a polyisocyanate compound (A4), At least one secondary amino group-containing alkoxysilane compound (A5) selected from alkoxysilane compounds containing one secondary amino group represented by the following formulas (6) to (8)
It may be a terminal alkoxysilylated anionic group-containing polymer obtained by reaction with.

[Chemical 14] (In the formula (6), R ^{1 to} R ⁷ and m are the same as above.)

[Chemical 15] (In the formula (7), R ^{1 to} R ⁸ and m are the same as above.)

[Chemical 16] (In the formula (8), R ^{1 to} R ⁸ and m are the same as above.)

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The anionic group-containing alkoxysilyl group-terminated polymer of the present invention is represented by the above formula (1) (hereinafter, the anionic group-containing alkoxysilyl group represented by the above formula (1). The terminal polymer may be referred to as “anionic group-containing alkoxysilyl group terminal polymer (A)”). W in the formula (1), that is, the residue W corresponding to the skeleton of the anionic group-containing polymer is represented by the above formula (2).
It has a structural unit represented by. Therefore, the residue W is
A structural unit derived from an anionic group-free polyol compound (A1) having a number average molecular weight of 500 or more, a structural unit derived from an anionic group non-containing polyol compound (A2) having a number average molecular weight of less than 500, and an anionic Anion group-free polyol compound (A1) having a structural unit derived from a group-containing polyol compound (A3) and a structural unit derived from a polyisocyanate compound (A4), wherein the number average molecular weight is 500 or more. A urethane bond is formed between the polyisocyanate compound (A4) and the anionic group-free polyol compound (A2) having a number average molecular weight of less than 500 and the anionic group-containing polyol compound (A3). That is, in the formula (2), the oxygen atom bonded to Y is an anionic group-free polyol compound (A1) having a number average molecular weight of 500 or more, and an anionic group-free polyol having a number average molecular weight of less than 500. Compound (A
2) or an oxygen atom derived from the hydroxyl group of the anionic group-containing polyol compound (A3). Further, the two nitrogen atoms in formula (2) (the nitrogen atom bonded to Z and the nitrogen atom on the opposite side to Z) are both nitrogen atoms derived from the isocyanate group of the polyisocyanate compound (A4). Is an atom. Furthermore, the nitrogen atom bonded to W in the above formula (1) is a nitrogen atom derived from the isocyanate group of the polyisocyanate compound (A4). That is, the anionic group-containing polymer relating to W has an isocyanate group at the end (that is, an anionic group-containing isocyanate group terminated polymer), and the nitrogen atom bonded to W is the anionic group-containing isocyanate. It is a nitrogen atom derived from the isocyanate group at the end of the group-terminated polymer.

Further, by using the secondary amino group-containing alkoxysilane compound (A5), the above formula (3)
X, which is an alkoxysilyl-containing group represented by- (5), can be introduced.

In the above formula (1), n is 1 to 4
Is an integer. It is preferable that n is an integer of 1 to 3 (particularly 2 or 3).

[Anionic group-free polyol compound (A1) having a number average molecular weight of 500 or more] A number average molecular weight of 50
Zero or more anionic group-free polyol compound (A1)
(Hereinafter, it may be referred to as "polyol (A1)")
Is a compound having no anionic group in the molecule and having at least two hydroxyl groups in the molecule, and is not particularly limited as long as its number average molecular weight is 500 or more. As the polyol (A1), for example, a polyether polyol having a number average molecular weight of 500 or more, a polyester polyol having a number average molecular weight of 500 or more, a polycarbonate polyol having a number average molecular weight of 500 or more, a polyolefin polyol having a number average molecular weight of 500 or more, Examples thereof include polyacrylic polyol having a number average molecular weight of 500 or more. The polyol (A1) can be used alone or in combination of two or more kinds.

Examples of the polyether polyol having a number average molecular weight of 500 or more include polyalkylene glycols such as polyethylene glycol, polypropylene glycol and polytetramethylene glycol, and a plurality of monomer components such as ethylene oxide-propylene oxide copolymer. Among the alkylene oxide-containing (alkylene oxide-other alkylene oxide) copolymers, there are polyether polyols having a number average molecular weight of 500 or more.

Examples of the polyester polyol having a number average molecular weight of 500 or more include, for example, condensation polymerization products of polyhydric alcohols and polycarboxylic acids; ring-opening polymerization products of cyclic esters (lactones); polyhydric alcohols and polycarboxylic acids. Among the reaction products of the three components of the cyclic ester and the cyclic ester, a polyester polyol having a number average molecular weight of 500 or more can be used. In the condensation polymerization product of polyhydric alcohol and polyhydric carboxylic acid, as the polyhydric alcohol, for example, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, trimethylene glycol, 1,4-tetramethylene diol,
1,3-tetramethylenediol, 2-methyl-1,3
-Trimethylene 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 (1,4-cyclohexanediol, etc.), bisphenols (bisphenol A, etc.), sugar alcohols (xylitol, sorbitol, etc.) and the like. On the other hand, as the polyvalent carboxylic acid, for example, an aliphatic dicarboxylic acid such as malonic acid, maleic acid, succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid; 1,4-cyclohexane Alicyclic dicarboxylic acids such as dicarboxylic acids; aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, orthophthalic acid, 2,6-naphthalenedicarboxylic acid, paraphenylenedicarboxylic acid and trimellitic acid. In the ring-opening polymer of cyclic ester, examples of the cyclic ester include propiolactone, β-methyl-δ-valerolactone and ε-caprolactone. In the reaction product of three kinds of components, as the polyhydric alcohol, the polycarboxylic acid and the cyclic ester, those exemplified above can be used.

Examples of the polycarbonate polyol having a number average molecular weight of 500 or more include, for example, a reaction product of a polyhydric alcohol and phosgene;
Examples include polycarbonate polyols of 00 or more. Specifically, in the reaction product of a polyhydric alcohol and phosgene, the polyhydric alcohol exemplified above can be used as the polyhydric alcohol. In the ring-opening polymer of cyclic carbonic acid ester, examples of the alkylene carbonate include ethylene carbonate, trimethylene carbonate, tetramethylene carbonate, hexamethylene carbonate and the like. The polycarbonate polyol having a number average molecular weight of 500 or more may be a compound having a number average molecular weight of 500 or more, having a carbonate bond in the molecule and having a hydroxyl group at the terminal, and having a carbonate bond and an ester bond. You may have.

As the polyolefin polyol having a number average molecular weight of 500 or more, a polyol having an olefin as a component of the skeleton (or main chain) of a polymer or copolymer and having at least two hydroxyl groups in the molecule (particularly at the terminal). And a number average molecular weight of 500 or more can be used. Examples of the olefin include carbon-terminal
An olefin having a carbon double bond (for example, ethylene,
Α-olefins such as propylene),
It may also be an olefin having a carbon-carbon double bond at a site other than the terminal (eg, isobutene), and further a diene (eg, butadiene, isoprene).
May be

As the polyacrylic polyol having a number average molecular weight of 500 or more, a (meth) acrylate is used as a component of the skeleton (or main chain) of the polymer or copolymer and at least a hydroxyl group is present in the molecule (particularly at the terminal). A polyol having two and having a number average molecular weight of 500 or more can be used. Examples of the (meth) acrylate include (meth) acrylic acid alkyl esters [eg,
Methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate , (Meth) acrylic acid C _1-20 alkyl ester such as decyl (meth) acrylate, dodecyl (meth) acrylate, octadecyl (meth) acrylate and the like] are preferably used.

In the polyolefin polyol or polyacryl polyol, an α, β-unsaturated compound having a hydroxyl group [eg, 2-hydroxyethyl (meth) acrylate, hydroxyalkyl (meth) acrylate such as 3-hydroxypropyl (meth) acrylate, etc.] can be used.

As the polyol (A1), a polyether polyol having a number average molecular weight of 500 or more, a polyester polyol having a number average molecular weight of 500 or more, and a polycarbonate polyol having a number average molecular weight of 500 or more can be preferably used.

The upper limit of the number average molecular weight of the polyol (A1) is not particularly limited as long as it is 500 or more, but it is preferably in the range of 500 to 10,000, for example. More preferable number average molecular weight is 500 to 30.
00.

[Anionic group-free polyol compound (A2) having a number average molecular weight of less than 500] Also, anionic group-free polyol compound (A2) having a number average molecular weight of less than 500 (hereinafter referred to as "polyol (A2)" May have no anionic group in the molecule,
There is no particular limitation as long as it is a compound having at least two hydroxyl groups in the molecule and has a number average molecular weight of less than 500. As the polyol (A2),
For example, polyhydric alcohol, castor oil, number average molecular weight 5
Polyether polyol less than 00, number average molecular weight 5
Polyester polyol less than 00, number average molecular weight 5
Examples thereof include a polycarbonate polyol having a number average molecular weight of less than 00, a polyolefin polyol having a number average molecular weight of less than 500, and a polyacrylic polyol having a number average molecular weight of less than 500. The polyol (A2) can be used alone or in combination of two or more kinds.

In the polyol (A2), the polyhydric alcohol includes the polyhydric alcohols exemplified above [for example, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, trimethylene glycol, 1,4-tetramethylene diol, 1, 3-tetramethylene diol, 2-methyl-1,3-trimethylene diol, 1,5-pentamethylene diol, neopentyl glycol, 1,6-hexamethylene diol, 3
-Methyl-1,5-pentamethylenediol, 2,4-
Diethyl-1,5-pentamethylenediol, glycerin, trimethylolpropane, trimethylolethane,
Cyclohexanediols (1,4-cyclohexanediol, etc.), bisphenols (bisphenol A, etc.), sugar alcohols (xylitol, sorbitol, etc.) are included.

In the polyol (A2), a polyether polyol having a number average molecular weight of less than 500, a polyester polyol having a number average molecular weight of less than 500, a polycarbonate polyol having a number average molecular weight of less than 500, and a polyolefin having a number average molecular weight of less than 500. Polyol,
As the polyacrylic polyol having a number average molecular weight of less than 500, the same polyether polyols and polyester polyols as those exemplified in the section of the polyol (A1),
Polycarbonate polyols, polyolefin polyols, and polyacrylic polyols having a number average molecular weight of less than 500 can be used.

The number average molecular weight of the polyol (A2) is not particularly limited as long as it is less than 500, but it is preferably in the range of 48 or more and less than 500, for example. More preferable number average molecular weight is 62 to 300.
Is.

In the present invention, a polyamine compound (for example, an aliphatic polyamine, an alicyclic polyamine, an aromatic polyamine, an araliphatic polyamine, hydrazine and a derivative thereof) may be used together with or in place of the polyol (A2). Etc.) may be used.

Examples of the aliphatic polyamine include:
Ethylenediamine, 1,3-trimethylenediamine,
1,4-tetramethylenediamine, 1,3-pentamethylenediamine, 1,5-pentamethylenediamine, 1,
6-hexamethylenediamine, 1,2-propylenediamine, 1,2-butylenediamine, 2,3-butylenediamine, 1,3-butylenediamine, 2-methyl-1,
5-pentamethylenediamine, 3-methyl-1,5-pentamethylenediamine, 2,4,4-trimethyl-1,
In addition to aliphatic diamines such as 6-hexamethylenediamine and 2,2,4-trimethyl-1,6-hexamethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine and the like can be mentioned.

As the alicyclic polyamine, for example, 1,
3-cyclopentanediamine, 1,4-cyclohexanediamine, 1,3-cyclohexanediamine, 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane, 1-amino-1-methyl-4-aminomethyl Cyclohexane, 1-amino-1-methyl-3-aminomethylcyclohexane, 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
Examples thereof include alicyclic diamines such as bis (aminomethyl) cyclohexane, isophoronediamine, norbornanediamine.

As the aromatic polyamine, m-phenylenediamine, p-phenylenediamine, 2,4-tolylenediamine, 2,6-tolylenediamine, naphthylene-
1,4-diamine, naphthylene-1,5-diamine,
4,4'-diphenyldiamine, 4,4'-diphenylmethanediamine, 2,4'-diphenylmethanediamine, 4,4'-diphenyletherdiamine, 2-nitrodiphenyl-4,4'-diamine, 2,2 '-Diphenylpropane-4,4'-diamine,3,3'-dimethyldiphenylmethane-4,4'-diamine,4,4'-
Examples thereof include aromatic diamines such as diphenylpropanediamine and 3,3′-dimethoxydiphenyl-4,4′-diamine.

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

Examples of hydrazine and its derivatives include hydrazine and dihydrazide compounds. Examples of dihydrazide compounds include carbodihydrazide (carbohydrazide), oxalic acid dihydrazide, malonic acid dihydrazide, succinic acid dihydrazide, glutaric acid dihydrazide, adipic acid dihydrazide and other aliphatic dicarboxylic acid dihydrazides; isophthalic acid dihydrazide, terephthalic acid And aromatic dicarboxylic acid dihydrazides; alicyclic dicarboxylic acid dihydrazides such as 1,4-cyclohexanedicarboxylic acid dihydrazide, and the like.

In the present invention, with the polyol (A1) or the polyol (A2), an anionic group such as a polythiol compound having no anionic group or a polyamine compound having no anionic group is contained. A compound which does not exist and which has a plurality of isocyanate-reactive groups having reactivity with an isocyanate group can be used in combination.

[Anionic group-containing polyol compound (A
3)] The anionic group-containing polyol compound (A3) (hereinafter sometimes referred to as “polyol (A3)”) has at least one anionic group in the molecule and has at least 2 in the molecule. There is no particular limitation as long as it is a compound having two hydroxyl groups. In the polyol (A3), a carboxyl group or a sulfo group can be preferably used as the anionic group, and the carboxyl group is most preferable. The polyol (A3) can be used alone or in combination of two or more kinds.

Examples of the polyol (A3) include a carboxyl group-containing polyol obtained by introducing a carboxyl group into the polyol exemplified in the section of the polyol (A1) or the polyol (A2). In the present invention, the polyol (A3) is preferably a low molecular weight polyol having an anionic group, and particularly a polyhydroxycarboxylic acid represented by the following formula (9) can be preferably used. (HO) _p L (COOH) _q (9) (In the formula (9), L represents a hydrocarbon moiety having 1 to 12 carbon atoms. P is an integer of 2 or more and q is an integer of 1 or more. It is.)

In the above formula (9), the hydrocarbon moiety of L is preferably an aliphatic hydrocarbon moiety,
It may be in the form of a straight chain or a branched chain. Also, p and q may be the same or different. Two or more hydroxyl groups may be attached to the same carbon atom or different carbon atoms. Furthermore, when q is 2 or more, two or more carboxyl groups may be bonded to the same carbon atom or different carbon atoms.

As such polyhydroxycarboxylic acid, dimethylolalkanoic acid (among others, 2,
2-dimethylolalkanoic acid) is preferred. Examples of dimethylolalkanoic acid include 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid, and 2,2-dimethylolpropionic acid.
2-dimethylolpentanoic acid, 2,2-dimethylolhexanoic acid, 2,2-dimethylolheptanoic acid, 2,2-
Examples thereof include dimethylol octanoic acid, 2,2-dimethylol nonanoic acid and 2,2-dimethylol decanoic acid.

In the present invention, the polyol (A3) has an anionic group such as a polythiol compound having an anionic group and a polyamine compound having an anionic group, and is reactive with an isocyanate group. A compound having a plurality of isocyanate-reactive groups having a can be used in combination.

[Polyisocyanate Compound (A4)] The polyisocyanate compound (A4) (hereinafter sometimes referred to as “polyisocyanate (A4)”) is a compound having at least two isocyanate groups in the molecule. Not limited. Examples of the polyisocyanate (A4) include aliphatic polyisocyanate, alicyclic polyisocyanate, aromatic polyisocyanate, and araliphatic polyisocyanate. Polyisocyanate (A4)
Can be used alone or in combination of two or more.

Examples of the aliphatic polyisocyanate include 1,3-trimethylene diisocyanate and 1,4-
Tetramethylene diisocyanate, 1,3-pentamethylene diisocyanate, 1,5-pentamethylene diisocyanate, 1,6-hexamethylene diisocyanate
1,2-propylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, 2-methyl-1,5-pentamethylene diisocyanate, 3-methyl-1,5- Pentamethylene diisocyanate, 2,
Aliphatic compounds such as 4,4-trimethyl-1,6-hexamethylene diisocyanate, 2,2,4-trimethyl-1,6-hexamethylene diisocyanate, 2,6-diisocyanate methylcaproate and lysine diisocyanate Examples thereof include diisocyanate.

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

Examples of aromatic polyisocyanates include m-phenylene diisocyanate, p-phenylene diisocyanate and 2,4-tolylene diisocyanate.
2,6-tolylene diisocyanate, naphthylene-
1,4-diisocyanate, naphthylene-1,5-diisocyanate, 4,4'-diphenyldiisocyanate
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'-
Examples thereof include aromatic diisocyanates such as diisocyanate.

As the araliphatic polyisocyanate,
For example, 1,3-xylylene diisocyanate, 1,4
-Xylylene diisocyanate, ω, ω'-diisocyanate-1,4-diethylbenzene, 1,3-bis (1
-Isocyanate-1-methylethyl) benzene, 1,
Examples thereof include araliphatic diisocyanates such as 4-bis (1-isocyanate-1-methylethyl) benzene and 1,3-bis (α, α-dimethylisocyanatomethyl) benzene.

As the polyisocyanate (A4), 1,
6-hexamethylene diisocyanate, 4,4'-methylenebis (cyclohexyl isocyanate), 1,3-
Bis (isocyanatomethyl) cyclohexane, 1,4
-Bis (isocyanatomethyl) cyclohexane, isophorone diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4 '
-Diphenylmethane diisocyanate, 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, norbornane diisocyanate, 1,3-bis (α, α-dimethylisocyanate methyl) benzene are preferred. Can be used for. When an aliphatic polyisocyanate or an araliphatic polyisocyanate is used as the polyisocyanate (A4), a resin with little discoloration can be obtained.

In the present invention, as the polyisocyanate (A4), the aliphatic polyisocyanate exemplified above is used.
Alicyclic polyisocyanate, aromatic polyisocyanate, dimer or trimer with araliphatic polyisocyanate, reaction product or polymer (for example, diphenylmethane diisocyanate dimer or trimer, A reaction product of trimethylolpropane and tolylene diisocyanate,
A reaction product of trimethylolpropane and hexamethylene diisocyanate, polymethylene polyphenyl isocyanate, polyether polyisocyanate, polyester polyisocyanate, etc.) can also be used.

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

[Secondary amino group-containing alkoxysilane compound (A5)] Secondary amino group-containing alkoxysilane compound (A5) (hereinafter sometimes referred to as "secondary amino group-containing alkoxysilane (A5)") ) Is the above formula (6),
It is an alkoxysilane compound containing one secondary amino group as the amino group represented by (7) or (8). The secondary amino group-containing alkoxysilane (A5) can be used alone or in combination of two or more kinds.

The secondary amino group-containing alkoxysilane (A5) represented by the above formula (6) is an amino group having only a primary amino group as the amino group represented by the following formula (10). Contained alkoxysilane compound (A5-1a) and unsaturated carboxylic acid ester (A5-2) represented by the following formula (11)
It is obtained by the reaction with.

[Chemical 17] (In the formula (10), R ^{1 to} R ³ and m are the same as above.)

[Chemical 18] (In the formula (11), R ^{4 to} R ⁷ are the same as above.)

Further, the secondary amino group-containing alkoxysilane (A5) represented by the above formula (7) or (8) is a primary or secondary amino group represented by the following formula (12). It is obtained by reacting an amino group-containing alkoxysilane compound (A5-1b) having an amino group with an unsaturated carboxylic acid ester (A5-2) represented by the formula (11).

[Chemical 19] (In the formula (12), R ^{1 to} R ³ , R ⁸ and m are the same as above.)

In the present invention, the alkyl group represented by R ¹ is, for example, an alkyl group having about 1 to 4 carbon atoms such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group and t-butyl group. Is preferred. Also, R
^As the alkyl group of ^2, the same alkyl group as the alkyl group of R ¹ can be used, but a methyl group or an ethyl group is preferable. When there are a plurality of R ¹ or R ² , a plurality of R ¹ or a plurality of R ² may be composed of the same R ¹ or R ² or different R ¹ or R ^2. May be. That is, the same alkoxy group may be bonded to the silicon atom, or two or more different alkoxy groups may be combined and bonded.

As the alkylene group for R ^3, an alkylene group having about 1 to 3 carbon atoms such as a methylene group, an ethylene group and a trimethylene group is preferable. Further, as the alkylene group for R ^8, an alkylene group having about 1 to 3 carbon atoms can be used as in the alkylene group for R ³ . In addition, as R ³ and R ⁸ , in addition to an alkylene group, an arylene group, an alkylene-arylene group, an alkylene-arylene-
A divalent hydrocarbon group composed only of hydrocarbon groups such as alkylene groups; alkylene-oxy-alkylene groups, alkylene-carbonyl-oxy-alkylene groups, alkylene-oxy-carbonyl-alkylene groups, alkylene-poly (oxyalkylene It is also possible to use various divalent groups constituted by various combinations of hydrocarbon groups such as groups) and other groups (oxy groups, carbonyl-oxy groups, etc.).

Incidentally, m is an integer of 1 to 3 (preferably 2 or 3).

The alkyl group represented by R ⁴ is, for example, a methyl group, an ethyl group, a propyl group, a butyl group, an isobutyl group, a t-butyl group, a hexyl group or the like having 1 to 6 carbon atoms.
To some extent alkyl groups. Furthermore, examples of the alkyl group of R ⁵ include an alkyl group having about 1 to 2 carbon atoms such as a methyl group and an ethyl group. Examples of the aryl group of R ⁵ include a phenyl group. Also,
In the alkoxycarbonyl group of R ⁵ , examples of the alkyl group moiety include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a s-butyl group, a t-butyl group, a pentyl group, an isopentyl group,
Alkyl having 1 to 20 carbon atoms such as hexyl group, heptyl group, octyl group, 2-ethylhexyl group, nonyl group, decyl group, isodecyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, hexadecyl group, octadecyl group, etc. Groups. In the aryloxycarbonyl group of R ⁵ , the aryl group moiety is, for example,
A phenyl group is mentioned. In the cycloalkyloxycarbonyl group for R ⁵ , examples of the cycloalkyl group moiety include a cyclohexyl group and the like. R ⁶
Examples of the alkyl group include an alkyl group having about 1 to 2 carbon atoms such as a methyl group and an ethyl group. R
Examples of the alkyl group of ⁷ include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, s-butyl group, t-butyl group, pentyl group, isopentyl group, hexyl group, heptyl group, octyl group. Base, 2
Examples thereof include an alkyl group having about 1 to 20 carbon atoms such as an ethylhexyl group, a nonyl group, a decyl group, an isodecyl group, an undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a hexadecyl group, and an octadecyl group. Further, the aryl group of R ⁷ includes a phenyl group, and the cycloalkyl group of R ⁷ includes a cyclohexyl group.

The unsaturated carboxylic acid ester is obtained by reacting the amino group-containing alkoxysilane compound (A5-1a) or the amino group-containing alkoxysilane compound (A5-1b) with the unsaturated carboxylic acid ester (A5-2). The carbon atom at the β-position in the carbon-carbon double bond of (A5-2) is an amino group (primary grade) in the amino group-containing alkoxysilane compound (A5-1a) or the amino group-containing alkoxysilane compound (A5-1b). The secondary amino group-containing alkoxysilane (A5) represented by any of the above formulas (6) to (8) is obtained by at least bonding to the nitrogen atom of the amino group or the secondary amino group). That is, the secondary amino group-containing alkoxysilane (A5) is an amino group-containing alkoxysilane compound (A5-1a) or an amino group-containing alkoxysilane compound (A5).
The nitrogen atom of the amino group in 5-1b) is a compound obtained by performing a Michael addition reaction on the unsaturated bond (carbon-carbon double bond) of the unsaturated carboxylic acid ester (A5-2). The reaction can be carried out in the presence or absence of a solvent, and heating or pressurization may be carried out during the reaction.

Examples of the amino group-containing alkoxysilane compound (A5-1a) having only a primary amino group as the amino group represented by the above formula (10) include aminomethyltrimethoxysilane and aminomethyl. Triethoxysilane, β-aminoethyltrimethoxysilane, β-aminoethyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltripropoxysilane, γ-aminopropyltriisosilane Aminoalkyltrialkoxysilanes such as propoxysilane and γ-aminopropyltributoxysilane; β-aminoethylmethyldimethoxysilane, β-aminoethylmethyldiethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxy Silane Such as γ- aminopropylmethyldi propoxy silane of (aminoalkyl) alkyl dialkoxy silane or aminoalkyl dialkyl (mono) alkoxysilanes corresponding to these.

The amino group-containing alkoxysilane compound (A5-1b) having a primary amino group and a secondary amino group as the amino group represented by the above formula (12) is, for example, N-β. N- (aminoalkyl) aminoalkyltrialkoxysilanes such as (aminoethyl) -γ-aminopropyltrimethoxysilane and N-β (aminoethyl) -γ-aminopropyltriethoxysilane; N-β (aminoethyl)- Examples thereof include N- (aminoalkyl) aminoalkylalkyldialkoxysilanes such as γ-aminopropylmethyldimethoxysilane and N-β (aminoethyl) -γ-aminopropylmethyldiethoxysilane.

In the present invention, the amino group-containing alkoxysilane compound (A5-1a) and the amino group-containing alkoxysilane compound (A5-1b) are easy to react and widely commercially available. From, for example, N-β (aminoethyl) -γ-aminopropyltrimethoxysilane, N-
-Β (aminoethyl) -γ-aminopropyltriethoxysilane, N-β (aminoethyl) -γ-aminopropylmethyldimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-amino Propylmethyldimethoxysilane, γ-
Aminopropylmethyldiethoxysilane can be preferably used.

Examples of the unsaturated carboxylic acid ester (A5-2) represented by the above formula (11) include acrylic acid ester, methacrylic acid ester, crotonic acid ester, isocrotonic acid ester and 2-butenoic acid ester. ,
In addition to 3-methyl-2-butenoic acid ester, 2-pentenoic acid ester, 2-octenoic acid ester, etc., unsaturated monovalent carboxylic acid esters such as cinnamic acid ester; maleic acid ester (mono or diester), fumaric acid ester (Mono- or diester), itaconic acid ester (mono- or diester), and the like, and the like, esters of unsaturated divalent carboxylic acids, and the like. The unsaturated carboxylic acid ester (A5-2) can be used alone or in combination of two or more kinds. When a plurality of ester moieties are included, the respective ester moieties may be the same or different.

As the unsaturated carboxylic acid ester (A5-2), acrylic acid ester, methacrylic acid ester (these may be collectively referred to as "(meth) acrylic acid ester" hereinafter), and maleic acid diester are preferable. Can be used. More specifically, as the (meth) acrylic acid ester, for example, methyl (meth) acrylate,
Ethyl (meth) acrylate, Butyl (meth) acrylate, Hexyl (meth) acrylate, Octyl (meth) acrylate, 2-Ethylhexyl (meth) acrylate,
Examples thereof include (meth) acrylic acid alkyl esters such as dodecyl (meth) acrylate and octadecyl (meth) acrylate. Further, maleic acid diesters include, for example, maleates such as dimethyl maleate, diethyl maleate, dibutyl maleate, dihexyl maleate, dioctyl maleate, di (2-ethylhexyl) maleate, didodecyl maleate, and dioctadecyl maleate. Acid dialkyl esters and the like are included.

[Anionic Group-Containing Alkoxysilyl Group Terminated Polymer (A)] As described above, the anionic group-containing alkoxysilyl group-terminated polymer (A) has the formula (1) above.
Is a polymer represented by, more specifically, a reaction product of a polyol (A1), a polyol (A2), a polyol (A3), a polyisocyanate (A4), and a secondary amino group-containing alkoxysilane (A5). A polyol (A1), a polyol (A2) and a polyol (A3),
Has a urethane bond in the molecule due to reaction with polyisocyanate (A4), and also has a polyol (A3) in the molecule
Is a polymer having an anionic group derived from, an alkoxysilyl group derived from a secondary amino group-containing alkoxysilane (A5) at the end of the main chain or a branched chain, and a side chain derived from an unsaturated carboxylic acid ester. . Therefore, the anionic group-containing alkoxysilyl group-terminated polymer (A) is, for example, an anionic group-containing polymer which is a reaction product of polyol (A1), polyol (A2), polyol (A3) and polyisocyanate (A4). And a terminal alkoxysilylated anionic group-containing polymer obtained by the reaction of the above with a secondary amino group-containing alkoxysilane (A5) is suitable.

More specifically, the anionic group-containing polymer is a reaction product of a polyol (A1), a polyol (A2), a polyol (A3) and a polyisocyanate (A4), and the reaction is a polyol compound. It can be carried out according to a known or commonly used method of reacting a polyisocyanate compound with a polyisocyanate compound to prepare a urethane prepolymer.
The anionic group-containing polymer is preferably one having an isocyanate group at the terminal.

The polyol (A1) and the polyol (A
2), polyol (A3) and polyisocyanate (A4)
When mixing or reacting with each other, a polymerization catalyst can be used to accelerate the reaction. Further, the reaction or mixing can be performed in a solvent.

The anionic group-containing polymer and the second
The reaction with the primary amino group-containing alkoxysilane (A5) can be carried out by mixing both and heating if necessary. By the reaction, the terminal isocyanate group of the anionic group-containing polymer is alkoxysilylated to prepare an anionic group-containing alkoxysilyl group-terminated polymer (A) which is a terminal alkoxysilylated anionic group-containing polymer. it can.

Upon mixing or reaction, a polymerization catalyst can be added as described above. As the polymerization catalyst, for example, a known or commonly used polymerization catalyst (curing catalyst) used when reacting a polyol compound with a polyisocyanate compound can be used. More specifically, examples of the polymerization catalyst include organic tin compounds, metal complexes, basic compounds such as amine compounds, and organic phosphoric acid compounds. Organotin compounds include, for example, dibutyltin dilaurate, dibutyltin malate, dibutyltin phthalate, stannous octylate, dibutyltin methoxide, dibutyltin diacetylacetate, dibutyltin diversate, and the like. As the metal complex, titanate compounds such as tetrabutyl titanate, tetraisopropyl titanate and triethanolamine titanate; carboxylic acid metal salts such as lead octylate, lead naphthenate, nickel naphthenate and cobalt naphthenate; aluminum acetylacetoate Examples thereof include metal acetylacetonate complexes such as nato complex and vanadium acetylacetonate complex.
Further, for basic compounds such as amine compounds, for example,
Aminosilanes such as γ-aminopropyltrimethoxysilane and γ-aminopropyltriethoxysilane; quaternary ammonium salts such as tetramethylammonium chloride and benzalkonium chloride; product name “DABCO” series manufactured by Sankyo Air Products Co., Ltd. "DABCO
BL ”series, 1,8-diazabicyclo [5.4.
[0] A straight-chain or cyclic tertiary amine or quaternary ammonium salt containing a plurality of nitrogen atoms such as undece-7-ene is included. Furthermore, as the organic phosphoric acid compound,
Examples thereof include monomethyl phosphoric acid, di-n-butyl phosphoric acid, triphenyl phosphate and the like.

A solvent can be used in the mixing or reaction.

When mixing, the order of mixing the respective components does not matter. However, in order to efficiently obtain the anionic group-containing alkoxysilyl group-terminated polymer (A), first, polyisocyanate (A4) is added to a mixture of polyol (A1), polyol (A2) and polyol (A3), If necessary, add a polymerization catalyst to react,
After preparing the anionic group-containing polymer, the secondary amino group-containing alkoxysilane (A5) is added to the reaction mixture and reacted to prepare the anionic group-containing alkoxysilyl group-terminated polymer (A). Is preferred.

In the present invention, the proportion of each component of polyol (A1), polyol (A2), polyol (A3), polyisocyanate (A4), and secondary amino group-containing alkoxysilane (A5) is not particularly limited. For example, polyisocyanate (A4), polyol (A1), polyol (A1)
2) and the polyol (A3), the ratio of the isocyanate group in the polyisocyanate (A4) / polyol (A1), the hydroxyl group (NCO / OH) in the polyol (A2) and the polyol (A3) (equivalent ratio) is 1
Greater than 1.5 or less (preferably greater than 1 and 1.3)
Below, it is more preferable to be selected from the range of more than 1 and 1.2 or less). The NCO / O
If the ratio of H is too large (for example, if it exceeds 1.5 (equivalent ratio)), the stability of the aqueous solid adhesive decreases and the contact property also decreases. On the other hand, if the NCO / OH ratio is too small (for example, 1 or less (equivalent ratio)), the silyl group cannot be introduced, and
The adhesiveness of the water-based solid adhesive is reduced.

Alternatively, the polyisocyanate (A4) is
The content of the isocyanate group in the anionic group-containing polymer is 0.05 to 2.0% by mass (preferably 0.1 to 2.0% by mass).
The content is preferably 1.5% by mass, and more preferably 0.3 to 1.0% by mass.
The content of the isocyanate group is too high (for example,
If it exceeds 2.0% by mass, or if it is too small (for example,
If it is less than 0.05% by mass), the adhesiveness of the water-based solid adhesive is lowered.

The ratio of the polyol (A1) to the polyol (A2) is not particularly limited, and for example, the hydroxyl group of the polyol (A1) / the hydroxyl group of the polyol (A2) (ratio) =
It is preferable to select from the range of about 0.05 to 4 in order to impart the contact property.

In the polyol (A3), the content of the anionic group in the anionic group-containing alkoxysilyl group-terminated polymer (A) is 0.2 to 5.0% by mass (preferably 0.5 to 4). 0.0 mass%, more preferably 0.8 to 3.
5% by mass) is preferable. If the content of the anionic group is too large (for example,
If it exceeds 5.0% by mass), the viscosity of the water-based solid adhesive increases and the workability decreases, and the water resistance after curing also decreases. On the other hand, if the content of the anionic group is too small (for example, less than 0.2% by mass), the dispersion stability of the resin component in the aqueous solid adhesive decreases.

Furthermore, in the secondary amino group-containing alkoxysilane (A5), the content of silicon atoms in the anionic group-containing alkoxysilyl group-terminated polymer (A) is 0.
It is preferable that the content thereof be 05 to 1.0% by mass (preferably 0.1 to 0.8% by mass, more preferably 0.2 to 0.6% by mass). If the silicon content is too high (eg, exceeds 1.0 mass%),
The stability of the water-based solid adhesive decreases, while if it is too small (for example, less than 0.05% by mass), the adhesion of the water-based solid adhesive decreases.

The amount of the unsaturated carboxylic acid ester (A5-2) used is such that the secondary amino group-containing alkoxysilane (A5) is
The amount is preferably such that at least one secondary amino group remains. For example, an amino group-containing alkoxysilane compound (A5-1a) or an amino group-containing alkoxysilane compound (A
It can be selected from the range of about 0.8 to 2 mol with respect to 1 mol of the primary amino group and the secondary amino group in 5-1b). The unsaturated carboxylic acid ester can be used by reacting it under the condition that at least the secondary amino group remains.

The anionic group-containing alkoxysilyl group-terminated polymer (A) of the present invention can be preferably used as a polymer of an adhesive component in an aqueous solid adhesive. In the present invention, when used as a polymer of an adhesive component in an aqueous solid adhesive, the anionic group-containing alkoxysilyl group-terminated polymer (A) is used as a basic compound (B), water (C) and a gelling agent (D). ) And can be used in combination.

[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 alone or in combination of two or more kinds. Examples of the basic inorganic compound include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; alkali metal carbonates such as sodium carbonate and potassium carbonate; alkali metal hydrogen carbonates such as sodium hydrogen carbonate and potassium hydrogen carbonate. An alkali metal compound such as an alkali metal acetate such as sodium acetate or potassium acetate, an alkaline earth metal hydroxide such as magnesium hydroxide; an alkaline earth metal compound such as an alkaline earth metal carbonate such as magnesium carbonate Besides, ammonia can be preferably used.

On the other hand, as the basic organic compound, amine compounds such as aliphatic amine, aromatic amine and basic nitrogen-containing heterocyclic compound can be preferably used. Examples of the aliphatic amine include trimethylamine, triethylamine, tripropylamine, triisopropylamine, tributylamine, triisobutylamine, tris-butylamine, tri-t-butylamine,
Trialkylamines such as tripentylamine and trihexylamine; dialkylamines such as dimethylamine, diethylamine and dibutylamine; monoalkylamines such as methylamine, ethylamine and butylamine;
Trialcohol amines such as trimethanolamine, triethanolamine, tripropanolamine, triisopropanolamine, tributanolamine, tripentanolamine, triisopentanolamine, trihexanolamine; dialcoholamines such as dimethanolamine, diethanolamine Examples include monoalcohol amines such as methanol amine and ethanol amine, as well as ethylene diamine and diethylene triamine. The aromatic amine includes, for example, N, N-dimethylaniline and the like. Examples of the basic nitrogen-containing heterocyclic compound include morpholine, piperidine, cyclic amines such as pyrrolidine, pyridine, α-picoline, and the like.
Examples include β-picoline, γ-picoline, quinoline, N-methylmorpholine and the like. As the amine compound,
Tertiary amine compounds such as trialkylamines and trialcoholamines are preferred.

In the present invention, as the basic compound (B), alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, ammonia and amine compounds can be preferably used. When the gelling agent (D) is a salt of an aliphatic carboxylic acid (for example, an alkali metal salt such as sodium salt), the basic compound (B) is an alkali metal hydroxide (sodium hydroxide). And potassium hydroxide) are preferred.

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

[Gelling agent (D)] The gelling agent (D) is not particularly limited and may be appropriately selected from known gelling agents. For example, aliphatic carboxylic acid having 8 or more carbon atoms. Salt (so-called “fatty acid soap”), a reaction product of a sugar alcohol having 4 or more carbon atoms and an aromatic aldehyde, an amino acid (eg, glutamic acid) and a higher fatty acid (eg,
A salt of a reaction product with stearic acid (so-called "amino acid soap") can be preferably used. The gelling agent (D) can be used alone or in combination of two or more kinds.

Examples of the aliphatic carboxylic acid having 8 or more carbon atoms include octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, dodecanoic acid (lauric acid), tridecanoic acid,
Use aliphatic saturated monocarboxylic acids such as tetradecanoic acid (myristic acid), pentadecanoic acid, hexadecanoic acid (palmitic acid), heptadecanoic acid, octadecanoic acid (stearic acid), and aliphatic unsaturated monocarboxylic acids such as oleic acid. be able to. In the present invention, an aliphatic saturated monocarboxylic acid is preferable, and among the aliphatic saturated monocarboxylic acids, carbon number 14 such as myristic acid and stearic acid is used.
A saturated aliphatic monocarboxylic acid of about 18 is suitable.
Examples of the salt form of the salt of an aliphatic carboxylic acid having 8 or more carbon atoms include alkali metal salts such as sodium salt and potassium salt, ammonium salt and the like, and the sodium salt form is preferable. preferable. Therefore, as the salt of the aliphatic carboxylic acid having 8 or more carbon atoms, sodium myristic acid salt or sodium stearate salt is most suitable.

Examples of sugar alcohols having 4 or more carbon atoms include tetrits such as trait and erythritol; pencites such as arabite, rivite and xylit; sorbit, mannitol, idiot, tarit, galactit (sulsit) and arit. Examples include monosaccharide alcohols such as hexit; heptit; octit; nonit; decit; dodecit. Among these sugar alcohols, sugar alcohols having 5 to 7 carbon atoms such as xylit and sorbit are preferable, and sorbit is particularly preferable. On the other hand, as an aromatic aldehyde,
For example, in addition to benzaldehyde, phthalaldehyde, isophthalaldehyde, terephthalaldehyde, carboxybenzaldehyde, nitrobenzaldehyde, cinnamaldehyde, salicylaldehyde, anisaldehyde and the like can be mentioned, and benzaldehyde is preferable. By the reaction of these sugar alcohols having 4 or more carbon atoms with an aromatic aldehyde, a benzalized product in which the sugar alcohol is benzalized is obtained, and in particular, a dibenzalized product into which two benzylidene groups are introduced is preferably used. it can.
In the present invention, examples of the reaction product of the sugar alcohol having 4 or more carbon atoms and the aromatic aldehyde include, for example, dibenzal xylit which is a reaction product of xylit and benzaldehyde, and dibenzal sorbit which is a reaction product of sorbit and benzaldehyde. And the like can be preferably used.

[Aqueous Solid Adhesive] An aqueous solid adhesive containing the anionic group-containing alkoxysilyl group-terminated polymer (A) of the present invention as an adhesive component comprises an anionic group-containing alkoxysilyl group-terminated polymer (A) and a base. Compound (B)
And water (C) and a gelling agent (D). As the aqueous solid adhesive, an aqueous resin composition comprising an anionic group-containing alkoxysilyl group-terminated polymer (A), a basic compound (B) and water (C) is gelled by the gelling agent (D). Is preferably provided. The aqueous resin composition may be a mixture of an anionic group-containing alkoxysilyl group-terminated polymer (A), a basic compound (B) and water (C), and by mixing the anionic group-containing alkoxysilyl group. It may be a reaction composition containing a reaction product obtained by reacting the terminal polymer (A) with the basic compound (B) and water (C). As the reaction between the anionic group-containing alkoxysilyl group-terminated polymer (A) and the basic compound (B), the anionic group in the anionic group-containing alkoxysilyl group-terminated polymer (A) is a basic compound (B). Include a neutralization reaction that is partially or wholly neutralized by. That is, the anionic group in the anionic group-containing alkoxysilyl group terminal polymer (A) is turned into a salt by the reaction between the anionic group-containing alkoxysilyl group terminal polymer (A) and the basic compound (B). Therefore, the anionic group-containing alkoxysilyl group-terminated polymer (A) may have a salt form.

On the other hand, the reaction between the anionic group-containing alkoxysilyl group-terminated polymer (A) and water (C) is as follows:
An example is a hydrolysis reaction in which the terminal alkoxysilyl group in the anionic group-containing alkoxysilyl group-terminated polymer (A) is hydrolyzed by water (C). That is, the reaction between the anionic group-containing alkoxysilyl group-terminated polymer (A) and water (C) causes the terminal alkoxysilyl group in the anionic group-containing alkoxysilyl group-terminated polymer (A) to partially or wholly. It has a silanol group and / or a siloxane bond. That is,
At least one alkoxyl group among the terminal alkoxysilyl groups in the anionic group-containing alkoxysilyl group-terminated polymer (A) is affected by the hydrolysis reaction with water (C). Therefore, the anionic group-containing alkoxysilyl group-terminated polymer (A) or a salt thereof with water (C) is a polymer in which the terminal alkoxysilyl group is hydrolyzed (ie, anionic group-containing alkoxysilyl group-terminated polymer). (A) or an alkoxysilyl group-hydrolyzed polymer of its salt). 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.

Therefore, the reaction product of the anionic group-containing alkoxysilyl group-terminated polymer (A) with the basic compound (B) and water (C) is an anionic group-containing alkoxysilyl group-terminated polymer. The anionic group in (A) is neutralized with the basic compound (B) to form a salt of the anionic group, and the terminal alkoxysilyl group is partially or wholly hydrolyzed with water (C). Aqueous silanolated polymers which are silanol groups and / or siloxane bonds. That is, the anionic group-containing alkoxysilyl group-terminated polymer (A) can be used in the form of a salt of the anionic group-containing alkoxysilyl group-terminated polymer (A) or an alkoxysilyl group-hydrolyzed polymer thereof. As the water-based solid adhesive, the anionic group in the anionic group-containing alkoxysilyl group-terminated polymer (A) is neutralized by the basic compound (B), and the terminal alkoxysilyl group is hydrolyzed by water (C). The aqueous resin composition is preferably gelled with the gelling agent (D).

Thus, the aqueous solid adhesive is a mixture of the anionic group-containing alkoxysilyl group terminated polymer (A), the basic compound (B), water (C) and the gelling agent (D). It can be prepared by the following, and the order of mixing is not particularly limited. As the water-based solid adhesive, an anionic group-containing alkoxysilyl group-terminated polymer (A) is blended with a basic compound (B) and water (C), and preferably vigorous stirring is carried out to carry out a neutralization reaction. Or by promoting a reaction such as a hydrolysis reaction to obtain an aqueous solution or an aqueous dispersion,
Furthermore, it can be prepared by adding a gelling agent (D) and, if necessary, an antifoaming agent and the like and mixing them by stirring or the like to form a gel. Since it is an aqueous solid adhesive,
In the case of molding into a specific shape, the molding method is not particularly limited, for example, by putting it in a container for molding into a specific shape before solidification, or by processing and molding into a specific shape after solidification. , Can be molded into a specific shape.

The basic compound (B) can be used in advance when preparing the anionic group-containing alkoxysilyl group-terminated polymer (A). Specifically, for example,
Polyol (A1), Polyol (A2), Polyol (A
When the reaction product of 3) and the polyisocyanate (A4) is reacted with the secondary amino group-containing alkoxysilane (A5), the basic compound (B) is added to give the basic compound (B). The reaction can be carried out in the presence.

The amount of the basic compound (B) used is an anionic group-containing alkoxysilyl group-terminated polymer (A).
It can be selected from the range of about 50 to 120 mol% (preferably 80 to 110 mol%) with respect to the anionic group therein.

The amount of water (C) used is 10% of the anionic group-containing alkoxysilyl group-terminated polymer (A).
65 to 900 parts by weight (preferably 10 parts by weight)
It can be selected from the range of about 0 to 400 parts by mass).

The amount of the gelling agent (D) used is 0.02 to 100 parts by mass (preferably 5 to 80 parts by mass) per 100 parts by mass of the anionic group-containing alkoxysilyl group-terminated polymer (A). Part) range. If the amount of the gelling agent (D) used is too small, it will be difficult to form a solid, and if it is too large, the adhesiveness of the aqueous solid adhesive will be reduced.

In the aqueous solid adhesive, the aqueous resin composition before gelation [that is, the aqueous resin composition comprising the anionic group-containing alkoxysilyl group-terminated polymer (A), the basic compound (B) and water (C)] And the hydroxyl value (OHV) thereof is not particularly limited, and may be, for example, 60
~ 400 mg-KOH / g (preferably 80-350 m
It can be selected from the range of about g-KOH / g). The neutralization rate of anionic groups such as carboxyl groups is not particularly limited, but is preferably 80% or more (preferably 90 to 100%), for example. Furthermore, the resin component is not particularly limited, but for example, 1
It can be selected from the range of about 0 to 60% by mass (preferably 20 to 50% by mass).

The water-based solid adhesive may be in the form of a completely water-based solid adhesive containing no organic solvent. Although the conventional commercially available water-based solid adhesive contains a small amount of an organic solvent, it contains the anionic group-containing alkoxysilyl group-terminated polymer (A) of the present invention as an adhesive component. The aqueous solid adhesive need not contain any organic solvent. The water-based solid adhesive may contain a hydrophilic organic solvent (water-soluble organic solvent) such as a ketone or a lower alcohol in order to adjust the viscosity of the aqueous solution or the aqueous dispersion. The organic solvent may be used alone or in combination of two or more kinds. Specifically, the ketones include acetone and the like. Further, examples of the lower alcohol include methanol, ethanol, propanol, isopropanol, butanol, and isobutanol. Monohydric alcohols such as s-butanol, t-butanol, pentanol, and hexanol; ethylene glycol, propylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,6-hexane. Examples thereof include polyhydric alcohols such as diol and glycerin. As the water-soluble organic solvent, propylene carbonate; dimethyl carbonate; trimethyl phosphate; polyoxyethylene diether, diester or diallyl ethers; glycol diether or diacetates; 1,3-dioxolane; N-methyl-
2-pyrrolidone or the like can be used. The amount of such an organic solvent used can be appropriately selected depending on the magnitude of the viscosity to be adjusted and the like. It can be selected from the range of about 1 part (preferably 1 to 50 parts by mass).

The water-based solid adhesive may contain a wettability-modified hydrophilic solvent. The wettability modifying hydrophilic solvent is not particularly limited, and examples thereof include N-methyl-2.
-Pyrrolidone, surfactants such as polyoxyethylene alkyl ether, sodium alginate, mucopolysaccharides, sodium acrylate and the like.

Furthermore, the water-based solid adhesive may contain a moisturizing agent. By using a moisturizer, the coatability of the aqueous solid adhesive can be improved. The moisturizer is not particularly limited, and known or commonly used moisturizers can be used. Specifically, examples of moisturizers include ethylene glycol, polyethylene glycol having a number average molecular weight of 400 or less, cellosolves such as ethylene glycol monoethyl ether, and ethylene glycol derivatives such as carbitols such as diethylene glycol monoethyl ether. Propylene glycol derivatives such as propylene glycol and propylene glycol monomethyl ether; polyhydric alcohols such as glycerin and 1,3-butanediol; polysaccharides such as sorbitol; alkanolamines such as monoethanolamine, diethanolamine and triethanolamine; 1 , 3-dimethyl-2
-Imidazolidinone and the like.

The above water-based solid adhesive includes a defoaming agent, a filler, a plasticizer, an antiaging agent, an ultraviolet absorber, an antioxidant,
Heat stabilizers, colorants (pigments and dyes, etc.), fungicides, wetting promoters, viscosity improvers, fragrances, various tackifiers (emulsion tackifiers, etc.), coupling agents (titanate coupling agents, aluminum cups) (A ring agent, etc.), a photocuring catalyst, an emulsifier, a surfactant, various additives or components such as an emulsion or latex, a cross-linking agent, and a solvent may be contained. Examples of the filler include calcium carbonate, calcium carbonate that has been subjected to various treatments, fumed silica, clay, talc, various balloons, noble silica, kaolin, and aluminum silicate. The plasticizer includes phthalic acid esters such as dioctyl phthalate and dibutyl phthalate; aliphatic carboxylic acid esters such as dioctyl adipate and dibutyl sebacate. Examples of the tackifier include stabilized rosin ester, polymerized rosin ester, terpene phenol, emulsion tackifier of petroleum resin, and the like. As the crosslinking agent, an isocyanate crosslinking agent, an epoxy crosslinking agent, a carbodiimide crosslinking agent, an aziridine crosslinking agent, a polyethyleneimine crosslinking agent, a melamine crosslinking agent, colloidal silica or the like can be used. The solvent is not particularly limited as long as it is compatible with the anionic group-containing alkoxysilyl group-terminated polymer (A), basic compound (B), water (C), gelling agent (D) and the like. Alternatively, any solvent may be used.

In the water-based solid adhesive, as described above,
As the polymer of the adhesive component, an anionic group-containing alkoxysilyl group-terminated polymer (A) obtained by alkoxysilylating the terminal of an anionic group-containing polymer with a secondary amino group-containing alkoxysilane (A5) is used. The group-containing alkoxysilyl group-terminated polymer (A) is a basic compound (B) and water (C) in an aqueous solid adhesive.
Since it is in the form of an aqueous silanolated polymer, after application of the aqueous solid adhesive, when the water in the aqueous solid adhesive evaporates and decreases, silanol groups in the aqueous silanolated polymer in the aqueous solid adhesive are reduced. Undergoes a condensation reaction to cause curing (crosslinking). Therefore, the polymer as an adhesive component in the water-based solid adhesive has reactivity, and reacts during curing to cause curing / crosslinking, thereby exhibiting adhesiveness. On the other hand, a polymer as an adhesive component in a conventional water-based solid adhesive does not react during curing and solidifies by evaporation of water to exhibit adhesiveness.

As described above, the polymer of the present invention has a skeleton having a urethane bond, but the terminal is alkoxysilylated with a secondary amino group-containing alkoxysilane (A5) and condensed with a silanol group. Since it has reactivity, it is not an ordinary polyurethane but an anionic group-containing alkoxysilyl group-terminated polymer. Therefore, the polymer of the present invention is not only different in structure from a polymer as an adhesive component in a conventional water-based solid adhesive, but also a mechanism for expressing adhesiveness, and the action / effect due to the difference in the polymer structure described below. It is significantly different as detailed.

That is, the aqueous solid adhesive containing the anionic group-containing alkoxysilyl group-terminated polymer (A) of the present invention as an adhesive component has a silanol group condensation reaction in the aqueous silanolated polymer in the aqueous solid adhesive.
Since it is mainly involved in curing, the dependency of the curing rate on the drying rate of water is less than that of the conventional one, and the initial adhesive strength is high. Further, the crosslinking reaction is progressing due to the decrease of water, and the crosslinking reaction is promoted even when water is present to some extent, and the cohesive force can be exhibited even while the water is retained.

In addition, the fact that the curing rate is high and the initial adhesive strength is high means that the ion center (anionic group such as a carboxylate salt) introduced into the molecule of the aqueous silanolated polymer to make it aqueous is used. It is also considered that the salt) functions as a catalyst for promoting the condensation reaction between the silanol groups.

As described above, since the water-based solid adhesive has a high initial adhesive strength, it is not necessary to temporarily press or press when adhering the adherends to each other, or the time required therefor can be shortened. Adhesive workability is good, and it is possible to easily attach a plurality of adherends. In particular, even in the case of completely aqueous solution containing no organic solvent, it is extremely advantageous in that the initial adhesive strength is excellent.

Furthermore, in the water-based solid adhesive containing the anionic group-containing alkoxysilyl group-terminated polymer (A) of the present invention as an adhesive component, the anionic group-containing alkoxysilyl group-terminated polymer ( A) may be a relatively low molecular weight polymer, for example having a number average molecular weight of 3,000 to 50,000.
(Preferably 10,000 to 30,000) can be selected from the range. Then, after curing, a siloxane bond is formed to become a higher molecular weight polymer.

Particularly in the present invention, since the polyol (A1) and the polyol (A2) are used in combination, excellent contact adhesiveness can be exhibited.

Therefore, unlike the conventional water-based solid adhesive, the water-based solid adhesive containing the anionic group-containing alkoxysilyl group-terminated polymer (A) of the present invention can be contact-adhered to the contact. It can be used as an adhesive-type stick-shaped adhesive (contact-type stick-shaped adhesive), and can bond even non-porous materials. In particular, the number average molecular weight of the anionic group-containing alkoxysilyl group-terminated polymer (A) is
When it is about tens of thousands, the aqueous resin composition comprising the anionic group-containing alkoxysilyl group-terminated polymer (A), the basic compound (B) and water (C) is prepared as an aqueous solution or a colloidal dispersion. It is suitable for forming a stick-like adhesive using the gelling agent (D).

The polymer of the present invention forms a cross-linked structure upon curing to form a network. Therefore, the water resistance and heat resistance of the adhesive portion after the adhesive is cured are also good. That is, the water-based polymer, after curing,
In addition to exhibiting excellent adhesiveness, it also exhibits excellent water resistance and heat resistance.

Moreover, since the polymer as an adhesive component in the aqueous solid adhesive containing the anionic group-containing alkoxysilyl group-terminated polymer (A) of the present invention as an adhesive component has a silanol group, it can be used as a porous material such as paper. Adhesiveness can be exhibited not only for high-quality materials but also for non-porous materials such as metals and glass. That is, the adherend that can be bonded with the aqueous solid adhesive is not particularly limited, and various adherends can be bonded as shown in the following specific examples.

Although the water-based solid adhesive contains water, the reason why the silanol group of the water-based silanol-containing polymer is stably present is not clear. For example, the silanol group is Since the condensation reaction between silanol groups is suppressed or prevented by being protected by a large amount of water molecules present therein, and / or the silanol group is a secondary amino group-containing alkoxysilane compound (A
Substituents bonded to the nitrogen atom of the secondary amino group or tertiary amino group derived from 5) (for example, a long-chain substituent derived from unsaturated carboxylic acid ester (A5-2) or its ester) It is believed that this is because the condensation reaction between silanol groups is suppressed or prevented by being protected by a site).
Therefore, although the aqueous solid adhesive containing the anionic group-containing alkoxysilyl group-terminated polymer (A) of the present invention as an adhesive component is a one-component cross-linking type aqueous adhesive, It has excellent stability and fast curing speed.

Moreover, since the water-based solid adhesive is a water-based type (especially, it may be completely water-free with no organic solvent), it has excellent handleability and workability, and is suitable for human body and environment. On the other hand, it is highly safe.

In particular, the water-based solid adhesive has an excellent shape-retaining property, is hard to be broken or broken during application, and is prevented from being damaged during application. Also, the slipperiness is good,
Easy to apply to the adherend by application.

Therefore, the water-based solid adhesive is extremely useful as a stick adhesive (particularly, a contact adhesive type stick adhesive).

In the present invention, the adherend to which the aqueous solid adhesive containing the anionic group-containing alkoxysilyl group-terminated polymer (A) as an adhesive component can be adhered is not particularly limited, and a porous material, Any non-porous material can be used, and adherends made of a wide range of materials can be used. More specifically, examples of the material of the adherend include wood materials such as wood, plywood, chipboard, particle board, and hardboard; inorganic materials such as slate boards, silica boards, mortar, and tiles; melamine resin makeup. Board, bakelite board, styrofoam,
Plastic materials such as various plastic films or molded products (for example, polyvinyl chloride film or molded product, polyester film or molded product, polystyrene film or molded product, polyolefin film or molded product, etc.); natural rubber, synthetic rubber, Rubber materials such as silicone rubber; paper-based materials such as corrugated paper, paperboard, and kraft paper, as well as difficult-to-adhere paper materials such as processed paper (for example, surface-treated processed paper such as moisture-proof paper), glass materials, metal materials (For example, iron, aluminum, stainless steel, copper, etc.),
Examples thereof include leather materials, fiber materials such as cloth and non-woven fabric, and the like. Although the conventional stick-shaped adhesive has been practically applied only to the adherend between porous materials such as paper, it contains the anionic group-containing alkoxysilyl group-terminated polymer (A) of the present invention as an adhesive component. The water-based solid adhesive can be applied to adherends made of a wide variety of materials, and in particular, can be used for adhesion between non-porous materials by contact adhesion.

The adherends may be adherends made of the same material or may be adherends made of different materials. The adherends may be used alone or in combination of two or more kinds.

Therefore, the water-based solid adhesive is, for example, a water-based solid adhesive for wood or paper for adhering wood products made of wood materials or paper products made of paper-based materials or poorly-adhesive paper materials (particularly water-based Solid adhesives); Water-based solid adhesives for leather and plastics (particularly for hobby) for bonding leather products made of leather materials and plastic products made of plastic materials; for bonding fibrous materials Water-based solid adhesives for textiles: Home-use water-based solid adhesives used in a wide range of household applications (particularly, water-based solid adhesives for repairing furniture); Adhesion of plastic plates, Styrofoam, plywood, wallpaper, interior decorations, etc. It can be suitably used as an industrial water-based solid adhesive or the like.

The water-based solid adhesive is applied to the adherends and then immediately adhered to each other, or after being applied to the adherends for a predetermined time, the tackiness is developed. It can be used by various methods such as a contact bonding method in which adherends are bonded to each other in a state of being present. That is, as described above, contact adhesion is possible even though it is an aqueous solid adhesive. In the present invention, as a contact bonding method, JIS K 680 is used.
As defined by 0, the two adherends are applied to the adhering surfaces of the adherends of the two adherends to be adhered to each other and are allowed to stand for a predetermined time, and the adhesiveness is developed. In addition to the method of sticking and adhering to each other, it is applied to the sticking surface of either one of the two adherends to be stuck A method in which two adherends are bonded to each other is also included. That is, in the present invention, the term “contact adhesion” means that when two or more adherends are applied to at least one of the adherends to be adhered and adhesiveness is developed after a predetermined time has elapsed. It means that they are stuck together and adhered.

[0109]

EFFECTS OF THE INVENTION The anionic group-containing alkoxysilyl group-terminated polymer (A) of the present invention is excellent in coating workability, is excellent in the fit after bonding, and has good adhesiveness to various plastics, metals and glass. Moreover, it can be suitably used as an adhesive component in an aqueous solid adhesive having excellent heat resistance and water resistance after curing.

The water-based solid adhesive of the present invention, which contains the anionic group-containing alkoxysilyl group-terminated polymer (A) as the adhesive component polymer, has excellent safety for the human body and the environment. Furthermore, the shape retention and slipperiness are excellent. Moreover, contact adhesion is possible even though it is a water-based solid adhesive. Therefore, the aqueous solid adhesive of the present invention is extremely useful as a stick adhesive.

[0111]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. In the following, unless otherwise specified, "part"
Indicates "parts by mass" and "%" indicates "% by mass". The materials used in the examples and comparative examples are as follows.

[Anionic group-free polyol compound having a number average molecular weight of 500 or more] (1) Trade name "PTMG2000" [manufactured by Mitsubishi Chemical Corporation, polytetramethylene ether glycol, number average molecular weight:
2000, hydroxyl value: 56.1 mg-KOH / g; sometimes referred to as "polyol (A1-1)". (2) Trade name "NS2471" [Asahi Denka Kogyo KK, polyester diol, number average molecular weight: 2000] , Hydroxyl value: 56.1 mg-KOH / g; "Polyol (A1-
2) ”] (3) Trade name“ Placcel 220EC ”[manufactured by Daicel Chemical Industries, Ltd., polycarbonate diol, number average molecular weight: 2000, hydroxyl value: 56.1 mg-KOH / g;
Sometimes referred to as "polyol (A1-3)."

[Anionic group-free polyol compound having a number average molecular weight of less than 500] (1) 1,4-butanediol ["polyol (A2-
1) ”)

[Anionic group-containing polyol compound] (1) 2,2-dimethylolbutanoic acid [hydroxyl value: 75
8.1 mg-KOH / g; sometimes referred to as "polyol (A3-1)"]

[Polyisocyanate compound] (1) Isophorone diisocyanate [isocyanate content (NCO content): 37.8%, IPDI; sometimes referred to as "polyisocyanate (A4-1)"]

[Secondary amino group-containing alkoxysilane compound] (1) Trade name “KBM602” [Shin-Etsu Chemical Co., Ltd., N
-[Beta] (aminoethyl)-[gamma] -aminopropylmethyldimethoxysilane]: 1 mol, 2-ethylhexyl acrylate: 2 mol, used and mixed at 50 [deg.] C.
And reacted for 7 days to obtain a reaction product [sometimes referred to as "amino group-containing alkoxysilane (A5-a)"]. (2) Product name “KBM603” [Shin-Etsu Chemical Co., Ltd., N
-[Beta] (aminoethyl)-[gamma] -aminopropyltrimethoxysilane]: 1 mole, 2-ethylhexyl acrylate: 2 moles, and mixed at 50 [deg.] C.
A reaction product [may be referred to as "amino group-containing alkoxysilane (A5-b)") was obtained by reacting for a day. (3) Product name “KBM903” [Shin-Etsu Chemical Co., Ltd., γ
-Aminopropyltrimethoxysilane]: 2-Ethylhexyl acrylate: used at a ratio of 1 mol with respect to 1 mol, mixed and reacted at 50 ° C. for 7 days to produce a reaction product [“amino group-containing alkoxysilane (A5 -c) "may be called].

[Basic Compound] (1) Sodium hydroxide

[Water] (1) Ion-exchanged water (deionized water)

[Gelling agent] (1) Sodium stearate

Example 1 In a four-neck separable flask equipped with a stirrer, a nitrogen inlet tube, a thermometer and a condenser, 100 parts of polyol (A1-1) and polyol (A3-
1): 16.7 parts, polyisocyanate (A4-1): 57
Parts, polyol (A2-1): 7.7 parts and acetone: 40
Parts were mixed and reacted at a temperature of 75 to 80 ° C. under a nitrogen stream for 3 hours to obtain a reaction mixture containing a carboxyl group-containing isocyanate group-terminated polymer having a residual isocyanate group of 0.4%. After 10 parts of the amino group-containing alkoxysilane (A5-a) was added to and mixed with the entire reaction mixture of the carboxyl group-containing isocyanate group-terminated polymer, 7
The reaction was carried out at a temperature of 5 to 80 ° C under a nitrogen stream for 1 hour to obtain a reaction mixture containing a carboxyl group-containing alkoxysilyl group-terminated polymer. Next, after cooling the reaction mixture containing the carboxyl group-containing alkoxysilyl group-terminated polymer to 40 ° C., an aqueous solution in which 294 parts of deionized water and 4.5 parts of sodium hydroxide were dissolved was mixed under high speed stirring. A dispersion was obtained. Acetone was distilled off from this dispersion liquid under reduced pressure at 45 to 50 ° C., and solid content was 40% by deionized water.
An aqueous silanolated resin composition adjusted to the above was obtained. Aqueous silanolated resin composition (stock solution): 100 parts, and sodium stearate: 7 parts were put into a flask immersed in a thermostat bath of 80 ° C. while stirring and mixed, and after 1 hour, taken out from the flask. Immediately put it in a stick container,
It was left to cool to obtain a stick adhesive.

Example 2 Aqueous silanolated resin composition (stock solution) obtained in the same manner as in Example 1: 100 parts,
Sodium stearate: 7 parts and glycerin: 10 parts were put into a flask immersed in an 80 ° C. constant temperature bath with stirring and mixed, and after 1 hour, taken out from the flask and immediately put in a stick container. Then, it was allowed to cool to obtain a stick adhesive.

(Examples 3 to 7) In the same manner as in Example 1 except that the compositions shown in Table 1 or 2 were used, respectively.
The stick-shaped adhesives according to Examples 3 to 7 were obtained.

Comparative Example 1 A stick adhesive was obtained in the same manner as in Example 1 except that the amino group-containing alkoxysilane (A5-a) was not used. That is, the comparative example 1
In the stick-shaped adhesive according to (3), the polymer terminal as an adhesive component is not silanolated in water. The composition is as shown in Table 2.

Comparative Example 2 A 4-neck separable flask equipped with a stirrer, a nitrogen inlet tube, a thermometer and a condenser was charged with 100 parts of polyol (A1-1) and polyol (A3-
1): 16.7 parts, polyisocyanate (A4-1): 4
Mixing 5.2 parts and acetone: 40 parts, 75-80 degreeC
The reaction was carried out at a temperature of 3 hours under a nitrogen stream to obtain a reaction mixture containing a carboxyl group-containing isocyanate group-terminated polymer having a residual isocyanate group of 2.0%. Amino group-containing alkoxysilane (A5-a): 4 was added to the whole reaction mixture of the carboxyl group-containing isocyanate group-terminated polymer.
After 4.4 parts were mixed and mixed, the reaction was carried out at a temperature of 75 to 80 ° C. for 1 hour under a nitrogen stream to obtain a reaction mixture containing a carboxyl group-containing alkoxysilyl group terminated polymer.
Next, after cooling the reaction mixture containing the carboxyl group-containing alkoxysilyl group-terminated polymer to 40 ° C., an aqueous solution in which 317 parts of deionized water and 4.5 parts of sodium hydroxide were dissolved was mixed under high speed stirring. A dispersion was obtained. Acetone was distilled off from the dispersion under reduced pressure at 45 to 50 ° C.,
An aqueous silanolated resin composition having a solid content adjusted to 40% with deionized water was obtained. Aqueous silanolated resin composition (stock solution): 100 parts, and sodium stearate: 7 parts were mixed with stirring in a flask immersed in a thermostat bath at 80 ° C., and after 1 hour, removed from the flask. Immediately after, it was placed in a stick container and allowed to cool to obtain a stick-shaped adhesive.

Comparative Example 3 A stick-like adhesive according to Comparative Example 3 was obtained in the same manner as Comparative Example 2 except that the composition shown in Table 2 was used.

Comparative Example 4 Commercially available urethane emulsion (trade name "Hydran HW311" manufactured by Dainippon Ink and Chemicals, Inc.)
(Undiluted solution): 100 parts and sodium stearate: 7 parts were put into a flask immersed in a thermostat bath of 80 ° C while stirring and mixed, and after 1 hour, taken out from the flask and immediately put in a stick container. It was put in and allowed to cool, but it could not be formed into a stick. The composition is as shown in Table 2.

(Comparative Example 5) As a stick adhesive,
A commercially available stick-shaped adhesive (trade name "Super Stick" manufactured by Konishi Co., Ltd .; main component: polyvinylpyrrolidone) was used.

Regarding various characteristics and ratios of the aqueous silanol resin compositions according to Examples 1 to 7,
The results are shown in Table 1 or Table 2. In Table 1 or Table 2, "NC
"O / OH (equivalent ratio)" means an isocyanate group in a polyisocyanate compound, an anionic group-free polyol compound having a number average molecular weight of 500 or more, an anionic group-free polyol compound having a number average molecular weight of less than 500, and an anionic group. The ratio (NCO / OH) (equivalent ratio) with the hydroxyl group in the group-containing polyol compound is shown. "Carboxyl group content (%)" indicates the content (%) of the carboxyl group (COOH) in the carboxyl group-containing alkoxysilyl group-terminated polymer. The "neutralization rate (%)" indicates the rate (%) in which the carboxyl group in the carboxyl group-containing alkoxysilyl group terminated polymer is neutralized with sodium hydroxide to form a salt.
The "resin content (%)" indicates the ratio (%) of the aqueous silanolized resin in the aqueous silanolized resin composition. "S
"i content (%)" indicates the content (%) of silicon atoms (Si) in the aqueous silanol resin.

[0129]

[Table 1]

[0130]

[Table 2]

(Evaluation) Regarding the stick-shaped adhesives according to Examples 1 to 7, Comparative Examples 1 to 3 and Comparative Example 5, the following stick shape retention evaluation method, stick slipperiness evaluation method, and adhesive strength evaluation were performed. Measurement method, water resistance evaluation method, heat resistance evaluation method, glass adhesion evaluation method, contact evaluation method, stick shape retention, stick slipperiness, adhesion strength, water resistance, heat resistance The adhesion to glass and the contact property were evaluated. The evaluation results are shown in Table 1 or Table 2.
Also described in. Comparative Example 4 could not be evaluated because it could not be molded into a stick shape.

[Evaluation Method of Stick Shape Retention] When the stick-shaped adhesive was applied to the surface of the Asada material, which was a hardwood, and the shape of the stick-shaped adhesive was visually observed and The stick shape retention property was evaluated according to the evaluation standard. The evaluation results are shown in the "stick shape retention" column of Table 1 or Table 2. (Evaluation Criteria) ◯: The original shape is maintained without breaking. Δ: A little broken. X: Fragile and immediately collapsed.

[Evaluation Method of Stick Slidability] The stickiness of the stick-shaped adhesive when the stick-shaped adhesive was applied to the surface of the Asada material, which is a hardwood, was evaluated by feeling, and the stick was evaluated according to the following criteria. The slipperiness was evaluated.
The evaluation results are shown in the column of "stick slipperiness" in Table 1 or Table 2. (Evaluation criteria) A: Very easy to apply. ○: Easy to apply. Δ: Slightly caught and difficult to apply. X: Extremely difficult to apply or not applicable.

[Measurement Method of Adhesive Strength] As an adherend, an asada / asada material (each 10
0 mm x 25 mm x 5 mm), Asada material (100 mm x
25 mm x 5 mm) / acrylonitrile-butadiene-
Styrene copolymer (ABS) molded plate (100 mm x 2
5 mm x 3 mm), Asada material (100 mm x 25 mm x
5 mm) / Stainless steel plate (100 mm x 25 mm x 2)
mm) and the stick-like adhesive is applied to one surface of both adherends three times in total (applied amount: about 30 g / m ² ) and the temperature:
Under the conditions of 23 ° C. and humidity: 55% RH, they were laminated and pressed with finger pressure. After that, temperature: 23 ° C and humidity: 55%
After curing for 3 days under the condition of RH, the shear bond strength (according to JIS K6850) was measured by an autograph manufactured by Shimadzu Corporation under the condition of a tensile speed of 5 mm / min to evaluate the bond strength. . The evaluation results are shown in the column of "Adhesive strength" in Table 1 or Table 2. In addition, in Table 1 or Table 2, when the adherend is an Asada material / Asada material, the column “Asada / Asada” is used, and for the Asada material / Acrylonitrile-butadiene-styrene copolymer molded plate is “Asada / ABS”. In the column of No. 2 and Asada material / stainless steel plate, it is shown in the column of “Asada / steel plate”.

[Evaluation Method of Water Resistance] As an adherend, an asada / asada material (each 100
mm × 25 mm × 5 mm), and apply the stick-shaped adhesive on one surface of both adherends three times in total (applied amount: about 30 g
/ M ² ), the temperature was 23 ° C., and the humidity was 55% RH. Then the temperature: 23
After curing for 3 days under conditions of ℃ and humidity: 55% RH,
After soaking in water at 23 ° C for 1 day, a tensile shear test (J
(According to IS K 6850) was performed to determine the adhesive strength, and the water resistance was evaluated according to the following evaluation criteria. The evaluation results are shown in the column of "water resistance" in Table 1 or Table 2. (Evaluation Criteria) O: Adhesive strength is 1.0 N / mm ² or more. Δ: Adhesive strength is 0.2 N / mm ² or more and less than 1.0 N / mm ² . X: The adhesive strength is less than 0.2 N / mm ² .

[Heat Resistance Evaluation Method] As the adherends, asada wood / asada wood (100 for each) was used as hardwood wood.
mm × 25 mm × 5 mm), and apply the stick-shaped adhesive on one surface of both adherends three times in total (applied amount: about 30 g
/ M ² ), the temperature was 23 ° C., and the humidity was 55% RH. Then the temperature: 23
After curing for 3 days under conditions of ℃ and humidity: 55% RH,
Tensile shear test (JIS
(According to K 6850) was performed to determine the adhesive strength, and the heat resistance was evaluated according to the following evaluation criteria. The evaluation results are shown in the “heat resistance” column of Table 1 or Table 2. (Evaluation Criteria) O: Adhesive strength is 1.0 N / mm ² or more. Δ: Adhesive strength is 0.2 N / mm ² or more and less than 1.0 N / mm ² . X: The adhesive strength is less than 0.2 N / mm ² .

[Evaluation Method of Adhesion to Glass] A stick-shaped adhesive was applied on a glass plate, copy paper was attached, and pressed with finger pressure. After that, temperature: 23 ° C and humidity:
After curing for 1 day under the condition of 55% RH, the tensile speed was 200 mm / mi by an autograph manufactured by Shimadzu Corporation.
The 180 ° peel adhesion strength was measured with n, and the adhesion to glass was evaluated according to the following evaluation criteria. The evaluation results are shown in the column "Adhesion to glass" in Table 1 or Table 2. (Evaluation Criteria) ◯: Paper was broken. X: The paper was not broken.

[Evaluation Method of Contact Property] As the adherend, a stainless steel plate / stainless steel plate (10
0 mm x 25 mm x 2 mm) and apply the stick adhesive to one surface of both adherends (application amount: about 30 g / m
² ) and under the conditions of temperature: 23 ° C. and humidity: 55% RH,
The open time of about 300 seconds was taken, and the pieces were pasted and pressed with finger pressure. Immediately thereafter, using an autograph manufactured by Shimadzu Corporation, under the condition of a pulling speed of 5 mm / min,
The shear adhesive strength (according to JIS K 6850) was measured, the adhesive strength was determined, and the contact property was evaluated according to the following evaluation criteria. The evaluation results are shown in the column of "contact property" in Table 1 or Table 2. (Evaluation Criteria) Good: Adhesive strength is 150 mN / mm ² or more and effective adhesive area is 70% or more. X: The adhesive strength is less than 50 mN / mm ² or the effective adhesive area is 10% or more and less than 30%. XX: Adhesion is impossible.

As is clear from Table 1 or Table 2, the stick-shaped adhesives of Examples 1 to 7 corresponding to the present invention have excellent fit after attachment and are easily attached to each other. And the workability of application (application workability) is good.

Also, the adhesiveness to plastic, metal and glass is good. Moreover, contact bonding can be performed.

Further, after coating, it has excellent water resistance and heat resistance.

On the other hand, in Comparative Example 1, the stick-like adhesive has low shape retention and slipperiness, low adhesion strength to various adherends, poor water resistance, and poor adhesion to glass. Further, it does not have contact adhesiveness. In Comparative Example 2 and Comparative Example 3, not only the water resistance is low, but also there is no contact property. Also, the adhesive strength to various adherends is low. In Comparative Example 4, it was not possible to even form a stick. In Comparative Example 5, the stick-like adhesive has good shape retention and slipperiness, but has poor adhesion strength to various adherends, water resistance, heat resistance, and adhesion to glass, and has a contact adhesiveness. I don't have it.

(Analysis of Polymer) Also obtained by reacting the carboxyl group-containing isocyanate group-terminated polymer obtained in Example 1 with the carboxyl group-containing isocyanate group-terminated polymer and amino group-containing alkoxysilane (A5-a). When the infrared absorption spectrum of the obtained carboxyl group-containing alkoxysilyl group terminated polymer was measured, the infrared absorption spectra shown in FIGS. 1 and 2 were obtained, respectively. For reference, an infrared absorption spectrum of polyisocyanate (A4-1) is shown in FIG. 3, and an infrared absorption spectrum of amino group-containing alkoxysilane (A5-a) is shown in FIG.

FIG. 1 is an infrared absorption spectrum of the carboxyl group-containing isocyanate group-terminated polymer obtained in Example 1. FIG. 2 is an infrared absorption spectrum of the carboxyl group-containing alkoxysilyl group-terminated polymer obtained in Example 1. Figure 3 shows polyisocyanate (A4-1)
Is an infrared absorption spectrum of. FIG. 4 is an infrared absorption spectrum of amino group-containing alkoxysilane (A5-a).

[0145] From FIG. 1 to FIG. 4, the peak near 2250 cm ^-1 which is observed in the infrared absorption spectrum according to Figure 1 (peak of FIG 1 2267.6cm ^-1), infrared absorption spectrum according to Figure 2 It was not observed in and disappeared.
The peak near 2250 cm ^-1 is also observed in the infrared absorption spectrum according to FIG. 3 (2258.
9 cm ^-1 peak), isocyanate group (-N = C =
This is the peak for O). In FIGS. 1 to 4, the horizontal axis represents the wave number (cm ⁻¹ ) and the vertical axis represents the transmittance (%
T).

[0146] Also, with the observed 1100 cm ^-1 near peak (peak of FIG 1 1111.1cm ^-1) in an infrared absorption spectrum according to Figure 1, a peak of the shoulder (FIG. 1 1046.1Cm ^-1 ) Is a peak near 1100 cm ^-1 observed in the infrared absorption spectrum of FIG. 2 (1111.5c in FIG. 2).
m ^-1 peak) and its shoulder (104 in Fig. 2)
9.7 cm ⁻¹ peak) and the relative intensity is different from that of the infrared absorption spectrum of FIG.
The intensity of the peak near ^-1 (the peak at 1111.5 cm ^-1 in FIG. 2) is equal to the shoulder (1049.7 in FIG. 2).
(cm ^-1 peak) relative to the intensity. The peak near 1100 cm ^-1 is observed in the infrared absorption spectrum according to FIG. 4 (10 in FIG. 4).
87.3 cm ⁻¹ peak) and Si—O—C.

Therefore, by reacting the carboxyl group-containing isocyanate group-terminated polymer with the amino group-containing alkoxysilane (A5-a), the isocyanate group at the terminal of the carboxyl group-containing isocyanate group-terminated polymer is alkoxysilylated to form a carboxyl group. It can be observed that the containing alkoxysilyl group terminated polymer is obtained.

[Brief description of drawings]

FIG. 1 is an infrared absorption spectrum of a carboxyl group-containing isocyanate group-terminated polymer obtained in Example 1.

2 is an infrared absorption spectrum of a carboxyl group-containing alkoxysilyl group-terminated polymer obtained in Example 1. FIG.

FIG. 3 is an infrared absorption spectrum of polyisocyanate (A4-1).

FIG. 4 is an infrared absorption spectrum of an amino group-containing alkoxysilane (A5-a).

─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] May 10, 2002 (2002.5.1)
0)

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be amended] Claims

[Correction method] Change

[Correction content]

[Claims]

[Chemical 1] [In the formula (1), W is a residue corresponding to the skeleton of the anionic group-containing polymer, and the nitrogen atom bonded to W is a nitrogen atom derived from the isocyanate group at the terminal of the anionic group-containing polymer. W has a structural unit represented by the following formula (2).

[Chemical 2] (In the formula (2), Y is a residue derived from the anionic group-free polyol compound (A1) having a number average molecular weight of 500 or more, and the anionic group-free polyol compound (A2) having a number average molecular weight of less than 500). Which is a residue derived from the anionic group-containing polyol compound (A3), and the oxygen atom bonded to Y has a number average molecular weight of 500 or more. An oxygen atom derived from the hydroxyl group of the compound (A1), the anionic group-free polyol compound (A2) or the anionic group-containing polyol compound (A3) having a number average molecular weight of less than 500. However, the number average as Y Residue derived from anionic group-free polyol compound (A1) having a molecular weight of 500 or more, and anionic group-free polyol compound having a number average molecular weight of less than 500 All of the residues derived from A2) and the anionic group-containing polyol compound (A3) are included, and Z is a residue derived from the polyisocyanate compound (A4). And the nitrogen atom on the opposite side to Z is a nitrogen atom derived from the isocyanate group of the polyisocyanate compound (A4).) X is the following formula (3), (4) or ( 5 shows an alkoxysilyl-containing group represented by 5).

[Chemical 3] (In the formula (3), R ¹ and R ² are the same or different,
It represents an alkyl group, and R ³ represents an alkylene group. Also,
R ⁴ and R ⁶ are the same or different and each represents a hydrogen atom or an alkyl group. R ⁵ represents a hydrogen atom or an alkyl group . R ⁷ represents an alkyl group, an aryl group or a cycloalkyl group.
m is an integer of 1 to 3. )

[Chemical 4] (In the formula (4), R ¹ and R ² are the same or different,
It represents an alkyl group, and R ³ represents an alkylene group. Also,
R ⁴ and R ⁶ are the same or different and each is a hydrogen atom or alkyl.
Indicates a group. R ⁵ is a hydrogen atom, an alkyl group, an aryl group,
Alkoxycarbonyl group, aryloxycarbonyl
And a cycloalkyloxycarbonyl group. R ⁷ is
An alkyl group, an aryl group or a cycloalkyl group is shown.
m is an integer of 1 to 3. R ⁸ represents an alkylene group,
It may be the same as or different from the alkylene group for R ³ . )

[Chemical 5] (In the formula (5), R ¹ and R ² are the same or different,
It represents an alkyl group, and R ³ represents an alkylene group. Also,
R ⁴ and R ⁶ are the same or different and each is a hydrogen atom or alkyl.
Indicates a group. R ⁵ is a hydrogen atom, an alkyl group, an aryl group,
Alkoxycarbonyl group, aryloxycarbonyl
And a cycloalkyloxycarbonyl group. R ⁷ is
An alkyl group, an aryl group or a cycloalkyl group is shown.
m is an integer of 1 to 3. R ⁸ represents an alkylene group,
It may be the same as or different from the alkylene group for R ^3.
May be. ) Furthermore, n represents an integer of 1 to 4. ]

[Chemical 6] (In the formula (6), R ¹ and R ² are the same or different,
It represents an alkyl group, and R ³ represents an alkylene group. Also,
R ⁴ and R ⁶ are the same or different and each is a hydrogen atom or alkyl.
Indicates a group. R ⁵ represents a hydrogen atom or an alkyl group. R ⁷ is
An alkyl group, an aryl group or a cycloalkyl group is shown.
m is an integer of 1 to 3. )

[Chemical 7] (In the formula (7), R ¹ and R ² are the same or different,
It represents an alkyl group, and R ³ represents an alkylene group. Also,
R ⁴ and R ⁶ are the same or different and each is a hydrogen atom or alkyl.
Indicates a group. R ⁵ is a hydrogen atom, an alkyl group, an aryl group,
Alkoxycarbonyl group, aryloxycarbonyl
And a cycloalkyloxycarbonyl group. R ⁷ is
An alkyl group, an aryl group or a cycloalkyl group is shown.
m is an integer of 1 to 3. R ⁸ represents an alkylene group,
It may be the same as or different from the alkylene group for R ^3.
May be. )

[Chemical 8] (In the formula (8), R ¹ and R ² are the same or different,
It represents an alkyl group, and R ³ represents an alkylene group. Also,
R ⁴ and R ⁶ are the same or different and each is a hydrogen atom or alkyl.
Indicates a group. R ⁵ is a hydrogen atom, an alkyl group, an aryl group,
Alkoxycarbonyl group, aryloxycarbonyl
And a cycloalkyloxycarbonyl group. R ⁷ is
An alkyl group, an aryl group or a cycloalkyl group is shown.
m is an integer of 1 to 3. R ⁸ represents an alkylene group,
It may be the same as or different from the alkylene group for R ^3.
May be. )

[Procedure Amendment 2]

[Document name to be amended] Statement

[Name of item to be corrected] 0005

[Correction method] Change

[Correction content]

That is, the present invention is an anionic group-containing alkoxysilyl group-terminated polymer represented by the following formula (1), a salt thereof, or an alkoxysilyl group-hydrolyzed polymer thereof.

[Chemical 9] [In the formula (1), W is a residue corresponding to the skeleton of the anionic group-containing polymer, and the nitrogen atom bonded to W is a nitrogen atom derived from the isocyanate group at the terminal of the anionic group-containing polymer. W has a structural unit represented by the following formula (2).

[Chemical 10] (In the formula (2), Y is a residue derived from the anionic group-free polyol compound (A1) having a number average molecular weight of 500 or more, and the anionic group-free polyol compound (A2) having a number average molecular weight of less than 500). Which is a residue derived from the anionic group-containing polyol compound (A3), and the oxygen atom bonded to Y has a number average molecular weight of 500 or more. An oxygen atom derived from the hydroxyl group of the compound (A1), the anionic group-free polyol compound (A2) or the anionic group-containing polyol compound (A3) having a number average molecular weight of less than 500. However, the number average as Y Residue derived from anionic group-free polyol compound (A1) having a molecular weight of 500 or more, and anionic group-free polyol compound having a number average molecular weight of less than 500 All of the residues derived from A2) and the anionic group-containing polyol compound (A3) are included, and Z is a residue derived from the polyisocyanate compound (A4). And the nitrogen atom on the opposite side to Z is a nitrogen atom derived from the isocyanate group of the polyisocyanate compound (A4).) X is the following formula (3), (4) or ( 5 shows an alkoxysilyl-containing group represented by 5).

[Chemical 11] (In the formula (3), R ¹ and R ² are the same or different,
It represents an alkyl group, and R ³ represents an alkylene group. Also,
R ⁴ and R ⁶ are the same or different and each represents a hydrogen atom or an alkyl group. R ⁵ represents a hydrogen atom or an alkyl group. R ⁷ represents an alkyl group, an aryl group or a cycloalkyl group.
m is an integer of 1 to 3. )

[Chemical 12] (In the formula (4), R ¹ and R ² are the same or different,
It represents an alkyl group, and R ³ represents an alkylene group. Also,
R ⁴ and R ⁶ are the same or different and each represents a hydrogen atom or an alkyl group. R ⁵ is a hydrogen atom, an alkyl group, an aryl group,
An alkoxycarbonyl group, an aryloxycarbonyl group and a cycloalkyloxycarbonyl group are shown. R ⁷ represents an alkyl group, an aryl group or a cycloalkyl group.
m is an integer of 1 to 3. R ⁸ represents an alkylene group,
It may be the same as or different from the alkylene group for R ³ . )

[Chemical 13] (In the formula (5), R ¹ and R ² are the same or different,
It represents an alkyl group, and R ³ represents an alkylene group. Also,
R ⁴ and R ⁶ are the same or different and each represents a hydrogen atom or an alkyl group. R ⁵ is a hydrogen atom, an alkyl group, an aryl group,
An alkoxycarbonyl group, an aryloxycarbonyl group and a cycloalkyloxycarbonyl group are shown. R ⁷ represents an alkyl group, an aryl group or a cycloalkyl group.
m is an integer of 1 to 3. R ⁸ represents an alkylene group,
It may be the same as or different from the alkylene group for R ³ . ) Furthermore, n represents an integer of 1 to 4. ]

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0007

[Correction method] Change

[Correction content]

The anionic group-containing alkoxysilyl group-terminated polymer represented by the above formula (1) has a number average molecular weight of 5
00 or more anionic group-free polyol compound (A
1), an anionic group-free polyol compound (A2) having a number average molecular weight of less than 500, an anionic group-containing polymer which is a reaction product of an anionic group-containing polyol compound (A3) and a polyisocyanate compound (A4), At least one secondary amino group-containing alkoxysilane compound (A5) selected from alkoxysilane compounds containing one secondary amino group represented by the following formulas (6) to (8)
It may be a terminal alkoxysilylated anionic group-containing polymer obtained by reaction with.

[Chemical 14] (In the formula (6), R ¹ and R ² are the same or different,
It represents an alkyl group, and R ³ represents an alkylene group. Also,
R ⁴ and R ⁶ are the same or different and each represents a hydrogen atom or an alkyl group. R ⁵ represents a hydrogen atom or an alkyl group. R ⁷ represents an alkyl group, an aryl group or a cycloalkyl group.
m is an integer of 1 to 3. )

[Chemical 15] (In the formula (7), R ¹ and R ² are the same or different,
It represents an alkyl group, and R ³ represents an alkylene group. Also,
R ⁴ and R ⁶ are the same or different and each represents a hydrogen atom or an alkyl group. R ⁵ is a hydrogen atom, an alkyl group, an aryl group,
An alkoxycarbonyl group, an aryloxycarbonyl group and a cycloalkyloxycarbonyl group are shown. R ⁷ represents an alkyl group, an aryl group or a cycloalkyl group.
m is an integer of 1 to 3. R ⁸ represents an alkylene group,
It may be the same as or different from the alkylene group for R ³ . )

[Chemical 16] (In the formula (8), R ¹ and R ² are the same or different,
It represents an alkyl group, and R ³ represents an alkylene group. Also,
R ⁴ and R ⁶ are the same or different and each represents a hydrogen atom or an alkyl group. R ⁵ is a hydrogen atom, an alkyl group, an aryl group,
An alkoxycarbonyl group, an aryloxycarbonyl group and a cycloalkyloxycarbonyl group are shown. R ⁷ represents an alkyl group, an aryl group or a cycloalkyl group.
m is an integer of 1 to 3. R ⁸ represents an alkylene group,
It may be the same as or different from the alkylene group for R ³ . )

[Procedure amendment 4]

[Document name to be amended] Statement

[Name of item to be corrected] 0045

[Correction method] Change

[Correction content]

The secondary amino group-containing alkoxysilane (A5) represented by the above formula (6) is an amino group having only a primary amino group as the amino group represented by the following formula (10). Contained alkoxysilane compound (A5-1a) and unsaturated carboxylic acid ester (A5-2) represented by the following formula (11)
Of these, R ⁵ is obtained by reaction with a compound in which R ⁵ is a hydrogen atom or an alkyl group.

[Chemical 17] (In the formula (10), R ^{1 to} R ³ and m are the same as above.)

[Chemical 18]    (In the formula (11), R^Four, R⁶Are the same or different
Represents a hydrogen atom or an alkyl group. R^FiveIs a hydrogen atom,
Alkyl group, aryl group, alkoxycarbonyl group,
Reeloxycarbonyl group, cycloalkyloxycal
Indicates a bonyl group. R ⁷Is an alkyl group, aryl group or
A chloroalkyl group is shown. )

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Norihiko Oda             4-7-9 Tsurumi, Tsurumi-ku, Osaka-shi, Osaka Prefecture             Inside Osaka Research Institute (72) Inventor Shunsuke Shibahara             4-7-9 Tsurumi, Tsurumi-ku, Osaka-shi, Osaka Prefecture             Inside Osaka Research Institute F-term (reference) 4J034 BA01 BA02 BA03 BA06 BA07                       CA03 CA04 CA05 CA14 CA15                       CA16 CA22 CB02 CB03 CB04                       CC03 CC06 CC12 CC26 CC29                       CC33 CC37 CC52 CC61 CC62                       CD04 CE03 DA01 DB04 DF01                       DF02 DF03 DF11 DF12 DF14                       DF15 DF16 DF20 DF21 DF22                       DG02 DG03 DG04 DG05 DG08                       DG09 DP12 DP18 DP19 HA01                       HA07 HA11 HA13 HB12 HC03                       HC08 HC09 HC12 HC13 HC22                       HC52 HC63 HC64 HC67 HC71                       HC73 JA02 LA12 LA32 MA04                       RA08 SA02 SB01 SB03 SB04                       SD02 SD03                 4J040 EF061 EF111 EF121 EF131                       EF181 EF291 EF301 EF351                       EK071 GA01 GA07 GA14                       GA15 GA20 HD23 HD41 HD42                       JA03 KA14 LA01 LA06 LA07                       LA08 MA02 MA05 MA08 MA09                       MA10

Claims (8)

[Claims] 1. An anionic group-containing alkoxysilyl group-terminated polymer represented by the following formula (1), a salt thereof, or an alkoxysilyl group-hydrolyzed polymer thereof. [Chemical 1] [In the formula (1), W is a residue corresponding to the skeleton of the anionic group-containing polymer, and the nitrogen atom bonded to W is a nitrogen atom derived from the isocyanate group at the terminal of the anionic group-containing polymer. W has a structural unit represented by the following formula (2). [Chemical 2] (In the formula (2), Y is a residue derived from the anionic group-free polyol compound (A1) having a number average molecular weight of 500 or more, and the anionic group-free polyol compound (A2) having a number average molecular weight of less than 500). Which is a residue derived from the anionic group-containing polyol compound (A3), and the oxygen atom bonded to Y has a number average molecular weight of 500 or more. An oxygen atom derived from the hydroxyl group of the compound (A1), the anionic group-free polyol compound (A2) or the anionic group-containing polyol compound (A3) having a number average molecular weight of less than 500. However, the number average as Y Residue derived from anionic group-free polyol compound (A1) having a molecular weight of 500 or more, and anionic group-free polyol compound having a number average molecular weight of less than 500 All of the residues derived from A2) and the anionic group-containing polyol compound (A3) are included, and Z is a residue derived from the polyisocyanate compound (A4). And the nitrogen atom on the opposite side to Z is a nitrogen atom derived from the isocyanate group of the polyisocyanate compound (A4).) X is the following formula (3), (4) or ( 5 shows an alkoxysilyl-containing group represented by 5). [Chemical 3] (In the formula (3), R ¹ and R ² are the same or different,
It represents an alkyl group, and R ³ represents an alkylene group. Also,
R ⁴ and R ⁶ are the same or different and each represents a hydrogen atom or an alkyl group. R ⁵ is a hydrogen atom, an alkyl group, an aryl group,
An alkoxycarbonyl group, an aryloxycarbonyl group and a cycloalkyloxycarbonyl group are shown. R ⁷ represents an alkyl group, an aryl group or a cycloalkyl group.
m is an integer of 1 to 3. ) [Chemical 4] (In the formula (4), R ^{1 to} R ⁷ and m are the same as above. R ⁸
Represents an alkylene group, which may be the same as or different from the alkylene group for R ³ . ) [Chemical 5] (In the formula ^{(5), R 1 ~R 8} , m is the same.) In addition, n is an integer of 1-4. ] 2. The anionic group-free polyol compound (A1) having a number average molecular weight of 500 or more has a number average molecular weight of 5
00 or more polyether polyol, number average molecular weight 5
00 or more polyester polyol, number average molecular weight is 5
The at least one anionic group-free polyol compound selected from a polycarbonate polyol having a number average molecular weight of 00 or more, a polyolefin polyol having a number average molecular weight of 500 or more, and a polyacrylic polyol having a number average molecular weight of 500 or more. A group-containing alkoxysilyl group-terminated polymer or a salt thereof or an alkoxysilyl group-hydrolyzed polymer thereof. 3. The anionic group-free polyol compound (A2) having a number average molecular weight of less than 500 is a polyhydric alcohol,
A polyether polyol having a number average molecular weight of less than 500,
A polyester polyol having a number average molecular weight of less than 500,
2. At least one anionic group-free polyol compound selected from a polycarbonate polyol having a number average molecular weight of less than 500, a polyolefin polyol having a number average molecular weight of less than 500, and a polyacrylic polyol having a number average molecular weight of less than 500. Or an anionic group-containing alkoxysilyl group-terminated polymer or salt thereof, or an alkoxysilyl group-hydrolyzed polymer thereof. 4. Anionic group-containing polyol compound (A
3) is dimethylol alkanoic acid, The anionic group-containing alkoxysilyl group-terminated polymer or a salt thereof or an alkoxysilyl group-hydrolyzed polymer thereof according to any one of claims 1 to 3. 5. The anionic group-containing alkoxysilyl group-terminated polymer represented by the formula (1) is a non-anionic group-containing polyol compound (A having a number average molecular weight of 500 or more).
1), an anionic group-free polyol compound (A2) having a number average molecular weight of less than 500, an anionic group-containing polymer which is a reaction product of an anionic group-containing polyol compound (A3) and a polyisocyanate compound (A4), At least one secondary amino group-containing alkoxysilane compound (A5) selected from alkoxysilane compounds containing one secondary amino group represented by the following formulas (6) to (8)
A terminal alkoxysilylated anionic group-containing polymer obtained by reaction with an anionic group-containing alkoxysilyl group-terminated polymer according to any one of claims 1 to 4, a salt thereof, or an alkoxysilyl group hydrolysis thereof. polymer. [Chemical 6] (In the formula (6), R ^{1 to} R ⁷ and m are the same as above.) (In the formula (7), R ^{1 to} R ⁸ and m are the same as above.) (In the formula (8), R ^{1 to} R ⁸ and m are the same as above.) 6. A polyisocyanate compound (A4), an anionic group-free polyol compound (A1) having a number average molecular weight of 500 or more, an anionic group-free polyol compound (A2) having a number average molecular weight of less than 500, and an anion. The ratio of the polyisocyanate compound (A4) to the polyisocyanate compound (A4) is such that the ratio of the isocyanate group / the number average molecular weight of the anionic group-free polyol compound (A1) is 500 or more, and the number average molecular weight of the anion is less than 500. The hydroxyl group (N) in the non-ionic group-containing polyol compound (A2) and the anionic group-containing polyol compound (A3)
The ratio of (CO / OH) (equivalent ratio) is more than 1 and not more than 1.5, and the anionic group-containing alkoxysilyl group-terminated polymer or salt thereof or the salt thereof according to any one of claims 1 to 5. Alkoxysilyl group hydrolyzed polymer. 7. The content of the anionic group in the anionic group-containing alkoxysilyl group-terminated polymer represented by the formula (1) is 0.2 to 5.0% by mass. An anionic group-containing alkoxysilyl group-terminated polymer or a salt thereof, or an alkoxysilyl group-hydrolyzed polymer thereof described in the above item. 8. The content of silicon atom in the anionic group-containing alkoxysilyl group-terminated polymer represented by the formula (1) is 0.05 to 1% by mass. An anionic group-containing alkoxysilyl group-terminated polymer or a salt thereof or an alkoxysilyl group-hydrolyzed polymer thereof described in 1.