JP2000169544A - Urethane resin and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a urethane resin having good storage stability and adhesiveness by effecting the nucleophilic addition reaction of the unsaturation of an α,β-unsaturated carbonyl compound with the amino group of an aminosilane compound and effecting the addition reaction of the secondary amino structure with an isocyanato-terminated urethane polymer. SOLUTION: Provided is a urethane resin of formula I. In formula I, A is the residue corresponding to the skeleton of the urethane polymer, n is 1-20; X is a group of formula II, III or IV (wherein R is a 1-6C alkyl; R1 is H or a 1-6C alkyl; R2 and R4 are each an alkylene optionally having a 1-10C side chain or an arylene; m is 1-3; Z is H, OR3 or R3 [wherein R3 is H, an organic group having a molecular weight of at most 500, a group of formula V (wherein R7 is an alkylene optionally having a 1-10C side chain; R8 is H or a 1-6C alkyl; R9 is a 1-6C alkyl; and x is 1-3) or NH2; R5 is H or -COOR10 (wherein R10 is a 1-20C alkyl); and R6 is H, -CH2COOH or methyl].

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a urethane-based resin and a method for producing the same, and more particularly, to a urethane resin excellent in adhesiveness, water resistance and storage stability suitable for applications such as adhesives, sealants and paints. The present invention relates to a system resin and a method for producing the same.

[0002]

2. Description of the Related Art Silicone-based resins in which the silicone-reactive group is an alkoxysilyl group and whose main chain has a polyether structure are called modified silicone resins,
It is widely used as a base polymer for adhesives, paints and the like. This modified silicone resin is a so-called moisture-curable polymer in which alkoxysilyl groups, which are silicone-reactive groups, are hydrolyzed and crosslinked by atmospheric moisture. This modified silicone resin is a one-part curable sealant, an adhesive,
Since it is often used industrially as a paint or the like, there is a problem of deep curability. Therefore, the main chain is provided with a polyether structure having hydrophilicity.

As described in JP-A-52-73998, this modified silicone resin is subjected to a step of once allylating hydroxyl groups of a polyether polyol. After adding a silylating agent such as chlorosilane, an alkoxylation reaction is performed with an alcohol to produce the compound. However, these manufacturing processes are complicated, and there is a disadvantage that manufacturing requires a long time. Modified silicone resins produced by these steps are widely commercially available, but are limited to those having a methyldimethoxysilyl terminal structure. This is because when the terminal structure is a trimethoxysilyl group, storage stability is lacking. Further, in this polymer, the bond between the terminal alkoxysilyl group and the polyether polyol in the main chain is a hydrocarbon group.

[0004] As described above, from the viewpoint of obtaining good storage stability, it is inevitable to limit to a methyldimethoxysilyl group having poor reactivity, and to provide a deep curing property, a polyether having poor adhesiveness is used for the main chain. It is unavoidable that the bond is a non-polar hydrocarbon group, so that the curing speed is slow and the adhesion and water resistance are poor. Therefore, many proposals have been made to improve adhesiveness and water resistance by blending an acrylic resin having good adhesiveness. For example, JP-A-63
A technique for blending an acrylic polymer as described in JP-A-1112642 and a technique for blending a special acryloyl group-containing compound as described in JP-A-9-255874 are known.

On the other hand, urethane-based resins in which the silicone-reactive group is an alkoxysilyl group and whose main chain has a polyether structure have long been known to react aminosilanes and mercaptosilanes with isocyanate-terminated prepolymers. ing. According to this method, the adhesion is improved, but the storage stability is poor, so that it has not yet been commercialized.

[0006]

SUMMARY OF THE INVENTION The present invention relates to a urethane resin whose silicone-reactive group is an alkoxysilyl group and whose main chain is represented by a polyether structure. It is an object of the present invention to provide a urethane resin capable of imparting properties, increasing the degree of freedom of the terminal alkoxysilyl group structure, and freely adjusting the curing rate.

[0007]

Means for Solving the Problems In order to achieve the above object, the present inventors have made intensive studies and found that the amino group of the aminosilane compound is nucleophilic to the unsaturated bond of the α, β-unsaturated carbonyl compound. After an addition reaction and conversion to an alkoxysilane compound having one secondary amino group structure, if this is added to an isocyanate group-terminated urethane prepolymer, a primary amino group having many crosslinking points has a secondary amino group having few crosslinking points. Because it is converted to a secondary amino group, the fluidity of the polymer is good,
It has been found that the storage stability can be essentially improved. Since the polymer obtained by this method has a urethane bond and a urea bond in the molecule, and further has a polar group derived from an α, β-unsaturated carbonyl compound, the polarity effective for adhesion is further improved, and the adhesion is remarkably improved. improves. During further research, they discovered that the reactivity of alkoxysilyl groups was different depending on the size of the polar group existing as a pendant group adjacent to the alkoxysilyl group, and used this finding to control the curing rate and physical properties. As a result, the present invention has been completed.

That is, the present invention provides the following general formula (1)

Embedded image The gist is a urethane-based resin represented by However, A is a residual group corresponding to the skeleton of the urethane polymer, n is 1 to 20, X
Represents a group represented by the following general formula (2), (3) or (4), respectively.

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Embedded image However, R is an alkyl group having 1 to 6 carbon atoms, R ¹ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R ² is a 1 to 6 carbon atom.
An alkylene group or an arylene group which may have 10 side chains, m is 1 to 3, Z is a hydrogen atom, OR ³ , R ³ or N
H ₂ and R ³ is a hydrogen atom, an organic group having a molecular weight of 500 or less, or a group represented by the following general formula (5);

Embedded image (R ⁷ is an alkylene group having 1 to 10 carbon atoms which may have a side chain, R ⁸ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R ⁹ is an alkyl group having 1 to 6 carbon atoms. , X represents 1 to 3.) R ⁴ is an alkylene group or an arylene group which may have a side chain having 1 to 10 carbon atoms, R ⁵ is a hydrogen atom or a formula —COO.
R ^{10 represents} a group represented by R ¹⁰ (R ¹⁰ represents an alkyl group having 1 to 20 carbon atoms), and R ⁶ represents a hydrogen atom, —CH ₂ COOH or a methyl group.

Further, the present invention relates to a urethane prepolymer obtained by reacting a polyol compound and a diisocyanate compound with a compound represented by the following formula (6), (7) or (8) (provided that Z, m, R, R ¹ ,
R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are as defined above. ) Is characterized by a method of producing the urethane-based resin (hereinafter referred to as a production method (1)).

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Further, the present invention provides a compound of the general formula (9) or the general formula (10)

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Embedded image (Where B is a residue corresponding to the skeleton of the polyol compound, Y is an oxygen atom or a sulfur atom,
R ¹¹ represents an organic group having a molecular weight of 500 or less, j represents 1 to 10, and l represents 1 to 10, respectively. ) And the following general formula (11):
A compound represented by the general formula (12) or (13) (where D is a residue corresponding to the skeleton of the diisocyanate compound and Z, m, R, R ¹ , R ² , R ³ , R ⁴ , R ⁵
And R ⁶ are as defined above. ) Is reacted (hereinafter referred to as a production method (2)).

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In the production method (1) of the present invention, the compound represented by the general formula (6) is an aminosilane compound represented by the following general formula (14) (where R, R ¹ and R ² are And an α, β-unsaturated carbonyl compound represented by the following general formula (15) (provided that Z and R ⁶
Is as defined above. ) Is a compound obtained by reacting

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In the production method (1) of the present invention, the compound represented by the general formula (7) or (8) is an aminosilane compound represented by the following general formula (16) (provided that
R, R ¹ , R ² and R ⁴ are as defined above. ) And an α, β-unsaturated carbonyl compound represented by the above general formula (15) or a maleic acid diester represented by the following general formula (17) (wherein R ³ and R ¹⁰ are as defined above). It is a compound obtained by the reaction.

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In the production method (2) of the present invention, the compound represented by the general formula (11), the general formula (12) or the general formula (13) can be obtained by converting the compound represented by the general formula (6) or the general formula (7) ) Or a compound obtained by reacting the compound represented by the general formula (8) with a diisocyanate compound in which the residue corresponding to the skeleton thereof is D.

Further, the present invention provides a urethane prepolymer obtained by reacting a polyol compound and a diisocyanate compound, an amine compound having a primary amino group and / or a secondary amino group in the molecule, and a compound represented by the following general formula: (1
8) The alkoxysilane compound represented by 8) (wherein, R and R ¹ have the same meanings as above. R ¹² may be a hydrogen atom or a methyl group, and R ¹³ may have a side chain having 1 to 10 carbon atoms.) An alkylene group or an arylene group).
In the molecule obtained by reacting the amine compound, the alkoxysilane compound and the α, β-unsaturated carbonyl compound represented by the general formula (15) or the maleic acid diester represented by the general formula (17), A gist of the present invention is a method for producing a urethane resin (hereinafter, referred to as production method (3)), which comprises reacting a compound having a secondary amino group (compound X).

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The present invention further comprises reacting the polyol compound represented by the general formula (9) or (10) with a compound (compound Y) obtained by reacting the compound X with a diisocyanate compound. A method for producing a urethane-based resin (hereinafter, referred to as a production method (4)) is characterized.

[0016]

BEST MODE FOR CARRYING OUT THE INVENTION The urethane resin of the present invention is represented by the above general formula (1). In the formula, A is a residue corresponding to the skeleton of the urethane prepolymer, and includes a repeating unit via a urethane bond generated when a usual urethane prepolymer is prepared. In the formula, X is represented by the above general formula (2), general formula (3) or general formula (4);
Z in those formulas is a hydrogen atom, OR ³ , R ³ or N
Is H _2, R ³ is a hydrogen atom or a group represented by a molecular weight of 500 or less organic group or the above general formula (5), the molecular weight of 500 or less of the organic groups R ^3, the production method of the present invention ( The above general formula (1) used in 1) and the production method (2)
It is a reactive residue of the α, β-unsaturated carbonyl compound shown in 5), and means a residue that is not included in the definitions of Z and R ³ . The same applies to the organic group having a molecular weight of 500 or less of R ¹¹ in the general formula (10). Specific examples of the α, β-unsaturated carbonyl compound are as described below.

The production method of the urethane resin of the present invention is not limited, but the above production method (1) or production method (2) is a preferred production method. Manufacturing method (1)
Is a polyol compound (hereinafter, referred to as compound (a)).
And a urethane prepolymer obtained by a urethanization reaction of a diisocyanate compound (hereinafter, referred to as compound (b)) with a compound represented by the above general formula (6), (7) or (8). Consisting of The compound represented by the general formula (6) includes an aminosilane compound represented by the general formula (14) (hereinafter, referred to as compound (c)) and an α, β-unsaturated carbonyl compound represented by the general formula (15) (Hereinafter, referred to as compound (e)). The compound represented by the general formula (7) or the general formula (8) includes the aminosilane compound represented by the general formula (16) (hereinafter, referred to as compound (d)) and the compound (e) or the general formula It can be produced by reacting a maleic acid diester represented by (17) (hereinafter, referred to as compound (f)).

In the production method (2), the polyol compound represented by the general formula (9) or (10) and the polyol compound represented by the general formula (11), (12) or (13) are used. Reacting the compound. The general formula (1
1), the compound represented by the general formula (12) or the general formula (13) is a compound represented by the general formula (6), the general formula (7) or the general formula (8) and a diisocyanate compound (hereinafter, compound ( g)).

Further, the present invention is characterized by a method for producing a urethane resin comprising the following production method (3) and production method (4). The production method (3) includes a urethane prepolymer obtained by reacting the compound (a) with the compound (b), and an amine compound having a primary amino group and / or a secondary amino group in the molecule. (Hereinafter, referred to as compound (h)) and the alkoxysilane compound represented by the general formula (18) (hereinafter, referred to as compound (i)).
Or a compound (compound X) having a secondary amino group in the molecule thereof obtained by reacting compound (h), compound (i) and compound (e) or compound (f). To react.

The production method (4) comprises a method of preparing a polyol compound represented by the general formula (9) or (10), the compound X and a diisocyanate compound (hereinafter, compound (j)
That. ) Is reacted with a compound (compound Y) obtained by reacting

Hereinafter, the compounds used in each of the above production methods will be described. Examples of the compound (a) include a polyether polyol, a polyester polyol, a polyolefin polyol, a polythiol compound, a polyamine compound, and others. Examples of the polyether polyol include diols such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, and bisphenol A. , Trimethylolethane, trimethylolpropane, triols such as glycerin, sorbitol and the like, and in the presence of one or more amines such as ammonia, ethylenediamine, urea, monomethyldiethanolamine, monoethyldiethanolamine, ethylene oxide, propylene Oxide, butylene oxide, random or block copolymers obtained by ring-opening polymerization of styrene oxide, etc., usually having a molecular weight of 50 to 25,000 It is used.

Examples of the polyester polyol include a polymer obtained by polycondensing a dicarboxylic acid alone or a mixture thereof such as maleic acid, fumaric acid, adipic acid, sebacic acid, phthalic acid and the above diols alone or a mixture.
Ring-opening polymers such as ε-caprolactone and valerolactone; active hydrogen compounds having two or more active hydrogens such as castor oil; and those having a molecular weight of 50 to 25,000 are usually used. Examples of the polyolefin polyol include a polyol having an ethylene / α-olefin skeleton and a polyol having a polyisobutylene skeleton.

As the polythiol compound, the general formula HS
-(R-SS) _n -R-SH (where R is -C _{2
H 4 -, - C 3 H} 6 -, - C 2 H 4 -O-C 2 H 4 -,
_{-C 2 H 4 -O-CH 2} -O-C 2 H 4 -, - C 3 H 6
_{-O-C 3 H 6 -O-} C 3 H 6 - or -C ₂ H ₄ -O-
(C ₂ H ₄ —O) _m —C ₂ H ₄ —, wherein n and m are
It is an integer of 2 to 50. )). Specifically, LP-282, LP-
55 (trade name: manufactured by Toray Thiokol).

The polyamine compounds include primary amino group-containing oligomers such as Jeffamine D-400,
-2000, D-4000, D-403, T-300
0, T-5000 (trade name: manufactured by Mitsui Texaco Chemical Co., Ltd.), acrylonitrile-butadiene copolymer rubber having primary amino groups at both ends ATMN1300X16 (trade name: manufactured by Ube Industries), containing secondary amino group Polymers and the like, a polymer containing only a secondary amino group as it is, in the case of a polymer containing a primary amino group,
A secondary amine compound obtained by nucleophilic addition of a primary amine and an equivalent amount of an α, β-unsaturated carbonyl compound (including a silane coupling agent having a (meth) acryloyl group) is used.

In addition to these, a diene monomer such as a polyol compound having an acrylic skeleton, a fluorine compound, a silicon atom, a nitrogen atom, a sulfur atom, an organic compound having an organic group having a rosin skeleton, or a polybutadiene skeleton is polymerized. A polyol compound having a skeleton of the obtained polymer is also included, and these may be properly used depending on the purpose of use and performance. Among the above compounds (a), a polyether polyol having a property of being able to cure to a deep part particularly in moisture curing is preferable. In particular, the best results are obtained with polyoxypropylene glycol.

The compound (b) includes, for example, aliphatic, alicyclic, araliphatic, aromatic diisocyanate compounds and the like. Hereinafter, specific examples thereof will be described.
Aliphatic diisocyanate compound: trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 1,2-
Butylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, 2,
4,4- or 2,2,4-trimethylhexamethylene diisocyanate, 2,6-diisocyanatomethylcaproate and the like. Alicyclic diisocyanate compound: 1,3-
Cyclopentene diisocyanate, 1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate, 3-isocyanatomethyl-3,5,5-
Trimethylcyclohexyl isocyanate, 4,4'-
Methylene bis (cyclohexyl isocyanate), methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, 1,3-
Bis (isocyanatomethyl) cyclohexane, 1,4
-Bis (isocyanatomethyl) cyclohexane, isophorone diisocyanate and the like. Aromatic diisocyanate compound: 1,3- or 1,4-xylylene diisocyanate or a mixture thereof, ω, ω'-diisocyanate-1,4-diethylbenzene, 1,3- or 1,4-bis (1-isocyanate -1-methylethyl) benzene or a mixture thereof. Aromatic diisocyanate compound: m-phenylene diisocyanate, p-
Phenylene diisocyanate, 4,4'-diphenyl diisocyanate, 1,5-naphthalene diisocyanate, 4,4'-diphenylmethane diisocyanate,
2,4- or 2,6-tolylene diisocyanate, 4,
4'-toluidine diisocyanate, 4,4'-diphenyl ether diisocyanate and the like. Other diisocyanate compounds: diisocyanates containing a sulfur atom such as phenyldiisothiocyanate.

Among the above compounds (b), 2,4- or 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, hexamethylene diisocyanate, 1,3- or 1,4-xylylene diisocyanate or a compound thereof Of isophorone diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, 1,4-bis (isocyanatomethyl) cyclohexane, and 4,4'-methylenebis (cyclohexylisocyanate). When an aliphatic diisocyanate compound is used, a resin with less discoloration can be obtained.

Examples of the compound (c) include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane and the like.

Compound (d) includes N-β (aminoethyl) -γ-aminopropyltrimethoxysilane, N-β
β (aminoethyl) -γ-aminopropyltriethoxysilane, N-β (aminoethyl) -γ-aminopropylmethyldimethoxysilane, N-β (aminoethyl) -γ
-Aminopropylmethyldiethoxysilane, and other special aminosilanes manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM
6063, X-12-896, KBM576, X-12
-565, X-12-580, X-12-5263, K
BM6123, X-12-575, X-12-562,
X-12-5202, X-12-5204, KBE97
03 and the like. Among the above-mentioned compounds (d), from the viewpoint of ease of reaction and wide availability on the market, N-
β (aminoethyl) -γ-aminopropyltrimethoxysilane, N-β (aminoethyl) -γ-aminopropyltriethoxysilane and N-β (aminoethyl) -γ-aminopropylmethyldimethoxysilane are preferred.

Examples of the α, β-unsaturated carbonyl compound (compound (e)) include (meth) acrylic compounds, vinyl ketone compounds, vinyl aldehyde compounds, and other compounds. As the (meth) acrylic compound, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate , Pentyl (meth) acrylate, amyl (meth) acrylate, isoamyl (meth) acrylate,
Hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl acrylate, nonyl (meth) acrylate,
Decyl (meth) acrylate, isodecyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, octadecyl (meth) acrylate, stearyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, Butoxyethyl (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, phenoxyethyl (meth) acrylate, polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate,
Methoxyethylene glycol (meth) acrylate, ethoxyethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, dicyclopentadienyl (meth) acrylate, dicyclopentanyl (meth) acrylate , Dicyclopentenyl (meth) acrylate, tricyclodecanyl (meth) acrylate, bornyl (meth) acrylate, isobornyl (meth) acrylate, diacetone (meth)
Acrylate, isobutoxymethyl (meth) acrylate, N-vinylpyrrolidone, N-vinylcaprolactam, N-vinylformaldehyde, N, N-dimethylacrylamide, t-octylacrylamide, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) Acrylate, 7-amino-3,7-dimethyloctyl (meth) acrylate, N, N-dimethyl (meth) acrylamide, N, N'-dimethylaminopropyl (meth) acrylamide, acryloylmorpholine, etc. Brand names: Aronix M-102, M-111, M-114, M-117,
Nippon Kayaku product name: Kayahard TC110S, R
629, R644, trade name: VISCOAT 3700 manufactured by Osaka Organic Chemical Co., Ltd., and the like.

Further, trimethylolpropane tri (meth) acrylate, pentaerythritol (meth) acrylate, pentaerythritol tetra (meth) acrylate, ethylene glycol di (meth) acrylate,
Tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,4
-Butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropanetrioxyethyl (meth) acrylate, tris (2-hydroxyethyl) isocyanurate Tri (meth) acrylate, tris (2-hydroxyethyl) isocyanurate di (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, epoxy (meth) acrylate obtained by adding (meth) acrylate to glycidyl ether of bisphenol A ) Polyfunctional compounds such as acrylates and commercial products of the polyfunctional compounds, trade names of Mitsubishi Chemical Corporation: Iupima UV, SA1002, SA2
007, trade name: Viscort 70, manufactured by Osaka Organic Chemical Company
0, Nippon Kayaku product name: Kayahard R604, D
PCA-20, DPCA-30, DPCA-60, DP
CA-120, HX-620, D-310, D-33
0, trade name of Toagosei Chemical Industry Co., Ltd .: Aronix M-
210, M-215, M-315, M-325 and the like.

In addition to the above compounds, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane having an alkoxysilyl group,
γ-methacryloxymethyldimethoxysilane, γ-methacryloxymethyldiethoxysilane, γ-acryloxypropyltrimethoxysilane, γ-acryloxymethyldimethoxysilane, and the like.

Examples of the vinyl ketone compound include vinyl acetone, vinyl ethyl ketone, vinyl butyl ketone and the like.
Examples of vinylaldehyde compounds include acrolein, methacrolein, and crotonaldehyde, and examples of other compounds include maleic anhydride, itaconic anhydride, itaconic acid, crotonic acid, N-methylolacrylamide, diacetoneacrylamide, and N- [3- (Dimethylamino) propyl] methacrylamide, N, N-dimethylacrylamide, N, N-diethylacrylamide, N-
t-octylacrylamide, N-isopropylacrylamide and the like. In addition to the above compounds, compounds containing a fluorine atom, a sulfur atom or a phosphorus atom therein are also included. Examples of the compound containing a fluorine atom include perfluorooctylethyl (meth) acrylate and trifluoroethyl (meth) acrylate, and examples of the compound containing a phosphorus atom include (meth) acryloxyethyl phenyl acid phosphate.

Among the above compounds (e), methyl acrylate, ethyl acrylate, propyl acrylate,
Butyl acrylate, t-butyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate and the like are preferred. Of these, methyl acrylate and ethyl acrylate are particularly preferred for imparting rapid curability, and 2-ethylhexyl acrylate and lauryl acrylate are particularly preferred for imparting flexibility. Compound (e) can be used alone or in combination of two or more.

Examples of the maleic acid diester (compound (f)) include dimethyl maleate, diethyl maleate, dibutyl maleate, di-2-ethylhexyl maleate,
Dioctyl maleate and the like can be mentioned, and these can be used alone or in combination of two or more. Among these, ease of reaction,
Dimethyl maleate, diethyl maleate, dibutyl maleate, and di-2-ethylhexyl maleate are preferred from the viewpoint of wide commercial availability. Compound (f) can be used alone or in combination of two or more.

The diisocyanate compound (compound (g)) used in the production method (2) is appropriately selected from the compounds (b).

The amine compound (compound (h)) used in the above production method (3) includes a compound (h-1) having only one or more primary amino groups in its molecule, There are a compound (h-2) having one or more primary amino groups and secondary amino groups and a compound (h-3) having only one or more secondary amino groups in the molecule. As the compound (h-1), propylamine, butylamine,
Isobutylamine, 2-butylamine, 1,2-dimethylpropylamine, hexylamine, 2-ethylhexylamine, amylamine, 3-pentylamine, isoamylamine, 2-octylamine, 3-methoxypropylamine, 3-propoxypropylamine, 3-butoxypropylamine, 3-isobutoxypropylamine,
Mono-primary amine compounds such as rosin amine, N-methyl-
3,3'-iminobis (propylamine), ethylenediamine, diethylenetriamine, triethylenediamine, pentaethylenediamine, 1,4-diaminobutane, 1,2-diaminopropane, ATU (3,9-bis (3-aminopropyl) -2 , 4,8,10-tetraoxaspiro [5.5] undecane), CTU guanamine, dodecanoic dihydrazide, hexamethylenediamine, m-xylylenediamine, dianisidine, 4,4 '
-Diamino-3,3'-diethyldiphenylmethane, diaminodiphenylether, 3,3'-dimethyl-4,
4'-diaminodiphenylmethane, tolidine base, m
-Toluylenediamine, o-phenylenediamine, m-
Examples include compounds having a plurality of primary amino groups, such as phenylenediamine, p-phenylenediamine, and melamine.

Compound (h-2) includes methylaminopropylamine, ethylaminopropylamine, ethylaminoethylamine, laurylaminopropylamine,
2-hydroxyethylaminopropylamine, 1- (2
-Aminoethyl) piperazine, N-aminopropylpiperazine and the like. Compound (h-3) includes piperazine, cis-2,6-dimethylpiperazine, cis-
2,5-dimethylpiperazine, 2-methylpiperazine,
N, N'-di-t-butylethylenediamine, 2-aminomethylpiperidine, 4-aminomethylpiperidine,
Examples thereof include 1,3-di- (4-piperidyl) -propane, 4-aminopropylaniline, 3-aminopyrrolidine, and homopiperazine. Compound (h) can be used alone or in combination of two or more.

The alkoxysilane compound (compound (i)) used in the above production methods (3) and (4) includes γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane,
γ-methacryloxymethyldimethoxysilane, γ-methacryloxymethyldiethoxysilane, γ-acryloxypropyltrimethoxysilane, γ-acryloxymethyldimethoxysilane, etc., and other product names manufactured by Shin-Etsu Chemical Co., Ltd .:
KBM503P and the like. Compound (i) is
One or two or more can be used. By using an alkoxysilane compound having a (meth) acryloyl group in the molecule, the polymer can be made multifunctional (that is, imparted with fast curing, toughness, heat resistance, and weather resistance). The reason is that it has excellent reactivity with the compound (c) and the compound (d), and can introduce a large number of hydrolyzable silyl groups into polymer terminals, thereby increasing the crosslink density.

The diisocyanate compound (compound (j)) used in the production method (4) is appropriately selected from the compounds (b).

Hereinafter, the respective manufacturing methods will be described.
The production method (1) comprises:
It comprises reacting a compound represented by the above general formula (6), (7) or (8). The reaction between the compound (c) and the compound (e) in the production method (1) is-
The reaction is performed at a temperature in the range of about 20 ° C. to + 150 ° C. for 1 to 1,000 hours to synthesize the compound (6) having a secondary amino group in one molecule. The reaction may be carried out in the presence of a medium such as an organic solvent, and there is no problem even if the reaction is carried out for more than 1,000 hours. The use ratio of the compound (c) and the compound (e) is such that the number of active hydrogens in the compound (c) is usually α with respect to 1 mol of the compound (c).
In this case, it is about (α-1) × (0.1 to 9) mol, but is appropriately adjusted according to reaction conditions, generated odor and the like. The reaction between the compound (d) and the compound (e) or the compound (f) is performed in the same manner as the reaction between the compound (c) and the compound (e). That is, the reaction is carried out at −20 ° C.
Perform at a temperature range of about + 150 ° C for 1 to 1,000 hours,
The compound having a secondary amino group in one molecule thereof (7)
Alternatively, the above compound (8) is synthesized. The reaction may be carried out in the presence of a medium such as an organic solvent, and there is no problem even if the reaction is carried out for more than 1,000 hours. The use ratio of the compound (d) and the compound (e) or the compound (f) is such that the compound (e) or the compound (f) is usually the compound (d) based on 1 mol of the compound (d). When the number of active hydrogens in the sample is β, it is about (β-1) × (0.1 to 9) mol, but is appropriately adjusted according to the reaction conditions, the odor generated, and the like. By reacting the urethane prepolymer with the compound (6), (7) or (8) obtained as described above, the urethane of the present invention represented by the general formula (1) Based resin can be manufactured. In this reaction, it is important that the isocyanate groups present in the urethane prepolymer are not present in the resulting urethane resin. This reaction is
Both are usually reacted at 0 to 90 ° C. for 1 to 8 hours. This reaction may be performed in the presence of a catalyst. Preferred catalysts include dialkyltin dicarboxylates such as dibutyltin dilaurate. In addition, this reaction may be performed in the presence of a medium such as an organic solvent, or may be performed for more than 8 hours without any problem. The compound (6), the compound (7) or the compound (8) is not limited to one kind, and two or more kinds may be used.

The production method (2) of the present invention comprises reacting a polyol (compound (a)) with the compound (11), the compound (12) or the compound (13). The compound (11), the compound (12) or the compound (13) is obtained by reacting the compound (6), the compound (7) or the compound (8) with the compound (g). The reaction between the compound (6), the compound (7) or the compound (8) and the compound (g) is performed in a temperature range of about -20 ° C to + 150 ° C, from 1 to 1,
The reaction is carried out for 000 hours to synthesize the compound (11), the compound (12) or the compound (13) having a secondary amino group in one molecule. The reaction may be carried out in the presence of a medium such as an organic solvent, and there is no problem even if the reaction is carried out for more than 1,000 hours. The compound (6), the compound (7) or the compound (8) is not limited to one type, and two or more types may be used. The use ratio of the compound (6), the compound (7) or the compound (8) and the compound (g) is usually the compound (6) or the compound (7) per 1 mol of the compound (g). ) Or the compound (8) is the compound (g)
When the number of isocyanate groups in the compound is γ, (γ-1)
X (0.1 to 9) mol, but is appropriately adjusted according to reaction conditions, cost, stability and the like. The above reaction may be performed in the presence of a medium such as an organic solvent, or may be performed for more than 1,000 hours without any problem. In the above reaction, a catalyst such as an organotin compound, an amine compound, or an organometallic compound may be added. The compound (11), the compound (12) or the compound (13) obtained as described above.
And the polyol compound (compound (a)), whereby the urethane-based resin of the present invention represented by the general formula (1) can be produced. This reaction is
Both are usually reacted at 0 to 90 ° C. for 1 to 8 hours. This reaction may be performed in the presence of a catalyst. Preferred catalysts include dialkyltin dicarboxylates such as dibutyltin dilaurate. In addition, this reaction may be performed in the presence of a medium such as an organic solvent, or may be performed for more than 8 hours without any problem. The compound (11), the compound (12) or the compound (13) is not limited to one kind but may be 2
More than one species may be used. In addition, the compound (a) is the compound (11), the compound (12) or the compound (1
Before reacting with 3), it may be reacted with the above compound (e).

In the production method (3) of the present invention, the urethane prepolymer is reacted with the compound (h) and the compound (i), or the compound (h), the compound (i) and the compound (E) or the above compound X obtained by reacting the above compound (f)
And reacting. The compound (h) and the compound (i) are reacted at a temperature of about −20 ° C. to + 150 ° C. for 1 to 1,000 hours to synthesize the compound X having a secondary amino group in the molecule. I do. The reaction may be carried out in the presence of a medium such as an organic solvent, and there is no problem even if the reaction is carried out for more than 1,000 hours. The ratio of the compound (h) to the compound (i) used is usually the compound (i) and the compound (h) per 1 mol of the compound (h).
When the number of active hydrogens in the sample is δ, (δ−1) × (0.
1 to 9) mol, but it is appropriately adjusted according to reaction conditions, generated odor and the like.

The compound (h) and the compound (i)
May be present in the presence of the compound (e) or the compound (f). Compound (e) or compound (f) may be used as a mixture with compound (i),
They may be used sequentially. Compound (e) or compound (f)
Is not limited to one type, and two or more types may be used. When the compound (e) or the compound (f) is present, the use ratio of the compound (h) to the compound (i) and the compound (e) or the compound (f) is 1 mol of the compound (h). On the other hand, the compound (i) and the compound (e) or the compound (f) usually have the number of active hydrogens in the compound (h) set to ε.
In this case, it is about (ε-1) × (0.1 to 9) mol, but is appropriately adjusted according to the reaction conditions, the odor generated, and the like. A urethane-based resin can be produced by reacting the compound X obtained as described above with the urethane prepolymer. In this reaction, as in the case of the production method (1), it is important that the isocyanate group present in the urethane prepolymer is not present in the obtained urethane-based resin. The reaction is performed in the same manner as in the case where the compound (6), the compound (7) or the compound (8) in (1) is reacted with the urethane prepolymer.

The production method (4) of the present invention comprises reacting the compound X obtained by the production method (3) with the compound (j) and the compound Y obtained by reacting the compound (j) with the polyol compound. The compound X and the compound (j) are reacted at a temperature of about −20 ° C. to + 150 ° C.,
The reaction is carried out for 1,000 hours to synthesize the compound Y having an isocyanate group in the molecule. The reaction may be carried out in the presence of a medium such as an organic solvent, and there is no problem even if the reaction is carried out for more than 1,000 hours. Compound X is not limited to one compound,
More than one species may be used. The compound X and the compound (j)
The use ratio of the compound X is usually (ζ−1) × (0.1 to 0.1 mol) when the number of isocyanate groups in the compound (j) is ζ with respect to 1 mol of the compound (j). 9) It is about a mole, but is appropriately adjusted according to reaction conditions, cost, stability and the like. The above reaction may be performed in the presence of a medium such as an organic solvent, or may be performed for more than 1,000 hours without any problem. In the above reaction, a catalyst such as an organotin compound, an amine compound, or an organometallic compound may be added. A urethane-based resin can be produced by reacting the compound Y obtained as described above with the polyol compound. This reaction is performed according to the production method (2).
And the above-mentioned compound (11), compound (12) or compound (13) is reacted with the polyol compound.

The urethane-based resin of the present invention and the urethane-based resins obtained by the above-mentioned production methods (3) and (4) are particularly suitable for adhesives, sealants, paints and the like. In order to achieve the same, a curing catalyst, a filler, a plasticizer, various additives, a solvent, a dehydrating agent, and the like may be further added and mixed according to the intended performance.

As the curing catalyst, an organic tin, a metal complex, a base such as an amine, an organic phosphate compound, and water (moisture in the air) can be used. Specifically, examples of the organic tin include dibutyltin dilaurate, dioctyltin dimaleate, dibutyltin phthalate, stannous octylate, dibutyltin methoxide, dibutyltin diacetylacetate, and dibutyltin diversate. As the metal complex, tetrabutyl titanate, tetraisopropyl titanate,
Titanate compounds such as triethanolamine titanate, metal carboxylate such as lead octylate, lead naphthenate, nickel naphthenate and cobalt naphthenate; metal acetylacetonate complexes such as aluminum acetylacetonate complex and vanadium acetylacetonate complex And the like. Examples of the base include aminosilanes such as γ-aminopropyltrimethoxysilane and γ-aminopropyltriethoxysilane; quaternary ammonium salts such as tetramethylammonium chloride and benzalkonium chloride; DABCO (registered trademark) manufactured by Sankyo Air Products Trademark) series, DABCO BL series, 1,8
And a plurality of nitrogen-containing linear or cyclic tertiary amines and quaternary ammonium salts such as -diazabicyclo [5.4.0] undec-7-ene. Examples of the organic phosphoric acid compound include monomethyl phosphoric acid, di-n-butyl phosphoric acid, and triphenyl phosphate.

Examples of the filler include calcium carbonate, various kinds of treated calcium carbonate, fumed silica, clay, talc, various kinds of balloons and the like. Examples of the plasticizer include phthalic acid esters such as dioctyl phthalate and dibutyl phthalate, and aliphatic carboxylic acid esters such as dioctyl adipate and dibutyl sebacate. Examples of the additives include an antioxidant, an ultraviolet absorber, a pigment, various tackifiers, a titanate coupling agent, an aluminum coupling agent, and the like. Any solvent may be used as long as it is compatible with the urethane resin and has a water content of 500 ppm or less.
Examples of the dehydrating agent include quick lime, magnesium oxide, orthosilicate, anhydrous sodium sulfate, zeolite, methyl silicate, ethyl silicate, vinylalkoxysilane, various alkylalkoxysilanes (commonly known as silane coupling agents), and the like.

[0049]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail with reference to embodiments. (Example 1) (1) 1 mol of polyoxypropylene diol having a number average molecular weight of 10,000 (Preminol 4010, trade name: manufactured by Asahi Glass Co., Ltd.) and 2 mol of Sumidur 44S (trade name: manufactured by Sumitomo Bayer Urethane Co., Ltd.) In a nitrogen atmosphere,
The mixture was reacted at 90 ° C. for 3 hours with stirring to obtain a urethane prepolymer (1). (2) KBE903 (trade name: manufactured by Shin-Etsu Chemical Co., Ltd., γ-
A reaction product (1-1) was obtained by reacting 1 mol of aminopropyltriethoxysilane) and 1 mol of 2-ethylhexyl acrylate at 23 ° C. for 7 days. On the other hand, KB
M903 (trade name: manufactured by Shin-Etsu Chemical Co., Ltd., γ-aminopropyltrimethoxysilane) was reacted at a ratio of 1 mol and 2-ethylhexyl acrylate at a ratio of 1 mol at 23 ° C. for 7 days to give a reaction product (1-2). Obtained. (3) 1 mol of urethane prepolymer (1) and 2 mol of reactant (1-1) are reacted at 90 ° C. for 1 hour to form a liquid urethane system in which all isocyanate groups (NCO) are silylated. Resin (1) was obtained. On the other hand, 1 mol of the urethane prepolymer (1) and 2.05 of the reactant (1-2) were used.
The mixture was reacted at a molar ratio of 90 ° C. for 1 hour to obtain a liquid urethane resin (2) in which all isocyanate groups (NCO) were silylated. The urethane-based resin (1) and the urethane-based resin (2) are each represented by X in the above general formula (1).
Is the above general formula (2), and in the general formula (2), Z is OR ³ . The storage stability of the urethane-based resin (1) and the urethane-based resin (2) was evaluated as follows. When the viscosity of the resin after standing at 50 ° C. for one month was 1.5 times or less the initial viscosity of the resin, it was evaluated as ○.

Example 2 (1) 1 mol of preminol 4010 and 2 mol of isophorone diisocyanate were reacted at 90 ° C. for 3 hours with stirring in a nitrogen atmosphere to obtain a urethane prepolymer (2). . (2) KBM602 (trade name: manufactured by Shin-Etsu Chemical Co., Ltd., N-
β (aminoethyl) -γ-aminopropylmethyldimethoxysilane) was reacted at a ratio of 1 mol and 2-ethylhexyl acrylate at a ratio of 2 mol at 50 ° C. for 7 days to obtain a reaction product (2-1). (3) 1 mol of urethane prepolymer (2) and 2 mol of reactant (2-1) are reacted at 90 ° C. for 1 hour to obtain a liquid urethane resin (3) in which NCO is completely silylated. I got In the urethane-based resin (3), in the general formula (1), X is the general formula (3) or the general formula (4), and in the formula (3) or the formula (4), Z is OR ³ . is there. The storage stability of the resin was ○.

Example 3 (1) 1 mol of KBM602 and 2 mol of ethyl acrylate
The reaction was carried out at 50 ° C. for 7 days at
1) was obtained. (2) The urethane prepolymer (2) is reacted at 1 mol and the reactant (3-1) at 2 mol at 90 ° C. for 1 hour to obtain a liquid urethane resin (4) in which NCO is completely silylated. I got In the urethane-based resin (4), in the general formula (1), X is the general formula (3) or the general formula (4), and in the formula (3) or the formula (4), Z is OR ³ . is there. The storage stability of the resin was ○.

Example 4 (1) 1 mol of KBM602 and 2 mol of lauryl acrylate were reacted at 50 ° C. for 7 days to obtain a reactant (4).
-1) was obtained. (2) The urethane prepolymer (2) is reacted at 1 mol and the reactant (4-1) at 2 mol at 90 ° C. for 1 hour to obtain a liquid urethane resin (5) in which NCO is completely silylated. I got In the urethane-based resin (5), in the general formula (1), X is the general formula (3) or the general formula (4), and in the formula (3) or the formula (4), Z is OR ³ . is there. The storage stability of the resin was ○.

Example 5 (1) 1 mol of KBM602, KBM5103 (trade name: manufactured by Shin-Etsu Chemical Co., Ltd., γ- (acryloxypropyl))
Trimethoxysilane) was reacted at a rate of 2 mol at 50 ° C. for 7 days to obtain a reaction product (5-1). (2) 1 mol of the urethane prepolymer (2) and 2.1 mol of the reactant (5-1) are reacted at 90 ° C. for 1 hour to form a liquid urethane resin in which all NCOs are silylated ( 6) was obtained. In the urethane-based resin (6), in the general formula (1), X is the general formula (3) or the general formula (4), and in the formula (3) or the formula (4), Z is OR ³ . is there. The storage stability of the resin was ○.

Example 6 (1) KBM603 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd., N-
1 mol of β (aminoethyl) -γ-aminopropyltrimethoxysilane) and 2 mol of diethyl maleate were reacted at 50 ° C. for 7 days to obtain a reaction product (6-1). (2) The urethane prepolymer (2) is reacted at 1 mol and the reactant (6-1) at 2 mol at 90 ° C. for 1 hour to form a liquid urethane resin (7) in which all NCO is silylated. I got In the urethane-based resin (7), in the general formula (1), X is the general formula (3) or the general formula (4), and in the formula (3) or the formula (4), Z is OR ³ . is there. The storage stability of the resin was ○.

Example 7 (1) 1 mol of KBM602 and 2 mol of 2-ethylhexyl acrylate were reacted at 50 ° C. for 7 days to obtain a reaction product (7-1). (2) 1 mol of the reaction product (7-1) and 1 mol of hexamethylene diisocyanate were reacted at 50 ° C. for 1 hour, and 1.6 mol of the obtained synthetic product and preminol 401 were obtained.
The reaction was carried out at 120 ° C. for 1 hour in the presence of 10 ppm of Stan BL (trade name: silver catalyst, manufactured by Sankyoki Seiki Co., Ltd.) at a ratio of 0 to 1 mol to obtain a liquid urethane resin (8). . In the urethane-based resin (8), in the general formula (1), X is the general formula (3) or the general formula (4);
In the formula (3) or the formula (4), Z is OR ³ .
The storage stability of the resin was ○.

Example 8 (1) 1 mol of KBM903 and 1 mol of tetrahydrofurfuryl methacrylate were reacted at 50 ° C. for 7 days to obtain a reaction product (8-1). (2) 1 mol of the urethane prepolymer (1) and 2.2 mol of the reactant (8-1) were reacted at 90 ° C. for 1 hour to form a liquid urethane resin in which all NCOs were silylated ( 9) was obtained. In the urethane-based resin (9), X is the general formula (2) in the general formula (1), and Z is OR ³ in the general formula (2). The storage stability of the resin was ○.

(Example 9) (1) KBM902 (trade name: manufactured by Shin-Etsu Chemical Co., Ltd., γ-
1 mol of aminopropylmethyldimethoxysilane) and 1 mol of methyl methacrylate were reacted at 50 ° C. for 7 days to obtain a reaction product (9-1). (2) 1 mol of the urethane prepolymer (2) and 2.2 mol of the reactant (9-1) were reacted at 90 ° C. for 1 hour to form a liquid urethane-based resin in which all NCOs were silylated ( 10) was obtained. In the urethane-based resin (10), X is the general formula (2) in the general formula (1), and Z is OR ³ in the general formula (2). The storage stability of the resin was ○.

Example 10 (1) 1 mol of KBM902 and 1 mol of isobutyl methacrylate were reacted at 50 ° C. for 7 days to obtain a reaction product (10-1). (2) 1 mol of reactant (10-1) and 1 mol of isophorone diisocyanate were reacted at 80 ° C. for 1 hour, and 2.1 mol of the obtained synthetic product was LP-282 (trade name: East Rethiocol) at 50 pp
m BL-19 (trade name, manufactured by Sankyo Air Products Co., Ltd., 3
(A secondary amine) at 80 ° C. for 10 hours. Thereafter, 0.1 mol of the reaction product (2-1) was added and reacted for 30 minutes to obtain a liquid urethane resin (11). In the urethane-based resin (11), X is the general formula (2) in the general formula (1), and Z is OR ³ in the general formula (2). The storage stability of the resin was ○.

Example 11 (1) 1 mol of KBM902 and 1 mol of phenoxyethyl acrylate were reacted at 23 ° C. for 7 days to obtain a reaction product (11-1). (2) Reaction of 1 mol of Jeffamine D-2000 (trade name: manufactured by Sankyo Texaco Chemical Co., Ltd., molecular weight: 2,000), 1 mol of isobutyl methacrylate, and 1 mol of 2-ethylhexyl acrylate at 50 ° C. for 5 days. As a result, a reaction product (11-2) was obtained. (3) 1 mol of the reactant (11-1) and 1 mol of isophorone diisocyanate are reacted at 80 ° C. for 1 hour, and 2.2 mol of the obtained synthetic product is obtained, the reactant (11-2).
Was reacted at 90 ° C. for 1 hour at a rate of 1 mol to obtain a liquid urethane resin (12). Urethane resin (1
2) In the general formula (1), X is the general formula (2), and in the formula (2), Z is OR ³ .
The storage stability of the resin was ○.

Example 12 (1) 1 mol of KBM903, 0.5 mol of cyclohexyl methacrylate, 0.5 mol of isobornyl acrylate.
After reacting 2 mol and 2-ethylhexyl acrylate at a rate of 0.3 mol at 50 ° C. for 7 days, the reaction product (12-
1) was obtained. (2) 1 mol of the urethane prepolymer (2) and 2.2 mol of the reactant (12-1) were reacted at 90 ° C. for 1 hour to form a liquid urethane resin in which all NCOs were silylated. 13) was obtained. The urethane-based resin (13) is a mixture of the above general formula (1), wherein X is the above general formula (2), and in the formula (2), Z is OR ³ . The storage stability of the resin was ○.

Example 13 (1) 1 mol of 3- (methylamino) -propylamine, 1 mol of KBM502 (trade name: γ-methacryloxypropylmethyldimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.) and methyl methacrylate At a rate of 1 mol at 50 ° C.
For 10 days to obtain a reaction product (13-1). (2) 1 mol of the urethane prepolymer (2) and 2.1 mol of the reactant (13-1) were reacted at 90 ° C. for 1 hour to form a liquid urethane-based resin in which all NCOs were silylated ( 14) was obtained. The storage stability of the resin was ○.

Example 14 (1) 3,9-bis (3-aminopropyl) -2,4
1 mol of 8,10-tetraoxaspiro [5.5] undecane, 1 mol of KBM502, 1 mol of methyl methacrylate, and 1 mol of ethyl acrylate in a ratio of 5 mol
The reaction was carried out at 0 ° C. for 10 days to obtain a reaction product (14-1). (2) 1 mol of urethane prepolymer (2) and 2.2 mol of reactant (14-1) were reacted at 90 ° C. for 1 hour to form a liquid urethane resin in which all NCOs were silylated ( 15) was obtained. The storage stability of the resin was ○.

Example 15 (1) A reaction product (15-1) was obtained by reacting 3- (dibutylamino) propylamine at 1 mol and KBM5103 at 1 mol at 23 ° C. for 5 days. (2) 1 mol of the urethane prepolymer (2) and 2.2 mol of the reactant (15-1) were reacted at 90 ° C. for 1 hour to form a liquid urethane-based resin in which all NCOs were silylated ( 16) was obtained. The storage stability of the resin was ○.

Example 16 (1) 1 mol of KBM603 and 1 mol of methyl methacrylate were reacted at 50 ° C. for 7 days, then 1 mol of 2-ethylhexyl acrylate was added, and the mixture was reacted at 50 ° C. for 7 days. The reaction product (16-1) was obtained. (2) 1 mol of the urethane prepolymer (2) and 2.2 mol of the reactant (16-1) were reacted at 90 ° C. for 1 hour to form a liquid urethane resin in which all NCOs were silylated ( 17) was obtained. In the urethane-based resin (17), in the general formula (1), X is the general formula (3) or the general formula (4), and in the formula (3) or the formula (4), Z is OR ³ . A mixture of some. The storage stability of the resin was ○.

Example 17 (1) 0.3 mol of KBM603 and 0.3 mol of KBM602.
7 mol, 1.0 mol of itaconic acid, 0.5 mol of methacrolein and 0.5 mol of acrylamide,
The reaction was carried out at 50 ° C. for 20 days to obtain a reaction product (17-1). (2) The urethane prepolymer (2) was reacted at a ratio of 1 mol and the reactant (17-1) at a ratio of 2.2 mol at 90 ° C. for 1 hour to form a liquid urethane resin in which all NCOs were silylated ( 18) was obtained. In the urethane-based resin (18), in the general formula (1), X is the general formula (3) or the general formula (4), and in the formula (3) or the formula (4), Z is OR ³ , It is a mixture of hydrogen atoms and NH ₂ . The storage stability of the resin was ○.

Example 18 (1) 1 mol of 3- (methylamino) -propylamine, 1 mol of 2-ethylhexyl acrylate, KBM
5103 was reacted at a rate of 1 mol at 50 ° C. for 7 days to obtain a reaction product (18-1). (2) 1 mol of the reaction product (18-1) and 1 mol of hexamethylene diisocyanate were reacted at 90 ° C. for 1 hour, and the obtained product was 1.8 mol and the preminol was 40 mol.
10 were reacted at a rate of 1 mol at 90 ° C. for 6 hours to obtain a liquid urethane resin (19). The storage stability of the resin was ○.

Example 19 (1) 1 mol of KBM602 and 1 mol of ethyl acrylate
1 mol of butyl acrylate was reacted at 50 ° C. for 7 days to obtain a reaction product (19-1). (2) 1 mol of the reaction product (19-1) and 1 mol of m-phenylene diisocyanate were reacted at 23 ° C. for 3 days.
R-45HT (trade name: Idemitsu Petrochemical Co., Ltd., hydroxyl-terminated liquid polybutadiene) was reacted at a rate of 1 mol at 60 ° C. for 3 hours to obtain a liquid urethane resin (20).
In the urethane-based resin (20), in the general formula (1), X is the general formula (3) or the general formula (4), and in the formula (3) or the general formula (4), Z is OR ³ . A mixture of some. The storage stability of the resin was ○.

To 100 g of the liquid urethane-based resins (9) to (18) obtained in Examples 8 to 17, 1% by weight of dibutyltin dilaurate was added, mixed with stirring, and allowed to stand at 23 ° C. A resin having good curability was obtained.
Further, the liquid urethane-based resin (2
0) 1 g of Stan BL was added to 100 g, and after mixing, 50 ° C.
After curing for 1 week, a tough rubber-like cured product was obtained.

Comparative Example 1 Urethane Prepolymer (2)
Was reacted at 90 ° C. at a ratio of 1 mol of KBM602 at 90 ° C., and an attempt was made to synthesize a polymer in which NCO was completely silylated. However, a gel was formed and no polymer was obtained.

Comparative Example 2 (1) 1 mol of KBM903 and 1 mol of butyl acrylate
The reaction was carried out at 23 ° C. for 3 days in a molar
-1) was obtained. (2) A liquid urethane resin (1 mol of urethane prepolymer (1) and a reaction product (20-1)) at a temperature of 90 ° C. at a rate of 0.2 mol to partially silylate NCO ( 21) was obtained. The storage stability of the resin was x.

(Comparative Example 3) This example is based on the method described in JP-A-52-73998. (1) To 1 gram mole of preminol 4010, 2.5 g atom of metallic sodium was added under a nitrogen atmosphere, and reacted at 60 ° C. for 5 hours to obtain a reaction product (21
-1) was obtained. (2) 1 mol of the reactant (21-1) and 2 mol of allyl chloride were reacted at 40 ° C. for 3 hours in a nitrogen atmosphere.
Reaction product (21-2) was obtained. (3) 1 mol of reaction product (21-2), 2 mol of methyldichlorosilane, 17 ml of a solution composed of 0.01 mol of chloroplatinic acid and 0.1 ml of isopropanol at 90 ° C. for 3 hours in a nitrogen atmosphere. The reaction product (21-
3) was obtained. (4) After reacting 1 mol of the reactant (21-3) cooled to -40 ° C and methanol at a ratio of 20 mol at -40 ° C for 5 hours, the reaction mixture was distilled under reduced pressure at 50 ° C to obtain a liquid reactant. (2
1-4) was obtained. The storage stability of the reaction product was ○.

(Curing speed test) Each urethane resin obtained in Examples 2 to 5 or the reaction product (21) obtained in Comparative Example 3
-4) A mixture of 100 g and 1 g of Stan BL was allowed to stand, and the time until the surface was peeled was measured, and the time was defined as the curing speed. The results are shown in Table 1.

[Table 1]

(Application Example 1) 90 g of the urethane-based resin (1), 10 g of the urethane-based resin (2) and calcium carbonate (manufactured by Nitto Powder Chemical Co., Ltd., trade name: NS23) obtained in Example 1
00) Put 100 g in a planetary mixer and
After dehydrating by heating at ~ 200 ° C, it is cooled, and KBM1003
(Product name: vinyltrimethoxysilane, manufactured by Sumitomo Bayer Urethane Co., Ltd.) 3 g, KBM903 1 g, KBM40
3 g (product name: Sumitomo Bayer Urethane Co., Ltd., γ-glucidoxypropyltrimethoxysilane), Stan BL
Was kneaded in an amount of 3 g to prepare an adhesive.

(Application Example 2) The same as Application Example 1 except that 100 g of the urethane resin (3) obtained in Example 2 was used instead of the urethane resin (1) and the urethane resin (2). To prepare an adhesive.

(Application Example 3) The same as Application Example 1 except that 100 g of the urethane resin (14) obtained in Example 13 was used instead of the urethane resin (1) and the urethane resin (2). To prepare an adhesive.

(Application Example 4) The same procedures as those of Application Example 1 were carried out except that 100 g of the reaction product (21-4) obtained in Comparative Example 3 was used instead of the urethane resin (1) and the urethane resin (2). An adhesive was prepared in the same manner.

Using the adhesives obtained in the above-mentioned application examples 1 to 4, the adherends Asada / Asada, Asada / ABS resin and Asada / Aluminum were bonded to each other and exposed under the following conditions. Tensile shear bond strength (N /
cm ² ) was measured according to JIS K 6850. Table 2 shows the results. Normal state: After bonding, cure for 7 days at 23 ° C. and 60% relative humidity, and measure at the above temperature and humidity. Water resistance: After curing in the same manner as in normal measurement, 23
The sample is immersed in water at 7 ° C. for 7 days and measured while wet. Heat resistance: After curing in the same manner as in normal measurement, 90
Exposure at 9 ° C. for 9 days, after cooling, measurement at 23 ° C. and 60% relative humidity.

[0078]

[Table 2] From Table 2, the adhesive prepared using the urethane-based resin of the present invention is superior to the adhesive using the reactant (21-4) obtained in Comparative Example 3 which is currently most frequently used. It turns out that it shows performance. From Table 2, it can be seen that the trifunctional alkoxysilyl group contributes to the improvement of the adhesive strength due to the increase of the crosslinking density, and that the urethane bond and the urea bond contribute to the improvement of the adhesiveness.

(Application Example 5) 100 g of the urethane resin (3) obtained in Example 2, 120 g of calcium carbonate (manufactured by Shiraishi Calcium Co., trade name: Shiraishihana CCR), 50 g of dioctyl phthalate, titanium oxide (manufactured by Ishihara Sangyo Co., Ltd.) , Trade name: Taipaque R820) 20 g was put into a planetary mixer, heated and dehydrated at 100 to 200 ° C., and then cooled,
3 g of KBM602, 2 g of KBM1003, and 2 g of dibutyltin dilaurate were kneaded to prepare a sealing material. The obtained sealing material was applied to aluminum / aluminum, and a tensile adhesion test was performed according to JIS A1439. Table 3 shows the results.

(Application Example 6) In the same manner as in Application Example 5, except that the urethane resin (5) obtained in Example 4 was used instead of the urethane resin (3) obtained in Example 2, Thus, a sealing material was prepared. Application example 5 of the obtained sealing material
A tensile adhesion test was performed in the same manner as in Example 1 and the results are shown in Table 3.

[0081]

[Table 3] As can be seen from Table 3, the sealing material prepared by using the urethane-based resin of the present invention exhibits excellent performance, and is obtained by increasing the length of the alkyl group of the compound (e) or the compound (f). It is clear that the sealing material can be made more elastic.

According to the present invention, bifunctional alkoxy groups,
Since trifunctional or higher polyfunctionality can be easily introduced, the amount to be introduced can be determined according to the target performance such as the curing speed. Also, from Table 1, control of reactivity, physical properties, etc. is also dependent on the length of the alkyl group of the unsaturated compound (compound (e), compound (f)) to be reacted with aminosilane (compound (c), compound (d)). It turns out that is possible. Furthermore, it has been found that the use of an alkoxysilane having a (meth) acryloxy group (compound (i)) can dramatically improve the curing rate. Example 7
As shown in (1), a prepolymer having a lower viscosity can be prepared by preparing an isocyanate silane in which a silylating agent is reacted with a diisocyanate compound in advance. This is because, unlike the step involving the urethane prepolymer, a small amount of the isocyanate silane can be reacted according to the target performance. Further, as shown in Examples 2 to 4, 7, and 9, when the terminal is dialkoxysilane, a resin having elongation can be prepared. Furthermore, as shown in Example 19, even a diol having a small molecular weight such as liquid polybutadiene alone can obtain a liquid urethane-based resin without gelation, so that the application range of the present invention can be said to be extremely wide. In Comparative Example 1,
It becomes a gel immediately after aminosilane introduction, and there is a problem in handling. Further, as shown in Comparative Example 2, it was found that it was difficult to prepare a prepolymer having excellent storage stability even if a part of the prepolymer having a small isocyanate group content was replaced with the silylating agent used in the present invention. Was. According to the present invention, as described above, it is possible to freely design a soft or hard material, a material having a fast or slow curing speed, a material having a strong or weak adhesive property, or the like according to the intended performance.

[0083]

The urethane resin of the present invention and the urethane resin obtained by the above production methods (3) and (4) of the present invention have an alkoxysilyl group as a hydrolyzable silicone-reactive group at the molecular terminal. The presence of a polar group derived from the compound (e) or the compound (f) in the vicinity thereof and the presence of a urea bond and a urethane bond in the main chain and the silicone functional portion are factors determining various effects. Therefore, the following effects are exhibited. (1) a highly polar carboxylic acid ester effective for adhesion;
Since it has an aldehyde, ketone, urea bond and a urethane bond, it exhibits a wide range of adhesion to metals, glass, wood, and the like, and particularly exhibits good adhesion to plastics, which are difficult-to-bond materials. (2) In the urethane-based resin of the present invention, even when the alkoxysilyl group is the most reactive trimethoxysilyl group, the storage stability is excellent, so that quick curability can be imparted. (3) Since the polar group exists near the alkoxysilyl group, the reactivity can be controlled by selecting the length of the molecule. (4) If the technical means of (2) and (3) are used together,
The curing speed can be freely adjusted. (5) A multifunctional resin can be easily obtained by using a (meth) acryloyl group-containing compound having an alkoxysilyl group.

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[Procedure amendment]

[Submission date] December 16, 1999 (1999.12.
16)

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] Claims

[Correction method] Change

[Correction contents]

[Claims]

Embedded image A urethane-based resin represented by However, A is a residual group corresponding to the skeleton of the urethane polymer, the nitrogen atom bonded to A in the general formula (1) is an atom derived from an isocyanate group at the end of the urethane polymer, n is 1 to 20, and X is The groups represented by the following general formulas (2), (3) and (4) are respectively shown.

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Embedded image However, R is an alkyl group having 1 to 6 carbon atoms, R ¹ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R ² is a 1 to 6 carbon atom.
An alkylene group or an arylene group which may have 10 side chains, m is 1 to 3, Z is a hydrogen atom, OR ³ , R ³ or N
H ₂ and R ³ is a hydrogen atom, an organic group having a molecular weight of 500 or less, or a group represented by the following general formula (5);

Embedded image (R ⁷ is an alkylene group having 1 to 10 carbon atoms which may have a side chain, R ⁸ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R ⁹ is an alkyl group having 1 to 6 carbon atoms. , X represents 1 to 3.) R ⁴ is an alkylene group or an arylene group which may have a side chain having 1 to 10 carbon atoms, R ⁵ is a hydrogen atom or a formula —COO.
R ^{10 represents} a group represented by R ¹⁰ (R ¹⁰ represents an alkyl group having 1 to 20 carbon atoms), and R ⁶ represents a hydrogen atom, —CH ₂ COOH or a methyl group.

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Embedded image (Where B is a residue corresponding to the skeleton of the polyol compound, Y is an oxygen atom or a sulfur atom,
R ¹¹ represents an organic group having a molecular weight of 500 or less, j represents 1 to 10, and l represents 1 to 10, respectively. ) And the following general formula (11):
A compound represented by the general formula (12) or (13) (where D represents a residue corresponding to the skeleton of the diisocyanate compound, and Z, m, R, R ¹ , R ² , R ³ , R ⁴ , R ⁵
And R ⁶ are as defined in claim 1. 2. The method for producing a urethane-based resin according to claim 1, wherein

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 ──────────────────────────────────────────────────続 き Continued on front page F-term (reference) 4J034 CA13 CA15 CA17 CB01 CB03 CB07 CC02 CC12 CC23 CC33 CC34 CC35 CC37 CC44 CC45 CC52 CC55 CC61 CC62 CC67 CD01 CD03 CD04 CD05 CD06 CD12 CD15 CE01 CE03 DA01 DA03 DA07 DB03 DB07 DD01 DD07 DD11 DF11 DF12 DF20 DF21 DF29 DG03 DG04 DG05 DG10 DG12 DG14 DG18 DG23 DG32 DP02 DP03 DP12 DP18 DP19 DR01 GA55 HA01 HA07 HA18 HB02 HB03 HC03 HC12 HC13 HC17 HC18 HC22 HC45 HC46 HC52 HC61 HC64 KC HC KC KK42K KD04 KD12 KD15 KE02 QA05 QB11 RA07 RA08

Claims (8)

[Claims] [Claim 1] The following general formula (1) A urethane-based resin represented by Here, A represents a residual group corresponding to the skeleton of the urethane polymer, n represents 1 to 20, and X represents a group represented by the following general formula (2), (3) or (4). Embedded image Embedded image Embedded image However, R is an alkyl group having 1 to 6 carbon atoms, R ¹ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R ² is a 1 to 6 carbon atom.
An alkylene group or an arylene group which may have 10 side chains, m is 1 to 3, Z is a hydrogen atom, OR ³ , R ³ or N
H ₂ , and R ³ is a hydrogen atom, an organic group having a molecular weight of 500 or less, or a group represented by the following general formula (5); (R ⁷ is an alkylene group having 1 to 10 carbon atoms which may have a side chain, R ⁸ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R ⁹ is an alkyl group having 1 to 6 carbon atoms. , X represents 1 to 3.) R ⁴ is an alkylene group or an arylene group which may have a side chain having 1 to 10 carbon atoms, R ⁵ is a hydrogen atom or a formula —COO.
R ^{10 represents} a group represented by R ¹⁰ (R ¹⁰ represents an alkyl group having 1 to 20 carbon atoms), and R ⁶ represents a hydrogen atom, —CH ₂ COOH or a methyl group. 2. A urethane prepolymer obtained by reacting a polyol compound and a diisocyanate compound with a compound represented by the following general formula (6), general formula (7) or general formula (8) (provided that Z, m, R, R ¹ , R ² , R ³ , R
⁴ , R ⁵ and R ⁶ are as defined above. 2. The method for producing a urethane-based resin according to claim 1, wherein Embedded image Embedded image Embedded image 3. General formula (9) or general formula (10) Embedded image (Where B is a residue corresponding to the skeleton of the polyol compound, Y is an oxygen atom or a sulfur atom,
R ¹¹ represents an organic group having a molecular weight of 500 or less, j represents 1 to 10, and l represents 1 to 10, respectively. ) And the following general formula (11):
A compound represented by the general formula (12) or (13) (where D represents a residue corresponding to the skeleton of the diisocyanate compound, and Z, m, R, R ¹ , R ² , R ³ , R ⁴ , R ⁵
And R ⁶ are as defined above. 2. The method for producing a urethane-based resin according to claim 1, wherein Embedded image Embedded image Embedded image 4. The compound represented by the above general formula (6)
An aminosilane compound represented by the following general formula (14) (where R, R ¹ and R ² are as defined above) and an α, β-unsaturated carbonyl compound represented by the following general formula (15) (provided that , Z and R ⁶ have the same meanings as defined above), and are compounds obtained by reacting the same with each other. Embedded image Embedded image 5. The compound represented by the general formula (7) or (8) is an aminosilane compound represented by the following general formula (16) (provided that R, R ¹ , R ² and R ⁴ are the same as those described above). Α, β represented by the above general formula (15)
-A compound obtained by reacting an unsaturated carbonyl compound or a maleic acid diester represented by the following general formula (17) (wherein R ³ and R ¹⁰ are as defined above). A method for producing the urethane resin according to claim 2. Embedded image Embedded image 6. The compound represented by the general formula (11), (12) or (13) is represented by the general formula (6), (7) or (8) The method for producing a urethane-based resin according to claim 3, wherein the compound and the remaining group corresponding to the skeleton are compounds obtained by reacting the diisocyanate compound (D). 7. A urethane prepolymer obtained by reacting a polyol compound and a diisocyanate compound, an amine compound having a primary amino group and / or a secondary amino group in the molecule, and a compound represented by the following general formula (18): An alkoxysilane compound represented by the formula (provided that R and R ¹ are as defined above; R ¹² is a hydrogen atom or a methyl group; R ¹³ is an alkylene group having 1 to 10 carbon atoms which may have a side chain; Or the amine compound,
A secondary amino compound is obtained in the molecule obtained by reacting the alkoxysilane compound with the α, β-unsaturated carbonyl compound represented by the general formula (15) or the maleic acid diester represented by the general formula (17). A method for producing a urethane-based resin, comprising reacting a compound having a group (compound X). Embedded image 8. A method comprising reacting a polyol compound represented by the general formula (9) or (10) with a compound (compound Y) obtained by reacting the compound X with a diisocyanate compound. A method for producing a urethane resin.