JP2009235194A - Alkoxysilane modified polyamide resin, its manufacturing method, hot melt adhesive, and resin cured article - Google Patents

Abstract

【選択図】なしThe present invention provides an alkoxysilane-modified polyamide resin excellent in heat resistance and mechanical strength, a method for producing the same, a hot melt adhesive, and a cured resin.
A terminal isocyanate obtained by reacting a polyester polycarboxylic acid obtained by a reaction between a polybasic acid and a polyhydric alcohol and a polyisocyanate compound in an excess ratio with respect to the carboxyl group. The cured resin obtained by curing the alkoxysilane-modified polyamide resin obtained by reacting the group-containing polyamide resin with the alkoxysilane compound represented by the general formula (1) is excellent in heat resistance and mechanical strength. .

[Selection figure] None

Description

  The present invention relates to an alkoxysilane-modified polyamide resin, a method for producing the same, a hot melt adhesive, and a cured resin.

  Conventionally, lactam is subjected to ring-opening polymerization by heating in the presence of a dicarboxylic acid to obtain a terminal carboxyl group polyamide, and the terminal isocyanate group polyamide obtained by reacting this with a diisocyanate compound is modified with an ω-aminoalkylalkoxysilane compound. It is known that the terminal alkoxysilyl polyamide thus used is used as a hot melt adhesive (for example, see Patent Document 1).

Further, a polyester diol obtained by reacting 1,6-hexanediol and sebacic acid is reacted with diphenylmethane diisocyanate to obtain a urethane prepolymer having an isocyanate group, and γ- (N-phenylamino) propyl It has been proposed to use a urethane prepolymer having an alkoxysilyl group obtained by reacting with trimethoxysilane as a reactive hot melt adhesive (for example, see Patent Document 2).
JP 59-172574 A JP 07-278320 A

However, with the hot melt adhesives described in Patent Document 1 and Patent Document 2, sufficient heat resistance and mechanical strength cannot be obtained, and further improvements in physical properties are desired.
An object of the present invention is to provide an alkoxysilane-modified polyamide resin excellent in heat resistance and mechanical strength, a method for producing the same, a hot melt adhesive, and a cured resin.

  In order to achieve the above object, the alkoxysilane-modified polyamide resin of the present invention comprises a polyester polycarboxylic acid and a polyisocyanate compound obtained by a reaction of a polybasic acid and a polyhydric alcohol, wherein the isocyanate group has a carboxyl group. It is characterized by being obtained by reacting a terminal isocyanate group-containing polyamide resin obtained by reacting in an excess ratio with an alkoxysilane compound represented by the following general formula (1).

(In the formula, R 1 represents an alkylene group having 1 to 20 carbon atoms, and R 2, R 3 and R 4 are the same as or different from each other, and represent an alkoxy group having 2 to 20 carbon atoms or an alkyl group having 1 to 20 carbon atoms. (However, at least one of R2, R3 and R4 represents an alkoxy group.)
In addition, the hot melt adhesive of the present invention reacts polyester polycarboxylic acid and polyisocyanate compound obtained by the reaction of polybasic acids and polyhydric alcohols at a ratio in which isocyanate groups are excessive with respect to carboxyl groups. It is characterized by containing an alkoxysilane-modified polyamide resin obtained by reacting a terminal isocyanate group-containing polyamide resin obtained by reacting with an alkoxysilane compound represented by the following general formula (1).

(In the formula, R 1 represents an alkylene group having 1 to 20 carbon atoms, and R 2, R 3 and R 4 are the same as or different from each other, and represent an alkoxy group having 2 to 20 carbon atoms or an alkyl group having 1 to 20 carbon atoms. (However, at least one of R2, R3 and R4 represents an alkoxy group.)
Further, the hot melt adhesive of the present invention is preferably a one-component moisture curable adhesive.

  Moreover, the resin cured product of the present invention reacts a polyester polycarboxylic acid obtained by the reaction of a polybasic acid and a polyhydric alcohol with a polyisocyanate compound at a ratio in which the isocyanate group is excessive with respect to the carboxyl group. It is characterized by being obtained by curing the resulting alkoxysilane-modified polyamide resin by reacting the obtained terminal isocyanate group-containing polyamide resin with an alkoxysilane compound represented by the following general formula (1). .

(In the formula, R 1 represents an alkylene group having 1 to 20 carbon atoms, and R 2, R 3 and R 4 are the same as or different from each other, and represent an alkoxy group having 2 to 20 carbon atoms or an alkyl group having 1 to 20 carbon atoms. (However, at least one of R2, R3 and R4 represents an alkoxy group.)
Further, in the method for producing an alkoxysilane-modified polyamide resin of the present invention, an isocyanate group is excessive with respect to a carboxyl group in a polyester polycarboxylic acid and a polyisocyanate compound obtained by a reaction between a polybasic acid and a polyhydric alcohol. The reaction is carried out in the presence of 0.001 to 10 mole parts of a catalyst selected from alkali metal salts and / or alkaline earth metal salts with respect to 100 mole parts of all carboxyl groups of the polyester polycarboxylic acid. Thus, a terminal isocyanate group-containing polyamide resin is obtained, and the terminal isocyanate group-containing polyamide resin is reacted with an alkoxysilane compound represented by the following general formula (1).

(In the formula, R 1 represents an alkylene group having 1 to 20 carbon atoms, and R 2, R 3 and R 4 are the same as or different from each other, and represent an alkoxy group having 2 to 20 carbon atoms or an alkyl group having 1 to 20 carbon atoms. (However, at least one of R2, R3 and R4 represents an alkoxy group.)
Moreover, in the manufacturing method of the alkoxysilane modified polyamide resin of this invention, it is suitable to make the said polyester polycarboxylic acid and the said polyisocyanate compound react at 120 degrees C or less.

In the method for producing an alkoxysilane-modified polyamide resin of the present invention, it is preferable that the terminal isocyanate group-containing polyamide resin and the alkoxysilane compound are reacted at 150 ° C. or lower.
In the method for producing an alkoxysilane-modified polyamide resin of the present invention, it is preferable that the catalyst is magnesium stearate.

The alkoxysilane-modified polyamide resin of the present invention can obtain the cured resin of the present invention having excellent heat resistance and mechanical strength, and can therefore be suitably used for the hot melt adhesive of the present invention.
Moreover, in the manufacturing method of the alkoxysilane modified polyamide resin of this invention, the resin cured material of this invention which is excellent in heat resistance and mechanical strength can be obtained easily.

The alkoxysilane-modified polyamide resin of the present invention can be obtained by reacting a terminal isocyanate group-containing polyamide resin obtained by reacting a polyester polycarboxylic acid and a polyisocyanate compound with an alkoxysilane compound.
In the present invention, the polyester polycarboxylic acid can be obtained by reacting a polybasic acid with a polyhydric alcohol.

  Examples of polybasic acids include oxalic acid, malonic acid, succinic acid, methyl succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, and other aliphatic dicarboxylic acids (having 11 to 13 carbon atoms). ), Hydrogenated dimer acid, maleic acid, fumaric acid, itaconic acid, orthophthalic acid, isophthalic acid, terephthalic acid, toluene dicarboxylic acid, dimer acid, and dicarboxylic acid such as het acid, and alkyl esters of these dicarboxylic acids. .

Polybasic acids include acid anhydrides derived from the carboxylic acids exemplified above, such as oxalic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, and 2-alkyl anhydride (12 to 18 carbon atoms). Succinic acid, tetrahydrophthalic anhydride, trimellitic anhydride, etc. are included.
Furthermore, polybasic acids include acid halides derived from the carboxylic acids exemplified above, such as oxalic acid dichloride, adipic acid dichloride, and sebacic acid dichloride.

These polybasic acids can be used alone or in combination of two or more. Preferably, dicarboxylic acid and its alkyl ester are mentioned.
Examples of the polyhydric alcohol include a diol having two hydroxyl groups and a polyol having three or more hydroxyl groups.
Examples of the diol include ethylene glycol, propylene glycol, trimethylene glycol, 1,4-butylene glycol, 1,3-butylene glycol, 1,2-butylene glycol, 1,5-pentanediol, and 3-methyl-1,5. -Pentanediol, 2,2-dimethyl-1,3-propanediol, neopentyl glycol, 1,6-hexanediol, 2,5-hexanediol, 2,2-diethyl-1,3-propanediol, 3, C2-22 alkanediols such as 3-dimethylolheptane, 2-ethyl-2-butyl-1,3-propanediol, 1,12-dodecanediol, 1,18-octadecanediol, such as 2-butene-1, 4-diol, 2,6-dimethyl-1-octene-3,8-diol, etc. Aliphatic diols such as Rukenjioru the like.

Examples of the diol include alicyclic diols such as 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, hydrogenated bisphenol A, or a C2-4 alkylene oxide adduct thereof.
Examples of the diol include aromatic diols such as resorcin, xylylene glycol, bishydroxyethoxybenzene, bishydroxyethylene terephthalate, bisphenol A, bisphenol S, bisphenol F, and C2-4 alkylene oxide adducts of these bisphenols. It is done.

Furthermore, examples of the diol include polyether diols such as diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polyethylene polypropylene block glycol, and polytetramethylene ether glycol.
Examples of polyols having three or more hydroxyl groups include glycerin, 2-methyl-2-hydroxymethyl-1,3-propanediol, 2,4-dihydroxy-3-hydroxymethylpentane, and 1,2,6-hexanetriol. , Trimethylolethane, trimethylolpropane, 2-methyl-2-hydroxymethyl-1,3-propanediol, 2,4-dihydroxy-3- (hydroxymethyl) pentane, 2,2-bis (hydroxymethyl) -3 -Triols such as butanol and other aliphatic triols (8 to 24 carbon atoms), for example, hydroxyl groups such as tetramethylolmethane, pentaerythritol, dipentaerythritol, D-sorbitol, xylitol, D-mannitol, D-mannitol Have 4 or more Estriol and the like.

These polyhydric alcohols can be used alone or in combination of two or more. Preferably, diol is mentioned.
The polyester polycarboxylic acid is a polybasic acid and a polyhydric alcohol, and the acid group (carboxyl group, carboxylic acid ester, acid anhydride group, acid halide) of the polybasic acid is more than the hydroxyl group of the polyhydric alcohol. (Specifically, COOH / OH exceeds 1.0, preferably 1.01 to 2.10) and is obtained by esterification reaction. Can do.

  The esterification reaction is, for example, a condensation reaction or a transesterification reaction, and may be a known condition. For example, an atmospheric pressure and an inert gas atmosphere, a reaction temperature of 100 to 250 ° C., and a reaction time of 1 to 50 If necessary, a catalyst (an organic tin catalyst, an organic titanium catalyst, an amine catalyst, an alkali metal salt or an alkaline earth metal salt described later), a solvent, or the like can be used.

  The polyester polycarboxylic acid thus obtained has a number average molecular weight of, for example, 200 to 20000, and preferably 500 to 10,000. The number average molecular weight can be measured by gel permeation chromatography (GPC). In GPC measurement, the number average molecular weight of a peak including the molecular weight (retention time) of the maximum frequency of the measured chromatogram is calculated with reference to a calibration curve created using standard polyethylene glycol. Thereby, the number average molecular weight is calculated as a converted value of standard polyethylene glycol.

The polyester polycarboxylic acid has an acid value of, for example, 5 to 600 mgKOH / g, preferably 10 to 250 mgKOH / g, and a hydroxyl value of, for example, 5 mgKOH / g or less, preferably 3 mgKOH / g or less.
Moreover, in polyester polycarboxylic acid, the viscosity (melt viscosity) in 100 degreeC measured with the cone plate viscometer becomes like this. Preferably it is 30000 mPa * s or less.

In the present invention, examples of the polyisocyanate compound include aliphatic polyisocyanate, alicyclic polyisocyanate, araliphatic polyisocyanate, and aromatic polyisocyanate.
Examples of the aliphatic polyisocyanate include hexamethylene diisocyanate (HDI), trimethylene diisocyanate, tetramethylene diisocyanate (TMDI), pentamethylene diisocyanate, 1,2-propylene diisocyanate, 1,2-, 2,3- or 1, Aliphatic diisocyanates such as 3-butylene diisocyanate, 2,4,4- or 2,2,4-trimethylhexamethylene diisocyanate, 2,6-diisocyanatomethylcaproate.

Examples of the alicyclic polyisocyanate include 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate, IPDI), 4,4'-, 2,4'- or 2,2'-dicyclohexyl. Methane diisocyanate or a mixture thereof (H ₁₂ MDI), 1,3- or 1,4-bis (isocyanatomethyl) cyclohexane or a mixture thereof (hydrogenated xylylene diisocyanate, H ₆ XDI), 2,5- or 2,6 -Bis (isocyanatomethyl) norbornane or a mixture thereof (NBDI), 1,3-cyclopentane diisocyanate, 1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate, methyl-2,4-cyclohexane diisocyanate, methyl-2 , 6-cyclohexane diisocyanate and the like.

Examples of the araliphatic polyisocyanate include 1,3- or 1,4-xylylene diisocyanate or a mixture thereof (XDI), 1,3- or 1,4-tetramethylxylylene diisocyanate or a mixture thereof (TMXDI), Examples thereof include araliphatic diisocyanates such as ω, ω′-diisocyanato-1,4-diethylbenzene.
Aromatic polyisocyanates include, for example, 4,4'-, 2,4'- or 2,2'-diphenylmethane diisocyanate or mixtures thereof (MDI), 2,4- or 2,6-tolylene diisocyanate or mixtures thereof (TDI), 3,3'-dimethoxybiphenyl-4,4'-diisocyanate, 1,5-naphthalene diisocyanate (NDI), m- or p-phenylene diisocyanate or mixtures thereof, 4,4'-diphenyl diisocyanate, 4, Aromatic diisocyanates such as 4'-diphenyl ether diisocyanate can be mentioned.

  In addition, the polyisocyanate compound includes a polyisocyanate of the above-described polyisocyanate (for example, a dimer, a trimer, etc.), and a biuret-modified product produced by, for example, reacting the above-described polyisocyanate or multimer with water. Allophanate-modified products produced by reaction with alcohol or the above-mentioned polyhydric alcohol, oxadiazine trione-modified products produced by reaction with carbon dioxide, or polyol-modified products produced by reaction with the above-mentioned polyhydric alcohol, etc. Is included. Furthermore, polyisocyanate compounds include sulfur-containing polyisocyanates such as phenyl diisothiocyanate.

These polyisocyanate compounds can be used alone or in combination of two or more. From the viewpoint of easy control of the side reaction, an aliphatic polyisocyanate, an alicyclic polyisocyanate, and an araliphatic polyisocyanate are preferable, and H ₆ XDI is more preferable.
The terminal isocyanate group-containing polyamide resin is obtained by mixing the polyester polycarboxylic acid and the polyisocyanate compound obtained as described above with a ratio of the isocyanate group of the polyisocyanate compound with respect to the carboxyl group of the polyester polycarboxylic acid (NCO / COOH). Can be obtained by blending at a ratio exceeding 1.0, preferably 1.05 to 2.50, and amidating them.

  When the equivalent ratio of NCO / COOH is in the above range, production can be stabilized. On the other hand, when the equivalent ratio of NCO / COOH is 1.00 or less, the isocyanate group content of the terminal isocyanate group-containing polyamide resin is lowered, and it may take a long time for moisture curing or may not be completely cured. . On the other hand, if the equivalent ratio of NCO / COOH is too high, the remaining amount of free polyisocyanate compound increases, and the polyisocyanate compound volatilizes during heating and melting, which may lower the working environment.

In the amidation reaction, although not particularly limited, for example, in the presence of a catalyst, the reaction temperature is 120 ° C. or less, preferably 40 to 120 ° C., more preferably 40 to 100 ° C., and the reaction time is 0.5 to 50 hours. The reaction is preferably carried out for 1 to 15 hours.
Examples of the catalyst include alkali metal salts and alkaline earth metal salts.
Examples of the alkali metal salt include lithium fluoride, lithium chloride, lithium hydroxide, sodium fluoride, sodium chloride, sodium hydroxide, potassium fluoride, potassium chloride, and potassium hydroxide.

Examples of the alkaline earth metal salt include calcium stearate, calcium perchlorate, calcium chloride, calcium hydroxide, magnesium stearate, magnesium perchlorate, magnesium chloride, magnesium hydroxide and the like.
The catalysts can be used alone or in combination of two or more. Preferably, from the viewpoint of amide selectivity in the amidation reaction, calcium stearate, calcium perchlorate, magnesium stearate, and magnesium perchlorate are preferable, and magnesium stearate is more preferable.

  Moreover, a catalyst is added in the ratio of 0.001-10 mol part with respect to 100 mol part of all the carboxyl groups of polyester polycarboxylic acid, for example, Preferably, it is 0.005-2 mol part. If the addition ratio of the catalyst is less than this, the amidation reaction does not proceed sufficiently and the productivity may be lowered. On the other hand, at more than this, the amide selectivity of the amidation reaction does not change, which may be economically disadvantageous.

  Further, when the reaction temperature is in the above range, production can be stabilized. On the other hand, when the reaction temperature exceeds 120 ° C., side reactions of isocyanate groups are promoted, and the isocyanate group content may be lower than the theoretical value, resulting in an increase in the viscosity of the resulting resin. Therefore, workability at the time of heat-melting may be reduced, and a desired resin cured product may not be obtained. On the other hand, when the reaction temperature is too low, the reaction between the carboxyl group of the polyester polycarboxylic acid and the isocyanate group of the isocyanate compound does not proceed sufficiently, and the productivity may decrease.

The amidation reaction can be preferably carried out under normal pressure, but it can also be carried out under reduced pressure while removing carbon dioxide generated during the reaction. Further, the amidation reaction can be carried out under pressure using carbon dioxide generated during the reaction. You can also
In the amidation reaction, the isocyanate group is decomposed when it reacts with water (such as moisture in the air). Therefore, this reaction is preferably carried out in an inert gas atmosphere in order to avoid contact with moisture in the air. As an inert gas, nitrogen gas, helium gas, etc. are mentioned, for example, Preferably nitrogen gas is mentioned.

In the amidation reaction, a solvent can be used if necessary.
In the amidation reaction, specifically, the polyester polycarboxylic acid, the isocyanate compound and the catalyst may be mixed at once, or the polyester polycarboxylic acid and the isocyanate compound are mixed in advance, and the mixture and the catalyst are mixed. Can also be mixed.
Further, the polyester polycarboxylic acid and the catalyst may be mixed in advance, and the mixture and the isocyanate compound may be mixed. Alternatively, the isocyanate compound and the catalyst may be mixed in advance, and the mixture and the polyester polycarboxylic acid may be mixed.

  In addition, when using a hydroxide such as lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, or magnesium hydroxide as a catalyst, when polyester polycarboxylic acid and hydroxide are mixed, Reacts to produce water. Therefore, in this case, after mixing, after removing moisture by dehydration, it is necessary to mix the mixture and the isocyanate compound. Thereby, decomposition | disassembly of the isocyanate group by the produced | generated water can be suppressed.

  In addition, said reaction can also be implemented in steps. For example, as a first step, a polyester polycarboxylic acid and a polyisocyanate compound are reacted at an NCO / COOH equivalent ratio of less than 1.0 to synthesize a terminal carboxyl group-containing polyamide resin. Next, as the second stage, the terminal carboxyl group-containing polyamide resin and the first stage polyisocyanate compound and a different polyisocyanate compound are reacted so that the equivalent ratio of NCO / COOH finally exceeds 1.0. Thus, a terminal isocyanate group-containing polyamide resin is obtained. By synthesizing the terminal isocyanate group-containing polyamide resin in this way, it is possible to obtain a resin in which the structural unit derived from the polyisocyanate compound is different between the molecular terminal and the molecule. In the two-stage reaction, the catalyst may be added to the first stage, may be added to the second stage, or may be added to both the first stage and the second stage.

In the amidation reaction, additives such as an antifoaming agent can be used as necessary.
The terminal isocyanate group-containing polyamide resin thus obtained has a number average molecular weight of, for example, 250 to 40,000, preferably 500 to 10,000. Further, the isocyanate group content is 90 to 110%, preferably 95 to 105% of the calculated value (theoretical value) from the blending ratio. When the isocyanate group content is in the above range, it can be completely moisture-cured in a relatively short period of time. The amidation rate is usually 76 to 100%, preferably 86 to 100%. When the amidation rate is in the above range, a cured resin product having excellent heat resistance, adhesiveness, and mechanical strength can be obtained.

And the alkoxysilane modified polyamide resin of this invention can be obtained by making the terminal isocyanate group containing polyamide resin obtained by the above and an alkoxysilane compound react.
The alkoxysilane compound is a primary amino group-containing alkoxysilane compound represented by the following general formula (1).

(In the formula, R 1 represents an alkylene group having 1 to 20 carbon atoms, and R 2, R 3 and R 4 are the same as or different from each other, and represent an alkoxy group having 2 to 20 carbon atoms or an alkyl group having 1 to 20 carbon atoms. (However, at least one of R2, R3 and R4 represents an alkoxy group.)
In the general formula (1), examples of the alkylene group having 1 to 20 carbon atoms represented by R1 include methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, dodecylene, tetradecylene, hexadecylene, Examples include octadecylene and eicosanylene. Preferably, a C1-C10 alkylene group, More preferably, a C1-C4 alkylene group is mentioned.

  Examples of the alkoxy group having 2 to 20 carbon atoms represented by R2, R3 and R4 include ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy, pentyloxy, isopentyloxy, neopentyloxy Hexyloxy, heptyloxy, octyloxy, nonyloxy, decyloxy, dodecyloxy, tetradecyloxy, hexadecyloxy, octadecyloxy, eicosanyloxy and the like. Preferably, a C2-C10 alkoxy group, More preferably, a C2-C4 alkoxy group is mentioned.

When the number of carbon atoms of the alkoxy group represented by R2, R3 and R4 is less than 2, gelation occurs in the reaction of the terminal isocyanate group-containing polyamide resin and the alkoxysilane compound in the production of the alkoxysilane-modified polyamide resin. There is.
Examples of the alkyl group having 1 to 20 carbon atoms represented by R2, R3 and R4 include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, sec-pentyl and hexyl. , Heptyl, n-octyl, isooctyl, 2-ethylhexyl, nonyl, decyl, isodecyl, dodecyl, tetradecyl, hexadecyl, octadecyl, eicosanyl and the like. Preferably, a C2-C10 alkyl group, More preferably, a C2-C4 alkyl group is mentioned.

  In the general formula (1), when one of R2, R3 and R4 is an alkoxy group and two are alkyl groups, the alkoxysilane compound of the general formula (1) is an aminoalkyl-dialkylmono When alkoxysilane is shown, two are alkoxy groups, and one is an alkyl group, the alkoxysilane compound of general formula (1) represents aminoalkyl-monoalkyl dialkoxysilane, and three are alkoxy groups In the case, the alkoxysilane compound of the general formula (1) represents aminoalkyl-trialkoxysilane.

  Specifically, as an alkoxysilane compound, aminoalkyl-dialkylmonoalkoxysilane includes, for example, aminomethyldimethylethoxysilane, aminomethyldiethylethoxysilane, β-aminoethyldimethylethoxysilane, β-aminoethyldiethylethoxysilane, γ -Aminopropyldimethylethoxylane, γ-aminopropyldiethylethoxylane, etc., and aminoalkyl-monoalkyl dialkoxysilanes include, for example, aminomethylmethyldiethoxysilane, aminomethylethyldiethoxysilane, β-aminoethylmethyl Diethoxysilane, β-aminoethylethyldiethoxysilane, γ-aminopropylmethyldiethoxysilane, γ-aminopropylethyldiethoxysilane, δ-aminobutylmethyldiet Shishiran and δ- aminobutyl ethyl diethoxy silane.

  Moreover, as an alkoxysilane compound, aminoalkyl-trialkoxysilane includes, for example, aminomethyltriethoxysilane, aminomethyltripropoxysilane, aminomethyltributoxysilane, β-aminoethyltriethoxysilane, β-aminoethyltripropoxysilane. , Β-aminoethyltributoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltripropoxysilane, γ-aminopropyltributoxysilane, δ-aminobutyltriethoxysilane, δ-aminobutyltripropoxysilane, δ -Aminobutyl tributoxysilane etc. are mentioned.

Of these alkoxysilane compounds, aminoalkyl-trialkoxysilane is preferable, and γ-aminopropyltriethoxysilane is more preferable.
These alkoxysilane compounds can be used alone or in combination of two or more.
The alkoxysilane-modified polyamide resin comprises a terminal isocyanate group-containing polyamide resin and an alkoxysilane compound at a ratio (NCO) in which the isocyanate group of the terminal isocyanate group-containing polyamide resin is substantially equivalent to the amino group of the alkoxysilane compound. / NH ₂ equivalent ratio is, for example, a ratio of 0.6 to 1.4, preferably 0.9 to 1.1), and obtained by urea reaction. Can do.

Although it does not restrict | limit especially in a urea-ized reaction, For example, reaction temperature 150 degrees C or less, Preferably it is 40-140 degreeC, More preferably, it is 40-120 degreeC, Reaction time 0.5-50 hours, Preferably, 1- Let react for 15 hours.
When the reaction temperature is in the above range, production can be stabilized. On the other hand, when the reaction temperature exceeds 150 ° C., a part of the alkoxysilyl group of the alkoxysilane compound undergoes a hydrolysis reaction to generate a silanol group, and further a condensation reaction with a silanol group or alkoxysilyl group of another molecule. Siloxane bonds are formed, the reaction mass is thickened, and productivity may be reduced. On the other hand, if the reaction temperature is too low, the reaction between the isocyanate group of the terminal isocyanate group-containing polyamide resin and the amino group of the alkoxysilane compound does not proceed sufficiently, and productivity may decrease.

In the urea reaction, isocyanate groups and aminoalkoxysilyl groups are decomposed when they react with water (such as moisture in the air). Therefore, this reaction is preferably carried out in an inert gas atmosphere in order to avoid contact with moisture in the air. As an inert gas, nitrogen gas, helium gas, etc. are mentioned, for example, Preferably nitrogen gas is mentioned.
In addition, in this reaction, specifically, the terminal isocyanate group-containing polyamide resin and the alkoxysilane compound may be mixed at once, or the terminal isocyanate group-containing polyamide resin is previously charged and the alkoxysilane compound is mixed therewith. In addition, an alkoxysilane compound may be charged in advance and a terminal isocyanate group-containing polyamide resin may be mixed therewith.

The alkoxysilane-modified polyamide resin thus obtained has a number average molecular weight of, for example, 500 to 40,000, preferably 500 to 10,000.
The alkoxysilane-modified polyamide resin is moisture-cured by hydrolysis of the alkoxysilyl group. Therefore, the alkoxysilane-modified polyamide resin can be used in various fields as a one-part moisture curable resin composition. In particular, it is useful as an adhesive component of a one-component moisture-curing hot melt adhesive.

When the alkoxysilane-modified polyamide resin is used as the adhesive component of the one-component moisture-curable hot melt adhesive, the mixing ratio of the alkoxysilane-modified polyamide resin is, for example, 1 part by weight with respect to 100 parts by weight of the hot-melt adhesive. Above, preferably 10 parts by weight or more.
A cured resin obtained by moisture-curing an alkoxysilane-modified polyamide resin (adhesive component of a hot melt adhesive) is excellent in heat resistance, adhesiveness, and mechanical strength. Moisture curing can usually be carried out at a high temperature, preferably with the addition of a curing catalyst.

Examples of the curing catalyst include organic tin, metal complex, base, and organic phosphoric acid.
Examples of the organic tin include dibutyltin dilaurate, dioctyltin dimaleate, dibutyltin phthalate, stannous octylate, dibutyltin methoxide, dibutyltin diacetylacetate, and dibutyltin diacetate.
Examples of the metal complex include titanate compounds such as tetrabutyl titanate, tetraisopropyl titanate, and triethanolamine titanate, for example, carboxylic acid metal salts such as lead octylate, lead naphthenate, nickel naphthenate, cobalt naphthenate, such as aluminum Examples thereof include metal acetylacetonate complexes such as acetylacetonate complexes and vanadium acetylacetonate complexes.

  Bases include methylamine, ethylamine, propylamine, isopropylamine, isopropyl alcoholamine, butylamine, 1-ethylbutylamine, isobutylamine, pentylamine, octylamine, laurylamine, monoethanolamine, diethylaminopropylamine, oleylamine, cyclohexylamine , Primary amines such as guanidine, 2-ethylhexylamine, triethylenetetramine, aniline, phenylenediamine, toluidine, toluylamine, benzylamine, xylenediamine, naphthylamine, such as dimethylamine, diethylamine, diethanolamine, diethylenetriamine, dibutylamine, N-methyl-butylamine, piperidine, diisopentylamine, N-ethylnaphthyl Secondary amines such as amine, benzylaniline, diphenylguanidine such as trimethylamine, triethylamine, triethanolamine, tripropylamine, tributylamine, N, N-dimethyl-butylamine, N, N-dimethyl-octylamine, N, Tertiary amines such as N-dimethyl-laurylamine, 1,4-diazabicyclo [2.2.2] octane (DABCO), 1,8-diazabicyclo [5.4.0] undec-7-ene (DBU) Examples thereof include quaternary ammonium salts such as tetramethylammonium chloride and benzalkonium chloride.

Examples of the organic phosphoric acid include monomethyl phosphoric acid, di-n-butyl phosphoric acid, and triphenyl phosphate. Furthermore, examples of the curing catalyst include other acidic catalysts and basic catalysts.
Of these curing catalysts, organic tin and metal complexes are preferable. These curing catalysts can be used alone or in combination of two or more. The blending ratio of the curing catalyst is, for example, 0.0001 to 10 parts by weight, preferably 0.001 to 5 parts by weight with respect to 100 parts by weight of the one-part moisture curable resin composition.

In addition, the one-component moisture curable resin composition containing the alkoxysilane-modified polyamide resin can be added with an additive as long as it does not inhibit the excellent effects of the present invention.
Examples of the additive include a silane coupling agent, and further, for example, an internal mold release agent, a tackifier, a softener, a stabilizer, an antioxidant, an ultraviolet absorber, a light stabilizer, a plasticizer, and a filler. , Dyes, pigments, fluorescent brighteners, antifoaming agents (similar to the antifoaming agents used by the amidation reaction described above) and the like.

  Examples of the silane coupling agent include alkoxysilanes such as tetramethoxysilane and tetraethoxysilane, such as N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ -Aminopropyltriethoxysilane, N-β- (aminoethyl) -γ-aminopropyltriethoxysilane, N-β- (aminoethyl) -γ-propylmethyldimethoxysilane, N, N '-(dimethoxymethylsilylpropyl) ) Aminosilanes such as ethylenediamine, N, N ′-(triethoxysilylpropyl) ethylenediamine, N-phenyl-γ-aminopropyltrimethoxysilane, such as γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyl Triethoxysilane, β- (3,4- Epoxysilanes such as (poxycyclohexyl) ethyltrimethoxysilane and di (γ-glycidoxypropyl) dimethoxysilane, vinylsilanes such as vinyltriethoxysilane, and isocyanate silanes such as γ-isocyanatopropyltrimethoxysilane For example, chlorosilanes such as vinyltrichlorosilane.

  Preferably, alkoxysilanes and aminosilanes are used, and tetraethoxysilane is more preferable. These silane coupling agents can be used alone or in combination of two or more. Moreover, the mixture ratio of a silane coupling agent is 0.01-50 weight part with respect to 100 weight part of 1 liquid moisture hardening type resin compositions, Preferably, it is 0.1-30 weight part.

Then, the one-component moisture-curable resin composition is easily moisture-cured by, for example, heating in the atmosphere at room temperature to 200 ° C. for 1 to 800 hours. The obtained resin cured product is excellent in heat resistance, adhesiveness, and mechanical strength.
When the one-component moisture-curable resin composition is used as a one-component moisture-curable hot melt adhesive, for example, a known coating machine such as a roll coater, a spray coating machine, or a hand gun equipped with a heating device. After heating and melting, the adherends can be bonded together by applying them to the adherends in various patterns. At this time, the adherend may be pasted before the hot melt adhesive is cured, but after the hot melt adhesive once cured is activated again, the adherend can be pasted. .

  The adherend is not particularly limited. For example, iron, copper, aluminum, tinplate, stainless steel (SUS), coated steel plate, zinc steel plate, polyethylene, polypropylene, PET, acrylic resin, ABS resin, vinyl chloride resin, polycarbonate, polyamide (Nylon, aramid), polystyrene, polyurethane, rubber, wood, plywood, particle board, cardboard, paper, cloth and the like.

EXAMPLES The present invention will be specifically described below with reference to examples and comparative examples, but the present invention is not limited to these. Moreover, the analysis and measurement of a synthesis example, a comparative synthesis example, an Example, and a comparative example were based on the following method.
(Acid value)
It was measured according to “Partial acid value” in Section 5.3 “Acid value” of JIS K6901 “Test method for liquid unsaturated polyester resin”.
(Hydroxyl value)
It was measured in accordance with 6.4 “hydroxyl value” of JIS K1557 “Polyurethane Polyether Test Method”.
(Isocyanate group content)
It was measured according to Section 6.3 “Isocyanate group content” of JIS K7301 “Test method for tolylene diisocyanate type prepolymer for thermosetting urethane elastomer”.
(Number average molecular weight)
0.03 g of the sample was dissolved in 10 ml of tetrahydrofuran at room temperature and then filtered through a filter having a pore size of 0.45 μm, and then measured using a gel permeation chromatograph (GPC) under the following conditions. For the number average molecular weight, the number average molecular weight of the peak including the maximum frequency molecular weight (retention time) of the measured chromatogram was calculated with reference to a calibration curve created using standard polyethylene glycol.
Apparatus: HLC-8020 (manufactured by Tosoh Corporation)
Column: TSKgel guardcolum HXL-L + G1000H XL + G2000H XL + G3000H XL manufactured by Tosoh Corporation
Eluent: Tetrahydrofuran Flow rate: 0.8 ml / min Column temperature: 40 ° C
Injection volume: 20 μl
Detector: RI
(Melt viscosity)
The viscosity (melt viscosity) was measured using a cone plate type rotational viscometer (manufactured by ICI) under the conditions of cone type: 100 P, rotation speed: 75 rpm, and temperature: 100 ° C.
(Amidation rate)
It calculated from NMR of the following conditions.
Apparatus: JNM-AL400 (manufactured by JEOL)
Frequency: 400MHz
Measurement temperature: Room temperature integration frequency: 128 times After dissolving 20 mg of sample in 0.65 ml of dimethyl sulfoxide-d6 (containing 0.05% TMS) at room temperature, ¹ H-NMR was measured under the above conditions. The amidation rate was calculated from the integral value of proton (H) of the isocyanate derivative and the integral value of proton (NH) in the amide.
(Heat resistance: softening start temperature)
A dynamic viscoelasticity test was carried out under the following conditions, and the temperature (softening start temperature) when the value of the storage elastic modulus (E ′) started to decrease rapidly was measured.
Apparatus: Dynamic viscoelasticity measuring apparatus DVA-200 (made by IT Measurement Control Co., Ltd.)
Sample: 2.5cm length between marked lines, 0.485cm width
Deformation mode: static tensile / dynamic stress ratio: 1.8 to 2.0
Set strain: 0.05 to 0.10% (E> 108 Pa)
Set temperature rise rate: 5 ° C / min Measurement frequency: 10Hz
(Tensile strength)
In accordance with JIS K7312 “Physical Test Method for Thermosetting Polyurethane Elastomer Molding”, Section 5 “Tensile Test”, the measurement was performed under the following conditions.
Equipment: Tensile tester RTA-500L-XL (Orientec)
Dumbbell: Dumbbell No. 4 thickness: 0.5-0.8mm
Temperature: 23 ° C
Humidity: 50% RH
Test speed: 300 mm / min Synthesis Example 1
(Production of polyester polycarboxylic acid (A))
A 5-liter flask equipped with a reflux condenser, a water separator, a nitrogen gas inlet tube, a thermometer and a stirrer was charged with 2045.1 parts by weight of adipic acid and 1306.5 parts by weight of neopentyl glycol (COOH / OH equivalent ratio: 1.12), and the temperature was raised with a mantle heater while introducing nitrogen.

  Distillation of water started when the temperature reached 150 ° C., the temperature was raised to 230 ° C. while distilling water, and dehydration condensation was continued at 230 ° C. With the acid value and hydroxyl value of the reaction product reaching predetermined values, the reaction product was withdrawn from the flask and cooled to obtain polyester polycarboxylic acid (A). The obtained polyester polycarboxylic acid (A) had an acid value of 53.7 mgKOH / g and a hydroxyl value of 0.4 mgKOH / g.

Comparative Synthesis Example 1
(Production of polyester polyol (A))
A 5 liter flask equipped with a reflux condenser, water separator, nitrogen gas inlet tube, thermometer and stirrer was charged with 1623.999 parts by weight of adipic acid, 1342.55 parts by weight of neopentyl glycol (OH / COOH). The equivalent ratio of 1.16) and 1.93 parts by weight of dibutyltin oxide were charged, and the temperature was raised with a mantle heater while introducing nitrogen.

  Distillation of water started when the temperature reached 150 ° C., the temperature was raised to 230 ° C. while distilling water, and dehydration condensation was continued at 230 ° C. When the hydroxyl value and acid value of the reaction product reached predetermined values, the reaction product was extracted from the flask and cooled to obtain a polyester polyol (A). The obtained polyester polyol (A) had a hydroxyl value of 53.5 mgKOH / g and an acid value of 0.6 mgKOH / g.

Example 1
(Production of terminal isocyanate group-containing polyamide resin (A))
In a 2 liter reaction flask equipped with a reflux condenser, a nitrogen gas inlet tube, a thermometer and a stirrer, 842.3 parts by weight of polyester polycarboxylic acid (A), 157.7 parts by weight of 1,3-bis (Isocyanatomethyl) cyclohexane (H ₆ XDI, trade name: Takenate 600, manufactured by Mitsui Chemicals Polyurethanes) (NCO / COOH equivalent ratio: 2.02), 0.240 parts by weight of magnesium stearate (polyester polycarboxylic acid) 0.050 mol part with respect to 100 mol parts of the carboxyl group) and 0.500 parts by weight of Florene AC-1190 (manufactured by Kyoeisha Chemical Co., Ltd., defoamer)

Thereafter, the temperature was raised to 70 ° C. with a mantle heater while introducing nitrogen, and then the reaction was continued at a reaction temperature of 70 ° C. for 8 hours to obtain a terminal isocyanate group-containing polyamide resin (A).
In the obtained terminal isocyanate group-containing polyamide resin (A), the isocyanate content was 3.7% by weight (theoretical value: 3.7% by weight).

Further, ¹ H-NMR of the obtained terminal isocyanate group-containing polyamide resin (A) was measured. From the NMR chart, the chemical shift when the integral value of the 0.7381H portion appearing at the chemical shift of 0.6 ppm of 10H of the alicyclic portion of the 1,3-bis (isocyanatomethyl) cyclohexane derivative is 0.7381. When the amidation rate was calculated from the integral value of NH of amide appearing at 7.8 ppm, it was 87%.

(Production of alkoxysilane-modified polyamide resin (A))
A 1 liter reaction flask equipped with a reflux condenser, a nitrogen gas inlet tube, a thermometer and a stirrer was charged with 500.0 parts by weight of a terminal isocyanate group-containing polyamide resin (A), and while introducing nitrogen, the mantle The temperature was raised to 90 ° C. with a heater.
Thereafter, 97.5 parts by weight of γ-aminopropyltriethoxysilane (trade name: KBE903, manufactured by Shin-Etsu Chemical Co., Ltd.) (NCO / NH ₂ equivalent ratio: 1.00) was added using a dropping funnel. It was dripped over 5 hours. After completion of dropping, the reaction was continued at 90 ° C. for 1 hour to obtain an alkoxysilane-modified polyamide resin (A).

In the obtained alkoxysilane-modified polyamide resin (A), the isocyanate group content was 0.1% by weight or less, the viscosity was 28200 mPa · s / 100 ° C., and the number average molecular weight was 4000.
(Production of hot melt adhesive (A) and resin cured product (A))
A plastic container is charged with 50 parts by weight of an alkoxysilane-modified polyamide resin (A), 0.5 parts by weight of stannous octylate, and 0.5 parts by weight of tetraethoxysilane, and 30 minutes at 100 ° C. in a vacuum dryer. Vacuum defoaming treatment was performed to prepare a one-component moisture-curing hot melt adhesive (A).

  An appropriate amount of Milax RS-102 (manufactured by Activator Chemical Co., Ltd.) as a release agent was applied to the surface and heated to 100 ° C., the hot melt adhesive (A) was cured to 0. After being cast to a thickness of 8 to 1.5 mm, left in air at 23 ° C. and 50% RH for 48 hours, and then moisture-cured for 48 hours at 80 ° C. and 30% RH. A cured product (A) was obtained.

When the heat resistance and tensile strength of the obtained cured resin (A) were measured by the above methods, the softening start temperature was 220 ° C. and the tensile strength was 4.16 MPa (see Table 1).
Comparative Example 1
(Production of terminal isocyanate group-containing polyamide resin (B))
To a 2 liter reaction flask equipped with a reflux condenser, a nitrogen gas inlet tube, a thermometer and a stirrer, 842.4 parts by weight of polyester polycarboxylic acid (A), 0.240 parts by weight of magnesium stearate (polyester) 0.050 mol part with respect to 100 mol parts of the carboxyl group of the polycarboxylic acid) and 0.500 parts by weight of Florene AC-1190 (manufactured by Kyoeisha Chemical Co., Ltd., defoaming agent) were charged.

Thereafter, the temperature was raised to 50 ° C. with a mantle heater while introducing nitrogen, and 157.6 parts by weight of 1,3-bis (isocyanatomethyl) cyclohexane (H ₆ XDI, trade name: Takenate 600, Mitsui Chemicals Polyurethane) (Equivalent ratio of NCO / COOH: 2.01). Thereafter, the temperature was raised to 70 ° C., and the reaction was continued at a reaction temperature of 70 ° C. for 7 hours to obtain a terminal isocyanate group-containing polyamide resin (B).

In the obtained terminal isocyanate group-containing polyamide resin (B), the isocyanate group content was 3.7% by weight (theoretical value 3.7% by weight).
Further, ¹ H-NMR of the obtained terminal isocyanate group-containing polyamide resin (B) was measured. From the NMR chart, the chemical shift when the integral value of the 0.7381H portion appearing at the chemical shift of 0.6 ppm of 10H of the alicyclic portion of the 1,3-bis (isocyanatomethyl) cyclohexane derivative is 0.7381. When the amidation rate was calculated from the integral value of NH of amide appearing at 7.8 ppm, it was 87%.

(Production of alkoxysilane-modified polyamide resin (B))
A 500 ml reaction flask equipped with a reflux condenser, a nitrogen gas inlet tube, a thermometer and a stirrer was charged with 259.1 parts by weight of a terminal isocyanate group-containing polyamide resin (B), and while introducing nitrogen, the mantle The temperature was raised to 70 ° C. with a heater.
Thereafter, using a dropping funnel, 40.9 parts by weight of γ-aminopropyltrimethoxysilane (trade name: KBM903, manufactured by Shin-Etsu Chemical Co., Ltd.) (NCO / NH ₂ equivalent ratio: 1.00) was added for 1 hour. Then, the production of alkoxysilane-modified polyamide resin (B) was attempted by dripping.

However, when the reaction was continued for 30 minutes at a reaction temperature of 70 ° C. after completion of dropping, gelation occurred and stirring was not possible.
Comparative Example 2
(Production of terminal isocyanate group-containing polyurethane resin (A))
A 500 ml reaction flask equipped with a reflux condenser, a nitrogen gas inlet tube, a thermometer and a stirrer was charged with 208.9 parts by weight of polyester polyol (A) and 41.1 parts by weight of 1,3-bis ( Isocyanatomethyl) cyclohexane (H ₆ XDI, trade name: Takenate 600, made by Mitsui Chemicals Polyurethane, isocyanate content 43.3% by weight) (equivalent ratio of NCO / OH: 2.13), and nitrogen was introduced. While raising the temperature to 75 ° C. with a mantle heater, the reaction was continued at a reaction temperature of 75 ° C. for 5 hours to obtain a terminal isocyanate group-containing polyurethane resin (A).

In the obtained terminal isocyanate group-containing polyurethane resin (A), the isocyanate group content was 3.6% by weight.
(Production of alkoxysilane-modified polyurethane resin (A))
A 500 ml reaction flask equipped with a reflux condenser, a nitrogen gas inlet tube, a thermometer and a stirrer was charged with 210.1 parts by weight of a terminal isocyanate group-containing polyurethane resin (A), and while introducing nitrogen, the mantle The temperature was raised to 90 ° C. with a heater.

Then, using a dropping funnel, 39.9 parts by weight of γ-aminopropyltriethoxysilane (trade name: KBE903, manufactured by Shin-Etsu Chemical Co., Ltd.) (NCO / NH ₂ equivalent ratio: 1.00) was 4.5. It was added dropwise over time. After completion of dropping, the reaction was continued for 1 hour to obtain an alkoxysilane-modified polyurethane resin (A).
In the obtained alkoxysilane-modified polyurethane resin (A), the isocyanate group content was 0.1% by weight or less.

(Production of hot melt adhesive (B) and cured resin (B))
A plastic container is charged with 50 parts by weight of an alkoxysilane-modified polyurethane resin (A), 0.5 parts by weight of stannous octylate, and 0.5 parts by weight of tetraethoxysilane, and is placed in a vacuum dryer at 100 ° C. for 30 minutes. Vacuum defoaming treatment was performed to prepare a one-component moisture-curing hot melt adhesive (B).

  An appropriate amount of Milax RS-102 (manufactured by Activator Chemical Co., Ltd.) as a release agent was applied to the surface and heated to 100 ° C., and the hot melt adhesive (B) was cured to 0. After being cast to a thickness of 8 to 1.5 mm, left in air at 23 ° C. and 50% RH for 48 hours, and then moisture-cured for 48 hours at 80 ° C. and 30% RH. A cured product (B) was obtained.

When the heat resistance and tensile strength of the obtained cured resin (B) were measured by the above methods, the softening start temperature was 180 ° C. and the tensile strength was 2.81 MPa (see Table 1).
Comparative Example 3
(Production of alkoxysilane-modified polyurethane resin (B))
Into a 500 ml reaction flask equipped with a reflux condenser, a nitrogen gas introduction tube, a thermometer and a stirrer, 205.1 parts by weight of the terminal isocyanate group-containing polyurethane resin (A) was charged, and while introducing nitrogen, the mantle The temperature was raised to 70 ° C. with a heater.

Thereafter, 44.9 parts by weight of N-phenyl-γ-aminopropyltrimethoxysilane (trade name: KBM573, manufactured by Shin-Etsu Chemical Co., Ltd.) (NCO / NH equivalent ratio: 1.00) was added using a dropping funnel. The solution was added dropwise over 1 hour. After completion of dropping, the reaction was continued for 2 hours to obtain an alkoxysilane-modified polyurethane resin (B).
In the obtained alkoxysilane-modified polyurethane resin (B), the isocyanate group content was 0.1% by weight or less.

(Production of hot melt adhesive (C) and cured resin (C))
A plastic container is charged with 50 parts by weight of an alkoxysilane-modified polyurethane resin (B), 0.5 parts by weight of stannous octylate, and 0.5 parts by weight of tetraethoxysilane, and is placed in a vacuum dryer at 100 ° C. for 30 minutes. Vacuum defoaming treatment was performed to prepare a one-component moisture-curing hot melt adhesive (C).

  An appropriate amount of Milax RS-102 (manufactured by Activator Chemical Co., Ltd.) as a release agent was applied to the surface and heated to 100 ° C., the hot-melt adhesive (C) was cured to 0. After being cast to a thickness of 8 to 1.5 mm, left in air at 23 ° C. and 50% RH for 48 hours, and then moisture-cured for 48 hours at 80 ° C. and 30% RH. A cured product (C) was obtained.

  When the heat resistance and tensile strength of the obtained cured resin (C) were measured by the above methods, the softening start temperature was 190 ° C. and the tensile strength was 3.41 MPa (see Table 1).

  The alkoxysilane-modified polyamide resin of the present invention is useful as an adhesive component of a one-part moisture-curable hot melt adhesive.

Claims (8)

Terminal isocyanate group-containing polyamide resin obtained by reacting a polyester polycarboxylic acid and a polyisocyanate compound obtained by the reaction of polybasic acids with a polyhydric alcohol at a ratio in which the isocyanate group is excessive with respect to the carboxyl group When,
An alkoxysilane-modified polyamide resin obtained by reacting with an alkoxysilane compound represented by the following general formula (1).

(In the formula, R 1 represents an alkylene group having 1 to 20 carbon atoms, and R 2, R 3 and R 4 are the same as or different from each other, and represent an alkoxy group having 2 to 20 carbon atoms or an alkyl group having 1 to 20 carbon atoms. (However, at least one of R2, R3 and R4 represents an alkoxy group.) Terminal isocyanate group-containing polyamide resin obtained by reacting a polyester polycarboxylic acid and a polyisocyanate compound obtained by the reaction of polybasic acids with a polyhydric alcohol at a ratio in which the isocyanate group is excessive with respect to the carboxyl group When,
A hot-melt adhesive comprising an alkoxysilane-modified polyamide resin obtained by reacting with an alkoxysilane compound represented by the following general formula (1).

(In the formula, R 1 represents an alkylene group having 1 to 20 carbon atoms, and R 2, R 3 and R 4 are the same as or different from each other, and represent an alkoxy group having 2 to 20 carbon atoms or an alkyl group having 1 to 20 carbon atoms. (However, at least one of R2, R3 and R4 represents an alkoxy group.)   The hot-melt adhesive according to claim 2, which is a one-component moisture-curing adhesive. Terminal isocyanate group-containing polyamide resin obtained by reacting a polyester polycarboxylic acid and a polyisocyanate compound obtained by the reaction of polybasic acids with a polyhydric alcohol at a ratio in which the isocyanate group is excessive with respect to the carboxyl group When,
A cured resin obtained by curing an alkoxysilane-modified polyamide resin obtained by reacting with an alkoxysilane compound represented by the following general formula (1).

(In the formula, R 1 represents an alkylene group having 1 to 20 carbon atoms, and R 2, R 3 and R 4 are the same as or different from each other, and represent an alkoxy group having 2 to 20 carbon atoms or an alkyl group having 1 to 20 carbon atoms. (However, at least one of R2, R3 and R4 represents an alkoxy group.) Polyester polycarboxylic acid obtained by reaction of polybasic acid and polyhydric alcohol and polyisocyanate compound, in a ratio that the isocyanate group is excessive with respect to the carboxyl group, 100 mol parts of all carboxyl groups of the polyester polycarboxylic acid In the presence of a catalyst selected from 0.001 to 10 mol parts of an alkali metal salt and / or an alkaline earth metal salt, a terminal isocyanate group-containing polyamide resin is obtained by reacting,
The terminal isocyanate group-containing polyamide resin;
The manufacturing method of the alkoxysilane modified polyamide resin characterized by making the alkoxysilane compound represented by following General formula (1) react.

(In the formula, R 1 represents an alkylene group having 1 to 20 carbon atoms, and R 2, R 3 and R 4 are the same as or different from each other, and represent an alkoxy group having 2 to 20 carbon atoms or an alkyl group having 1 to 20 carbon atoms. (However, at least one of R2, R3 and R4 represents an alkoxy group.)   The method for producing an alkoxysilane-modified polyamide resin according to claim 5, wherein the polyester polycarboxylic acid and the polyisocyanate compound are reacted at 120 ° C or lower.   The method for producing an alkoxysilane-modified polyamide resin according to claim 5 or 6, wherein the terminal isocyanate group-containing polyamide resin and the alkoxysilane compound are reacted at 150 ° C or lower.   The method for producing an alkoxysilane-modified polyamide resin according to any one of claims 5 to 7, wherein the catalyst is magnesium stearate.