CN101501094A - Polyamide resin containing terminal isocyanate group, alkoxysilane-modified polyamide resin, processes for production of the resins, hot-melt adhesive agent, and cured resin product - Google Patents
Polyamide resin containing terminal isocyanate group, alkoxysilane-modified polyamide resin, processes for production of the resins, hot-melt adhesive agent, and cured resin product Download PDFInfo
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- CN101501094A CN101501094A CNA2007800291255A CN200780029125A CN101501094A CN 101501094 A CN101501094 A CN 101501094A CN A2007800291255 A CNA2007800291255 A CN A2007800291255A CN 200780029125 A CN200780029125 A CN 200780029125A CN 101501094 A CN101501094 A CN 101501094A
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Abstract
A polyamide resin having a terminal isocyanate group can be produced by reacting an oligomer having a terminal carboxyl group and a polyisocyanate compound at such a ratio that the amount of an isocyanate group becomes excess relative to that of a carboxyl group. An alkoxysilane-modified polyamide resin can be produced by reacting the polyamide resin having a terminal isocyanate group with an alkoxysilane compound containing a secondary amine.
Description
Technical field
The present invention relates to a kind ofly contain the polyamide resin of terminal isocyanate group, alkoxysilane-modified polyamide resin and their manufacture method, contain the hotmelt of above-mentioned resin and the resin cured matter of these resins.
Background technology
So far, the reaction carbamate prepolymer that obtain, that contain terminal isocyanate group by the pure and mild polyisocyanates of polyester polyols is (for example referring to the following patent documentation 1) that is widely known by the people as reactive hot melt adhesive.
And then, as reactive hot melt adhesive, also known have the carbamate prepolymer by containing terminal isocyanate group and contain the carbamate prepolymer that contains alkoxysilyl (for example referring to following patent documentation 2) that the reaction of amino silane coupling agent obtains.
For above-mentioned reactive hot melt adhesive, the multiple scheme that imports amido linkage for thermotolerance and physical strength are improved in polyester polyol is disclosed so far.
For example, disclose block polyvalent alcohol by having polyester segment and polyamide segment, with polyisocyanate compound or have the compound reaction of water-disintegrable silyl obtains, wet-cured type hot-melt adhesive composition (for example referring to following patent documentation 3).
In addition, also disclose, made this urea derivative and the polyamide reaction that contains carboxyl, obtained wet cross-linking type hot-melt adhesive (for example referring to following patent documentation 4) thus by vulcabond and alkoxyl group alkylidene amino silane reaction urea synthesis derivative.
Patent documentation 1: the spy opens the 2003-277717 communique
Patent documentation 2: the spy opens flat 7-278320 communique
Patent documentation 3: the spy opens flat 10-110153 communique
Patent documentation 4: the flat 1-503149 communique of special table
Summary of the invention
Yet, in the patent documentation 3 described wet-cured type hot-melt adhesive compositions, import amido linkage by polyamide segment is modified as polyester segment.
In addition, in the patent documentation 4 described wet cross-linking type hot-melt adhesives, at first, make vulcabond and alkoxyl group alkylidene amino silane reaction, the urea synthesis derivative by making this urea derivative and the polyamide reaction that contains carboxyl, imports amido linkage.
But, in the above-mentioned hotmelt, all can not obtain sufficient thermotolerance and physical strength, expectation further improves rerum natura.
The object of the present invention is to provide a kind of thermotolerance and the polyamide resin physical strength excellence, that contain terminal isocyanate group, alkoxysilane-modified polyamide resin and their manufacture method, contain the hotmelt of above-mentioned resin and the resin cured matter of above-mentioned resin.
To achieve these goals, the polyamide resin that contains terminal isocyanate group of the present invention is characterised in that, is to be that excessive ratio react obtain with isocyanate group with respect to carboxyl by making the oligopolymer that contains terminal carboxyl(group) and polyisocyanate compound.
In the polyamide resin that contains terminal isocyanate group of the present invention, the above-mentioned oligopolymer that contains terminal carboxyl(group) is preferably selected from polyester polycarboxylic acid and the dimeracid that is obtained by polynary acids and polyol reaction.
Alkoxysilane-modified polyamide resin of the present invention is characterised in that, is by the above-mentioned polyamide resin that contains terminal isocyanate group is obtained with the alkoxysilane compound containing trialkylsilyl group in molecular structure reaction that contains secondary amine.
In the alkoxysilane-modified polyamide resin of the present invention, the above-mentioned oligopolymer that contains terminal carboxyl(group) is preferably selected from polyester polycarboxylic acid and the dimeracid that is obtained by polynary acids and polyol reaction.
In the alkoxysilane-modified polyamide resin of the present invention, above-mentioned alkoxysilane compound containing trialkylsilyl group in molecular structure is preferably as follows to be stated shown in the general formula (1).
(in the formula, R1 represents the alkylidene group of carbonatoms 1～20, and R2 represents the alkyl of carbonatoms 1～20, and R3, R4 and R5 are same to each other or different to each other, the alkoxyl group or the alkyl of expression carbonatoms 1～20.Wherein, the expression of at least one among R3, R4 and R5 alkoxyl group.)
Hotmelt of the present invention is characterised in that and contains above-mentioned polyamide resin and/or the above-mentioned alkoxysilane-modified polyamide resin that contains terminal isocyanate group.
Hotmelt of the present invention is preferably a fluidity wet-cured type tackiness agent.
Resin cured matter of the present invention is characterised in that, is that above-mentioned polyamide resin and/or the above-mentioned alkoxysilane-modified polyamide resin curing that contains terminal isocyanate group is obtained.
The manufacture method that contains the polyamide resin of terminal isocyanate group of the present invention is characterised in that, make the oligopolymer that contains terminal carboxyl(group) and polyisocyanate compound with respect to above-mentioned total carboxyl 100 molar part that contain the oligopolymer of terminal carboxyl(group) be catalyzer 0.001～10 molar part, that be selected from an alkali metal salt and/or alkaline earth salt in the presence of, be that excessive ratio is reacted with isocyanate group with respect to carboxyl.
In the manufacture method of the polyamide resin that contains terminal isocyanate group of the present invention, preferably make its reaction below 120 ℃.
In the manufacture method of the polyamide resin that contains terminal isocyanate group of the present invention, above-mentioned catalyzer is preferably Magnesium Stearate.
In the manufacture method of the polyamide resin that contains terminal isocyanate group of the present invention, the above-mentioned oligopolymer that contains terminal carboxyl(group) is preferably selected from polyester polycarboxylic acid and the dimeracid that is obtained by polynary acids and polyol reaction.
The manufacture method of alkoxysilane-modified polyamide resin of the present invention is characterised in that, makes the above-mentioned alkoxysilane compound containing trialkylsilyl group in molecular structure reaction that contains the polyamide resin of terminal isocyanate group and contain secondary amine.
In the manufacture method of alkoxysilane-modified polyamide resin of the present invention, above-mentioned oligopolymer and the above-mentioned polyisocyanate compound that contains terminal carboxyl(group) reacted below 120 ℃.
In the manufacture method of alkoxysilane-modified polyamide resin of the present invention, above-mentioned polyamide resin and the above-mentioned alkoxysilane compound containing trialkylsilyl group in molecular structure that contains terminal isocyanate group reacted below 150 ℃.
In the manufacture method of alkoxysilane-modified polyamide resin of the present invention, above-mentioned catalyzer is preferably Magnesium Stearate.
In the manufacture method of alkoxysilane-modified polyamide resin of the present invention, the above-mentioned oligopolymer that contains terminal carboxyl(group) is preferably selected from polyester polycarboxylic acid and the dimeracid that is obtained by polynary acids and polyol reaction.
In the manufacture method of alkoxysilane-modified polyamide resin of the present invention, above-mentioned alkoxysilane compound containing trialkylsilyl group in molecular structure is preferably as follows to be stated shown in the general formula (1).
(in the formula, R1 represents the alkylidene group of carbonatoms 1～20, and R2 represents the alkyl of carbonatoms 1～20, and R3, R4 and R5 are same to each other or different to each other, the alkoxyl group or the alkyl of expression carbonatoms 1～20.Wherein, the expression of at least one among R3, R4 and R5 alkoxyl group.)
In the polyamide resin that contains terminal isocyanate group of the present invention, import amido linkage by making the oligopolymer and the polyisocyanate compound reaction that contain terminal carboxyl(group).And then, by making this polyamide resin that contains terminal isocyanate group and the alkoxysilane compound containing trialkylsilyl group in molecular structure reaction that contains secondary amine, can obtain alkoxysilane-modified polyamide resin of the present invention.
Therefore, polyamide resin and the alkoxysilane-modified polyamide resin that contains terminal isocyanate group of the present invention has excellent thermotolerance and physical strength, for example can be used for hotmelt etc.
In addition, in the manufacture method of the polyamide resin that contains terminal isocyanate group of the present invention and the manufacture method of alkoxysilane-modified polyamide resin of the present invention, can easily import the amido linkage that can improve thermotolerance and physical strength.
Embodiment
At first, at length set forth the polyamide resin that contains terminal isocyanate group of the present invention.
The polyamide resin that contains terminal isocyanate group of the present invention can obtain by making the oligopolymer and the polyisocyanate compound reaction that contain terminal carboxyl(group).
Among the present invention, the oligopolymer that contains terminal carboxyl(group) is to contain carboxyl, number-average molecular weight in molecular end to be for example 200～40000, preferred 500～10000 polycarboxylic acid.Number-average molecular weight can be passed through gel permeation chromatography (GPC) and measure.During GPC measures, be benchmark, calculate the number-average molecular weight at the peak of the molecular weight (retention time) that comprises maximum frequency in the chromatogram of mensuration with the typical curve that uses the making of standard polyoxyethylene glycol.Thus, number-average molecular weight is calculated as the scaled value of standard polyoxyethylene glycol.In addition, contain in the oligopolymer of terminal carboxyl(group), adopt the viscosity under 100 ℃ that cone-and-plate viscometer measures to be preferably below the 30000mPas.
As the above-mentioned oligopolymer that contains terminal carboxyl(group), for example can enumerate polyester polycarboxylic acid, dimeracid.
Polyester polycarboxylic acid for example can obtain by polynary acids and polyol reaction.
As polynary acids, for example can enumerate dicarboxylic acid such as oxalic acid, propanedioic acid, succsinic acid, methylsuccinic acid, pentanedioic acid, hexanodioic acid, pimelic acid, suberic acid, nonane diacid, sebacic acid, other aliphatic dicarboxylic acids (carbonatoms 11～13), hydrogenated dimer acids, toxilic acid, fumaric acid, methylene-succinic acid, phthalic acid, m-phthalic acid, terephthalic acid, toluene dioctyl phthalate, dimeracid, hexachloro endoethylene tetrahydrophthalic acid, and the alkyl ester of above-mentioned dicarboxylic acid.
In addition, comprise the acid anhydrides that obtains by the above-mentioned carboxylic acid derivatives of enumerating in the polynary acids, for example comprise oxalic acid acid anhydride, succinyl oxide, maleic anhydride, Tetra hydro Phthalic anhydride, 2-alkyl (carbonatoms 12～18) succinyl oxide, tetrahydronaphthalic anhydride, trimellitic acid 1,2-anhydride etc.
And then polynary acids also comprises the deutero-acyl halides of being enumerated by above-mentioned such as carboxylic acid, for example comprises oxalyl dichloro, adipyl chloride, sehacoyl chloride etc.
Above-mentioned polynary acids may be used singly or two or more kinds thereof.Preferably enumerate dicarboxylic acid and alkyl ester thereof.
As polyvalent alcohol, for example can enumerate the dibasic alcohol with 2 hydroxyls, polyvalent alcohol with 3 above hydroxyls.
As dibasic alcohol, for example can enumerate ethylene glycol, propylene glycol, 1, ammediol, 1, the 4-butyleneglycol, 1,3 butylene glycol, 1, the 2-butyleneglycol, 1, the 5-pentanediol, the 3-methyl isophthalic acid, the 5-pentanediol, 2, neopentyl glycol, 1, the 6-hexylene glycol, 2, the 5-hexylene glycol, 2,2-diethyl-1, ammediol, 3,3-dihydroxymethyl heptane, 2-ethyl-2-butyl-1, ammediol, 1, the 12-dodecanediol, 1, C2-22 alkanediols such as 18-octadecandiol, 2-butylene-1 for example, the 4-glycol, 2,6-dimethyl-1-octene-3, aliphatic diols such as alkenediols such as 8-glycol.
In addition,, for example can enumerate 1, alicyclic diols such as 4-cyclohexane diol, 1,4 cyclohexane dimethanol, Hydrogenated Bisphenol A or its C2-4 alkylene oxide affixture as dibasic alcohol.
In addition, as dibasic alcohol, for example can enumerate the aromatic diols such as C2-4 alkylene oxide affixture of Resorcinol, xylylene-glycol, dihydroxyl phenetole, terephthalic acid dihydroxyl ethyl, dihydroxyphenyl propane, bisphenol S, Bisphenol F, above-mentioned bisphenols.
And then, as dibasic alcohol, for example can enumerate polyether glycols such as glycol ether, triglycol, dipropylene glycol, polyoxyethylene glycol, polypropylene glycol, polyethylene polypropylene glycol block polymer (polyethylenepolypropylene block glycol), polytetramethylene ether diol.
As polyvalent alcohol with 3 above hydroxyls, can enumerate for example glycerol, 2-methyl-2-hydroxymethyl-1, ammediol, 2,4-dihydroxyl-3-hydroxymethyl pentane, 1,2, the 6-hexanetriol, trimethylolethane, TriMethylolPropane(TMP), 2-methyl-2-hydroxymethyl-1, ammediol, 2,4-dihydroxyl-3-(hydroxymethyl) pentane, 2,2-two (hydroxymethyl)-3-butanols and other aliphatics trivalent alcohols trivalent alcohols such as (carbonatomss 8～24), for example tetramethylol methane, tetramethylolmethane, Dipentaerythritol, the D-sorbyl alcohol, Xylitol, D-mannitol (D-mannitol), D-mannitol (D-mannite) etc. has the polyvalent alcohol of 4 above hydroxyls etc.
Above-mentioned polyvalent alcohol may be used singly or two or more kinds thereof.Preferably enumerate dibasic alcohol.
Polyester polycarboxylic acid can followingly obtain; be in a ratio of excessive ratio (COOH/OH surpasses 1.0 ratio, preferred 1.01～2.10 ratio) with the acidic group (carboxyl, carboxylicesters, anhydride group, acyl halide) of polynary acids and hydroxyl groups and cooperate polynary acids and polyvalent alcohol, make its generation esterification and obtain.
Esterification for example is condensation reaction or transesterification reaction, can be known condition, for example, be normal pressure, inert gas atmosphere, its temperature of reaction is 100～250 ℃, its reaction times is 1～50 hour, as required, can use catalyzer (organotin catalysts, organic titanium catalyzer, amine catalyst, following an alkali metal salt or alkaline earth salt etc.) or solvent etc.
The number-average molecular weight of the polyester polycarboxylic acid that obtains as mentioned above is 200～20000 for example, is preferably 500～10000.In addition, its acid number is preferably 10～250mgKOH/g for for example 5～600mgKOH/g, and its hydroxyl value for example is below the 5mgKOH/g, to be preferably below the 3mgKOH/g.
Dimeracid by vegetable fatty acids (for example is, ready denier oil acid, soya fatty acid etc.) 2 dipolymers that above intermolecular polymerizations reaction generates by unsaturated acid, as industrial raw material, the dipolymer of unsaturated fatty acids that contains carbonatoms 18 is as principal constituent (about 71～76 weight % of dimeracid amount), and contains monomer acids or trimer acid.
As dimeracid, for example preferred the use by molecular distillation, the refining high purity dimeracid of having removed trimer acid, monomer acids, eliminated the hydrogenated dimer acids of unsaturated link(age) by hydrogenation, by molecular distillation, refining removed trimer acid, monomer acids and eliminated the hydrogenation high purity dimeracid of unsaturated link(age) by hydrogenation, more preferably use hydrogenation high purity dimeracid.
As the oligopolymer that contains terminal carboxyl(group), can distinguish separately and to use or and with polyester polycarboxylic acid and dimeracid.
Among the present invention,, for example can enumerate aliphatic polyisocyante, alicyclic polyisocyanates, aromatic-aliphatic polyisocyanates, aromatic polyisocyanate etc. as polyisocyanate compound.
As aliphatic polyisocyante, for example can enumerate hexamethylene diisocyanate (HDI), 1,3-trimethylene diisocyanate, tetramethylene vulcabond, pentamethylene vulcabond, 1,2-trimethylene diisocyanate, 1,2-, 2,3-or 1,3-butylidene vulcabond, 2,4,4-or 2,2,4-trimethylammonium hexamethylene diisocyanate, 2, aliphatic diisocyanates such as the diisocyanate based methyl caproate of 6-.
As alicyclic polyisocyanates, for example can enumerate 3-isocyanatomethyl-3,5,5-3-methyl cyclohexanol based isocyanate (isophorone diisocyanate, IPDI), 4,4 '-, 2,4 '-or 2,2 '-dicyclohexyl methane diisocyanate or its mixture (H
12MDI), 1,3-or 1, two (isocyanatomethyl) hexanaphthenes of 4-or its mixture (hydrogenation xylylene diisocyanate, H
6XDI), 2,5-or 2, two (isocyanatomethyl) norbornanes of 6-or its mixture (NBDI), 1,3-pentamethylene vulcabond, 1,4-cyclohexyl diisocyanate, 1,3-cyclohexyl diisocyanate, methyl-2,4-cyclohexyl diisocyanate, methyl-2, alicyclic diisocyanates such as 6-cyclohexyl diisocyanate.
As the aromatic-aliphatic polyisocyanates, for example can enumerate 1,3-or 1,4-xylylene diisocyanate or its mixture (XDI), 1,3-or 1,4-tetramethyl-xylylene diisocyanate or its mixture (TMXDI), ω, ω '-diisocyanate based-1, aromatic-aliphatic vulcabond such as 4-diethylbenzene.
As aromatic polyisocyanate, for example can enumerate 4,4 '-, 2,4 '-or 2,2 '-diphenylmethanediisocyanate or its mixture (MDI), 2,4-or 2,6-tolylene diisocyanate or its mixture (TDI), 3,3 '-dimethoxy-biphenyl base-4,4 '-vulcabond, 1,5-naphthalene diisocyanate (NDI) ,-or right-phenylene diisocyanate or its mixture, 4,4 '-diphenyl diisocyanate, 4,4 '-aromatic diisocyanates such as diphenyl ether vulcabond.
In addition, polyisocyanate compound comprise the polymkeric substance (for example, dipolymer, trimer etc.) of above-mentioned polyisocyanates or for example the biuret modified body that generates of the reaction by above-mentioned polyisocyanates or polymkeric substance and water, the allophanate-modified body that generates by reaction with alcohol or above-mentioned polyvalent alcohol, generate De oxadiazine triketone (oxadiazinetrion) modification body or the polyalcohol modified body that generates by reaction etc. by reaction with above-mentioned polyvalent alcohol with carbonic acid gas.And, comprise the polyisocyanates of sulfur-bearings such as phenyl diisothio-cyanate in the polyisocyanate compound.
Above-mentioned polyisocyanate compound may be used singly or two or more kinds thereof.From being easy to control the viewpoint consideration of side reaction, preferably enumerate aliphatic polyisocyante, alicyclic polyisocyanates, aromatic-aliphatic polyisocyanates.
The polyamide resin that contains terminal isocyanate group can followingly obtain, is that excessive ratio (NCO/COOH surpasses 1.0 ratio, preferred 1.05～2.50 ratio) cooperates the oligopolymer and the polyisocyanate compound that contain terminal carboxyl(group) with the isocyanate group of polyisocyanate compound with respect to the carboxyl of the oligopolymer that contains terminal carboxyl(group), makes it that amidate action take place and obtains.
The equivalence ratio of NCO/COOH can stably manufactured in above-mentioned scope the time.On the one hand, if the equivalence ratio of NCO/COOH is below 1.00, the isocyanate group containing ratio that then contains the polyamide resin of terminal isocyanate group sometimes reduces, and consumed time is long or can not completely solidified during moisture curing.On the other hand, if the equivalence ratio of NCO/COOH is too high, then the remaining quantity of free polyisocyanate compound increases sometimes, and polyisocyanate compound volatilization during heating and melting, operating environment are poor.
Amidate action does not have special restriction, but for example can make it in the presence of catalyzer, in temperature of reaction is below 120 ℃, preferred 40～120 ℃, more preferably 40～100 ℃, and the reaction times is to react under 0.5～50 hour, preferred 1～15 hour condition.
As catalyzer, preferably enumerate an alkali metal salt, alkaline earth salt.As an alkali metal salt, for example can enumerate lithium fluoride, lithium chloride, lithium hydroxide, Sodium Fluoride, sodium-chlor, sodium hydroxide, Potassium monofluoride, Repone K, potassium hydroxide etc.In addition, as alkaline earth salt, for example can enumerate calcium stearate, calcium perchlorate, calcium chloride, calcium hydroxide, Magnesium Stearate, magnesium perchlorate, magnesium chloride, magnesium hydroxide etc.Catalyzer may be used singly or two or more kinds thereof.Acid amides from amidate action optionally viewpoint is considered, preferably enumerates calcium stearate, calcium perchlorate, Magnesium Stearate, magnesium perchlorate, more preferably enumerates Magnesium Stearate.
In addition, catalyzer for example can be the ratio interpolation of 0.001～10 molar part, preferred 0.005～2 molar part with total carboxyl 100 molar part with respect to the oligopolymer that contains terminal carboxyl(group).The adding proportion of catalyzer than aforementioned proportion after a little while, amidate action does not carry out fully sometimes, productivity reduces.On the other hand, even surpass aforementioned proportion, the acid amides selectivity of amidate action is also constant, and is unfavorable to economy sometimes.
In addition, temperature of reaction can stably manufactured in above-mentioned scope the time.On the one hand, when temperature of reaction surpasses 120 ℃, promote side reaction, the isocyanate group containing ratio of isocyanate group to be lower than the viscosity rising of theoretical value, gained resin sometimes.Operation reduction when therefore, having heating and melting, can not obtain the situation of desired resin cured matter.On the other hand, reaction temperature is spent when low, and the reaction that contains the isocyanate group of the carboxyl of oligopolymer of terminal carboxyl(group) and isocyanate compound is not sometimes carried out fully, productivity reduces.
In addition, amidate action can preferably be implemented under normal pressure, while but the carbonic acid gas that generates also can remove dereaction the time under reduced pressure implement, and then the carbonic acid gas that also can generate by reaction time adding of causing, depressed enforcement.
In addition, in the amidate action, isocyanate group and water (airborne moisture etc.) reaction will be decomposed.Therefore, this reaction should be avoided contacting with airborne moisture as far as possible, preferably implements under inert gas atmosphere.As rare gas element, for example can enumerate nitrogen, helium etc., preferably enumerate nitrogen.
In addition, amidate action also can use solvent in case of necessity.
Particularly, this reaction can disposable mixing contains oligopolymer, isocyanate compound and the catalyzer of terminal carboxyl(group), in addition, also can be pre-mixed the oligopolymer and the isocyanate compound that contain terminal carboxyl(group), again with its mixture and catalyst mix.
In addition, also can be pre-mixed the oligopolymer and the catalyzer that contain terminal carboxyl(group), its mixture and isocyanate compound are mixed, also can be pre-mixed isocyanate compound and catalyzer, its mixture and the oligopolymer that contains terminal carboxyl(group) are mixed.
Need to prove, as catalyzer, when using oxyhydroxide such as lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium hydroxide, if will contain the oligopolymer and the oxyhydroxide of terminal carboxyl(group) mixes, above-mentioned substance water generation reaction then.Therefore, at this moment, must after mixing, remove moisture, then its mixture and isocyanate compound be mixed by processed.The isocyanate group that causes of the water that can suppress to generate is decomposed thus.
Need to prove that above-mentioned reaction also can progressively be implemented.For example, at first as the 1st step, make the oligopolymer that contains terminal carboxyl(group) and polyisocyanate compound be lower than 1.0 and react the synthetic polyamide resin that contains terminal carboxyl(group) with the equivalence ratio of NCO/COOH.Then, as the 2nd step, make the polyamide resin that contains terminal carboxyl(group) and with the diverse polyisocyanate compound reaction of the polyisocyanate compound in the 1st step, finally make the equivalence ratio of its NCO/COOH surpass 1.0, obtain containing the polyamide resin of terminal isocyanate group.Synthetic as mentioned above when containing the polyamide resin of terminal isocyanate group, can access in molecular end and molecule from the different resin of the structural unit of polyisocyanate compound.In above-mentioned 2 steps reaction, catalyzer can add in the 1st step, also can add in the 2nd step, and then also can all add in the 1st step and two steps of the 2nd step.
The number-average molecular weight of the polyamide resin that contains terminal isocyanate group that obtains as mentioned above is 250～40000 for example, is preferably 500～10000.In addition, its isocyanate group containing ratio for the calculated value that obtains according to the cooperation ratio 90～110%, be preferably 95～105%.The isocyanate group containing ratio is in above-mentioned scope the time, can be between than short-term in moisture curing fully.Therefore, the carbonic acid gas that generates during moisture curing does not enter in the resin cured matter, can prevent that bond strength from reducing.In addition, amidation rate is generally 76～100%, is preferably 86～100%.The amidation rate can access the resin cured matter with excellent thermotolerance, binding property, physical strength in above-mentioned scope the time.
Contain the polyamide resin of terminal isocyanate group owing to have isocyanate group, so moisture-curable in molecular end.Therefore, the polyamide resin that contains terminal isocyanate group can be used as a fluidity wet-cured type resin combination and is used for multiple field.Particularly, useful as the bonding composition of a fluidity wet-cured type hotmelt.
To contain under the situation of polyamide resin as the bonding composition of a fluidity wet-cured type hotmelt of terminal isocyanate group, the cooperation ratio of polyamide resin that contains terminal isocyanate group is with respect to 100 weight part hotmelts, for example be 1 weight part above, be preferably more than 10 weight parts.
The resin cured matter that the polyamide resin moisture curing that contains terminal isocyanate group is obtained has excellent thermotolerance, binding property, physical strength.Moisture curing usually can be at normal temperatures, implement under the condition of catalyst-free.Need to prove, also can add following curing catalysts.
Next, describe alkoxysilane-modified polyamide resin of the present invention in detail.
Alkoxysilane-modified polyamide resin of the present invention can obtain with the alkoxysilane compound containing trialkylsilyl group in molecular structure reaction that contains secondary amine by making the above-mentioned polyamide resin that contains terminal isocyanate group.
The alkoxysilane compound containing trialkylsilyl group in molecular structure that contains secondary amine is the silane compound that has at least 1 secondary amine and at least 1 alkoxyl group concurrently, for example shown in following general formula (1).
(in the formula, R1 represents the alkylidene group of carbonatoms 1～20, and R2 represents the alkyl of carbonatoms 1～20, and R3, R4 and R5 are same to each other or different to each other, the alkoxyl group or the alkyl of expression carbonatoms 1～20.Wherein, the expression of at least 1 among R3, R4 and R5 alkoxyl group.)
In the general formula (1), the alkylidene group of the carbonatoms of representing as R1 1～20 for example can be enumerated methylene radical, ethylidene, propylidene, butylidene, pentylidene, hexylidene, inferior heptyl, octylene, nonamethylene, inferior decyl, inferior dodecyl, inferior tetradecyl, inferior hexadecyl, inferior octadecyl, inferior eicosyl etc.Can preferably enumerate the alkylidene group of carbonatoms 1～10, more preferably enumerate the alkylidene group of carbonatoms 1～4.
The alkyl of the carbonatoms of representing as R2 1～20 for example can be enumerated aliphatic alkyl, alicyclic alkyl, aromatic-aliphatic alkyl, aromatic hydrocarbyl.
As aliphatic alkyl, can preferably enumerate the alkyl of carbonatomss 1～10 such as methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, sec-butyl, the tertiary butyl, amyl group, isopentyl, sec.-amyl sec-pentyl secondary amyl, hexyl, heptyl, n-octyl, iso-octyl, 2-ethylhexyl, nonyl, decyl, the alkyl of preferred carbonatoms 1～4.
As alicyclic alkyl, can preferably enumerate the cycloalkyl of carbonatomss 3～8 such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, suberyl, ring octyl group.
As the aromatic-aliphatic alkyl, can preferably enumerate benzyl, the 1-phenylethyl, the 2-phenylethyl, the 1-phenyl propyl, the 2-phenyl propyl, the 3-phenyl propyl, diphenyl methyl, adjacent, between or right-methyl-benzyl, adjacent, between or right-Ethylbenzyl, adjacent, between or right-isopropyl benzyl, adjacent, between or right-tertiary butyl benzyl, 2,3-, 2,4-, 2,5-, 2,6-, 3,4-or 3, the 5-dimethyl benzyl, 2,3,4-, 3,4,5-or 2,4, the 6-trimethyl benzyl, 5-sec.-propyl-2-methyl-benzyl, 2-sec.-propyl-5-methyl-benzyl, 2-methyl-5-tertiary butyl benzyl, 2,4-, 2,5-or 3,5-di-isopropyl benzyl, 3,5-two-tertiary butyl benzyl, 1-(2-aminomethyl phenyl) ethyl, 1-(3-aminomethyl phenyl) ethyl, 1-(4-aminomethyl phenyl) ethyl, 1-(2-isopropyl phenyl) ethyl, 1-(3-isopropyl phenyl) ethyl, 1-(4-isopropyl phenyl) ethyl, 1-(2-tert-butyl-phenyl) ethyl, 1-(4-tert-butyl-phenyl) ethyl, 1-(2-sec.-propyl-4-aminomethyl phenyl) ethyl, 1-(4-sec.-propyl-2-aminomethyl phenyl) ethyl, 1-(2, the 4-3,5-dimethylphenyl) ethyl, 1-(2, the 5-3,5-dimethylphenyl) ethyl, 1-(3, the 5-3,5-dimethylphenyl) ethyl, the aralkyl of carbonatomss 7～16 such as 1-(3, the 5-di-tert-butyl-phenyl) ethyl.
As aromatic hydrocarbyl, can preferably enumerate the aryl of carbonatomss 6～14 such as phenyl, tolyl, xylyl, xenyl, naphthyl, anthryl, phenanthryl, Azulene base.
The alkoxyl group of the carbonatoms of representing as R3, R4 and R5 1～20 for example can be enumerated methoxyl group, oxyethyl group, propoxy-, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert.-butoxy, pentyloxy, isopentyloxy, neopentyl oxygen, hexyloxy, octyloxy, last of the ten Heavenly stems oxygen base, dodecyloxy, tetradecyloxyaniline, n-Hexadecane oxygen base, octadecane oxygen base, eicosane oxygen base etc.Can preferably enumerate the alkoxyl group of carbonatoms 1～10, more preferably enumerate the alkoxyl group of carbonatoms 1～4.
The alkyl of the carbonatoms of representing as R3, R4 and R5 1～20 for example can be enumerated methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, sec-butyl, the tertiary butyl, amyl group, isopentyl, sec.-amyl sec-pentyl secondary amyl, hexyl, heptyl, n-octyl, iso-octyl, 2-ethylhexyl, nonyl, decyl, isodecyl, dodecyl, tetradecyl, hexadecyl, octadecyl, eicosyl etc.Can preferably enumerate the alkyl of carbonatoms 1～10, more preferably enumerate the alkyl of carbonatoms 1～4.
In addition, in the general formula (1), among R3, R4 and the R5 1 is an alkoxyl group, 2 under the situation of alkyl in addition, the alkoxysilane compound containing trialkylsilyl group in molecular structure of general formula (1) is represented N-hydrocarbon substituted-amino alkyl-dialkyl group monoalkoxy silane, 2 is alkoxyl group, in addition 1 under the situation of alkyl, the alkoxysilane compound containing trialkylsilyl group in molecular structure of general formula (1) is represented N-hydrocarbon substituted-amino alkyl-monoalkyl dialkoxy silicane, under the situation that 3 are alkoxyl group, the alkoxysilane compound containing trialkylsilyl group in molecular structure of general formula (1) is represented N-hydrocarbon substituted-amino alkyl-trialkoxy silane.In the general formula (1), alkoxysilane compound containing trialkylsilyl group in molecular structure is preferably N-hydrocarbon substituted-amino alkyl-trialkoxy silane.
As above-mentioned alkoxysilane compound containing trialkylsilyl group in molecular structure, particularly for example can enumerate N-phenyl-gamma-amino propyl trimethoxy silicane, N-phenyl-γ-An Jibingjisanyiyangjiguiwan, N-phenyl-gamma-amino propyl group methyl dimethoxysilane, N-phenyl-gamma-amino propyl group methyldiethoxysilane, N-phenyl-gamma-amino propyl group ethyl dimethoxy silane, N-phenyl-gamma-amino propyl group ethyl diethoxy silane, N-phenyl-gamma-amino ethyl trimethoxy silane, N-phenyl-gamma-amino ethyl triethoxysilane, N-phenyl-gamma-amino ethyl-methyl dimethoxy silane, N-phenyl-gamma-amino ethyl-methyl diethoxy silane, N-phenyl-gamma-amino ethyl diethyldithiocarbamate dimethoxy silane, N-phenyl-N-phenyl amino alkyl-organoalkoxysilanes such as gamma-amino ethyl diethyldithiocarbamate diethoxy silane.
In addition, can enumerate N-ethyl-gamma-amino propyl trimethoxy silicane, N-ethyl-gamma-amino propyl group methyl dimethoxysilane, N-methyl-gamma-amino propyl trimethoxy silicane, N-methyl-N-alkylamino alkyl-organoalkoxysilanes such as gamma-amino propyl group methyl dimethoxysilane.
Can preferably enumerate N-phenyl-gamma-amino propyl trimethoxy silicane, N-methyl-gamma-amino propyl trimethoxy silicane.Above-mentioned alkoxysilane compound containing trialkylsilyl group in molecular structure may be used singly or two or more kinds thereof.
Alkoxysilane-modified polyamide resin can followingly obtain, isocyanate group with the polyamide resin that contains terminal isocyanate group cooperates polyamide resin and the alkoxysilane compound containing trialkylsilyl group in molecular structure that contains terminal isocyanate group with respect to the ratio (NCO/NH is 0.6～1.4 ratio, preferred 0.9～1.1 ratio) that the amino of alkoxysilane compound containing trialkylsilyl group in molecular structure is roughly equivalent, makes it that urea reaction take place and obtains.
The urea reaction does not have special restriction, for example can be below 150 ℃ in temperature of reaction, preferred 40～140 ℃, more preferably under 40～120 ℃, the reaction times is to make its reaction under 0.5～50 hour, preferred 1～15 hour condition.
Temperature of reaction can stably manufactured in above-mentioned scope the time.On the one hand, when temperature of reaction surpasses 150 ℃, sometimes the part generation hydrolysis reaction of the alkoxysilyl of alkoxysilane compound containing trialkylsilyl group in molecular structure, generate silanol, and then form siloxane bond by condensation reaction with the silanol group or the alkoxysilyl of another molecule, reaction mass viscosity increases, and productivity reduces.On the other hand, reaction temperature is spent when low, and the reaction that contains the amino of the isocyanate group of polyamide resin of terminal isocyanate group and alkoxysilane compound containing trialkylsilyl group in molecular structure is not sometimes carried out fully, and productivity reduces.
In addition, in the urea reaction, decompose when isocyanate group and aminoalkoxy silyl and water (airborne moisture etc.) reaction.Therefore, this reaction should be avoided contacting with airborne moisture, preferably implements under inert gas atmosphere.As rare gas element, for example can enumerate nitrogen, helium etc., preferably enumerate nitrogen.
In addition, particularly, this reaction can disposable mixing contains the polyamide resin and the alkoxysilane compound containing trialkylsilyl group in molecular structure of terminal isocyanate group, in addition, also can add the polyamide resin that contains terminal isocyanate group in advance, to mixed oxyalkyl silane compound wherein, and then, also can add alkoxysilane compound containing trialkylsilyl group in molecular structure in advance, to wherein mixing the polyamide resin that contains terminal isocyanate group.
The number-average molecular weight of the alkoxysilane-modified polyamide resin that obtains as mentioned above is 500～40000 for example, is preferably 500～10000.In addition, urea rate (alkoxysilane-modified rate) is generally 76～100%, is preferably 86～100%.The urea rate can access the resin cured matter with excellent thermotolerance, binding property, physical strength in above-mentioned scope the time.
Alkoxysilane-modified polyamide resin is by the hydrolysis of alkoxysilyl, moisture curing.Therefore, alkoxysilane-modified polyamide resin can be used as a fluidity wet-cured type resin combination and is used for various fields.Particularly useful as the bonding composition of a fluidity wet-cured type hotmelt.
Under the situation of alkoxysilane-modified polyamide resin composition as the bonding composition of a fluidity wet-cured type hotmelt, the cooperation ratio of alkoxysilane-modified polyamide resin for example is more than 1 weight part, is preferably more than 10 weight parts with respect to 100 weight part hotmelts.
The resin cured matter that alkoxysilane-modified polyamide resin moisture curing is obtained has excellent thermotolerance, binding property, physical strength.Moisture curing can at high temperature, preferably add curing catalysts usually to be implemented.
Need to prove, comprise the polyamide resin that contains terminal isocyanate group and/or a fluidity wet-cured type resin combination of alkoxysilane-modified polyamide resin, can in the scope of not destroying excellent effect of the present invention, add additive in case of necessity.
As additive, for example can enumerate curing catalysts, silane coupling agent, internal mold release, tackifier, tenderizer, stablizer, antioxidant, UV light absorber, photostabilizer, softening agent, weighting agent, dyestuff, pigment, white dyes etc.
As curing catalysts, for example can enumerate organotin, metal complex, alkali, organic phosphoric acid etc.
As organotin, for example can enumerate dibutyl tin laurate, two oxysuccinic acid dioctyl tins, phthalic acid dibutyl tin, stannous octoate, dibutyl methoxyl group tin, dibutyl tin diacetyl acetonate, dibutyltin diacetate etc.
As metal complex, can enumerate titanate compound classes such as tetrabutyl titanate, titanium isopropylate, trolamine titanic acid ester, carboxylic metallic salts such as lead octoate 36, lead naphthenate, naphthoic acid nickel, naphthoic acid cobalt for example, for example, cetylacetone metallic such as aluminium acetylacetonate coordination compound, vanadium acetylacetonate coordination compound coordination compound etc.
As alkali, can enumerate methylamine, ethylamine, propyl group amine, isopropylamine, Yi Bingchunan, butylamine, the 1-N-Ethylbutylamine, isobutylamine, amylamine, octyl amine, lauryl amine, monoethanolamine, diethylamino propyl group amine, oleyl amine, cyclo-hexylamine, guanidine, the 2-DEHA, Triethylenetetramine (TETA), aniline, phenylenediamine, Tolylamine, toluamide, benzyl amine, benzene dimethylamine, primary amine such as ALPHA-NAPHTHYL AMINE, dimethyl amine for example, diethylamide, diethanolamine, diethylenetriamine, dibutylamine, N-methyl-butylamine, piperidines, diisoamyl amine, N-ethyl ALPHA-NAPHTHYL AMINE, benzylaniline, secondary amine such as diphenylguanidine, Trimethylamine for example, triethylamine, trolamine, tripropylamine, tributylamine, N, N-dimethyl-butylamine, N, N-dimethyl-octyl amine, N, N-dimethyl-lauryl amine, 1,4-diazabicyclo (2.2.2) octane (DABCO), 1,8-diazabicyclo (5.4.0) 11 carbon-7-alkene tertiary amines such as (DBU), for example tetramethyl ammonium chloride, quaternary ammonium salts such as benzalkonium chloride etc.
As the organic phosphoric acid compound, can enumerate monomethyl phosphoric acid, di-n-butyl phosphoric acid, triphenylphosphate etc.And then, also can enumerate other an acidic catalyst, basic catalyst etc.
Preferably enumerate organotin, metal complex.Above-mentioned curing catalysts may be used singly or two or more kinds thereof.In addition, the cooperation ratio of curing catalysts is 0.0001～10 weight part for example, is preferably 0.001～5 weight part with respect to 100 weight parts, one fluidity wet-cured type resin combination.
As silane coupling agent, can enumerate for example tetramethoxy-silicane, alkoxyl silicone alkanes such as tetraethoxysilane, N-β-(amino-ethyl)-gamma-amino propyl trimethoxy silicane for example, the gamma-amino propyl trimethoxy silicane, γ-An Jibingjisanyiyangjiguiwan, N-β-(amino-ethyl)-γ-An Jibingjisanyiyangjiguiwan, N-β-(amino-ethyl)-γ-propyl group methyl dimethoxysilane, N-(dimethoxy-methyl silyl propyl group) ethylene diamine, N-(triethoxysilylpropyltetrasulfide) ethylene diamine, N-phenyl-aminosilane classes such as gamma-amino propyl trimethoxy silicane, γ-glycidoxypropyltrime,hoxysilane for example, γ-glycidoxy propyl-triethoxysilicane, β-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane, epoxy radicals silicone hydride classes such as two (γ-glycidoxy propyl group) dimethoxy silane, vinyl silanes class such as vinyltriethoxysilane for example, for example γ-isocynate silane classes such as propyl isocyanate base Trimethoxy silane, for example chlorosilane class such as vinyl trichloro silane etc.
Preferably enumerate alkoxyl silicone alkanes, aminosilane class.Above-mentioned silane coupling agent can use separately or also use more than 2 kinds.In addition, the cooperation ratio of silane coupling agent is 0.01～50 weight part for example, is preferably 0.1～30 weight part with respect to 100 weight parts, one fluidity wet-cured type resin combination.
One fluidity wet-cured type resin combination for example in atmosphere, normal temperature～200 ℃ are down by heating 1～800 hour moisture curing easily.The gained resin cured matter has excellent thermotolerance, binding property, physical strength.
In addition, when one fluidity wet-cured type resin combination is used as the hotmelt of a fluidity wet-cured type, for example can use be equipped with heating unit, roller coating machine, spraying machine, hand gun known coating machine heating and meltings such as (Hand gun), then, with multiple pattern application on adherend, the adherend of fitting thus.At this moment, can be before hotmelt solidifies the applying adherend, also temporary transient solidified hotmelt can be heated once again and make its activation, then, the applying adherend.
Adherend does not have special restriction, for example can enumerate iron, copper, aluminium, tinned(sheet)iron, stainless steel (SUS), coated steel plate, zinc steel plate, polyethylene, polypropylene, PET, acrylic resin, ABS resin, vinyl chloride resin, polycarbonate, polymeric amide (nylon, aramid fiber), polystyrene, polyurethane(s), rubber, timber, glued board, hardboard, duricrust paper, paper, cloth etc.
[embodiment]
Below, according to synthesis example, embodiment and comparative example, the present invention is described, but the present invention is not limited thereto.In addition, the analysis of synthesis example, embodiment and comparative example, mensuration are carried out in accordance with the following methods.
(acid number)
" part acid number " according to JIS K6901 " aqueous unsaturated polyester resin test method " 5.3 " acid numbers " measured.
(hydroxyl value)
6.4 " hydroxyl values " according to JIS K1557 " urethane polyethers test method " are measured.
(isocyanate group containing ratio)
6.3 " isocyanate group containing ratios " according to JIS K7301 " thermoset carbamate resilient material with tolylene diisocyanate type prepolymer test method " are measured.(number-average molecular weight)
At room temperature with the 0.03g sample dissolution in the 10ml tetrahydrofuran (THF), then, after filtering with the strainer of aperture 0.45 μ m, adopt gel permeation chromatography (GPC) to measure under the following conditions.Number-average molecular weight is to be benchmark with the typical curve that uses the standard polyoxyethylene glycol to be made into, and the stratographic of calculating mensuration comprises the number-average molecular weight at the peak of the molecular weight of maximum frequency (retention time).
Device: HLC-8020 (Dong Caoshe system)
Chromatographic column: Dong Caoshe system TSKgel guardcolum HXL-L+G1000H XL+G2000H XL+G3000H XL
Elutriant: tetrahydrofuran (THF)
Flow: 0.8ml/ minute
Chromatogram column temperature: 40 ℃
Injection rate: 20 μ l
Detector: RI
(melt viscosity)
Use cone-plate type rotational viscosimeter (ICI society system), in circular cone kind: 100P, rotation number: 75rpm, temperature: measure under 100 ℃ the condition.
(amidation rate)
(1) for by the polyester polycarboxylic acid manufacturing contain the polyamide resin of terminal isocyanate group the time
NMR by following condition calculates.
Device: JNM-AL400 (JEOL society system)
Frequency: 400MHz
Measure temperature: room temperature
Cumulative number: 128 times
At room temperature with the 20mg sample dissolution behind 0.65ml dimethyl sulfoxide (DMSO)-d6 (containing 0.05%TMS), measure under these conditions
1H-NMR.The amidation rate is calculated by the integrated value of the proton (H) of isocyanate derivates and the integrated value of the proton in the acid amides (NH).
(2) for by the dimeracid manufacturing contain the polyamide resin of terminal isocyanate group the time
Obtain carbon dioxide production according to minimizing, calculate the amidation rate according to following formula with respect to the reaction afterreaction weight of material of total add-on.
(total add-on-reacted reaction mass weight)/((adding dimeracid amount/adding dimeracid COOH equivalent) * 44) * 100 (%)
(urea rate)
NMR by following condition calculates.
Device: JNM-AL400 (JEOL society system)
Frequency: 400MHz
Measure temperature: room temperature
Cumulative number: 128 times
At room temperature with the 20mg sample dissolution behind 0.65ml dimethyl sulfoxide (DMSO)-d6 (containing 0.05%TMS), measure under these conditions
1H-NMR.
When (1) alkoxysilane compound containing trialkylsilyl group in molecular structure has the phenyl substituted-amino
The urea rate is by the derivative of the alkoxysilane compound containing trialkylsilyl group in molecular structure with phenyl substituted-amino and have the integrated value (A) of proton (H) of the alkoxysilane compound containing trialkylsilyl group in molecular structure of phenyl substituted-amino and the integrated value (B) with proton (H) of the alkoxysilane compound containing trialkylsilyl group in molecular structure of phenyl substituted-amino is calculated according to following formula.
The urea rate=(A-B)/A * 100 (%)
When (2) alkoxysilane compound containing trialkylsilyl group in molecular structure has alkyl-substituted amino
The urea rate is calculated by the integrated value of the proton (NH) in the acid amides of the alkoxyl silicone alkane derivatives with alkyl-substituted amino and the integrated value of the proton in the urea (NH).
(thermotolerance: quality reduces by 10% temperature)
According to JIS K7120 " the thermogravimetric quantity measuring methods of plastics ", be that dry air, inflow gas amount are that 200ml/ minute, rate of heating are to measure the thermogravimetric amount under 10 ℃/minute the condition at inflow gas, calculate rate of mass reduction M according to following formula
L(%).Stable on heating evaluation is with rate of mass reduction M
LThe temperature that is at 10% o'clock is represented.
M
L＝(m
0-m
t)/m
0×100
m
0: the quality (mg) before the heating
m
t: temperature after heating t (℃) time quality (mg)
(thermotolerance: the beginning softening temperature)
Carry out dynamic viscoelastic test under the following conditions, the temperature (beginning remollescent temperature) the when value of measuring energy storage Young's modulus (E ') begins to reduce sharp.
Device: Measurement of Dynamic Viscoelasticity device DVA-200 (IT Keisoku Seigyo society system)
Sample: length 2.5cm, width 0.485cm between graticule
Deformation pattern: stretch
Quiet/the dynamic stress ratio: 1.8～2.0
Set distortion: 0.05～0.10% (E〉108Pa)
Set heat-up rate: 5 ℃/minute
Measure frequency: 10Hz
(tensile strength)
According to 5 " tension tests " of JIS K7312 " physical test method of heat-curable urethane resilient material forming composition ", measure under the following conditions.
Machine: tensile testing machine RTA-500L-XL (ORIENTEC society system)
Dumbbell (Dumbbell): No. 4 dumbbells
Thickness: 0.5～0.8mm
Temperature: 23 ℃
Humidity: 50% RH
Trial speed: 300mm/ minute
Synthesis example 1 (manufacturing of polyester polycarboxylic acid (A))
Take into account and add 2045.1 weight part hexanodioic acids and the 1306.5 weight part neopentyl glycol (equivalence ratios of COOH/OH: 1.12) in 5 liters of flasks of whipping appts to reflux exchanger, water separation device, nitrogen ingress pipe, temperature are housed, import nitrogen on one side, with mantle heater heat up on one side.
Begin to distillate water when reaching 150 ℃, be warming up to 230 ℃, then, continue dehydrating condensation down at 230 ℃ while water is distillated.The moment that the acid number of reaction product, hydroxyl value are arrived prescribed value takes out reaction product, cools off as terminal point from flask, obtain polyester polycarboxylic acid (A).The acid number of gained polyester polycarboxylic acid (A) is that 54.8mgKOH/g, hydroxyl value are 2.7mgKOH/g.
Synthesis example 2 (manufacturing of polyester polycarboxylic acid (B))
Except that the terminal point that changes dehydrating condensation, the method according to identical with synthesis example 1 obtains polyester polycarboxylic acid (B).The acid number of gained polyester polycarboxylic acid (B) is that 53.7mgKOH/g, hydroxyl value are 0.4mgKOH/g.
Synthesis example 3 (manufacturing of polyester polyol (A))
1.16), and 1.93 weight part Dibutyltin oxides take into account and add 1623.99 weight part hexanodioic acids, the 1342.55 weight part neopentyl glycol (equivalence ratio of OH/COOH: in 5 liters of flasks of whipping appts to reflux exchanger, water separation device, nitrogen ingress pipe, temperature are housed, import nitrogen on one side, with mantle heater heat up on one side.
Begin to distillate water when reaching 150 ℃, be warming up to 230 ℃, then, continue dehydrating condensation down at 230 ℃ while water is distillated.The hydroxyl value of reaction product, when acid number reaches prescribed value, reaction product is taken out from flask, cooled off, obtain polyester polyol (A).The hydroxyl value of gained polyester polyol (A) is that 53.5mgKOH/g, acid number are 0.6mgKOH/g.
Embodiment 1
(containing the manufacturing of the polyamide resin (A) of terminal isocyanate group)
2.10), 0.253 weight part Magnesium Stearate (carboxyl 100 molar part with respect to polyester polycarboxylic acid are 0.053 molar part), and 0.500 weight part Flowlen AC-1190 (common prosperity society chemistry system, defoamer) take into account and add 834.1 weight part polyester polycarboxylic acids (A), 165.9 weight parts 1 in 2 liters of reaction flasks of whipping appts to reflux exchanger, nitrogen ingress pipe, temperature are housed, two (isocyanatomethyl) hexanaphthenes (trade(brand)name: Takenate600, Mitsui Chemicals urethane society system) of 3-(equivalence ratio of NCO/COOH:.
Then, Yi Bian import nitrogen,, obtain containing the polyamide resin (A) of terminal isocyanate group Yi Bian after being warming up to 100 ℃ with mantle heater, under 100 ℃ of temperature of reaction, should reacting and continue 5 hours.
Gained contains in the polyamide resin (A) of terminal isocyanate group, and the isocyanate group containing ratio is that 3.7 weight % (theoretical value 3.7 weight %), viscosity are that 6400mPas/100 ℃, number-average molecular weight are 4800.
In addition, the mensuration gained contains the polyamide resin (A) of terminal isocyanate group
1H-NMR.By the NMR spectrogram, according to 1, the integrated value of the 0.7346H part that occurs in chemical shift 0.6ppm place among the 10H of the alicyclic moiety of two (isocyanatomethyl) cyclohexane derivants of 3-is the integrated value of the NH of acid amides 0.7346 o'clock, that occur in chemical shift 7.8ppm place, calculate the amidation rate, the result is 89%.
(manufacturing of hotmelt (A) and resin cured matter (A))
In plastic containers, add the polyamide resin (A) that 50 weight parts contain terminal isocyanate group, handled 30 minutes 100 ℃ of following vacuum defoamations, make a fluidity wet-cured type hotmelt (A) with Vacuumdrier.
Be coated with in right amount on the surface MIRAX RS-102 (Katsuzai Chemicals society system) as releasing agent, be heated on 100 ℃ the SUS plate, casting hotmelt (A), making the thickness of the cured article behind the moisture curing is 0.2～0.8mm, then, under 23 ℃, 50%RH air, make its moisture curing, obtain resin cured matter (A).
When adopting aforesaid method to measure the thermotolerance of gained resin cured matter (A), tensile strength, it is that 377 ℃, tensile strength are 16.7MPa (referring to table 1) that quality reduces by 10% temperature.
Embodiment 2
(containing the manufacturing of the polyamide resin (B) of terminal isocyanate group)
Except that temperature of reaction is become 110 ℃ from 100 ℃, obtain containing the polyamide resin (B) of terminal isocyanate group by the method identical with embodiment 1.
Gained contains in the polyamide resin (B) of terminal isocyanate group, and the isocyanate group containing ratio is that 3.5 weight % (theoretical value 3.7 weight %), viscosity are that 14000mPas/100 ℃, number-average molecular weight are 7200.
In addition, the mensuration gained contains the polyamide resin (B) of terminal isocyanate group
1H-NMR.According to the NMR spectrogram, by 1, the integrated value of the 0.7346H part that occurs in chemical shift 0.6ppm place among the 10H of the alicyclic moiety of two (isocyanatomethyl) cyclohexane derivants of 3-is the integrated value of the NH of acid amides 0.7346 o'clock, that occur in chemical shift 7.8ppm place, calculate the amidation rate, the result is 76%.
(manufacturing of hotmelt (B) and resin cured matter (B))
Except that using the polyamide resin (B) contain terminal isocyanate group to replace containing the polyamide resin (A) of terminal isocyanate group, make hotmelt (B) by the method identical with embodiment 1, obtain resin cured matter (B).
When adopting aforesaid method to measure the thermotolerance of gained resin cured matter (B), tensile strength, it is that 376 ℃, tensile strength are 15.1MPa (referring to table 1) that quality reduces by 10% temperature.
Embodiment 3
(containing the manufacturing of the polyamide resin (C) of terminal isocyanate group)
Take into account and add 202.0 weight parts 1 in 1 liter of reaction flask of whipping appts to reflux exchanger, nitrogen ingress pipe, temperature are housed, two (isocyanatomethyl) hexanaphthenes (trade(brand)name: Takenate600, Mitsui Chemicals urethane society system, isocyanate group containing ratio 43.3 weight %) of 3-, 0.308 weight part Magnesium Stearate (carboxyl 100 molar part with respect to dimeracid are 0.050 molar part), and 0.250 weight part Flowlen AC-1190 (common prosperity society chemistry system, defoamer), import nitrogen on one side, with mantle heater be warming up to 70 ℃ on one side.
Then, add 298.1 weight part hydrogenation high purity dimeracid (trade(brand)name: PRIPOL1009, Uniqema corporate system, acid number the 196mgKOH/g) (equivalence ratios of NCO/COOH: 2.00), be warming up to 100 ℃, under 100 ℃ of temperature of reaction, this reaction was continued 4 hours, obtain containing the polyamide resin (C) of terminal isocyanate group.
Gained contains in the polyamide resin (C) of terminal isocyanate group, and the isocyanic ester containing ratio is that 9.2 weight % (theoretical value 9.6 weight %), viscosity are that 5400mPas/100 ℃, number-average molecular weight are 2300.
In addition, obtain amount of carbon dioxide by the reaction afterreaction weight of material minimizing with respect to total add-on, amount of carbon dioxide is calculated the amidation rate thus, and the result is 87%.
(manufacturing of hotmelt (C) and resin cured matter (C))
In plastic containers, add the polyamide resin (C) that 50 weight parts contain terminal isocyanate group, handled 30 minutes 100 ℃ of following vacuum defoamations, make a fluidity wet-cured type hotmelt (C) with Vacuumdrier.
Be coated with in right amount on the surface MIRAX RS-102 (Katsuzai Chemicals society system) as releasing agent, be heated on 100 ℃ the SUS plate, casting hotmelt (C), after making the thickness of the cured article behind the moisture curing be 0.2～0.8mm, under 23 ℃, 50%RH air, make its moisture curing, obtain resin cured matter (C).
Adopt aforesaid method to measure thermotolerance, the tensile strength of gained resin cured matter (C), it is that 362 ℃, tensile strength are 41.9MPa (referring to table 1) that quality reduces by 10% temperature.
Comparative example 1
(containing the manufacturing of the urethane resin (A) of terminal isocyanate group)
Take into account and add 837.5 weight part polyester polyols (A) and 162.5 weight parts 1 in 2 liters of reaction flasks of whipping appts to reflux exchanger, nitrogen ingress pipe, temperature are housed, two (isocyanatomethyl) hexanaphthene (trade(brand)name: Takenate600, Mitsui Chemicals urethane society system, isocyanic ester containing ratio 43.3 weight the %) (equivalence ratios of NCO/OH: 2.10) of 3-, import nitrogen on one side, be warming up to 75 ℃ with mantle heater on one side, under 75 ℃ of temperature of reaction, this reaction was continued 5 hours, obtain containing the urethane resin (A) of terminal isocyanate group.
Gained contains in the urethane resin (A) of terminal isocyanate group, and the isocyanic ester containing ratio is that 3.4 weight %, viscosity are that 3900mPas/100 ℃, number-average molecular weight are 3700.
(manufacturing of hotmelt (D) and resin cured matter (D))
In plastic containers, add urethane resin (A) 50 weight parts that contain terminal isocyanate group, handled 30 minutes 100 ℃ of following vacuum defoamations, make a fluidity wet-cured type hotmelt (D) with Vacuumdrier.
Be coated with in right amount on the surface MIRAX RS-102 (Katsuzai Chemicals society system) as releasing agent, be heated on 100 ℃ the SUS plate, casting hotmelt (D), making the thickness of the cured article behind the moisture curing is 0.2～0.8mm, then, under 23 ℃, 50%RH air, make its moisture curing, obtain resin cured matter (D).
Adopt aforesaid method to measure thermotolerance, the tensile strength of gained resin cured matter (D), it is that 342 ℃, tensile strength are 12.6MPa (referring to table 1) that quality reduces by 10% temperature.
Comparative example 2
(containing the manufacturing of the urethane resin (B) of terminal isocyanate group)
To reflux exchanger is housed, nitrogen ingress pipe, temperature is taken into account and is added 295.5 weight parts, two polyalcohols (hydroxyl value 200mgKOH/g) in 1 liter of reaction flask of whipping appts, 204.5 weight part 1, two (isocyanatomethyl) hexanaphthene (trade(brand)names: Takenate600 of 3-, Mitsui Chemicals urethane society system, isocyanic ester containing ratio 43.3 weight %) (the equivalence ratio of NCO/OH: 2.00), and 0.100 weight part stannous octoate, import nitrogen on one side, be warming up to 80 ℃ with mantle heater on one side, under 80 ℃ of temperature of reaction, this reaction was continued 4 hours, obtain containing the urethane resin (B) of terminal isocyanate group.
Gained contains in the urethane resin (B) of terminal isocyanate group, and the isocyanic ester containing ratio is 9.0 weight %.
(manufacturing of hotmelt (E) and resin cured matter (E))
In plastic containers, add urethane resin (B) 50 weight parts that contain terminal isocyanate group, handled 30 minutes 100 ℃ of following vacuum defoamations, make a fluidity wet-cured type hotmelt (E) with Vacuumdrier.
Be coated with in right amount on the surface MIRAX RS-102 (Katsuzai Chemicals society system) as releasing agent, be heated on 100 ℃ the SUS plate, casting hotmelt (E), making the thickness of the cured article behind the moisture curing is 0.2～0.8mm, then, under 23 ℃, 50% RH air, make its moisture curing, obtain resin cured matter (E).
Adopt aforesaid method to measure thermotolerance, the tensile strength of gained resin cured matter (E), it is that 325 ℃, tensile strength are 31.4MPa (referring to table 1) that quality reduces by 10% temperature.
Embodiment 4
(containing the manufacturing of the polyamide resin (D) of terminal isocyanate group)
Take into account and add 842.4 weight part polyester polycarboxylic acids (B), 0.240 weight part Magnesium Stearate (carboxyl 100 molar part with respect to polyester polycarboxylic acid are 0.050 molar part), and 0.500 weight part Flowlen AC-1190 (common prosperity society chemistry system, defoamer) in 2 liters of reaction flasks of whipping appts to reflux exchanger, nitrogen ingress pipe, temperature are housed.
Then, import nitrogen on one side, with mantle heater be warming up to 50 ℃ on one side, then, add 157.6 weight parts 1, two (isocyanatomethyl) hexanaphthene (trade(brand)name: Takenate600, Mitsui Chemicals urethane society the system) (equivalence ratios of NCO/COOH: 2.01) of 3-.Then, be warming up to 70 ℃, under 70 ℃ of temperature of reaction, this reaction continued 7 hours, obtain containing the polyamide resin (D) of terminal isocyanate group.
Gained contains in the polyamide resin (D) of terminal isocyanate group, and the isocyanate group containing ratio is 3.7 weight % (theoretical value 3.7 weight %).
In addition, the mensuration gained contains the polyamide resin (D) of terminal isocyanate group
1H-NMR.According to the NMR spectrogram, by 1, the integrated value of the 0.7381H part that occurs in chemical shift 0.6ppm place among the 10H of the alicyclic moiety of two (isocyanatomethyl) cyclohexane derivants of 3-is the integrated value of the NH of acid amides 0.7381 o'clock, that occur in chemical shift 7.8ppm place, calculate the amidation rate, the result is 87%.
(manufacturing of alkoxysilane-modified polyamide resin (A))
Take into account and add 500.0 weight parts in 1 liter of reaction flask of whipping appts and contain the polyamide resin (D) of terminal isocyanate group to reflux exchanger, nitrogen ingress pipe, temperature are housed, Yi Bian import nitrogen, Yi Bian be warming up to 70 ℃ with mantle heater.
Then, splashed into 112.5 weight part N-phenyl-gamma-amino propyl trimethoxy silicanes (trade(brand)name: KBM573, chemical industry society of SHIN-ETSU HANTOTAI system) (equivalence ratio of NCO/NH: 1.00) through 1 hour with dropping funnel.After splashing into end, make it continue reaction 2 hours down, obtain alkoxysilane-modified polyamide resin (A) at 70 ℃.
In the alkoxysilane-modified polyamide resin of gained (A), the isocyanate group containing ratio is that 0.1 weight % is following, viscosity is that 2600mPas/100 ℃, number-average molecular weight are 3700.
In addition, measure the alkoxysilane-modified polyamide resin of gained (A)
1H-NMR.According to the NMR spectrogram, the integrated value of the 5H of the N-phenyl-gamma-amino propyl trimethoxy silicane derivative that occurs in chemical shift 6.4～7.5ppm place and the phenyl moiety of N-phenyl-gamma-amino propyl trimethoxy silicane be 5.0000 o'clock, be 0.2984 in the integrated value of the 5H of the phenyl moiety of the N-phenyl-gamma-amino propyl trimethoxy silicane of chemical shift 6.4～7.1ppm place appearance.When calculating the urea rate according to above-mentioned value is 94%.
(manufacturing of hotmelt (F) and resin cured matter (F))
In plastic containers, add the alkoxysilane-modified polyamide resins of 50 weight parts (A), 0.5 weight part stannous octoate, reach 0.5 weight part tetraethoxysilane, handled 30 minutes 100 ℃ of following vacuum defoamations with Vacuumdrier, make a fluidity wet-cured type hotmelt (F).
Be coated with in right amount on the surface MIRAX RS-102 (Katsuzai Chemicals society system) as releasing agent, be heated on 100 ℃ the SUS plate, casting hotmelt (F), making the thickness of the cured article behind the moisture curing is 0.8～1.5mm, then, under air, after placing 48 hours under 23 ℃, the condition of 50% RH, under 80 ℃, the condition of 30% RH, made its moisture curing, obtain resin cured matter (F) through 48 hours.
Adopt aforesaid method to measure thermotolerance, the tensile strength of gained resin cured matter (F), it is that 230 ℃, tensile strength are 5.24MPa (referring to table 2) that the result begins the remollescent temperature.
Embodiment 5
(containing the manufacturing of the polyamide resin (E) of terminal isocyanate group)
Take into account and add 1084.3 weight part polyester polycarboxylic acids (B), 0.309 weight part Magnesium Stearate (carboxyl 100 molar part with respect to polyester polycarboxylic acid are 0.050 molar part), and 0.650 weight part Flowlen AC-1190 (common prosperity society chemistry system, defoamer) in 2 liters of reaction flasks of whipping appts to reflux exchanger, nitrogen ingress pipe, temperature are housed.
Then, Yi Bian import nitrogen, Yi Bian be warming up to 50 ℃ with mantle heater, then, use dropping funnel to splash into 129.4 weight parts 1 through 2 minutes, two (isocyanatomethyl) hexanaphthenes (trade(brand)name: Takenate600, Mitsui Chemicals urethane society system) of 3-, maturation 5 minutes.Then, splashed into 86.3 weight parts 1 through 10 minutes, (whole equivalence ratios of NCO/COOH: 2.14), the temperature that splashes into after the end is 70 ℃ to two (isocyanatomethyl) hexanaphthenes of 3-.Then, under 70 ℃ of temperature of reaction, proceed this reaction 8 hours, obtain containing the polyamide resin (E) of terminal isocyanate group.
Gained contains in the polyamide resin (E) of terminal isocyanate group, and the isocyanate group containing ratio is 3.9 weight % (theoretical value 4.0 weight %).
In addition, the mensuration gained contains the polyamide resin (E) of terminal isocyanate group
1H-NMR.According to the NMR spectrogram, by 1, the integrated value of the 0.7381H part that occurs in chemical shift 0.6ppm place among the 10H of the alicyclic moiety of two (isocyanatomethyl) cyclohexane derivants of 3-is the integrated value of the NH of acid amides 0.7381 o'clock, that occur in chemical shift 7.8ppm place, calculate the amidation rate, the result is 98%.
(manufacturing of alkoxysilane-modified polyamide resin (B))
1.00), splash into temperature and temperature of reaction becomes 120 ℃ adding polyamide resin (E) that 242.7 weight parts contain terminal isocyanate group replaces containing the polyamide resin (D) of terminal isocyanate group, is the 57.3 weight parts (equivalence ratios of NCO/NH: with the quantitative change that splashes into of N-phenyl-gamma-amino propyl trimethoxy silicane, in addition, adopt the method identical, obtain alkoxysilane-modified polyamide resin (B) with embodiment 4.
In the alkoxysilane-modified polyamide resin of gained (B), the isocyanate group containing ratio is that 0.1 weight % is following, viscosity is that 6100mPas/100 ℃, number-average molecular weight are 4400.
In addition, measure the alkoxysilane-modified polyamide resin of gained (B)
1H-NMR.According to the NMR spectrogram, the integrated value of the 5H of the N-phenyl-gamma-amino propyl trimethoxy silicane derivative that occurs in chemical shift 6.4～7.5ppm place and the phenyl moiety of N-phenyl-gamma-amino propyl trimethoxy silicane be 5.0000 o'clock, be 0.8405 in the integrated value of the 5H of the phenyl moiety of the N-phenyl-gamma-amino propyl trimethoxy silicane of chemical shift 6.4～7.1ppm place appearance.Calculate the urea rate according to above-mentioned value, the result is 83%.
(manufacturing of hotmelt (G) and resin cured matter (G))
Except that using the alkoxysilane-modified polyamide resins of 50 weight parts (B) to replace the alkoxysilane-modified polyamide resin (A), adopt the method identical with embodiment 4, manufacturing hotmelt (G) obtains resin cured matter (G).
Adopt aforesaid method to measure thermotolerance, the tensile strength of gained resin cured matter (G), it is that 220 ℃, tensile strength are 3.96MPa (referring to table 2) that the result begins the remollescent temperature.
Embodiment 6
(manufacturing of alkoxysilane-modified polyamide resin (C))
Become 130 ℃ by 120 ℃ except that splashing into temperature and temperature of reaction, adopt the method identical, obtain alkoxysilane-modified polyamide resin (C) with embodiment 5.
In the alkoxysilane-modified polyamide resin of gained (C), the isocyanate group containing ratio is that 0.1 weight % is following, viscosity is that 6400mPas/100 ℃, number-average molecular weight are 4100.
In addition, measure the alkoxysilane-modified polyamide resin of gained (C)
1H-NMR.According to the NMR spectrogram, the integrated value of the 5H of the N-phenyl-gamma-amino propyl trimethoxy silicane derivative that occurs in chemical shift 6.4～7.5ppm place and the phenyl moiety of N-phenyl-gamma-amino propyl trimethoxy silicane be 5.0000 o'clock, be 0.8363 in the integrated value of the 5H of the phenyl moiety of the N-phenyl-gamma-amino propyl trimethoxy silicane of chemical shift 6.4～7.1ppm place appearance.Calculate the urea rate according to above-mentioned value, the result is 83%.
(manufacturing of hotmelt (H) and resin cured matter (H))
Except that using the alkoxysilane-modified polyamide resins of 50 weight parts (C) to replace the alkoxysilane-modified polyamide resin (A), adopt the method identical with embodiment 4, manufacturing hotmelt (H) obtains resin cured matter (H).
Adopt aforesaid method to measure thermotolerance, the tensile strength of gained resin cured matter (H), it is that 230 ℃, tensile strength are 4.34MPa (referring to table 2) that the result begins the remollescent temperature.
Embodiment 7
(manufacturing of alkoxysilane-modified polyamide resin (D))
Become 150 ℃ by 120 ℃ except that splashing into temperature and temperature of reaction, adopt the method identical, obtain alkoxysilane-modified polyamide resin (D) with embodiment 5.
In the alkoxysilane-modified polyamide resin of gained (D), the isocyanate group containing ratio is that 0.1 weight % is following, viscosity is that 5300mPas/100 ℃, number-average molecular weight are 4200.
In addition, measure the alkoxysilane-modified polyamide resin of gained (D)
1H-NMR.According to the NMR spectrogram, the integrated value of the 5H of the N-phenyl-gamma-amino propyl trimethoxy silicane derivative that occurs in chemical shift 6.4～7.5ppm place and the phenyl moiety of N-phenyl-gamma-amino propyl trimethoxy silicane be 5.0000 o'clock, be 0.8829 in the integrated value of the 5H of the phenyl moiety of the N-phenyl-gamma-amino propyl trimethoxy silicane of chemical shift 6.4～7.1ppm place appearance.Calculate the urea rate according to above-mentioned value, the result is 82%.
(manufacturing of hotmelt (I) and resin cured matter (I))
Except that using the alkoxysilane-modified polyamide resins of 50 weight parts (D) to replace the alkoxysilane-modified polyamide resin (A), adopt the method identical with embodiment 4, manufacturing hotmelt (I) obtains resin cured matter (I).
Adopt aforesaid method to measure thermotolerance, the tensile strength of gained resin cured matter (I), it is that 220 ℃, tensile strength are 4.00MPa (referring to table 2) that the result begins the remollescent temperature.
Embodiment 8
(containing the manufacturing of the polyamide resin (F) of terminal isocyanate group)
Add 1000.9 weight part polyester polycarboxylic acids (B), 0.285 weight part Magnesium Stearate (carboxyl 100 molar part with respect to polyester polycarboxylic acid are 0.050 molar part), 0.600 weight part Flowlen AC-1190, with 1, the addition of two (isocyanatomethyl) hexanaphthenes of 3-becomes the 199.1 weight parts (equivalence ratio of NCO/COOH: 2.14), in addition, adopt the method identical, obtain containing the polyamide resin (F) of terminal isocyanate group with embodiment 4.
Gained contains in the polyamide resin (F) of terminal isocyanate group, and the isocyanate group containing ratio is 4.0 weight % (theoretical value 4.0 weight %).
In addition, the mensuration gained contains the polyamide resin (F) of terminal isocyanate group
1H-NMR.According to the NMR spectrogram, by 1, the integrated value of the 0.7381H part that occurs in chemical shift 0.6ppm place among the 10H of the alicyclic moiety of two (isocyanatomethyl) cyclohexane derivants of 3-is the integrated value of the NH of acid amides 0.7381 o'clock, that occur in chemical shift 7.8ppm place, calculate the amidation rate, the result is 87%.
(manufacturing of alkoxysilane-modified polyamide resin (E))
Add polyamide resin (F) that 253.1 weight parts contain terminal isocyanate group replace containing terminal isocyanate group polyamide resin (D), splash into 46.9 weight part N-methyl-gamma-amino propyl trimethoxy silicanes (equivalence ratio of NCO/NH: 1.00) replace N-phenyl-gamma-amino propyl trimethoxy silicane, in addition, adopt the method identical, obtain alkoxysilane-modified polyamide resin (E) with embodiment 4.
In the alkoxysilane-modified polyamide resin of gained (E), the isocyanate group containing ratio is that 0.1 weight % is following, viscosity is that 2100mPas/100 ℃, number-average molecular weight are 3200.
In addition, measure the alkoxysilane-modified polyamide resin of gained (E)
1H-NMR.According to the NMR spectrogram, by the integrated value of the NH of the acid amides of the N-methyl-gamma-amino propyl trimethoxy silicane derivative that occurs at chemical shift 7.8ppm place be 0.8700 o'clock, in the integrated value of the NH of the urea of chemical shift 6.1～6.2ppm place appearance, calculate the urea rate, the result is 99%.
(manufacturing of hotmelt (J) and resin cured matter (J))
Except that using the alkoxysilane-modified polyamide resins of 50 weight parts (E) to replace the alkoxysilane-modified polyamide resin (A), adopt the method identical with embodiment 4, manufacturing hotmelt (J) obtains resin cured matter (J).
Adopt aforesaid method to measure thermotolerance, the tensile strength of gained resin cured matter (J), it is that 280 ℃, tensile strength are 5.17MPa (referring to table 2) that the result begins the remollescent temperature.
Embodiment 9
(containing the manufacturing of the polyamide resin (G) of terminal isocyanate group)
Take into account and add 202.0 weight parts 1 in 1 liter of reaction flask of whipping appts to reflux exchanger, nitrogen ingress pipe, temperature are housed, two (isocyanatomethyl) hexanaphthenes (trade(brand)name: Takenate600, Mitsui Chemicals urethane society system, isocyanic ester containing ratio 43.3 weight %) of 3-, 0.103 weight part Magnesium Stearate (carboxyl 100 molar part with respect to dimeracid are 0.017 molar part), and 0.250 weight part Flowlen AC-1190 (common prosperity society chemistry system, defoamer), import nitrogen on one side, with mantle heater be warming up to 60 ℃ on one side.
Then, add 298.0 weight part hydrogenation high purity dimeracid (trade(brand)name: PRIPOL1009, Uniqema corporate system, acid number the 196mgKOH/g) (equivalence ratios of NCO/COOH: 2.00), be warming up to 70 ℃, under 70 ℃ of temperature of reaction, this reaction was continued 7 hours, obtain containing the polyamide resin (G) of terminal isocyanate group.
Gained contains in the polyamide resin (G) of terminal isocyanate group, and the isocyanic ester containing ratio is that 10.0 weight % (theoretical value 9.6 weight %), viscosity are that 1800mPas/100 ℃, number-average molecular weight are 1800.
In addition, obtain amount of carbon dioxide by the reacted reaction mass weight minimizing with respect to total add-on, calculate the amidation rate according to this amount of carbon dioxide, the result is 89%.
(manufacturing of alkoxysilane-modified polyamide resin (F))
Take into account and add 419.6 weight parts in 1 liter of reaction flask of whipping appts and contain the polyamide resin (G) of terminal isocyanate group to reflux exchanger, nitrogen ingress pipe, temperature are housed, Yi Bian import nitrogen, Yi Bian be warming up to 75 ℃ with mantle heater.
Then, use dropping funnel to splash into 254.9 weight part N-phenyl-gamma-amino propyl trimethoxy silicanes (trade(brand)name: KBM573, chemical industry society of SHIN-ETSU HANTOTAI system) (equivalence ratio of NCO/NH: 1.00) through 1.5 hours.After splashing into end, this reaction was continued 2 hours, obtain alkoxysilane-modified polyamide resin (F).
In the alkoxysilane-modified polyamide resin of gained (F), the isocyanic ester containing ratio is that 0.1 weight %, viscosity are that 2000mPas/100 ℃, number-average molecular weight are 1600.
(manufacturing of hotmelt (K) and resin cured matter (K))
Except that using the alkoxysilane-modified polyamide resins of 50 weight parts (F) to replace the alkoxysilane-modified polyamide resin (A), adopt the method identical with embodiment 4, manufacturing hotmelt (K) obtains resin cured matter (K).
Adopt aforesaid method to measure thermotolerance, the tensile strength of gained resin cured matter (K), it is that 240 ℃, tensile strength are 54.5MPa (referring to table 2) that the result begins the remollescent temperature.
Comparative example 3
(manufacturing of alkoxysilane-modified polyamide resin (G))
The add-on that will contain the polyamide resin (D) of terminal isocyanate group becomes 259.1 weight parts, splashes into 40.9 weight part gamma-amino propyl trimethoxy silicanes (trade(brand)name: KBM903, chemical industry society of SHIN-ETSU HANTOTAI system) (NCO/NH
2Equivalence ratio: 1.00) replace N-phenyl-gamma-amino propyl trimethoxy silicane, in addition, adopt the method identical, attempt manufacturing alkoxysilane-modified polyamide resin (F) with embodiment 4.
But, splash into end after, under 70 ℃ of temperature of reaction, this reaction continued moment of 30 minutes, gelation takes place, can not stir.
Comparative example 4
(containing the manufacturing of the urethane resin (C) of terminal isocyanate group)
Take into account and add 208.9 weight part polyester polyols (A) and 41.1 weight parts 1 in 500 milliliters of reaction flasks of whipping appts to reflux exchanger, nitrogen ingress pipe, temperature are housed, two (isocyanatomethyl) hexanaphthene (trade(brand)name: Takenate600, Mitsui Chemicals urethane system, isocyanic ester containing ratio 43.3 weight the %) (equivalence ratios of NCO/OH: 2.13) of 3-, import nitrogen on one side, be warming up to 75 ℃ with mantle heater on one side, under 75 ℃ of temperature of reaction, this reaction was continued 5 hours, obtain containing the urethane resin (C) of terminal isocyanate group.
Gained contains in the urethane resin (C) of terminal isocyanate group, and the isocyanate group containing ratio is 3.6 weight %.
(manufacturing of alkoxysilane-modified urethane resin (A))
Take into account and add the urethane resin (C) that 205.1 weight parts contain terminal isocyanate group in 500 milliliters of reaction flasks of whipping appts to reflux exchanger, nitrogen ingress pipe, temperature are housed, import nitrogen on one side, with mantle heater be warming up to 70 ℃ on one side.
Then, use dropping funnel to splash into 44.9 weight part N-phenyl-gamma-amino propyl trimethoxy silicanes (trade(brand)name: KBM573, chemical industry society of SHIN-ETSU HANTOTAI system) (equivalence ratio of NCO/NH: 1.00) through 1 hour.After splashing into end, this reaction was continued 2 hours, obtain alkoxysilane-modified urethane resin (A).
In the alkoxysilane-modified urethane resin of gained (A), the isocyanate group containing ratio is below the 0.1 weight %.
(manufacturing of hotmelt (L) and resin cured matter (L))
In plastic containers, add the alkoxysilane-modified urethane resins of 50 weight parts (A), 0.5 weight part stannous octoate, reach 0.5 weight part tetraethoxysilane, handled 30 minutes 100 ℃ of following vacuum defoamations with Vacuumdrier, make a fluidity wet-cured type hotmelt (L).
Be coated with in right amount on the surface MIRAX RS-102 (Katsuzai Chemicals society system) as releasing agent, be heated on 100 ℃ the SUS plate, casting hotmelt (L), making the thickness of the cured article behind the moisture curing is 0.8～1.5mm, then, under air, after placing 48 hours under 23 ℃, the condition of 50% RH, under 80 ℃, the condition of 30% RH, made its moisture curing, obtain resin cured matter (L) through 48 hours.
Adopt aforesaid method to measure thermotolerance, the tensile strength of gained resin cured matter (L), it is that 190 ℃, tensile strength are 3.41MPa (referring to table 3) that the result begins the remollescent temperature.
Comparative example 5
(manufacturing of alkoxysilane-modified urethane resin (B))
Take into account and add the urethane resin (C) that 223.2 weight parts contain terminal isocyanate group in 500 milliliters of reaction flasks of whipping appts to reflux exchanger, nitrogen ingress pipe, temperature are housed, import nitrogen on one side, with mantle heater be warming up to 70 ℃ on one side.
Then, use dropping funnel to splash into 36.5 weight part N-methyl-gamma-amino propyl trimethoxy silicane (equivalence ratio of NCO/NH: 1.01) through 1 hour.After splashing into end, this reaction was continued 2 hours, obtain alkoxysilane-modified urethane resin (B).
In the alkoxysilane-modified urethane resin of gained (B), the isocyanate group containing ratio is below the 0.1 weight %.
(manufacturing of hotmelt (M) and resin cured matter (M))
Except that using the alkoxysilane-modified urethane resins of 50 weight parts (B) to replace the alkoxysilane-modified urethane resin (A), adopt the method identical with comparative example 4, manufacturing hotmelt (M) obtains resin cured matter (M).
Adopt aforesaid method to measure thermotolerance, the tensile strength of gained resin cured matter (M), it is that 240 ℃, tensile strength are 4.40MPa (referring to table 3) that the result begins the remollescent temperature.
Comparative example 6
(manufacturing of alkoxysilane-modified urethane resin (C))
Take into account and add 323.2 weight parts in 1 liter of reaction flask of whipping appts and contain the urethane resin (B) of terminal isocyanate group to reflux exchanger, nitrogen ingress pipe, temperature are housed, Yi Bian import nitrogen, Yi Bian be warming up to 80 ℃ with mantle heater.
Then, use dropping funnel to splash into 176.8 weight part N-phenyl-gamma-amino propyl trimethoxy silicanes (trade(brand)name: KBM573, chemical industry society of SHIN-ETSU HANTOTAI system) (equivalence ratio of NCO/NH: 1.00) through 1.5 hours.After splashing into end, this reaction was continued 2 hours, obtain alkoxysilane-modified urethane resin (C).
In the alkoxysilane-modified urethane resin of gained (C), the isocyanic ester containing ratio is below the 0.1 weight %.
(manufacturing of hotmelt (N) and resin cured matter (N))
Except that using the alkoxysilane-modified urethane resins of 50 weight parts (C) to replace the alkoxysilane-modified urethane resin (A), adopt the method identical with comparative example 4, manufacturing hotmelt (N) obtains resin cured matter (N).
Adopt aforesaid method to measure thermotolerance, the tensile strength of gained resin cured matter (N), it is that 190 ℃, tensile strength are 44.2MPa (referring to table 3) that the result begins the remollescent temperature.
Comparative example 7
(manufacturing of alkoxysilane-modified isocyanic ester)
Take into account and add 142.1 weight part N-phenyl-gamma-amino propyl trimethoxy silicanes (trade(brand)name: KBM573, chemical industry society of SHIN-ETSU HANTOTAI system) in 500 milliliters of reaction flasks of whipping appts to reflux exchanger, nitrogen ingress pipe, temperature are housed, import nitrogen on one side, with mantle heater be warming up to 70 ℃ on one side.
Then, add 107.9 weight parts 1, two (isocyanatomethyl) hexanaphthene (trade(brand)name: Takenate600, Mitsui Chemicals urethane society system, isocyanic ester containing ratio 43.3 weight the %) (equivalence ratios of NCO/NH: 2.00) of 3-, this reaction was continued 3 hours, obtain alkoxysilane-modified isocyanic ester.
In the alkoxysilane-modified isocyanic ester of gained, the isocyanate group containing ratio is 9.3 weight.
(manufacturing of alkoxysilane-modified polyamide resin (H))
Take into account and add 174.5 weight part polyester polycarboxylic acids (B), 0.049 weight part Magnesium Stearate (carboxyl 100 molar part with respect to polyester polycarboxylic acid are 0.050 molar part), and 0.125 weight part Flowlen AC-1190 (chemistry society of common prosperity society system, defoamer) in 500 milliliters of reaction flasks of whipping appts to reflux exchanger, nitrogen ingress pipe, temperature are housed, import nitrogen on one side, with mantle heater be warming up to 70 ℃ on one side.
Then, add the alkoxysilane-modified isocyanic ester of the 75.5 weight parts (equivalence ratio of NCO/COOH: 1.00).After splashing into end, this reaction was continued 7 hours, obtain alkoxysilane-modified polyamide resin (H).
In the alkoxysilane-modified polyamide resin of gained (H), the isocyanate group containing ratio is below the 0.1 weight %.
(manufacturing of hotmelt (O) and resin cured matter (O))
Except that using the alkoxysilane-modified polyamide resins of 50 weight parts (H) to replace the alkoxysilane-modified urethane resin (A), adopt the method identical with comparative example 4, manufacturing hotmelt (O) obtains resin cured matter (O).
Adopt aforesaid method to measure thermotolerance, the tensile strength of gained resin cured matter (O), it is that 200 ℃, tensile strength are 3.50MPa (referring to table 3) that the result begins the remollescent temperature.
Need to prove, provide above-mentioned explanation, but this explanation only is for example, can not do limited explanation as the embodiment of enumerating among the present invention.Those of ordinary skill conspicuous variation of the present invention in present technique field all is included in the application's the claim scope.
Utilizability on the industry
The polyamide that contains terminal isocyanate group of the present invention and alkoxysilane-modified Polyamide is as fluidity wet-cured type resin combinations such as hotmelts, various workers Industry can be used in the field effectively.
Claims (18)
1, a kind of polyamide resin that contains terminal isocyanate group is characterized in that, is to be that excessive ratio reaction obtain with isocyanate group with respect to carboxyl by making the oligopolymer that contains terminal carboxyl(group) and polyisocyanate compound.
2, the polyamide resin that contains terminal isocyanate group as claimed in claim 1 is characterized in that, the described oligopolymer that contains terminal carboxyl(group) is selected from polyester polycarboxylic acid and the dimeracid that is obtained by polynary acids and polyol reaction.
3, a kind of alkoxysilane-modified polyamide resin is characterized in that, be to obtain by the polyamide resin that contains terminal isocyanate group is reacted with the alkoxysilane compound containing trialkylsilyl group in molecular structure that contains secondary amine,
The described polyamide resin that contains terminal isocyanate group is to be that excessive ratio reaction obtain with isocyanate group with respect to carboxyl by making the oligopolymer that contains terminal carboxyl(group) and polyisocyanate compound.
4, alkoxysilane-modified polyamide resin as claimed in claim 3 is characterized in that, the described oligopolymer that contains terminal carboxyl(group) is selected from polyester polycarboxylic acid and the dimeracid that is obtained by polynary acids and polyol reaction.
5, alkoxysilane-modified polyamide resin as claimed in claim 3 is characterized in that, described alkoxysilane compound containing trialkylsilyl group in molecular structure shown in following general formula (1),
In the formula, R1 represents the alkylidene group of carbonatoms 1～20, and R2 represents the alkyl of carbonatoms 1～20, and R3, R4 and R5 are same to each other or different to each other, the alkoxyl group or the alkyl of expression carbonatoms 1～20, wherein, at least 1 expression alkoxyl group among R3, R4 and the R5.
6, a kind of hotmelt is characterized in that, comprises the polyamide resin and/or the alkoxysilane-modified polyamide resin that contain terminal isocyanate group,
The described polyamide resin that contains terminal isocyanate group is to be that excessive ratio reaction obtain with isocyanate group with respect to carboxyl by making the oligopolymer that contains terminal carboxyl(group) and polyisocyanate compound,
Described alkoxysilane-modified polyamide resin is by the described polyamide resin that contains terminal isocyanate group is obtained with the alkoxysilane compound containing trialkylsilyl group in molecular structure reaction that contains secondary amine.
7, hotmelt as claimed in claim 6 is characterized in that, is a fluidity wet-cured type tackiness agent.
8, a kind of resin cured matter is characterized in that, is that polyamide resin and/or the curing of alkoxysilane-modified polyamide resin that will contain terminal isocyanate group obtains,
The described polyamide resin that contains terminal isocyanate group is to be that excessive ratio reaction obtain with isocyanate group with respect to carboxyl by making the oligopolymer that contains terminal carboxyl(group) and polyisocyanate compound,
Described alkoxysilane-modified polyamide resin is by the described polyamide resin that contains terminal isocyanate group is obtained with the alkoxysilane compound containing trialkylsilyl group in molecular structure reaction that contains secondary amine.
9, a kind of manufacture method that contains the polyamide resin of terminal isocyanate group is characterized in that, makes the oligopolymer and the polyisocyanate compound that contain terminal carboxyl(group),
Is excessive ratio with isocyanate group with respect to carboxyl,
With respect to described total carboxyl 100 molar part that contain the oligopolymer of terminal carboxyl(group) be 0.001～10 molar part, be selected from catalyzer in an alkali metal salt and/or the alkaline earth salt in the presence of, react.
10, the manufacture method that contains the polyamide resin of terminal isocyanate group as claimed in claim 9 is characterized in that, makes it in reaction below 120 ℃.
11, the manufacture method that contains the polyamide resin of terminal isocyanate group as claimed in claim 9 is characterized in that, described catalyzer is a Magnesium Stearate.
12, the manufacture method that contains the polyamide resin of terminal isocyanate group as claimed in claim 9 is characterized in that, the described oligopolymer that contains terminal carboxyl(group) is selected from polyester polycarboxylic acid and the dimeracid that is obtained by polynary acids and polyol reaction.
13, a kind of manufacture method of alkoxysilane-modified polyamide resin, it is characterized in that, make the oligopolymer that contains terminal carboxyl(group) and polyisocyanate compound with isocyanate group with respect to carboxyl be excessive ratio, with respect to described total carboxyl 100 molar part that contain the oligopolymer of terminal carboxyl(group) be 0.001～10 molar part, be selected from catalyzer in an alkali metal salt and/or the alkaline earth salt in the presence of reaction, obtain containing the polyamide resin of terminal isocyanate group
Make the described alkoxysilane compound containing trialkylsilyl group in molecular structure reaction that contains the polyamide resin of terminal isocyanate group and contain secondary amine.
14, the manufacture method of alkoxysilane-modified polyamide resin as claimed in claim 13 is characterized in that, described oligopolymer and the described polyisocyanate compound that contains terminal carboxyl(group) reacted below 120 ℃.
15, the manufacture method of alkoxysilane-modified polyamide resin as claimed in claim 13 is characterized in that, described polyamide resin and the described alkoxysilane compound containing trialkylsilyl group in molecular structure that contains terminal isocyanate group reacted below 150 ℃.
16, the manufacture method of alkoxysilane-modified polyamide resin as claimed in claim 13 is characterized in that, described catalyzer is a Magnesium Stearate.
17, the manufacture method of alkoxysilane-modified polyamide resin as claimed in claim 13 is characterized in that, the described oligopolymer that contains terminal carboxyl(group) is selected from polyester polycarboxylic acid and the dimeracid that is obtained by polynary acids and polyol reaction.
18, the manufacture method of alkoxysilane-modified polyamide resin as claimed in claim 13 is characterized in that, described alkoxysilane compound containing trialkylsilyl group in molecular structure shown in following general formula (1),
In the formula, R1 represents the alkylidene group of carbonatoms 1～20, and R2 represents the alkyl of carbonatoms 1～20, and R3, R4 and R5 are same to each other or different to each other, the alkoxyl group or the alkyl of expression carbonatoms 1～20, and wherein, at least 1 among R3, R4 and the R5 is alkoxyl group.
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| JP2006271136 | 2006-10-02 | ||
| JP271136/2006 | 2006-10-02 | ||
| JP042864/2007 | 2007-02-22 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105131380A (en) * | 2015-08-18 | 2015-12-09 | 合肥市再德高分子材料有限公司 | High-performance modified carboxylated acrylonitrile butadiene rubber composite material |
| CN111201285A (en) * | 2017-10-13 | 2020-05-26 | 尤尼吉可株式会社 | Paste containing nickel nanowires |
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2007
- 2007-09-07 CN CNA2007800291255A patent/CN101501094A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105131380A (en) * | 2015-08-18 | 2015-12-09 | 合肥市再德高分子材料有限公司 | High-performance modified carboxylated acrylonitrile butadiene rubber composite material |
| CN111201285A (en) * | 2017-10-13 | 2020-05-26 | 尤尼吉可株式会社 | Paste containing nickel nanowires |
| CN111201285B (en) * | 2017-10-13 | 2023-03-31 | 尤尼吉可株式会社 | Paste containing nickel nanowires |
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