CN1788030A - Aqueous silylated urethane composition, aqueous adhesives for wrapping, and aqueous contact adhesives - Google Patents

Abstract

An aqueous silylated urethane composition useful as an aqueous adhesive which is highly safe, develops excellent tack in a short time, and is excellent in initial bond strength. The aqueous silylated urethane composition is characterized by comprising (A) an alkoxysilyl-terminated urethane prepolymer having an anionic group and a tertiary amino group which prepolymer is produced by reacting a polyol compound (A1) free from anionic groups, a polyol compound (A2) having an anionic group, a compound (A3) having a tertiary amino group and an isocyanate-reactive group, a polyisocyanate compound (A4), an alkoxysilane compound (A5) having an isocyanate-reactive group, and an amine chain extender (A6), (B) a basic compound, and (C) water.

Description

Silylated urethane waterborne compositions and water-based adhesives for wrapping and water-based contact adhesives

Technical field

The present invention relates to silylated urethane waterborne compositions and water-based adhesives for wrapping and water-based contact adhesives, in more detail, relate to safe, in addition, show the excellent needed time of clinging power short, the initial stage is excellent in adhesion and equal productive silylated urethane waterborne compositions and water-based adhesives for wrapping and water-based contact adhesives can bring into play and use the solvent based caking agent time.

Background technology

In the past, as adhesives for wrapping, mainly used the solvent type polyurethane resin class caking agent that the initial stage is excellent in adhesion and clinging power is excellent.But, in recent years,, expect safe caking agent from environmental problem or pathogenic house problem etc.Therefore, up to now, as adhesives for wrapping, though proposed various water-based type caking agents, present situation is, reaches not only that to show the adhesive time long, and the clinging power deficiency, in fact, particularly uses industrial also failing.

On the other hand, the resin combination of using as water-based type caking agent, opening the 2003-48946 communique as the spy puts down in writing, present inventors have developed a kind of silylated urethane waterborne compositions, described composition contains when containing the anionic property group, has the polymkeric substance (the alkoxysilyl end polymer that contains the anionic property group) of alkoxysilyl endways.In this silylated urethane waterborne compositions, owing to used the alkoxysilyl end polymer that contains the anionic property group, therefore, make moderate progress for reaching the time or the clinging power ratio aqueous adhesive in the past that show adhesion, but when comparing with the caking agent of solvent based, therefore can't say very fully, we can say that use range is restricted.Like this, still have room for improvement for reaching the time or the clinging power that show adhesion, expectation has excellent clinging power and reaches the further exploitation of the water-based type caking agent of shortening of time that shows clinging power.

Summary of the invention

The objective of the invention is to, provide safe, to show the needed time of excellent clinging power in addition short, silylated urethane waterborne compositions that the initial stage is excellent in adhesion and water-based adhesives for wrapping and water-based contact adhesives.

Another object of the present invention is to, productive silylated urethane waterborne compositions and water-based adhesives for wrapping and water-based contact adhesives equal in the time of can bringing into play and use the solvent based caking agent also is provided.

Present inventors are for solving found that of above-mentioned problem further investigation, specific silylated urethane waterborne compositions shows the time weak point that excellent clinging power needs, initial stage tackiness excellence, in addition, owing to be water-based, therefore safe and when using as adhesives for wrapping, equal productivity in the time of can having given play to and use the solvent based caking agent, thus the present invention finished.

That is, the present invention relates to a kind of silylated urethane waterborne compositions, it is characterized in that, said composition contains following (A) composition, (B) composition and (C) composition.

(A) the terminal polyurethane prepolymer of the alkoxysilyl that contains anionic property group and uncle's amino that the polyol compound (A1) that does not contain the anionic property group, the polyol compound (A2) that contains the anionic property group, the compound (A3) that contains uncle's amino and isocyanate-reactive group, polyisocyanate compound (A4), the alkoxysilane compound containing trialkylsilyl group in molecular structure (A5) that contains isocyanate-reactive group and amine chain extender (A6) reaction are obtained

(B) basic cpd

(C) water

In silylated urethane waterborne compositions of the present invention, the terminal polyurethane prepolymer of alkoxysilyl (A) that contains anionic property group and uncle's amino also can be, by by the polyol compound that does not contain the anionic property group (A1), the polyol compound (A2) that contains the anionic property group, the compound (A3) that contains uncle's amino and isocyanate-reactive group, and the polyurethane prepolymer that contains anionic property group and uncle's amino that obtains of the reaction of polyisocyanate compound (A4), react with the alkoxysilane compound containing trialkylsilyl group in molecular structure that contains isocyanate-reactive group (A5), make isocyanate group partly alkoxyl silicone alkanisation and the alkoxyl silicone alkanisation anionic property group that contains terminal portions that obtains and the polyurethane prepolymer of uncle's amino of the end of the above-mentioned polyurethane prepolymer that contains anionic property group and uncle's amino, again by amine chain extender (A6), make residual isocyanate group in the polyurethane prepolymer of the above-mentioned anionic property group that contains terminal portions ground alkoxyl silicone alkanisation and uncle's amino, with the amino reaction of above-mentioned amine chain extender (A6) chain extension the anionic property group that contains the alkoxyl silicone alkanisation and the polyurethane prepolymer of uncle's amino.

As such silylated urethane waterborne compositions, preferably comprise anionic property group in the polyurethane prepolymer (A) of the alkoxysilyl end that contains anionic property group and uncle's amino by basic cpd (B) neutralization and terminal alkoxysilyl by the aqueous silane of water (C) hydrolysis alcoholization polyurethane prepolymer compositions.

In the present invention, as the above-mentioned polyol compound (A2) that contains the anionic property group, the preferred anionic group is a carboxyl, can preferably use the dihydroxymethyl paraffinic acid.

As the above-mentioned compound (A3) that contains uncle's amino and isocyanate-reactive group, preferably contain the tertiary amine compounds of a plurality of isocyanate-reactive groups, more preferred N, two (hydroxyl-organic group)-N-alkylamines of N-.

In addition, in the present invention, as the alkoxysilane compound containing trialkylsilyl group in molecular structure that contains isocyanate-reactive group (A5), the preferred alkoxysilane compound containing trialkylsilyl group in molecular structure that contains secondary amino group that obtains of alkoxysilane compound containing trialkylsilyl group in molecular structure by containing primary amino at least and esters of unsaturated carboxylic acids reaction more preferably reacts the alkoxysilane compound containing trialkylsilyl group in molecular structure that contains secondary amino group that obtains by alkoxysilane compound containing trialkylsilyl group in molecular structure and the esters of unsaturated carboxylic acids that contains primary amino and secondary amino group.

In the terminal polyurethane prepolymer of the alkoxysilyl that contains anionic property group and uncle's amino (A), as the preferred 0.4meq/g of the content of anionic property group or more than the 0.4meq/g, as the preferred 0.15meq/g of the content of uncle's amino or more than the 0.15meq/g.Ratio preferred tertiary amino/anionic property group (mol ratio)=0.2～1 as above-mentioned anionic property group and uncle's amino.

In addition, as the ratio of amino of the uncle in the terminal polyurethane prepolymer of the alkoxysilyl that contains anionic property group and uncle's amino (A) and alkoxysilane group, preferred tertiary amino/alkoxysilyl (mol ratio)=1.0～5.5.

In addition, the present invention comprises water-based adhesives for wrapping or water-based contact adhesives, it is characterized in that, contains above-mentioned silylated urethane waterborne compositions.

The simple declaration of accompanying drawing

Fig. 1 is the summary sectional drawing that the section form of the MDF by sealing machine applying polyolefins sheet is shown.

Fig. 2 is the summary sectional drawing that the section form of the MDF by sealing machine applying polyolefins sheet is shown.

Fig. 3 is the summary sectional drawing that the section form of the MDF by sealing machine applying polyolefins sheet is shown.

Fig. 4 is that the MDF that is illustrated in section form shown in Figure 1 goes up the summary sectional drawing by the state of sealing machine applying polyolefins sheet.

Fig. 5 is that the MDF that is illustrated in section form shown in Figure 2 goes up the summary sectional drawing by the state of sealing machine applying polyolefins sheet.

Fig. 6 is that the MDF that is illustrated in section form shown in Figure 3 goes up the summary sectional drawing by the state of sealing machine applying polyolefins sheet.

The preferred plan that carries out an invention

In silylated urethane waterborne compositions of the present invention, the terminal polyurethane prepolymer of alkoxysilyl (A) that contains anionic property group and uncle's amino obtains by the polyol compound (A1) that does not contain the anionic property group, the polyol compound (A2) that contains the anionic property group, the compound (A3) that contains uncle's amino and isocyanate-reactive group, polyisocyanate compound (A4), the alkoxysilane compound containing trialkylsilyl group in molecular structure (A5) that contains isocyanate-reactive group and amine chain extender (A6) reaction.

[not conforming to the polyol compound (A1) that the anionic property group is arranged]

Do not conform to polyol compound (A1) that the anionic property group is arranged (below be sometimes referred to as " polyvalent alcohol (A1) "),, then have no particular limits so long as intramolecularly does not have the compound that anionic property group and intramolecularly have 2 hydroxyls at least.Polyvalent alcohol (A1) can be used in combination separately or more than 2 kinds or 2 kinds.

(A1) can enumerate as polyvalent alcohol, for example, and polyvalent alcohol, polyether glycol, polyester polyol, polycarbonate polyol, polyolefin polyhydric alcohol, polyacrylic polyvalent alcohol, castor-oil plant wet goods.

In polyvalent alcohol (A1), polyvalent alcohol comprises, for example, ethylene glycol, glycol ether, propylene glycol, dipropylene glycol, trimethylene, 1, the 4-tetramethylene glycol, 1, the 3-tetramethylene glycol, the 2-methyl isophthalic acid, the 3-trimethylene, 1,5-pentamethylene glycol, neopentyl glycol, 1, the 6-hexamethylene glycol, the 3-methyl isophthalic acid, 5-pentamethylene glycol, 2,4-diethyl-1,5-pentamethylene glycol, glycerine, TriMethylolPropane(TMP), trimethylolethane, cyclohexanediol class (1,4-cyclohexanediol etc.), bisphenols (dihydroxyphenyl propane etc.), glycitols (Xylitol or Sorbitol Powder etc.) etc.

As polyether glycol, can enumerate, for example, polyalkylene glycols such as polyoxyethylene glycol, polypropylene glycol, polytetramethylene glycol, and the multipolymer that contains a plurality of epoxy alkane as monomer component (epoxy alkane-other epoxy alkane) of other PEP-101 etc. etc.

As polyester polyol, can adopt, for example, the polycondensate of polyvalent alcohol and polycarboxylic acid; The ring-opening polymerization polymer of cyclic ester (lactone); The reactant that generates by polyvalent alcohol, polycarboxylic acid and 3 kinds of compositions of cyclic ester etc.In the polycondensate of polyvalent alcohol and polycarboxylic acid,, can use above-mentioned illustrative polyvalent alcohol as polyvalent alcohol.On the other hand,, can enumerate aliphatic dicarboxylic acids such as propanedioic acid, toxilic acid, succsinic acid, pentanedioic acid, hexanodioic acid, suberic acid, nonane diacid, sebacic acid, dodecanedioic acid as polycarboxylic acid; 1, the 4-cyclohexyl dicarboxylic acid waits the ester ring type dicarboxylic acid; Terephthalic acid, m-phthalic acid, phthalic acid, 2,6-naphthalene dicarboxylic acids, to aromatic dicarboxylic acids such as benzene dicarboxylic acid, trimellitic acid etc.In addition, in the ring-opening polymerization polymer of cyclic ester,, can enumerate as cyclic ester, for example, propiolactone, Beta-methyl-δ-Wu Neizhi, 6-caprolactone etc.In the reactant that generates by 3 kinds of compositions,, can use above-mentioned illustrative material etc. as polyvalent alcohol, polycarboxylic acid, cyclic ester.

As polycarbonate polyol, can enumerate, for example, the reactant of polyvalent alcohol and carbonyl chloride; The ring-opening polymerization polymer of cyclic carbonate (alkylene carbonates etc.) etc.Particularly, in the reactant of polyvalent alcohol and carbonyl chloride,, can use above-mentioned illustrative polyvalent alcohol as polyvalent alcohol.In addition, in the ring-opening polymerization polymer of cyclic carbonate,, can enumerate ethylene carbonate, carbonic acid trimethylene ester, carbonic acid tetramethylene ester, carbonic acid hexa-methylene ester etc. as alkylene carbonates.In addition, polycarbonate polyol also can be that intramolecularly has carbonic acid ester bond, end to be can also have carbonic acid ester bond and ester bond simultaneously by the compound of hydroxyl.

Polyolefin polyhydric alcohol is the polyvalent alcohol that contains 2 hydroxyls at least as skeleton (or main chain) composition and the intramolecularly (particularly endways) of polymkeric substance or multipolymer with alkene.As above-mentioned alkene, can be the alkene (for example, alpha-olefin such as ethene, propylene etc.) that end has carbon-to-carbon double bond, also can be in addition position beyond endways have a carbon-to-carbon double bond alkene (for example, iso-butylene etc.), can also be diolefine (for example, divinyl, isoprene etc.).

The polyacrylic polyvalent alcohol is to be the composition of skeleton (or main chain) of polymkeric substance or multipolymer and the polyvalent alcohol that intramolecularly contains 2 hydroxyls at least with (methyl) acrylate.Preferably use (methyl) alkyl acrylate [for example, (methyl) vinylformic acid C such as (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) propyl acrylate, (methyl) butyl acrylate, (methyl) Ethyl acrylate, (methyl) Octyl acrylate, (methyl) 2-EHA, (methyl) decyl acrylate, (methyl) vinylformic acid dodecane ester, (methyl) vinylformic acid stearyl as (methyl) acrylate _1-20Alkyl ester etc.].

In addition, in polyolefin polyhydric alcohol or polyacrylic polyvalent alcohol, for importing hydroxyl to intramolecularly, copolymer composition as alkene or (methyl) acrylate, can use α with hydroxyl, β-unsaturated compound [for example, (methyl) acrylic acid hydroxy alkyl ester such as (methyl) 2-Hydroxy ethyl acrylate, (methyl) vinylformic acid 3-hydroxy propyl ester etc.]

Can preferably use polyether glycol, polyester polyol, polycarbonate polyol as polyvalent alcohol (A1).

[polyol compound (A2) that contains the anionic property group]

The polyol compound (A2) (below, be sometimes referred to as polyvalent alcohol (A2)) that contains the anionic property group so long as intramolecularly has the compound that 1 anionic property group and intramolecularly have 2 hydroxyls at least at least, then has no particular limits.In polyvalent alcohol (A2), preferably use carboxyl, sulfo group as the anionic property group, wherein, the most preferred carboxyl.Polyvalent alcohol (A2) can use more than 2 kinds or 2 kinds alone or in combination.

As polyvalent alcohol (A2), can enumerate, for example, in the polyvalent alcohol shown in above-mentioned polyvalent alcohol (A1) item, import the polyvalent alcohol that contains carboxyl of carboxyl etc.In the present invention,, preferably have the low molecular weight polyols of anionic property group, especially, can preferably use multi-hydroxy carboxy acid with following formula (1) expression as polyvalent alcohol (A2).

(HO) _XL(COOH) _Y (1)

(here, in formula (1), L represents that carbonatoms is 1～12 hydrocarbon part.X is the integer more than 2 or 2, and Y is the integer more than 1 or 1.)

In above-mentioned formula (1), as the hydrocarbon part of L, preferred aliphat hydrocarbon part, straight chain shape or any one of branch's catenate form arranged.In addition, X, Y can be the same or different.Hydroxyl more than 2 or 2 can be combined on the same carbon atom, also can be combined on the different carbon atoms, in addition, Y is 2 or 2 when above, carboxyl more than 2 or 2 can be combined on the same carbon atom, can be combined on the different carbon atoms.

As such multi-hydroxy carboxy acid, particularly preferred dihydroxymethyl paraffinic acid (especially 2,2-dihydroxymethyl paraffinic acid).Can enumerate as the dihydroxymethyl paraffinic acid, for example, 2,2-dimethylol propionic acid, 2,2-dimethylolpropionic acid, 2,2-dihydroxymethyl valeric acid, 2,2-dihydroxymethyl caproic acid, 2,2-dihydroxymethyl enanthic acid, 2, the 2-dihydroxymethyl is sad, 2,2-dihydroxymethyl n-nonanoic acid, 2,2-dihydroxymethyl capric acid etc.

[compound (A3) that contains uncle's amino and isocyanate-reactive group]

Contain uncle's amino and isocyanate-reactive gene compound (A3) (below, be sometimes referred to as " isocyanate-reactive compound (A3) that contains uncle's amino ") as long as intramolecularly contains the compound that at least 1 uncle's amino and intramolecularly contain 1 isocyanate-reactive group at least, then have no particular limits.The isocyanate-reactive compound (A3) that contains uncle's amino can use separately also and can be used in combination more than 2 kinds or 2 kinds.

In the isocyanate-reactive compound that contains uncle's amino (A3), as uncle's amino (disubstituted amido), also can be by having alkyl (aryl such as phenyl for example; Alkyl such as methyl, ethyl, propyl group, butyl; Cycloalkyl such as cyclohexyl etc.) etc. substituting group forms uncle's amino.This alkyl can also have other substituting groups (for example, alkoxyl group, aryloxy, cycloalkyloxy, carbalkoxy, aryloxy carbonyl, cycloalkoxycarbonyl, acyl group etc.).

Number as the intramolecular uncle's amino in the isocyanate-reactive compound that contains uncle's amino (A3) has no particular limits, and can select preferred 1～3 (being more preferably 1 or 2, preferred especially 1) from for example 1～6 scope.Like this, isocyanate-reactive compound (A3) intramolecularly that contains uncle's amino can have a plurality of uncle's amino, but especially preferably only has uncle's amino.In addition, have a plurality of uncles when amino, uncle's amino can be just a kind of, also can make up more than 2 kinds or 2 kinds.

In addition, contain in the isocyanate-reactive compound (A3) of uncle's amino, as isocyanate-reactive group, get final product so long as isocyanate group is had reactive group, have no particular limits, can enumerate, for example, hydroxyl, primary amino or secondary amino group, sulfydryl etc., preferred hydroxyl, primary amino or secondary amino group, preferred especially hydroxyl.Isocyanate-reactive compound (A3) molecule that contains uncle's amino can only have 1 isocyanate-reactive group and also can have a plurality of.Like this, as the number of the intramolecularly isocyanate-reactive group in the isocyanate-reactive compound that contains uncle's amino (A3) so long as at least 1 get final product, have no particular limits, but can select preferred especially 2 from the scope of for example 1～6 (preferred 1～3).In addition, when having a plurality of isocyanate-reactive group, isocyanate-reactive group can be a kind, also can make up more than 2 kinds or 2 kinds.

In the isocyanate-reactive compound that contains uncle's amino (A3), isocyanate-reactive group also can directly be combined on the nitrogen-atoms of uncle's amino, but preferably passes through the group combination of divalent.Can enumerate as such divalent group, for example, the divalent alkyl that alkylidene group, alkenylene (ア リ レ Application base), alkylidene group-alkenylene, alkylidene group-alkenylene-alkylidene group etc. only are made of alkyl; Oxygen-alkylidene group, alkylidene group-oxygen-alkylidene group, alkylidene group-carbonyl-oxygen-alkylidene group, alkylidene group-oxygen-carbonyl-alkylidene group, alkylidene group-poly-(oxo alkylidene group) base [poly-(alkylene oxide)-alkylidene group] waits by the various various divalent groups that constitute of alkyl and other base (oxygen base, carbonyl-oxygen etc.) etc.

The isocyanate-reactive compound (A3) that contains uncle's amino has the form that uncle's amino is incorporated into various organic groups.Have no particular limits as the amino bonded organic group of uncle, but preferred alkyl.As such alkyl, can enumerate, for example, aliphatic alkyl (for example, alkyl such as methyl, ethyl, propyl group, sec.-propyl, butyl, amyl group, hexyl etc.), ester ring type alkyl (for example, cycloalkyl such as cyclohexyl etc.), aryl radical (for example, aryl such as phenyl etc.) etc.Alkyl can also have the substituting group more than a kind or 2 kinds or 2 kinds; as this substituting group; can enumerate; for example; other alkyl, isocyanate-reactive group are (for example; hydroxyl, primary amino, secondary amino group, sulfydryl etc.), non-isocyanate reactive group (for example, uncle's amino, alkoxyl group, aryloxy, cycloalkyloxy, carbalkoxy, aryloxy carbonyl, cycloalkoxycarbonyl, acyl group etc.) etc.

Therefore, can use the tertiary amine compounds that contains a plurality of isocyanate-reactive groups as the isocyanate-reactive compound that contains uncle's amino (A3).As such tertiary amine compounds that contains a plurality of isocyanate-reactive groups, then have no particular limits so long as contain the tertiary amine compounds of a plurality of isocyanate-reactive groups, but can enumerate, for example, on 1 nitrogen-atoms in conjunction with in 1 organic group (organic group that contains isocyanate-reactive group) that contains isocyanate-reactive group, tertiary amine compounds [tertiary amine compounds (A3-1) that contains the organic group of 1 isocyanate-reactive group] in conjunction with the form of 2 organic groups (organic group that contains alkyl) that contain alkyl, on 1 nitrogen-atoms in conjunction with in 2 organic groups that contain isocyanate-reactive group, in conjunction with the tertiary amine compounds [tertiary amine compounds (A3-2) that contains the organic group of 2 isocyanate-reactive groups] of the form of 1 organic group that contains alkyl, on 1 nitrogen-atoms in conjunction with the tertiary amine compounds [tertiary amine compounds (A3-3) that contains the organic group of three carbimide reactive groups] of the form of 3 organic groups that contain isocyanate-reactive group, on 1 nitrogen-atoms in conjunction with 2 uncle's amino that contain isocyanate-reactive group each other directly or the tertiary amine compounds of the group bonded form by divalent [tertiary amine compounds (A3-4)] etc. with uncle's amino of 2 organic groups that contain 2 isocyanate-reactive groups.

Particularly, tertiary amine compounds (A3-1) as the organic group that contains 1 isocyanate-reactive group, when isocyanate-reactive group is " tertiary amine compounds that contains the organic group of 1 hydroxyl " of hydroxyl, can enumerate, for example, N-methylol-N, N dimethylamine, N-(2-hydroxyethyl)-N, N dimethylamine, N-(3-hydroxypropyl)-N, N dimethylamine, N-(2-hydroxypropyl)-N, N dimethylamine, N-(4-hydroxybutyl)-N, N dimethylamine, N-methylol-N, N dimethylamine, N-(2-hydroxyethyl)-N, N dimethylamine, N-(3-hydroxypropyl)-N, N dimethylamine, N-(2-hydroxypropyl)-N, N dimethylamine, N-(4-hydroxybutyl)-N, N dimethylamine, N-(2-hydroxyethyl)-N, the N-dipropyl amine, N-(2-hydroxyethyl)-N, the N-Diisopropylamine, N-(2-hydroxyethyl)-N, N-hydroxyalkyl-N such as N-Di-n-Butyl Amine, N-dialkylamine; N-[methylol-poly-(oxidation methylene radical)]-N, N dimethylamine, N-[2-hydroxyethyl-poly-(oxidation ethylidene)]-N, N dimethylamine, N-[3-hydroxypropyl-poly-(oxypropylene)]-N, N dimethylamine, N-[2-hydroxypropyl-poly-(oxidation isopropylidene)]-N, N dimethylamine, N-[4-hydroxybutyl-poly-(oxybutylene)]-N, N dimethylamine, N-[methylol-poly-(oxidation methylene radical)]-N, N dimethylamine, N-[2-hydroxyethyl-poly-(oxidation ethylidene)]-N, N dimethylamine, N-[3-hydroxypropyl-poly-(oxypropylene)]-N, N dimethylamine, N-[2-hydroxypropyl-poly-(oxidation isopropylidene)]-N, N dimethylamine, N-[4-hydroxybutyl-poly-(oxybutylene)]-N, N dimethylamine, N-[2-hydroxyethyl-poly-(oxidation ethylidene)]-N, the N-dipropyl amine, N-[2-hydroxyethyl-poly-(oxidation ethylidene)]-N, the N-Diisopropylamine, N-[2-hydroxyethyl-poly-(oxidation ethylidene)]-N, N-[hydroxyalkyls such as N-Di-n-Butyl Amine-poly-(alkylidene oxide)]-N, N-(hydroxyl-organic group)-N such as N-dialkylamine, the N-dialkylamine, or N-methylol-N, the N-pentanoic, N-(2-hydroxyethyl)-N, the N-pentanoic, N-(3-hydroxypropyl)-N, the N-pentanoic, N-(2-hydroxypropyl)-N, the N-pentanoic, N-(4-hydroxybutyl)-N, N-hydroxyalkyl-N such as N-pentanoic, the N-diarylamine; N-[methylol-poly-(oxidation methylene radical)]-N, N-pentanoic, N-[2-hydroxyethyl-poly-(oxidation ethylidene)]-N, N-pentanoic, N-[3-hydroxypropyl-poly-(oxypropylene)-N, N-pentanoic, N-[2-hydroxypropyl-poly-(oxidation isopropylidene)-N, N-pentanoic, N-[4-hydroxybutyl-poly-(oxybutylene)-N, N such as N-pentanoic, N-[hydroxyalkyl-poly-(alkylidene oxide)]-N, N such as N-diarylamine, N-two (hydroxyl-organic group)]-N, the N-diarylamine; Their N-(hydroxyl-organic group)-N of correspondence, N-bicyclic alkyl amine etc.

In addition, tertiary amine compounds (A3-1) as the organic group that contains 1 isocyanate-reactive group, when isocyanate-reactive group is " tertiary amine compounds that contains the organic group of 1 uncle or secondary amino group " of amino (primary amino or secondary amino group), can enumerate, for example, the corresponding tertiary amine compounds of material of giving an example with above-mentioned conduct " tertiary amine compounds that contains the organic group of 1 hydroxyl ".

Tertiary amine compounds (A3-2) as the organic group that contains 2 isocyanate-reactive groups, when isocyanate-reactive group is " tertiary amine compounds that contains the organic group of 2 hydroxyls " of hydroxyl, can enumerate, for example, N, two (the methylol)-N-methylamines of N-, N, two (2-the hydroxyethyl)-N-methylamines of N-, N, two (3-the hydroxypropyl)-N-methylamines of N-, N, two (2-the hydroxypropyl)-N-methylamines of N-, N, two (4-the hydroxybutyl)-N-methylamines of N-, N, two (the methylol)-N-ethamine of N-, N, two (2-the hydroxyethyl)-N-ethamine of N-, N, two (3-the hydroxypropyl)-N-ethamine of N-, N, two (2-the hydroxypropyl)-N-ethamine of N-, N, two (4-the hydroxybutyl)-N-ethamine of N-, N, two (2-the hydroxyethyl)-N-propylamine of N-, N, two (2-the hydroxyethyl)-N-Isopropylamines of N-, N, two (2-the hydroxyethyl)-N such as N-n-Butyl Amine 99 of N-, two (the hydroxyalkyl)-N-alkylamines of N-; N, two [hydroxymethyl-poly-(oxidation methylene radical)]-N-methylamines of N-, N, two [2-hydroxyethyl-poly-(oxidation ethylidene)]-N-methylamines of N-, N, two [3-hydroxypropyl-poly-(oxypropylene)]-N-methylamines of N-, N, two [2-hydroxypropyl-poly-(oxidation isopropylidene)]-N-methylamines of N-, N, two [4-hydroxybutyl-poly-(oxybutylene)]-N-methylamines of N-, N, two [hydroxymethyl-poly-(oxidation methylene radical)]-N-ethamine of N-, N, two [2-hydroxyethyl-poly-(oxidation ethylidene)]-N-ethamine of N-, N, two [3-hydroxypropyl-poly-(oxypropylene)]-N-ethamine of N-, N, two [2-hydroxypropyl-poly-(oxidation isopropylidene)]-N-ethamine of N-, N, two [4-hydroxybutyl-poly-(oxybutylene)]-N-ethamine of N-, N, two [2-hydroxyethyl-poly-(oxidation ethylidene)]-N-propylamine of N-, N, two [2-hydroxyethyl-poly-(oxidation ethylidene)]-N-Isopropylamines of N-, N, two [2-hydroxyethyl-poly-(oxidation ethylidene)]-N such as N-n-Butyl Amine 99 of N-, two [hydroxyalkyl-poly-(alkylidene oxide)]-N such as N-alkylamine of N-, two (hydroxyl-organic group)-N-alkylamines of N-, or N, two (the methylol)-N-aniline of N-, N, two (2-the hydroxyethyl)-N-aniline of N-, N, two (3-the hydroxypropyl)-N-aniline of N-, N, two (2-the hydroxypropyl)-N-aniline of N-, N, two (4-the hydroxybutyl)-N such as N-aniline of N-, two (the hydroxyalkyl)-N-arylaminess of N-; N, two [hydroxymethyl-poly-(oxidation methylene radical)]-N-aniline of N-, N, two [2-hydroxyethyl-poly-(oxidation ethylidene)]-N-aniline of N-, N, two [3-hydroxypropyl-poly-(oxypropylene)]-N-aniline of N-, N, two [2-hydroxypropyl-poly-(oxidation isopropylidene)]-N-aniline of N-, N, two [4-hydroxybutyl-poly-(oxybutylene)]-N such as N-aniline of N-, N-two [hydroxyalkyl-N such as poly-(alkylidene oxide) 1-N-arylamines, two (hydroxyl-organic group)-N-arylaminess of N-; Their N of correspondence, two (hydroxyl-organic group)-N-Cycloalkyl amines of N-etc.

In addition, tertiary amine compounds (A3-2) as the organic group that contains 2 isocyanate-reactive groups, when isocyanate-reactive group is " tertiary amine compounds that contains the organic group of 2 uncles or secondary amino group " of amino (primary amino or secondary amino group), can enumerate, for example, the corresponding tertiary amine compounds of material of giving an example with above-mentioned conduct " tertiary amine compounds that contains the organic group of 2 hydroxyls ".

As the tertiary amine compounds (A3-3) of the organic group that contains 3 isocyanate-reactive groups, when isocyanate-reactive group is " tertiary amine compounds that contains the organic group of 3 hydroxyls " of hydroxyl, can enumerate, for example, N, N, N-three (methylol) amine, N, N, N-three (2-hydroxyethyl) amine, N, N, N-three (3-hydroxypropyl) amine, N, N, N-three (2-hydroxypropyl) amine, N, N, N such as N-three (4-hydroxybutyl) amine, N, N-three (hydroxyalkyl)-N-amine; N, N, N-three [hydroxymethyl-poly-(oxidation methylene radical)] amine, N, N, N-three [2-hydroxyethyl-poly-(oxidation ethylidene)] amine, N, N, N-three [3-hydroxypropyl-poly-(oxypropylene)] amine, N, N, N-three [2-hydroxypropyl-poly-(oxidation isopropylidene)] amine, N, N, N such as N-three [4-hydroxybutyl-poly-(oxybutylene)] amine, N, N such as N-three [hydroxyalkyl-poly-(alkylidene oxide)] amine, N, N-three (hydroxyl-organic group) amine etc.

In addition, tertiary amine compounds (A3-3) as the organic group that contains 3 isocyanate-reactive groups, when isocyanate-reactive group is " tertiary amine compounds that contains the organic group of 3 uncles or secondary amino group " of amino (primary amino or secondary amino group), can enumerate, for example, correspond to the tertiary amine compounds of material for example with above-mentioned conduct " tertiary amine compounds that contains the organic group of 3 hydroxyls ".

As the tertiary amine compounds (A3-4) of uncle's amino, when isocyanate-reactive group is " tertiary amine compounds with uncle's amino of 2 organic groups that contain 2 hydroxyls " of hydroxyl, can enumerate with 2 organic groups that contain 2 isocyanate-reactive groups, for example, N, N, N ', N '-four (methylol) ethylene diamine, N, N, N ', N '-four (2-hydroxyethyl) ethylene diamine, N, N, N ', N '-four (3-hydroxypropyl) ethylene diamine, N, N, N ', N '-four (2-hydroxypropyl) ethylene diamine, N, N, N ', N such as N '-four (4-hydroxybutyl) ethylene diamine, N, N ', N such as N '-four (hydroxyl-alkyl) Alkylenediamine, N, N ', N '-four (hydroxyl-organic radical) Alkylenediamine etc.

In addition, tertiary amine compounds (A3-4) as uncle's amino with 2 organic groups that contain 2 isocyanate-reactive groups, at isocyanate-reactive group during for " the tertiary amine compounds " of amino (primary amino or secondary amino group) with uncle's amino of 2 organic groups that contain 2 uncles or secondary amino group, can enumerate, for example, the corresponding tertiary amine compounds of material of giving an example with above-mentioned conduct " tertiary amine compounds " with uncle's amino of 2 organic groups that contain 2 hydroxyls.

[polyisocyanate compound (A4)]

Polyisocyanate compound (A4) (below, be sometimes referred to as " polyisocyanates (A4) ") then has no particular limits so long as have the compound of 2 isocyanate groups at least at intramolecularly.In the polyisocyanates (A4), for example, comprise aliphatic polyisocyante, ester ring type polyisocyanates, aromatic polyisocyanate, aromatic-aliphatic polyisocyanates etc.Polyisocyanates (A4) can be used in combination separately or more than 2 kinds or 2 kinds.

As aliphatic polyisocyante, can enumerate, for example, 1, the 3-trimethylene diisocyanate, 1, the 4-tetramethylene diisocyanate, 1, the 3-pentamethylene diisocyanate, 1, the 5-pentamethylene diisocyanate, 1, the 6-hexamethylene diisocyanate, the propylene vulcabond, 1,2-butylidene vulcabond, 2,3-butylidene vulcabond, 1,3-butylidene vulcabond, the 2-methyl isophthalic acid, the 5-pentamethylene diisocyanate, the 3-methyl isophthalic acid, the 5-pentamethylene diisocyanate, 2,4,4-trimethylammonium-1,6-hexamethylene diisocyanate, 2,2,4-trimethylammonium-1, the 6-hexamethylene diisocyanate, 2,6-vulcabond methyl caproate, aliphatic diisocyanates such as lysinediisocyanate etc.

As the ester ring type polyisocyanates, can enumerate, for example, 1,3-pentamethylene vulcabond, 1, the 4-cyclohexyl diisocyanate, 1, the 3-cyclohexyl diisocyanate, 3-methyl isocyanate-3,3,5-3-methyl cyclohexanol based isocyanate, 4,4 '-methylene-bis (cyclohexyl isocyanate), methyl-2, the 4-cyclohexyl diisocyanate, methyl-2, the 6-cyclohexyl diisocyanate, 1, two (isocyanic acid methyl) hexanaphthenes of 3-, 1, two (isocyanic acid methyl) hexanaphthenes of 4-, isophorone diisocyanate, ester ring type vulcabond such as norbornene alkyl diisocyanate etc.

As aromatic polyisocyanate, can enumerate, for example, the metaphenylene vulcabond, to phenylene vulcabond, 2,4-toluene support vulcabond, 2,6-toluene support vulcabond, naphthylidene-1, the 4-vulcabond, naphthylene-1,4,4 '-diphenyl diisocyanate, 4,4 '-diphenylmethanediisocyanate, 2,4 '-diphenylmethanediisocyanate, 4,4 '-the phenyl ether vulcabond, 2-nitro phenylbenzene-4,4 '-vulcabond, 2,2 '-diphenyl propane-4,4 '-vulcabond, 3,3 '-dimethyl diphenylmethane-4,4 '-vulcabond, 4,4 '-the diphenyl propane vulcabond, 3,3 '-dimethoxy phenylbenzene-4,4 '-aromatic diisocyanates such as vulcabond etc.

As the aromatic-aliphatic polyisocyanates, can enumerate, for example, 1,3-xylylene vulcabond, 1,4-xylylene vulcabond, ω, ω '-vulcabond-1,4-diethylbenzene, 1, two (1-isocyanic ester-1-methylethyl) benzene, 1 of 3-, two (1-isocyanic ester-1-methylethyl) benzene, 1 of 4-, aromatic-aliphatic vulcabond such as two (α, the alpha-alpha-dimethyl isocyanic ester methyl) benzene of 3-etc.

As polyisocyanates (A4), can preferably use 1, the 6-hexamethylene diisocyanate, 4,4 '-methylene-bis (cyclohexyl isocyanate), 1, two (isocyanic ester methyl) hexanaphthenes of 3-, 1, two (isocyanic ester methyl) hexanaphthenes of 4-, isophorone diisocyanate, 2,4-toluene support vulcabond, 2,6-toluene support vulcabond, 4,4 '-diphenylmethanediisocyanate, 1, the 3-eylylene diisocyanate, 1, the 4-eylylene diisocyanate, norbornene alkyl diisocyanate, 1, two (α, the alpha-alpha-dimethyl isocyanic ester methyl) benzene of 3-.In addition, as polyisocyanates (A4),, can obtain the few resin of variable color if when using aliphatic polyisocyante, ester ring type polyisocyanates or aromatic-aliphatic polyisocyanates.

In addition, in the present invention, also can use by above-mentioned illustrative aliphatic polyisocyante as polyisocyanates (A4), the ester ring type polyisocyanates, aromatic polyisocyanate, dipolymer that the aromatic-aliphatic polyisocyanates obtains or trimer, resultant of reaction or polymkeric substance (for example dipolymer of diphenylmethanediisocyanate or trimer, the resultant of reaction of TriMethylolPropane(TMP) and toluene support vulcabond, the resultant of reaction of TriMethylolPropane(TMP) and hexamethylene diisocyanate, polymethylene multi-phenenyl isocyanate, the polyethers polyisocyanates, polyester polyisocyanates etc.) etc.

In addition, in the present invention, can use diisothiocyanic acid ester compound (for example, phenyl diisothio-cyanate etc.) simultaneously with polyisocyanates (A4).

[alkoxysilane compound containing trialkylsilyl group in molecular structure (A5) that contains isocyanate-reactive group]

As the alkoxysilane compound containing trialkylsilyl group in molecular structure that contains isocyanate-reactive group (A5) (below, be sometimes referred to as " organoalkoxysilane (A5) that contains isocyanate-reactive group "), so long as intramolecularly has 1 isocyanate-reactive group at least and intramolecularly has 1 alkoxysilane compound containing trialkylsilyl group in molecular structure at least, then have no particular limits.The organoalkoxysilane (A5) that contains isocyanate-reactive group can be used in combination separately or more than 2 kinds or 2 kinds.

, can enumerate so long as isocyanate groups is had reactive group then have no particular limits as isocyanate-reactive group, for example, primary amino, secondary amino group, sulfydryl, isocyanate group, hydroxyl etc., preferred uncle or secondary amino group, sulfydryl.In addition, isocyanate-reactive group can be a kind ofly also can make up more than 2 kinds or 2 kinds.

In the present invention, can preferably use the alkoxysilane compound containing trialkylsilyl group in molecular structure (A5-1) that contains uncle or secondary amino group, the alkoxysilane compound containing trialkylsilyl group in molecular structure (A5-2) that contains sulfydryl as the organoalkoxysilane that contains isocyanate-reactive group (A5).

In addition, as containing the uncle or the alkoxysilane compound containing trialkylsilyl group in molecular structure (A5-1) of secondary amino group (below be sometimes referred to as " containing amino organoalkoxysilane (A5-1) ") so long as intramolecularly has 1 uncle or secondary amino group at least, and intramolecularly has the silane compound of 1 alkoxyl group at least, then has no particular limits.Therefore, contain amino organoalkoxysilane (A5-1),, also can contain the uncle's amino more than 1 or 1 as amino.In addition, as the alkoxysilane compound containing trialkylsilyl group in molecular structure that contains sulfydryl (A5-2), (below be sometimes referred to as " organoalkoxysilane (A5-2) that contains sulfydryl ") is so long as intramolecularly has 1 sulfydryl at least, and intramolecularly has the silane compound of 1 alkoxyl group at least, then has no particular limits.

In containing the organoalkoxysilane of isocyanate-reactive group (A5), as alkoxyl group, can preferably use, for example, C such as methoxyl group, oxyethyl group, propoxy-, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert.-butoxy _1～4Alkoxyl group.Can enumerate methoxyl group, oxyethyl group, propoxy-(especially methoxyl group, oxyethyl group) as the alkoxyl group that is more preferably.Such alkoxyl group is combined on the Siliciumatom of the organoalkoxysilane (A5) that contains isocyanate-reactive group usually, normally 1～3 of its number (preferred 2 or 3).In addition, alkoxyl group can be used in combination separately or more than 2 kinds or 2 kinds.That is, on the Siliciumatom that contains the organoalkoxysilane of isocyanate-reactive group (A5), can be in conjunction with same alkoxyl group, can be in conjunction with the different alkoxyl group of combination more than 2 kinds or 2 kinds.

In addition, when isocyanate-reactive group was amino, secondary amino group or uncle's amino were by having alkyl (for example, aryl such as phenyl; Alkyl such as methyl, ethyl, propyl group, butyl; Cycloalkyl such as cyclohexyl etc.) etc. substituting group can form secondary amino group or uncle's amino.In addition, this alkyl can also have other substituting group (for example, alkoxyl group, aryloxy, cycloalkyloxy, carbalkoxy, aryloxy carbonyl, cycloalkoxycarbonyl, acyl group etc.).

In addition, isocyanate-reactive group (primary amino, secondary amino group or sulfydryl etc.) preferably passes through the group combination of divalent though can directly be combined on the Siliciumatom.As such divalent group, can enumerate, for example, the divalent alkyl that alkylidene group, alkenylene, alkylidene group-alkenylene, alkylidene group-alkenylene-alkylidene group etc. only are made of alkyl; The various various divalent groups that constitute by alkyl and other base (oxygen base, carbonyl-oxygen base etc.) such as alkylidene group-oxygen-alkylidene group, alkylidene group-carbonyl-oxygen-alkylidene group, alkylidene group-oxygen-carbonyl-alkylidene group, alkylidene group-poly-(alkylidene oxide) base etc.

Therefore, for example, the organoalkoxysilane (A5) that contains isocyanate-reactive group is when containing amino organoalkoxysilane (A5-1), also can contain amino with the form of aminoalkyl group.Can enumerate as such aminoalkyl group, for example, amino-C such as amino methyl, 1-amino-ethyl, 2-amino-ethyl, 1-aminopropyl, 2-aminopropyl, 3-aminopropyl _1～3Alkyl or (have 1 alkyl as substituent amino-C corresponding to their secondary amino group _1～3Alkyl etc.) or uncle's amino (have 2 alkyl as substituent amino C _1～3Alkyl etc.) etc.In addition, on the nitrogen-atoms in secondary amino group or uncle's amino, substituting groups such as the alkyl of replacement can also have amino.That is, for example also can be, N-aminoalkyl group-aminoalkyl group, N-[N-(aminoalkyl group) aminoalkyl group] form of aminoalkyl group.In addition, can also have primary amino and secondary amino group simultaneously.The number of uncle or secondary amino group has no particular limits, but normally 1 or 2.

More specifically, as the organoalkoxysilane that contains isocyanate-reactive group (A5) is when for example containing amino organoalkoxysilane (A5-1), as isocyanate-reactive group with following formula (2a) expression, can preferably use the amino organoalkoxysilane that contains that only has primary amino, isocyanate-reactive group as following formula (2b) expression, can preferably use the amino organoalkoxysilane that contains with primary amino and secondary amino group, as isocyanate-reactive group with following formula (2c) expression, can preferably use the amino organoalkoxysilane that contains that only has secondary amino group, when being the organoalkoxysilane (A5-2) that contains sulfydryl, isocyanate-reactive group as with following formula (2d) expression can preferably use the organoalkoxysilane that contains sulfydryl that only has sulfydryl.

(in formula (2a)～(2d), R ¹, R ²Identical or different, expression alkyl, R ³, R ⁴Represent alkylidene group, R respectively ⁵Expression aryl, alkyl or cycloalkyl.In addition, m is 1～3 integer.In addition, the R in the formula (2b) ³And R ⁴Alkylidene group can be identical also can be different.)

In above-mentioned formula (2a)～(2d), as R ¹Alkyl, preference is as, the alkyl of carbonatomss about 1～4 such as methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, the tertiary butyl.In addition, as R ²Alkyl, can use and R ¹The same alkyl of alkyl, but preferable methyl or ethyl.As R ³Alkylidene group, the alkylidene group of carbonatomss about 1～3 such as preferred methylene radical, ethylidene, trimethylene.In addition, as R ⁴Alkylidene group, with above-mentioned R ³Alkylidene group use the alkylidene group of carbonatoms about 1～3 equally.In addition, at R ⁵In, preferably use phenyl as aryl, as alkyl, preferably use the alkyl of carbonatomss about 1～4 such as methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, the tertiary butyl, preferably use cyclohexyl as cycloalkyl.In addition, m is 1～3 integer.

More specifically, as isocyanate-reactive group with above-mentioned formula (2a) expression, as the amino organoalkoxysilane that contains that only has primary amino, can enumerate, for example, amino methyl Trimethoxy silane, the amino methyl triethoxyl silane, the beta-aminoethyl Trimethoxy silane, the beta-aminoethyl triethoxyl silane, the gamma-amino propyl trimethoxy silicane, γ-An Jibingjisanyiyangjiguiwan, gamma-amino propyl group tripropoxy silane, gamma-amino propyl group three isopropoxy silane, aminoalkyl group trialkoxy silanes such as gamma-amino propyl group three butoxy silanes; (aminoalkyl group) alkyl-dialkoxysilanes of beta-aminoethyl methyl dimethoxysilane, beta-aminoethyl methyldiethoxysilane, gamma-amino propyl group methyl dimethoxysilane, gamma-amino propyl group methyldiethoxysilane, gamma-amino propyl group methyl dipropoxy silane etc. or their aminoalkyl group dialkyl group (list) organoalkoxysilane of correspondence etc.

Isocyanate-reactive group as above-mentioned formula (2b) expression, as the amino organoalkoxysilane that contains with primary amino and secondary amino group, can enumerate, for example, N-β (amino-ethyl)-gamma-amino propyl trimethoxy silicane, N-β (amino-ethyl)-N-such as γ-An Jibingjisanyiyangjiguiwan (aminoalkyl group) aminoalkyl group trialkoxy silane; N-(aminoalkyl group) aminoalkyl group alkyl-dialkoxysilanes such as N-β (amino-ethyl)-gamma-amino propyl group methyl dimethoxysilane, N-β (amino-ethyl)-gamma-amino propyl group methyldiethoxysilane etc.

In addition, as isocyanate-reactive group with above-mentioned formula (2c) expression, as the amino organoalkoxysilane that contains that only has secondary amino group, can enumerate, for example N-phenyl-beta-aminoethyl Trimethoxy silane, N-phenyl-N-phenyl-beta-aminoethyl trialkoxy silanes such as beta-aminoethyl triethoxyl silane; N-phenyl-gamma-amino propyl trimethoxy silicane, N-phenyl-γ-An Jibingjisanyiyangjiguiwan, N-phenyl-gamma-amino propyl group tripropoxy silane, N-phenyl-N-phenyl-gamma-amino propyl trialkoxy silanes such as gamma-amino propyl group three butoxy silanes, or their N-phenyl amino alkyl of correspondence (list or two) alkyl (two or single) organoalkoxysilane, in addition, can also enumerate, with have above-mentioned substituting group be phenyl secondary amino group contain the amino corresponding N-alkylamino of organoalkoxysilane alkyltrialkoxysilaneand (for example, N-methyl-3-TSL 8330, N-ethyl-3-TSL 8330, N-n-propyl-3-TSL 8330, N-normal-butyl-amino methyl Trimethoxy silane, N-normal-butyl-2-amino-ethyl Trimethoxy silane, N-normal-butyl-3-TSL 8330, N-normal-butyl-3-aminopropyltriethoxywerene werene, N-normal-butyl-3-aminopropyl tripropoxy silane etc.) or N-alkylamino alkyl (single or two) alkyl (two or single) organoalkoxysilane etc.

In the present invention, as containing amino organoalkoxysilane (A5-1), also can commodity in use name " KBM6063 ", trade(brand)name " X-12-869 ", trade(brand)name " KBM576 ", trade(brand)name " X-12-565 ", trade(brand)name " X-12-580 ", trade(brand)name " X-12-5263 ", trade(brand)name " X-12-666 ", trade(brand)name " KBM6123 ", trade(brand)name " X-12-575 ", trade(brand)name " X-12-577 ", trade(brand)name " X-12-563B ", trade(brand)name " X-12-730 ", trade(brand)name " X-12-562 ", trade(brand)name " X-12-5202 ", trade(brand)name " X-12-5204 ", trade(brand)name " KBE9703 " (above is chemical industry society of SHIN-ETSU HANTOTAI system) etc.Therefore, as containing amino organoalkoxysilane (A5-1), can also use, N-(the amino amyl group of 5-)-gamma-amino propyl trimethoxy silicane, N-β [N-β (amino-ethyl) amino-ethyl]-gamma-amino propyl trimethoxy silicane, 1, two (γ-trimethoxysilyl-propyl group amino) ethane of 2-, two (γ-trimethoxysilyl-propyl group) amine, the alkoxy silane compound that N-β (amino-ethyl)-β (4-aminomethyl phenyl) ethyl trimethoxy silane and corresponding their carbonatoms of alkyl (alkyl or alkylidene group etc.) are different etc., or have other groups (styrene type unsaturated group when having uncle or secondary amino group, the olefin type unsaturated group, carboxyl etc.) alkoxy silane compound, the alkoxy silane compound that has the form (hydrochloride etc.) of salt when having uncle or secondary amino group, the alkoxy silane compound that has a plurality of alkoxysilyls when having uncle or secondary amino group.

In addition, as isocyanate-reactive group with above-mentioned formula (2d) expression, as the organoalkoxysilane that contains sulfydryl, can enumerate, for example mercapto methyl Trimethoxy silane, mercapto methyl triethoxyl silane, β-mercaptoethyl Trimethoxy silane, β-mercaptoethyl triethoxyl silane, γ-Qiu Jibingjisanjiayangjiguiwan, γ-sulfydryl propyl-triethoxysilicane, γ-sulfydryl propyl group tripropoxy silane, γ-sulfydryl propyl group three isopropoxy silane, γ-mercaptoalkyl trialkoxy silanes such as sulfydryl propyl group three butoxy silanes; (mercaptoalkyl) alkyl-dialkoxysilanes such as β-mercaptoethyl methyl dimethoxysilane, β-mercaptoethyl methyldiethoxysilane, γ-sulfydryl propyl group methyl dimethoxysilane, γ-sulfydryl propyl group methyldiethoxysilane, γ-sulfydryl propyl group methyl dipropoxy silane or corresponding their mercaptoalkyl dialkyl group (list) organoalkoxysilane etc.

In the present invention, as the organoalkoxysilane that contains isocyanate-reactive group (A5),, can preferably use and contain amino organoalkoxysilane (A5-1) from viewpoints such as easy reaction, extensive commercially available acquisition are easy.In containing amino organoalkoxysilane (A5-1), as isocyanate-reactive group, as the amino organoalkoxysilane that contains that has primary amino at least, preferably for example use N-β (amino-ethyl)-gamma-amino propyl trimethoxy silicane, N-β (amino-ethyl)-γ-An Jibingjisanyiyangjiguiwan, N-β (amino-ethyl)-gamma-amino propyl group methyl dimethoxysilane, gamma-amino propyl trimethoxy silicane.In addition, as isocyanate-reactive group, the amino organoalkoxysilane that contains as only having secondary amino group preferably for example uses N-phenyl-gamma-amino propyl trimethoxy silicane, N-normal-butyl-3-TSL 8330.

Have again, as containing amino organoalkoxysilane (A5-1), also can be above-mentioned illustrated contain at least primary amino (particularly primary amino and secondary amino group) as the alkoxysilane compound containing trialkylsilyl group in molecular structure of isocyanate-reactive group (below, be sometimes referred to as " organoalkoxysilane that contains primary amino ") and with esters of unsaturated carboxylic acids (A5-3) reaction obtain contain at least secondary amino group as the alkoxysilane compound containing trialkylsilyl group in molecular structure of isocyanate-reactive group (below, be sometimes referred to as " ester change contain amino organoalkoxysilane (A5-4) ".Contain amino organoalkoxysilane (A5-4) preferably alkoxysilane compound containing trialkylsilyl group in molecular structure by containing primary amino at least and the alkoxysilane compound containing trialkylsilyl group in molecular structure that contains secondary amino group, preferred especially the use as what ester changed by alkoxysilane compound containing trialkylsilyl group in molecular structure that contains primary amino and secondary amino group and the alkoxysilane compound containing trialkylsilyl group in molecular structure that contains secondary amino group that obtains with esters of unsaturated carboxylic acids (A5-3) reaction by obtaining with esters of unsaturated carboxylic acids (A5-3) reaction.

Contain such ester and be transformed in the amino organoalkoxysilane (A5-4),,, then have no particular limits so long as at least 1 (all preferred) among the carboxylic acid group of unsaturated carboxylic acid (carboxyl) is the compound of the form of ester as esters of unsaturated carboxylic acids (A5-3).As esters of unsaturated carboxylic acids (A5-3), can be unsaturated 1 yuan of carboxylicesters, also can be unsaturated multi-carboxylate (for example, unsaturated 2 yuan of carboxylicesterss etc.).Esters of unsaturated carboxylic acids (A5-3) can be used in combination separately or more than 2 kinds or 2 kinds.

As esters of unsaturated carboxylic acids (A5-3), preferably at the compound that forms on the carbon atom of carbon-to-carbon double bond directly in conjunction with carboxyl or its ester (for example, carbalkoxy, cycloalkoxycarbonyl, aryloxy carbonyl etc.).As such compound, can enumerate, for example, acrylate, methacrylic ester, crotonate, methacrylic acid ester, 2-butylene acid esters, 3-methyl-2-butene acid esters, 2-pentenoate, 2-octene acid esters etc., and, unsaturated 1 yuan of carboxylicesters such as laurate; Maleic acid ester (list or diester), fumarate (list or diester), itaconic ester unsaturated 2 yuan of carboxylicesterss such as (list or diester) etc.

In esters of unsaturated carboxylic acids (A5-3), as ester moiety, can enumerate, methyl esters, ethyl ester, propyl ester, isopropyl ester, butyl ester, isobutyl ester, secondary butyl ester, the tert-butyl ester, pentyl ester, isopentyl ester, own ester, heptyl ester, monooctyl ester, 2-ethylhexyl, the ninth of the ten Heavenly Stems ester, the last of the ten Heavenly stems, ester, isodecyl ester, undecane ester, dodecane ester, tridecane ester, tetradecane ester, n-Hexadecane ester, octadecane ester etc. were from the ester (alkyl ester etc.) of aliphatic hydrocarbon; Cyclohexyl, isobornyl thiocyanoacetate, norbornene ester, Dicyclopentadiene (DCPD) ester, two pentamethylene esters (ジ シ Network ロ ペ Application ニ Le エ ス テ Le), two cyclopentenes esters, tricyclodecenyl esters etc. are from the ester (cyclic hydrocarbon radical ester etc.) of ester ring type hydrocarbon; Phenyl ester, benzyl ester etc. are from ester (aromatic ester etc.) of aromatic hydrocarbons etc.In addition, when having a plurality of ester moiety, each ester moiety can be the same or different.

As esters of unsaturated carboxylic acids (A5-3), in above-mentioned illustrative esters of unsaturated carboxylic acids, preferably use acrylate, methacrylic ester (following sometimes they are referred to as " (methyl) acrylate "), maleic acid diester.More specifically, as (methyl) acrylate, can enumerate, for example, (methyl) alkyl acrylates such as (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) butyl acrylate, (methyl) Ethyl acrylate, (methyl) Octyl acrylate, (methyl) 2-EHA, (methyl) vinylformic acid dodecane ester, (methyl) vinylformic acid octadecane ester etc.In addition, in the maleic acid diester, for example, comprise dialkyl maleates such as dimethyl maleate, ethyl maleate, dibutyl maleinate, toxilic acid dihexyl, dioctyl maleate, toxilic acid two (2-ethylhexyl) ester, toxilic acid two (dodecyl) ester, toxilic acid two (octadecyl) ester etc.

More specifically, reaction obtains as the organoalkoxysilane that contains primary amino and esters of unsaturated carboxylic acids (A5-3) contains secondary amino group at least and can enumerate as the alkoxysilane compound containing trialkylsilyl group in molecular structure of isocyanate-reactive group [ester change contain amino organoalkoxysilane (A5-4)], and the carbon atom of the β position in the carbon-to-carbon double bond of esters of unsaturated carboxylic acids (A5-3) is combined in the compound on the nitrogen-atoms of the amino in the organoalkoxysilane that contains primary amino etc. at least.That is, ester changes, and to contain amino organoalkoxysilane (A5-4) be that nitrogen-atoms by the amino in the organoalkoxysilane that contains primary amino carries out the compound that reversal of the Michael addition obtains to the unsaturated link(age) (carbon-to-carbon double bond) of esters of unsaturated carboxylic acids (A5-3).This reaction can be carried out in the solvent existence or not.In addition, also can heat or pressurize during reaction.

Particularly, the amino organoalkoxysilane (A5-4) that contains as the ester transformation, for example, the organoalkoxysilane that contains primary amino is only to have the alkoxysilane compound containing trialkylsilyl group in molecular structure of primary amino as the isocyanate-reactive group of representing with above-mentioned formula (2a), esters of unsaturated carboxylic acids (A5-3) is during with the esters of unsaturated carboxylic acids of following formula (3) expression, can represent with following formula (4).

(in formula (3), R ⁶, R ⁸Identical or different, expression hydrogen atom or alkyl.R ⁷Expression alkyl, aryl or cycloalkyl.R ⁹Expression hydrogen atom, alkyl, aryl, carbalkoxy, aryloxy carbonyl, cycloalkoxycarbonyl)

(in formula (4), R ¹～R ³, R ⁶～R ⁹And m is identical with above-mentioned definition.)

In addition, the amino organoalkoxysilane (A5-4) that contains as the ester transformation, for example, the organoalkoxysilane that contains primary amino is to have primary amino and secondary amino group as the alkoxysilane compound containing trialkylsilyl group in molecular structure with the isocyanate-reactive group of above-mentioned formula (2b) expression, esters of unsaturated carboxylic acids (A5-3) is during with the esters of unsaturated carboxylic acids of above-mentioned formula (3) expression, can represent with following formula (5a) or following formula (5b).

(at (5a) and (5b), R ¹～R ⁴, R ⁶～R ⁹And m is identical with above-mentioned definition.)

In above-mentioned formula (3), (4), (5a) reach (5b), R ¹～R ⁴And m is same as described above.Particularly, as R ¹Alkyl, for example, carbonatomss such as preferable methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, the tertiary butyl are about 1～4 alkyl.In addition, as R ²Alkyl, can use and R ¹The same alkyl of alkyl, but preferable methyl or ethyl.As R ³Alkylidene group, the alkylidene group of carbonatomss about 1～3 such as preferred methylene radical, ethylidene, trimethylene.In addition, as R ⁴Alkylidene group, can with above-mentioned R ³Alkylidene group similarly to use carbonatoms be about 1～3 alkylidene group.In addition, m is 1～3 integer.

In addition, as R ⁶Alkyl, can enumerate, for example, carbonatomss such as methyl, ethyl are about 1～2 alkyl etc.As R ⁷Alkyl, can enumerate, for example, the alkyl of carbonatomss about 1～20 such as methyl, ethyl, propyl group, butyl, isobutyl-, the tertiary butyl, hexyl, octyl group, 2-ethylhexyl.In addition, as R ⁷Aryl, can enumerate phenyl, as R ⁷Cycloalkyl, can enumerate cyclohexyl etc.As R ⁸Alkyl, can enumerate, for example, the alkyl of carbonatomss such as methyl, ethyl, propyl group, butyl, isobutyl-, the tertiary butyl, hexyl about 1～6 etc.Have again, as R ⁹Alkyl, can enumerate, for example, carbonatomss such as methyl, ethyl are about 1～2 alkyl etc.As R ⁹Aryl, can enumerate phenyl.In addition, at R ⁹Carbalkoxy, aryloxy carbonyl, cycloalkoxycarbonyl in, as moieties, aryl moiety, cycloalkyl moiety, preferably use at above-mentioned R ⁷In illustrative alkyl, aryl, cycloalkyl.

In the present invention, as containing amino organoalkoxysilane (A5), preferably contain the alkoxysilane compound containing trialkylsilyl group in molecular structure [especially using the organoalkoxysilane (A5-4) of the ester transformation of above-mentioned formula (4), above-mentioned formula (5a) or above-mentioned formula (5b) expression] of secondary amino group at least

[amine chain extender (A6)]

As amine chain extender (A6) so long as intramolecularly has the aminated compounds of the amino (primary amino or secondary amino group etc.) beyond 1 uncle's amino get final product, but the preferred polyamines that has a plurality of uncle's amino amino in addition at intramolecularly that uses.The number of the amino (functionality amino) beyond intramolecular uncle's amino of such polyamines then has no particular limits as long as be 2 at least, but can select from the scope of (preferred 2～4, be more preferably 2～3) for example 2～6.For amine chain extender (A6), for example, comprise aliphatic polyamine, ester ring type polyamines, aromatic polyamine, aromatic-aliphatic polyamines, hydrazine and derivative thereof etc.Amine chain extender (A6) can be used in combination separately or more than 2 kinds or 2 kinds.

Particularly, in amine chain extender (A6), can enumerate as aliphatic polyamine, for example, ethylene diamine, 1,3-trimethylene diamines, 1, the 4-tetramethylene-diamine, 1, the 3-five methylene diamine, 1, the 5-five methylene diamine, 1, the 6-hexamethylene-diamine, 1, the 2-trimethylene diamine, 1, the 2-butylene diamine, 2, the 3-butylene diamine, 1, the 3-butylene diamine, the 2-methyl isophthalic acid, the 5-five methylene diamine, the 3-methyl isophthalic acid, the 5-five methylene diamine, 2,4,4-trimethylammonium-1, the 6-hexamethylene-diamine, 2,2,4-trimethylammonium-1, aliphatie diamines such as 6-hexamethylene-diamine, and diethylenetriamine, Triethylenetetramine (TETA), tetren, penten etc.

As the ester ring type polyamines, can enumerate, for example, 1,3-pentamethylene diamines, 1, the 4-cyclohexane diamine, 1, the 3-cyclohexane diamine, 1-amino-3-amino methyl-3,5, the 5-trimethyl-cyclohexane, 1-amino-1-methyl-4-amino methyl hexanaphthene, 1-amino-1-methyl-3-amino methyl hexanaphthene, 4,4 '-methylene-bis (cyclo-hexylamine), 4,4 '-methylene-bis (3-methyl-cyclohexyl base amine), methyl-2, the 3-cyclohexane diamine, methyl-2, the 4-cyclohexane diamine, methyl-2, the 6-cyclohexane diamine, 1, two (amino methyl) hexanaphthenes of 3-, 1, two (amino methyl) hexanaphthenes of 4-, isophorone diamine, ester ring type diamines such as norbornane diamines etc.

As aromatic polyamine, can enumerate, for example, mphenylenediamine, Ursol D, 2, the 4-tolylene diamine, 2, the 6-tolylene diamine, naphthylidene-1, the 4-diamines, naphthylidene-1, the 5-diamines, 4,4 '-diphenyl diamine, 4,4 '-the ditan diamines, 2,4 '-the ditan diamines, 4,4 '-the phenyl ether diamines, 2-nitro phenylbenzene-4,4 '-diamines, 2,2 '-diphenyl propane-4,4 '-diamines, 3,3 '-dimethyl diphenylmethane-4,4 '-diamines, 4,4 '-the diphenyl propane diamines, 3,3 '-dimethoxy phenylbenzene-4,4 '-aromatic diamines such as diamines etc.

As the aromatic-aliphatic polyamines, can enumerate, for example, 1,3-xylylene diamines, 1,4-xylylene diamines, α, α, α ', α '-tetramethyl--1,3-xylylene diamines, α, α, α ', α '-tetramethyl--1,4-xylylene diamines, ω, ω '-diamines-1,4-diethylbenzene, 1, two (1-amino-1-methylethyl) benzene, 1 of 3-, two (1-amino-1-methylethyl) benzene, 1 of 4-, aromatic-aliphatic diamines such as two (α, the alpha-alpha-dimethyl amino methyl) benzene of 3-etc.

As hydrazine and derivative thereof, can enumerate, for example, hydrazine, two hydrazine class compounds etc.Contain in two hydrazine class compounds, for example, aliphatic dicarboxylic acid two hydrazine classes such as carbonization two hydrazines (symmetrical diaminourea), oxalic acid two hydrazines, propanedioic acid two hydrazines, succsinic acid two hydrazines, pentanedioic acid two hydrazines, hexanodioic acid two hydrazines; Aromatic dicarboxylic acid two hydrazine classes such as m-phthalic acid two hydrazines etc., terephthalic acid two hydrazines; 1, ester ring type dicarboxylic acid such as 4-cyclohexane dicarboxylic acid two hydrazines two hydrazine classes etc.

As amine chain extender (A6), can preferably use ethylene diamine, 1,3-five methylene diamine, 1,6-hexamethylene-diamine, diethylenetriamine, Triethylenetetramine (TETA), 4,4 '-methylene-bis (cyclo-hexylamine), 4,4 '-methylene-bis (3-methyl-cyclohexyl base amine), 1, two (amino methyl) hexanaphthenes of 3-, isophorone diamine, norbornane diamines, 1, hydrazine and derivatives thereof such as aliphatics such as 3-xylylene diamines, ester ring type and aromatic-aliphatic polyamines or hydrazine, carbonization two hydrazines.

[polyurethane prepolymer (A) that contains the alkoxysilyl end of anionic property group and uncle's amino]

Contain anionic property group and uncle's amino the alkoxysilyl end polyurethane prepolymer (A) as mentioned above, be polyvalent alcohol (A1), polyvalent alcohol (A2), the isocyanate-reactive compound (A3) that contains uncle's amino, polyisocyanates (A4), the organoalkoxysilane (A5) that contains isocyanate-reactive group, and the resultant of reaction of amine chain extender (A6), be by the anionic property group of intramolecularly from polyvalent alcohol (A2), with the uncle amino of intramolecularly from the isocyanate-reactive compound that contains uncle's amino (A3), with the alkoxysilyl of main chain end from the organoalkoxysilane that contains isocyanate-reactive group (A5), and the polyurethane prepolymer that obtains from the amido reaction of the isocyanate group of polyisocyanates (A4) and amine chain extender (A6) with urea key position.Have again, the polyurethane prepolymer (A) that contains the alkoxysilyl end of anionic property group and uncle's amino, optionally, the side chain [ester group (base)] that has the esters of unsaturated carboxylic acids that relates to from the organoalkoxysilane that contains isocyanate-reactive group (A5) with ester bond.

Polyurethane prepolymer (A) as the alkoxysilyl end that contains anionic property group and uncle's amino also can be, for example, by by polyvalent alcohol (A1), polyvalent alcohol (A2), contain the polyurethane prepolymer that contains anionic property group and uncle's amino that the reaction of the isocyanate-reactive compound (A3) of uncle's amino and polyisocyanates (A4) obtains, reaction with the organoalkoxysilane that contains isocyanate-reactive group (A5), make the isocyanate group polyurethane prepolymer that contains anionic property group and uncle's amino of the alkoxysilylization of the terminal portions that obtains of alkoxysilylization partly of the end of the above-mentioned polyurethane prepolymer that contains anionic property group and uncle's amino, further by amine chain extender (A6), the amino that makes isocyanate group residual in the polyurethane prepolymer that contains anionic property group and uncle's amino of alkoxysilylization of above-mentioned end part and above-mentioned amine chain extender (A6) react and chain extension the polyurethane prepolymer that contains anionic property group and uncle's amino of alkoxysilylization.

More specifically, the polyurethane prepolymer that contains anionic property group and uncle's amino is polyvalent alcohol (A1), polyvalent alcohol (A2), contains the isocyanate-reactive compound (A3) of uncle's amino and the resultant of reaction of polyisocyanates (A4) that this reaction can be reacted the method known and even commonly used of modulating polyurethane prepolymer with polyol compound and polyisocyanate compound and be carried out.Preferred terminal for isocyanate groups as the polyurethane prepolymer that contains anionic property group and uncle's amino.

In addition, make polyvalent alcohol (A1), polyvalent alcohol (A2), contain that the isocyanate-reactive compound (A3) of uncle's amino and polyisocyanates (A4) mix or when reacting, for promoting reaction, can use polymerizing catalyst.In addition, reaction or mixing can be carried out in solvent.

In addition, the reaction that contains the polyurethane prepolymer of anionic property group and uncle's amino and the organoalkoxysilane (A5) that contains isocyanate-reactive group can optionally be undertaken by heating by mixing the two.By such polyurethane prepolymer that contains anionic property group and uncle's amino and the reaction that contains the organoalkoxysilane (A5) of isocyanate-reactive group, can make the above-mentioned isocyanate group alkoxy silanization that contains the polyurethane prepolymer end of anionic property group and uncle's amino, modulation contains the polyurethane prepolymer that contains the anionic property group of the alkoxyl silicone alkanisation of terminal portions.In addition, when carrying out this mixing or reaction, can use polymerizing catalyst as mentioned above.In addition, when above-mentioned mixing or reaction, can use solvent.

As above-mentioned polymerizing catalyst, can use, for example, the polymerizing catalyst known and even commonly used (curing catalysts) that uses when polyol compound and polyisocyanate compound reaction.More specifically,, can enumerate basic cpds such as organo-tin compound, metal complex, amine compound, organic phosphoric acid compound etc. as polymerizing catalyst.Organo-tin compound comprises, for example, and dibutyl tin laurate, toxilic acid dibutyl tin, phthalic acid dibutyl tin, stannous octoate, methyl alcohol dibutyl tin, diacetyl acetic acid dibutyl tin, two tertiary monocarboxylic acids (バ one サ テ one ト) dibutyl tin etc.In addition,, can enumerate titanate compound classes such as tetrabutyl titanate, titanium isopropylate, triethanolamine titanate as metal complex; Carboxylic metallic salts such as lead octoate 36, lead naphthenate, nickel naphthenate, cobalt naphthenate; Cetylacetone metallic coordination compoundes such as aluminium acetylacetonate coordination compound, acetyl acetone vanadium coordination compound etc.In addition, basic cpds such as aminated compounds comprise, for example, and silicane such as gamma-amino propyl trimethoxy silicane, γ-An Jibingjisanyiyangjiguiwan; Quaternary ammonium salt such as Tetramethylammonium chloride, benzalkonium chloride; Three altogether trade(brand)name " DABCO " series or " DABCOBL " series of making of エ ア プ ロ Network Star societies, contain 1, straight chain or the cyclic tertiary amine or the quaternary ammonium salt etc. of 8-diazabicyclo [5.4.0] undecylene-a plurality of nitrogen-atoms such as 7-alkene.In addition,, can enumerate mono phosphoric acid ester methyl esters, phosphoric acid di-n-butyl, triphenylphosphate etc. as the organic phosphoric acid compound.

In addition, the polyurethane prepolymer that contains anionic property group and uncle's amino of the alkoxyl silicone alkanisation of above-mentioned end part and the reaction of amine chain extender (A6) can be passed through to mix the two, and optionally be undertaken by heating.By this reaction, the amino of the isocyanate group of remaining end and above-mentioned amine chain extender (A6) reacts in the polyurethane prepolymer that contains anionic property group and uncle's amino of above-mentioned end part alkoxyl silicone alkanisation, the polyurethane prepolymer that contains anionic property group and uncle's amino that makes above-mentioned end part alkoxyl silicone alkanisation is by chain extension, and modulation is as the polyurethane prepolymer (A) of the alkoxysilyl end that contains anionic property group and uncle's amino of the polyurethane prepolymer of the anionic property group that contains the alkoxyl silicone alkanisation and uncle's amino.Carrying out this mixing or when reaction, can with the above-mentioned polymerizing catalyst that similarly adds.As polymerizing catalyst, the catalyzer known and even commonly used (curing catalysts) that uses in the time of can using for example polyol compound and polyisocyanate compound reaction.

Especially, the polyurethane prepolymer that contains anionic property group and uncle's amino of above-mentioned end part alkoxyl silicone alkanisation and the mixing or the reaction of amine chain extender (A6), can the polyurethane prepolymer that contains anionic property group and uncle's amino of above-mentioned end part alkoxyl silicone alkanisation or its reaction mixture [also can contain basic cpd (B)] before water (C) disperses, disperse in or disperse after any time carry out, but preferably in dispersion or after the dispersion, carry out.Promptly, preferably when the polyurethane prepolymer that contains anionic property group and uncle's amino with terminal portions alkoxyl silicone alkanisation is dispersed in the water (C), in water, add simultaneously amine chain extender (A6), or add amine chain extender (A6) and mixing after being dispersed in the water, make the polyurethane prepolymer that contains anionic property group and uncle's amino and amine chain extender (A6) reaction of above-mentioned end part alkoxyl silicone alkanisation.

Like this, can modulate the polyurethane prepolymer (A) of the alkoxysilyl end that contains anionic property group and uncle's amino.In addition, when carrying out these mixing, need not consider the order by merging of each composition.But, polyurethane prepolymer (A) for the alkoxysilyl end that obtains containing anionic property group and uncle's amino efficiently, preferably at first at polyvalent alcohol (A1), polyvalent alcohol (A2), with add polyisocyanates (A4) in the mixture of the isocyanate-reactive compound that contains uncle's amino (A3), optionally adding polymerizing catalyst again reacts, modulation contains after the polyurethane prepolymer of anionic property group and uncle's amino, interpolation contains the organoalkoxysilane (A5) of isocyanate-reactive group and reacts in this reaction mixture, modulate the polyurethane prepolymer that contains anionic property group and uncle's amino of terminal portions alkoxyl silicone alkanisation thus, then, again amine chain extender (A6) and water (C) are added simultaneously, the polyurethane prepolymer that contains anionic property group and uncle's amino of terminal portions alkoxyl silicone alkanisation is dispersed in the water, at this moment, the polyurethane prepolymer that contains anionic property group and uncle's amino of terminal portions alkoxyl silicone alkanisation carries out chain extension by amine chain extender (A6), and modulation contains the anionic property group of alkoxyl silicone alkanisation and the polyurethane prepolymer of uncle's amino.

In the polyurethane prepolymer (A) of the alkoxysilyl end that contains anionic property group and uncle's amino, polyvalent alcohol (A1), polyvalent alcohol (A2), the isocyanate-reactive compound (A3) that contains uncle's amino, polyisocyanates (A4), the organoalkoxysilane (A5) that contains isocyanate-reactive group and each components in proportions of amine chain extender (A6) have no particular limits.For example as polyisocyanates (A4), polyvalent alcohol (A1), polyvalent alcohol (A2) and the ratio that contains the isocyanate-reactive compound (A3) of uncle's amino, can be from the isocyanate group/polyvalent alcohol (A1) the polyisocyanates (A4), polyvalent alcohol (A2) and the isocyanate-reactive group (NCO/NCO reactive group) (equivalence ratio) that contains hydroxyl in the isocyanate-reactive compound (A3) of uncle's amino for greater than 1 but in the scope selection of (preferred 1.02～1.5, be more preferably 1.05～1.4) 2.0 or 2.0 below.When the ratio of this NCO/NCO reactive group is excessive (when for example surpassing 2.0 (equivalence ratios)), it is difficult that the control of the reaction during chain extension (crosslinking reaction) becomes, the dispersed reduction.On the other hand, when the ratio of this NCO/NCO reactive group is too small (for example when (equivalence ratio) below 1.0 or 1.0), chain extension and silyl import and can not fully carry out, and not only up to the time lengthening that shows viscosity, and rerum natura also reduces.

Perhaps, polyisocyanates (A4) ratio that also can become 0.3～7.0 quality % (preferred 0.4～4.0 quality %, more preferred 0.5～3.0 quality %) with the content of the isocyanate groups in the polyurethane prepolymer that contains anionic property group and uncle's amino contains.The control of the reaction (crosslinking reaction) the when content of isocyanate group is too much during when 7.0 quality % (for example surpass) chain extension difficulty that becomes, the dispersed reduction.On the other hand, when less than 0.3 quality % (for example) reaction times became very long when the content of isocyanate group was very few, had again, and chain extension and silyl import and can not fully carry out, and water tolerance reduces, and curing speed is also slack-off in addition.

Polyvalent alcohol (A2) is that above (for example 0.4～0.7meq/g, preferred 0.4～0.6meq/g) ratio contain for 0.4meq/g or 0.4meq/g with the content of the anionic property group in the polyurethane prepolymer (A) of the alkoxysilyl end that contains anionic property group and uncle's amino preferably.When the content of this anionic property group was too much, the viscosity of the polyurethanes waterborne compositions of silanization uprised, and operability descends, and simultaneously, the water tolerance after the curing reduces.On the other hand, when the content of this anionic property group is very few (for example not enough 0.4meq/g), the dispersion stabilization of the resinous principle in the silylated urethane waterborne compositions reduces, and clinging power reduces simultaneously.

The isocyanate-reactive compound (A3) that contains uncle's amino is that above (0.15～0.8meq/g for example, preferred 0.15～0.6meq/g) ratio contains for 0.15meq/g or 0.15meq/g with the uncle's amino content in the polyurethane prepolymer (A) of the alkoxysilyl end that contains anionic property group and uncle's amino preferably.If the content of this uncle's amino is too much, the viscosity that contains the polyurethane prepolymer (A) of alkoxysilyl end of anionic property group and uncle's amino or silylated urethane waterborne compositions uprises operability and reduces.On the other hand, when the content of this uncle's amino is very few when 0.15meq/g (for example not enough), the clinging power of polyurethane prepolymer (A) that contains the alkoxysilyl end of anionic property group and uncle's amino reduces, and it is elongated to show the needed time of clinging power, and the initial stage cementability reduces.

Preferably (preferred 0.05～0.3meq/g) ratio contains the organoalkoxysilane (A5) that contains isocyanate-reactive group for 0.05～0.4meq/g for example with the silicon atom content in the polyurethane prepolymer (A) of the alkoxysilyl end that contains anionic property group and uncle's amino.When this silicone content is too much when 0.4meq/g (for example, surpass), because the molecular weight of prepolymer diminishes, clinging power diminishes, and showing the needed time of clinging power has elongated tendency.On the other hand, if very few when 0.05meq/g (for example not enough), because the molecular weight of prepolymer is excessive, the epithelium rerum natura hardening when showing viscosity, the wettability variation, on the contrary, clinging power reduces, and has again, and tack retention hour also shortens.By control silicone content (molecular weight of prepolymer) can control clinging power, to the time that shows viscosity, tack retention hour.

In addition, when using esters of unsaturated carboxylic acids (A5-3), the organoalkoxysilane (A5-4) that contains amino that the preferred ester of its usage quantity changes remains the amount of 1 secondary amino group at least.For example, can be that the scope about 0.8～2 mole is selected from respect to 1 mole of the primary amino the organoalkoxysilane that contains primary amino or secondary amino group.In addition, esters of unsaturated carboxylic acids (A5-3) can use under the residual condition of secondary amino group at least in reaction.

The usage quantity of amine chain extender (A6), preferably be equivalent to the polyurethane prepolymer by containing anionic property group and uncle's amino and contain the amount of the isocyanate group (not carrying out the alkoxyl silicone alkanisation and the isocyanate group of residual end) of the end in the polyurethane prepolymer that contains anionic property group and uncle's amino of the terminal portions alkoxyl silicone alkanisation that the reaction of the organoalkoxysilane (A5) of isocyanate-reactive group obtains, but also can from, for example, be that 0.5～1.0 normal scope is selected with respect to this isocyanate group 1 equivalent.

In the present invention, the polyurethane prepolymer (A) that contains the alkoxysilyl end of anionic property group and uncle's amino, the anionic property group that contains in the molecule and the ratio of uncle's amino, preferred tertiary amino/anionic property group (mol ratio)=0.2～1 (preferred 0.3～0.9).The ratio that contains anionic property group in the polyurethane prepolymer (A) of alkoxysilyl end of anionic property group and uncle's amino and uncle's amino is uncle's amino/anionic property group (mol ratio)=0.2～1 o'clock, can shorten showing the needed time of clinging power effectively, and can improve clinging power.

In addition, the polyurethane prepolymer (A) that contains the alkoxysilyl end of anionic property group and uncle's amino, the uncle's amino that contains in the molecule and the ratio of alkoxysilyl, preferred tertiary amino/alkoxysilyl (mol ratio)=1.0～5.5 (preferred 1.5～5.5, more preferred 1.6～4.0).Uncle in the polyurethane prepolymer (A) of the alkoxysilyl end by will containing anionic property group and uncle's amino ratio amino and alkoxysilyl is adjusted into uncle's amino/alkoxysilyl (mol ratio)=1.0～5.5 (by the molecular weight of telomerized polymer and the interaction between polymer molecule), can effectively shorten showing the needed time of clinging power, and improve the initial stage cementability.

Like this, in the present invention, contain the anionic property group that contains in the molecule of polyurethane prepolymer (A) of alkoxysilyl end of anionic property group and uncle's amino and the ratio of uncle's amino by control, or uncle is amino and the ratio of alkoxysilyl (anionic property group particularly, the ratio of uncle's amino and alkoxysilyl), can have slightly under the evaporable situation at water, the interaction of anionic property group and uncle's amino is increased sharply, in addition, by silanol condensation each other, quick-gelatinizing, compare with aqueous adhesive in the past, can shorten arriving the time that shows viscosity significantly, can also show excellent clinging power.That is, given play to excellent performance by the synergy of anionic property group, uncle's amino, silyl.

[basic cpd (B)]

As basic cpd (B), can be alkaline inorganic compound, also can be alkaline organic compound.Basic cpd (B) can use more than 2 kinds or 2 kinds alone or in combination.As alkaline inorganic compound, the preferred use, for example, alkali metal hydroxides such as sodium hydroxide, potassium hydroxide; Alkaline carbonate such as yellow soda ash, salt of wormwood; Alkali metal hydrocarbonate such as sodium bicarbonate, saleratus; Alkaline-earth metal oxyhydroxide such as the alkali metal compound of alkali metal acetate such as sodium-acetate, Potassium ethanoate etc. or magnesium hydroxide; The alkaline earth metal compound of alkaline earth metal carbonates such as magnesiumcarbonate etc., and ammonia.

On the other hand, as alkaline organic compound, the preferred use, for example, aminated compoundss such as fatty amine, aromatic amine, alkaline nitrogen-containing heterocycle compound.As fatty amine, can enumerate.For example, trialkylamines such as Trimethylamine 99, triethylamine, tripropyl amine, tri-isopropyl amine, Tributylamine, tri-isobutylamine, tri sec-butylamine, three TERTIARY BUTYL AMINE, triamylamine, trihexylamine; Dialkylamines such as dimethylamine, diethylamine, dibutylamine; Monoalkylamine such as methylamine, ethamine, butylamine; Three hydramine such as trimethanolamine, trolamine, tripropanol amine, tri-isopropanolamine, three butanolamines, three amylalcohol amine, three isoamyl hydramine, three hexanol amine; Glycol amine such as dimethanolamine, diethanolamine; Single hydramine such as carbinolamine, thanomin etc., and quadrol, diethylenetriamine etc.Aromatic amine comprises, for example, and N, accelerine etc.Can enumerate as alkaline nitrogen-containing heterocycle compound, for example, cyclic amine such as morpholine, piperidines, tetramethyleneimine, and pyridine, α-Jia Jibiding, beta-picoline, γ-picoline, quinoline, N-methylmorpholine etc.

In the present invention, as basic cpd (B), preferably use ammonia or aminated compounds.In aminated compounds, tertiary amine compounds such as preferred trialkylamine or three hydramine.

[water (C)]

In the present invention, as water (C), can use tap water, ion exchanged water or pure water etc.

[silylated urethane waterborne compositions]

Silylated urethane waterborne compositions of the present invention comprises polyurethane prepolymer (A) and the basic cpd (B) and the water (C) of the alkoxysilyl end that contains anionic property group and uncle's amino.Particularly, the silylated urethane waterborne compositions can be the mixture of the polyurethane prepolymer (A), basic cpd (B) and the water (C) that contain the alkoxysilyl end of anionic property group and uncle's amino, also can be to comprise the response composite that makes the resultant of reaction that polyurethane prepolymer (A), basic cpd (B) and the water (C) of the alkoxysilyl end that contains anionic property group and uncle's amino reacts by this mixing.As the reaction of the polyurethane prepolymer (A) and the basic cpd (B) of the alkoxysilyl end that contains anionic property group and uncle's amino, can enumerate in the polyurethane prepolymer (A) of the alkoxysilyl end that contains anionic property group and uncle's amino the anionic property group by basic cpd (B) partly or the neutralization reaction that is neutralized universally.Promptly, the polyurethane prepolymer (A) of the alkoxysilyl end by containing anionic property group and uncle's amino and the reaction of basic cpd (B), the anionic property group that contains in the polyurethane prepolymer (A) of alkoxysilyl end of anionic property group and uncle's amino becomes salt.

On the other hand, as the reaction of the polyurethane prepolymer (A) and the water (C) of the alkoxysilyl end that contains anionic property group and uncle's amino, the alkoxysilyl that can enumerate the end in the polyurethane prepolymer (A) of the alkoxysilyl end that contains anionic property group and uncle's amino is by water and the hydrolysis reaction of hydrolysis.Promptly, the polyurethane prepolymer (A) of the alkoxysilyl end by containing anionic property group and uncle's amino and the reaction of water (C), the alkoxysilyl that contains the end in the polyurethane prepolymer (A) of alkoxysilyl end of anionic property group and uncle's amino partly or wholly becomes silanol group and/or siloxane bond.That is, contain at least 1 alkoxyl group in the alkoxysilyl of the end in the polyurethane prepolymer (A) of alkoxysilyl end of anionic property group and uncle's amino and be subjected to influence with the hydrolysis reaction of water (C).In addition, so-called silanol group is meant the group that contains the Siliciumatom that has 1 hydroxyl at least, also can have the substituting group of alkoxyl group etc.

Therefore, as the above-mentioned resultant of reaction that contains polyurethane prepolymer (A), basic cpd (B) and water (C) reaction of the alkoxysilyl end of anionic property group and uncle's amino, can enumerate, contain anionic property group in the polyurethane prepolymer (A) of alkoxysilyl end of anionic property group and uncle's amino by the salt of basic cpd (B) neutralization becoming anionic property group, and terminal alkoxysilyl is partly or wholly become the aqueous silane alcoholization polyurethane prepolymer of silanol group and/or siloxane bond by the water hydrolysis.That is, in the present invention, preferably contain the aqueous siliconiting polyurethanes composition of above-mentioned aqueous silane alcoholization polyurethane prepolymer as the silylated urethane waterborne compositions.

Like this, in the present invention, the silylated urethane waterborne compositions can mix and modulates containing the polyurethane prepolymer (A) of alkoxysilyl end of anionic property group and uncle's amino and basic cpd (B) and water (C), and its blended has no particular limits in proper order.As silylated urethane waterborne polymeric of the present invention, in the polyurethane prepolymer (A) of the alkoxysilyl end that contains anionic property group and uncle's amino, cooperate basic cpd (B) and water (C), preferably by carrying out violent stirring etc., promote reactions such as neutralization reaction or hydrolysis reaction, be modulated into the aqueous solution or aqueous dispersions.

In addition, in the present invention, basic cpd (B) or water (C) can use when modulation contains the polyurethane prepolymer (A) of alkoxysilyl end of anionic property group and uncle's amino in advance.Particularly, for example, when the resultant of reaction of polyvalent alcohol (A1), polyvalent alcohol (A2), the isocyanate-reactive compound (A3) that contains uncle's amino and polyisocyanates (A4) reacts with the organoalkoxysilane (A5) that contains isocyanate-reactive group, by adding basic cpd (B), can in the presence of basic cpd (B), carry out above-mentioned reaction.

In the present invention, basic cpd (B) is not only at the polyurethane prepolymer that contains anionic property group and uncle's amino with contain organoalkoxysilane (A5) when reaction of isocyanate-reactive group, and can use in any time that modulation contains the process of the polyurethane prepolymer (A) of alkoxysilyl end of anionic property group and uncle's amino or silylated urethane waterborne compositions.Particularly, basic cpd (B) can be at polyvalent alcohol (A1), polyvalent alcohol (A2), contain the isocyanate-reactive compound (A3) and polyisocyanates (A4) reaction of uncle's amino, when modulation contains the polyurethane prepolymer of anionic property group and uncle's amino, or the polyurethane prepolymer that contains anionic property group and uncle's amino reacts with the organoalkoxysilane (A5) that contains isocyanate-reactive group, any reaction when modulation contains the polyurethane prepolymer (A) of alkoxysilyl end of anionic property group and uncle's amino etc. is constantly or after the reaction, and the polyurethane prepolymer (A) that will contain the alkoxysilyl end of anionic property group and uncle's amino is distributed to water (C) use such as when middle.

In addition, water (C), for example, with polyvalent alcohol (A1), polyvalent alcohol (A2), contain the resultant of reaction of the isocyanate-reactive compound (A3) of uncle's amino and polyisocyanates (A4) and contain the polyurethane prepolymer that contains anionic property group and uncle's amino of the terminal portions alkoxyl silicone alkanisation that organoalkoxysilane (A5) reaction of isocyanate-reactive group obtains, further, with amine chain extender (A6) reaction and chain extension the time or before, by adding entry (C), carry out above-mentioned chain extending reaction in the dispersion of polyurethane prepolymer in water that contains anionic property group and uncle's amino of part alkoxyl silicone alkanisation or after disperseing endways.

In the present invention, usage quantity as basic cpd (B), with respect to the anionic property group in the polyurethane prepolymer (A) of the alkoxysilyl end that contains anionic property group and uncle's amino, can select from the scope about 50～120 moles of % (preferred 80～110 moles of %).

In addition, in the present invention, as the usage quantity of water (C),, can select from the scope about 65～900 mass parts (preferred 100～400 mass parts) with respect to polyurethane prepolymer (A) 100 mass parts of the alkoxysilyl end that contains anionic property group and uncle's amino.

Among the present invention, in the silylated urethane waterborne compositions,, have no particular limits as its hydroxyl value (OHV), can from, for example, 60～400mg-KOH/g (select by preferred about 80～350mg-KOH/g) scope.In addition,, have no particular limits as the resin part, but can from, for example, scope about 10～60 quality % (preferred 20～50 quality %) is selected.

In addition, among the present invention,, can be the form of silylated urethane waterborne compositions that does not contain the complete water-based of organic solvent fully as the silylated urethane waterborne compositions.In addition, for viscosity of adjusting its aqueous solution or aqueous dispersions etc., can also contain hydrophilic organic solvents (water-miscible organic solvent) such as ketone, lower alcohol in the silylated urethane waterborne compositions.This organic solvent can use more than 2 kinds or 2 kinds alone or in combination.Particularly, contain acetone etc. in the ketone.In addition,, can enumerate as lower alcohol, for example, 1 yuan of alcohol such as methyl alcohol, ethanol, propyl alcohol, Virahol, butanols, isopropylcarbinol, sec-butyl alcohol, the trimethyl carbinol, amylalcohol, hexanol; Ethylene glycol, propylene glycol, 1,2-butyleneglycol, 1,3 butylene glycol, 1,4-butyleneglycol, 1, polyvalent alcohols such as 6-hexylene glycol, glycerine etc.In addition, as water-miscible organic solvent, can use Texacar PC; Methylcarbonate; Trimethyl phosphite 99; The diether of polyethylene oxide, diester or diallyl ether class; The diether of glycol or diacetate esters class; 1,3-two oxa-s penta ring; N-N-methyl-2-2-pyrrolidone N-etc.Usage quantity as such organic solvent can be according to the suitably selections such as size of the viscosity of adjusting, for example, with respect to polyurethane prepolymer (A) 100 mass parts of the alkoxysilyl end that contains anionic property group and uncle's amino, can select from the scope about 0～100 mass parts (preferred 0～50 mass parts).

In addition, also can contain wettability modified hydrophilic solvent in the silylated urethane waterborne compositions.As this wettability modified hydrophilic solvent, can enumerate, for example, tensio-active agents such as N-N-methyl-2-2-pyrrolidone N-, polyethylene oxide alkyl ethers, sodiun alginate, mucopolysaccharide, sodium acrylate etc.

In the present invention, can also contain various additives or composition, solvents etc. such as packing material, softening agent, antiager, UV light absorber, oxidation inhibitor, thermo-stabilizer, tinting material (pigment or dyestuff etc.), mould inhibitor, moistening promotor, viscous modifier, spices, various tackifier (emulsified tackifier etc.), coupler (titanate ester coupler, aluminium class coupler etc.), light-cured catalyst, emulsifying agent, tensio-active agent, latex or latex, linking agent, wetting Agent for Printing Inks, defoamer in the silylated urethane waterborne compositions.For example,, can enumerate lime carbonate or implemented the white carbon black of lime carbonate, vapor phase process, potter's clay, talcum, various microballoon, neutrality (ノ イ Block Le) silicon-dioxide, kaolin, pure aluminium silicate of various processing etc. as packing material.In addition, softening agent comprises phthalates such as dioctyl phthalate (DOP), dibutyl phthalate; Aliphatic carboxylic acid esters, such as Octyl adipate, Uniflex DBS etc.As tackifier, can enumerate, for example, emulsified tackifier such as stabilization rosin ester, polymerized rosin ester, terpene phenolic, petroleum resinoid etc.As linking agent, can use isocyanates linking agent, epoxies linking agent, carbodiimide linking agent, ethylenimine linking agent, poly-second to embrace imines class linking agent, melamine class linking agent, colloid silica etc.In addition, as solvent, so long as then have no particular limits, can use solvent arbitrarily with the good material of the silylated urethane waterborne compositions intermiscibility of polyurethane prepolymer (A), basic cpd (B) and the water (C) of the alkoxysilyl end that contains anionic property group and uncle's amino.

[aqueous adhesive etc.]

Above-mentioned silylated urethane waterborne compositions can be used as aqueous adhesive or aqueous coating agent (water-borne coatings etc.) uses, and particularly, preferably uses as aqueous adhesive (especially water-based adhesives for wrapping or water-based contact adhesives).In addition, the silylated urethane waterborne compositions can also be as uses such as tackiness agent, laminating material, sealing priming paint, priming paint, cementing agent, sealing materials except that as aqueous adhesive or the aqueous coating agent.That is, various treatment agents such as aqueous adhesive or aqueous coating agent contain above-mentioned silylated urethane waterborne compositions.

Contain the aqueous adhesive of silylated urethane waterborne compositions or aqueous coating agent etc., because above-mentioned silylated urethane waterborne compositions has above-mentioned formation, the tack at initial stage (initial stage cementability or initial stage adaptation etc.) excellence.Particularly, because the silylated urethane waterborne compositions is as its component of polymer, can use the polyurethane prepolymer (A) of the alkoxysilyl end that contains anionic property group and uncle's amino, therefore can be in the excellent clinging power of short period of time performance, performance excellent initial cementability or initial stage adaptation.Its reason is also uncertain, but think because, when the polyurethane prepolymer (A) of the alkoxysilyl end that contains anionic property group and uncle's amino solidifies, even the water in the silylated urethane waterborne compositions can reduce hardly, but in its intramolecularly or the intermolecular interaction that also can produce anionic property group and uncle's amino, thus, on the surface, molecular weight sharply increases.

In addition, contain anionic property group and uncle's amino the alkoxysilyl end polyurethane prepolymer (A) if in the ratio of alkoxysilyl be proper proportion with respect to the ratio of uncle's amino, then can balance good and show clinging power that the molecular weight from the polyurethane prepolymer (A) of the alkoxysilyl end that contains anionic property group and uncle's amino itself produces and the clinging power that causes from the amino relevant interaction of uncle effectively, also be because this point, can shorten showing the excellent needed time of clinging power significantly, can improve the initial stage cementability effectively.

And, in silylated urethane waterborne compositions of the present invention, even the state of excellent clinging power water conservation also can show rapidly.This be because, water only has some volatilization, by producing the interaction relevant, show suitable clinging power (viscosity rising), in addition with tertiary amine, the molecular weight of polyurethane prepolymer (A) that contains the alkoxysilyl end of anionic property group and uncle's amino by adjustment is suitable molecular weight (molecular-weight average), then can give the suitableeest clinging power, have again, even maintenance moisture content is former state, crosslinking reaction also can be carried out, and You Yi clinging power can show rapidly thus.

In addition, owing to use amine chain extender (A6), curing speed is accelerated as chainextender.

Especially, because above-mentioned silylated urethane waterborne compositions comprises polyurethane prepolymer (A), basic cpd (B) and the water (C) of the alkoxysilyl end that contains anionic property group and uncle's amino, even in water, the silanol group of the polyurethane prepolymer of aqueous silane alcoholization exists highly stablely.Its reason determines as yet, but be considered to since in the system a large amount of water moleculess that exist protected silanol group, suppress or prevent condensation reaction between the silanol group, stability improves.In addition; also think silanol group; be bonded to from as containing of the alkoxysilane compound containing trialkylsilyl group in molecular structure (A5) that contains isocyanate-reactive group amino organoalkoxysilane (A5-1) secondary amino group or the substituting group on the nitrogen-atoms of uncle's amino (for example; from the long-chain substituting group of esters of unsaturated carboxylic acids (A5-3) or its ester moiety etc.) protection; suppress or prevent condensation reaction between the silanol group, stability further improves.

Therefore, contain the aqueous adhesive of silylated urethane waterborne compositions or aqueous coating agent etc. and can be used as the aqueous adhesive of single-liquid type or the single-liquid type treatment agents such as aqueous coating agent of single-liquid type.

In addition, the water of silylated urethane waterborne compositions in system is by (for example, when being coated on open surface or when being coated on the porous material etc.) under evaporation or the dry condition that reduces such as volatilization, fast setting.And, this solidified curing speed is little to the dependency of the rate of drying of water, when particularly the silylated urethane waterborne compositions being used as aqueous adhesive or aqueous coating agent (water-borne coatings etc.), the curing speed of this aqueous adhesive or aqueous coating agent is all littler than in the past aqueous adhesive or aqueous coating agent for the dependency of the rate of drying of water.This be because, be coated with the silylated urethane waterborne compositions after, when the evaporation of water in this waterborne compositions reduced, the silanol group in the aqueous silane alcoholization polyurethane prepolymer in the waterborne compositions caused condensation reaction, produces thus and solidifies (crosslinked).That is, be considered to owing to mainly be that the condensation reaction of the silanol group in the aqueous silane alcoholization polyurethane prepolymer in the waterborne compositions has participated in curing.

In addition, carry out crosslinking reaction,,, also can show cohesive force even keep the moisture former state even this crosslinking reaction exists water also can carry out to a certain extent by the minimizing of water.

Have, because the polyurethane prepolymer (A) of alkoxysilyl end that contains anionic property group and uncle's amino is by amine chain extender (A6) and chain extension, so intramolecularly has the urea key again, and cohesive force is very high.

Therefore, silylated urethane waterborne compositions of the present invention shows the time weak point that excellent clinging power needs, initial stage tack (initial stage cementability etc.) excellence, and simultaneously, curing speed is exceedingly fast, and has the different voltinism of tachy steroling is arranged.

In addition, think that curing speed accelerates, during the adaptation at initial stage uprises, also with because Water-borne modification and ion center that the intramolecularly of hydrotropisms's silanolate polyurethane prepolymer imports the salt of anionic property group (carboxylate salt etc.) to have brought into play function as the promotion catalyzer of the condensation reaction between silanol group relevant.

Like this, above-mentioned silylated urethane waterborne compositions no matter be water-based whether, curing speed is all very fast, and, can show excellent clinging power, initial stage tack (initial stage cementability or initial stage adaptation etc.) excellence in the short period of time.Therefore, when the silylated urethane waterborne compositions is used as various treatment agents such as for example aqueous adhesive (water-based adhesives for wrapping etc.), equal productivity in the time of can bringing into play and use the solvent based caking agent.Particularly, when the silylated urethane waterborne compositions is used as the water-based adhesives for wrapping, coating water-based adhesives for wrapping on plastic, this coated face (for example is fitted in the porous scutum, laminated wood, shaving board (パ one チ Network ボ one ト), MDF etc.) etc. on the base material, and owing to can show excellent clinging power in the short period of time this moment, given play to the excellent initial cementability, therefore have equal productivity during with the adhesives for wrapping that uses solvent based, can carry out sealing of base material by the sheet of plastics manufacturing.And, because the bonding strength height at initial stage even substrate surface has concaveconvex shape, and can not produce the slit between the sheet of plastics manufacturing and the base material yet, can promptly the sheet card of plastics manufacturing be combined on the base material with the adaptation of excellence.

Especially, contain the aqueous adhesive of silylated urethane waterborne compositions, have excellent storage stability, can be modulated into the single-liquid type caking agent of water-based.Therefore, by with the water-based adhesives for wrapping as single-liquid type, the operability in the time of can significantly improving encapsulating operation from this point, can further improve productivity.That is, adhesives for wrapping in the past mainly uses the binary liquid shape caking agent of solution class, during encapsulating operation, host and solidifying agent 2 liquid must be mixed, but in the present invention,, can save host and solidifying agent blended mixed processes by making the single-liquid type adhesives for wrapping of water-based.

In addition, be meant by the sheet of bond layer as adhesives for wrapping (for example, water-based adhesives for wrapping etc.) to be fitted on the base material with the plastics manufacturing, thus, the caking agent that uses when sealing base material by the sheet of plastics manufacturing.When sealing base material by the sheet of plastics manufacturing, usually use and on the sheet that plastics are made, be coated with after the adhesives for wrapping, the adhesives for wrapping coated face of the sheet of this plastics manufacturing is fitted in method on the base material, but the encapsulating method of the base material of the sheet of employing plastics manufacturing has no particular limits, in such sealing, the industrial sealing machine that can use infantees machine, forming press, curved surface splicing machine, mould (vacuum mould etc.), adopt soft roller, be called as sealing of tetrahedrallayer press etc. and use machine, various sealing has commercially available with machine.

As above-mentioned base material, can preferably use, for example, the base material of making by porous material, but the wooden materials of porous matter such as woodboard of preferred especially laminated wood, shaving board, MDF (porous matter wood materials) etc.Shape as base material has no particular limits, and for example, can be that the surface has concavo-convex base material, also can be that the surface is the tabular base material of planar.

In addition, the sheet as above-mentioned plastics are made has no particular limits, for example, and the sheet that the polyester such as sheet that preferably use polyethylene terephthalate to make are made; The sheet that polyvinyl chloride is made; The sheet that the polyolefine such as sheet that the sheet that polyethylene is made, polypropylene are made are made, but also can be the sheet that adopts other resins.The size of the sheet of plastics manufacturing or thickness etc. have no particular limits, and can suitably select.

Because silylated urethane waterborne compositions of the present invention can be used as the formation with contact cementability, therefore also can be used as the water-based contact adhesives and use.Like this, when the silylated urethane waterborne compositions is used as the water-based contact adhesives, this water-based contact adhesives is because initial stage bonding strength height, therefore, make when being fitted each other, needn't carry out the precompressed pressing, can shorten the time that it needs by convered structure, bonding operability is good, and it is a plurality of by convered structure easily to fit.Particularly, even do not contain the water-based completely of organic solvent fully, the initial stage bonding strength is also excellent, is very favourable in this.

In addition, in the silylated urethane waterborne compositions, the polyurethane prepolymer (A) that contains the alkoxysilyl end of anionic property group and uncle's amino also can be the lower polymkeric substance of molecular weight ratio, for example, number-average molecular weight can be selected from the scope about 3000～50000 (preferred 10000～30000).And, after the curing, can form siloxane bond and become more high molecular weight polymers.

Like this, the silylated urethane waterborne compositions can be used as aqueous adhesive or aqueous coating agent (particularly aqueous adhesive) uses, and in above-mentioned aqueous adhesive, preferably uses as water-based adhesives for wrapping or water-based contact adhesives.

Particularly, owing to be (especially, owing to can be the complete water-based that does not contain organic solvent fully also) of water-based type, property handled or operability excellence be to human body or environmental safety height.

In addition, has silanol group owing to contain the polyurethane prepolymer (A) of the alkoxysilyl end of anionic property group and uncle's amino, therefore contain the aqueous adhesive (particularly water-based contact adhesives) of silylated urethane waterborne compositions or aqueous coating agent etc., also show good cementability or adaptation not only to porous materials such as paper, and for non-porous materials such as metal or glass.That is,, shown in following concrete example, can use various base materials as the base material that can be suitable for above-mentioned aqueous adhesive or aqueous coating agent etc. (by convered structure or coating body etc.).

As above-mentioned base material can be any one of porous material, non-porous material for example.More specifically,, can enumerate as by the material of convered structure, for example, wood materials such as timber, laminated wood, wood chip sheet material, shaving board, hardboard; Slabstone, calcium silicate board with microporous (Gui カ Le plate), plaster, watt etc. inanimate matter material; Melamine resin decorative sheet, resol plate, polystyrene foamed, various plastics film or moulding product plastic materials such as (for example, polyvinyl chloride film or moulding product, polyester film or moulding product, polystyrene film or moulding product, polyolefins film or moulding product etc.); Elastomeric materials such as natural rubber, synthetic rubber, silicon rubber; Paper materials such as corrugation paperboard, paperboard, kraft paper, and converted paper (for example, surface-treated converted papers such as water-proof paper etc.) fibrous materials such as etc. difficult bonding paper material, glass material, metallic substance (for example, iron, aluminium, stainless steel, copper etc.), leather substance, cloth, non-woven fabrics etc.

Like this, contain the base material that the aqueous adhesive of silylated urethane waterborne compositions or aqueous coating agent etc. go for containing extensive material, particularly bonding by contact, can be used in each other bonding of porous matter.

Base material as by bonding fit the time can be the base material that contains with a kind of material, also can be the base material that contains different materials.Base material can be distinguished alone or in combination more than 2 kinds or 2 kinds.

In addition, the aqueous adhesive that contains the silylated urethane waterborne compositions as use, applying is by the method for convered structure, have no particular limits, can adopt, for example, the method that directly will be fitted each other after the coating on by convered structure by convered structure or on by convered structure after the coating through specific time, showing under the state of cementability the whole bag of tricks such as contact adhering method that will be fitted each other by convered structure.In addition, in the present invention, as the contact adhering method, not only comprise regulation as JIS K 6800, be coated on fit 2 by two in the convered structure by on the binding face of convered structure, through specific time, fit 2 by convered structure and bonding method showing under the state of cementability, also comprise 2 of being coated on applying by in the convered structure any one by on the binding face of convered structure, through specific time, fit 2 under the state of cementability by convered structure and bonding method showing.That is, in the present invention, so-called contact is bonding, be meant be coated on applying by on any one the binding face at least in the convered structure, through behind the specific time, fit 2 under the state of cementability by convered structure and bonding showing.

As mentioned above, because silylated urethane waterborne compositions of the present invention has above-mentioned formation, so safe, in addition, show the time weak point that excellent clinging power needs, the initial stage is excellent in adhesion, same productivity in the time of can having given play to and use the solvent based caking agent is arranged again.Therefore, above-mentioned silylated urethane waterborne compositions is useful as water-based adhesives for wrapping or water-based contact adhesives.

Embodiment

Below, by embodiment the present invention is described more specifically, but the present invention is not subjected to the qualification of these embodiment.In addition, below, unless otherwise specified, " part " expression " mass parts ", " % " expression " quality % ".The material that uses in embodiment and comparative example is as follows.

[polyol compound (A1) that does not contain the anionic property group]

(1) trade(brand)name " PTMG2000 " [Mitsubishi Chemical society system, polytetramethylene ether diol, number-average molecular weight: 2000, hydroxyl value: 57.4mg-KOH/g; Be sometimes referred to as " polyvalent alcohol (A1-a) "]

(2) trade(brand)name " NS2471 " [Xu Dianhuagongyeshe system, polyester glycol, number-average molecular weight: 2000, hydroxyl value: 56.1mg-KOH/g; Be sometimes referred to as " polyvalent alcohol (A1-b) "]

(3) 1,4-butyleneglycols [being sometimes referred to as " polyvalent alcohol (A1-c) "]

[polyol compound (A2) that contains the anionic property group]

(1) 2,2-dimethylol propionic acid [hydroxyl value: 837.3mg-KOH/g; Be sometimes referred to as " polyvalent alcohol (A2-a) "]

(2) 2,2-dimethylolpropionic acid [hydroxyl values: 754.0mg-KOH/g; Be sometimes referred to as " polyvalent alcohol (A2-b) "]

[compound (A3) that contains uncle's amino and isocyanate-reactive group]

(1) N-methyl-diethanolamine [N, two (2-hydroxyethyl)-N-methylamines of N-; Hydroxyl value: 941.6mg-KOH/g; Be sometimes referred to as " polyvalent alcohol (A3-a) "]

(2) N-normal-butyl-diethanolamine [N, two (2-hydroxyethyl)-N-n-Butyl Amine 99s of N-; Hydroxyl value: 695.9mg-KOH/g; Be sometimes referred to as " polyvalent alcohol (A3-b) "]

(3) N, two [2-hydroxyethyl-poly-(ethylene oxide-propylene oxide)]-N-ethamine [so-called [amine polyol] of N-; Number-average molecular weight: 2000, hydroxyl value: 55.7mg-KOH/g; Be sometimes referred to as " polyvalent alcohol (A3-c) "]

[polyisocyanate compound (A4)]

(1) isophorone diisocyanate [isocyanic ester containing ratio (NCO containing ratio): 37.8%, IPDI; Be sometimes referred to as " polyisocyanates (A4-a) "]

[alkoxysilane compound containing trialkylsilyl group in molecular structure (A5) that contains isocyanate-reactive group]

(1) trade(brand)name " KBM903 " [chemical industry society of SHIN-ETSU HANTOTAI system, gamma-amino propyl trimethoxy silicane; Be sometimes referred to as " containing amino organoalkoxysilane (A5-a) "]

(2) trade(brand)name " KBM573 " [chemical industry society of SHIN-ETSU HANTOTAI system, N-phenyl-gamma-amino propyl trimethoxy silicane; Be sometimes referred to as " containing amino organoalkoxysilane (A5-b) "]

(3) with respect to trade(brand)name " KBM602 " [chemical industry society of SHIN-ETSU HANTOTAI system, N-β (amino-ethyl)-gamma-amino propyl group methyl dimethoxysilane]: 1 mole, use 2-EHA: 2 moles ratio, mix, reacted 7 days down at 50 ℃, obtain resultant of reaction [being sometimes referred to as " containing amino organoalkoxysilane (A5-c) "]

(4) with respect to trade(brand)name " KBM602 " [chemical industry society of SHIN-ETSU HANTOTAI system, N-β (amino-ethyl)-gamma-amino propyl group methyl dimethoxysilane]: 1 mole, use n-butyl acrylate: 2 moles ratio, mix, reacted 7 days down at 50 ℃, obtain resultant of reaction [being sometimes referred to as " containing amino organoalkoxysilane (A5-d) "]

(5) with respect to trade(brand)name " KBM903 " [chemical industry society of SHIN-ETSU HANTOTAI system, gamma-amino propyl trimethoxy silicane]: 1 mole, use 2-EHA: 2 moles ratio, mix, reacted 7 days down at 50 ℃, obtain resultant of reaction [being sometimes referred to as " containing amino organoalkoxysilane (A5-e) "]

[chainextender]

(1) isophorone diamine [amine chain extender; Be sometimes referred to as " chainextender (A6-a) "]

(2) quadrol [amine chain extender; Be sometimes referred to as " chainextender (A6-b) "]

[basic cpd (B)]

(1) triethylamine

[water (C)]

(1) ion exchanged water (deionized water)

(embodiment 1)

In having 4 mouthfuls of flasks of nitrogen ingress pipe, thermometer, condenser and whipping appts, cooperate polyvalent alcohol (A1-a): 150 parts, polyvalent alcohol (A2-b): 20 parts, polyvalent alcohol (A3-a): 8 parts, polyisocyanates (A4-a): 75.2 parts and methylethylketone (MEK): 100 parts, under 80～85 ℃ temperature, nitrogen gas stream, carry out reaction in 6 hours, obtain containing remaining isocyanate group and be the reaction mixture of 2.0% the terminal polyurethane prepolymer of the isocyanate group that contains carboxyl and uncle's amino.

Then, contain in the reaction mixture total amount of the terminal polyurethane prepolymer of isocyanate group of carboxyl and uncle's amino at this, cooperate and to contain amino organoalkoxysilane (A5-a): 6.5 parts and mix after, under 80～85 ℃ temperature, nitrogen gas stream, carry out reaction in 1 hour, obtain containing the isocyanate group of carboxyl and uncle's amino and the reaction mixture of the terminal polyurethane prepolymer of alkoxysilyl.

Have again, after this reaction mixture that contains the isocyanate group of carboxyl and uncle's amino and the terminal polyurethane prepolymer of alkoxysilyl is cooled to 40 ℃, cooperate triethylamine: 13.6 parts, under the high-speed stirring, add and dissolved chainextender (A6-a) in advance in the 496g deionized water: 5.7 parts the aqueous solution obtains dispersion liquid.Under reduced pressure, heat up in a steamer MEK from this dispersion liquid under 45～50 ℃ after, obtain solids component being adjusted to 36% silylated urethane waterborne compositions by deionized water.

(embodiment 2～13)

Except that making the composition that is shown in table 1 or 2, similarly to Example 1, obtain the silylated urethane waterborne compositions that embodiment 2～13 relates to respectively.

(comparative example 1～2,6)

Except that make shown in the table 3 form, similarly to Example 1, obtain silylated urethane waterborne compositions or polyurethanes waterborne compositions that comparative example 1～2,6 relates to respectively.

(comparative example 3)

Except that make shown in the table 3 form, similarly to Example 1, obtain containing remaining isocyanate group and be the reaction mixture of 2.0% the terminal polyurethane prepolymer of the isocyanate group that contains carboxyl and uncle's amino.Then, contain in the reaction mixture total amount of the terminal polyurethane prepolymer of isocyanate group of carboxyl and uncle's amino at this, cooperate and to contain amino organoalkoxysilane (A5-c): 20.6 parts, as 1 of chainextender, the 4-butyleneglycol: 3.0 parts and mix after, under 80～85 ℃ temperature, nitrogen gas stream, carry out reaction in 2 hours, obtain containing the reaction mixture of the terminal polyurethane prepolymer of alkoxysilyl of carboxyl and uncle's amino.Have again, after this reaction mixture that contains the isocyanate group of carboxyl and uncle's amino and the terminal polyurethane prepolymer of alkoxysilyl is cooled to 40 ℃, cooperate triethylamine: 13.6 parts and mix, under the high-speed stirring, add 507 parts of deionized waters, obtain dispersion liquid.Under reduced pressure, heat up in a steamer MEK from this dispersion liquid under 45～50 ℃ after, obtain solids component being adjusted to 36% silylated urethane waterborne compositions by deionized water.

(comparative example 4～5,7)

Except that make shown in the table 3 form, same with comparative example 3, obtain silylated urethane waterborne compositions or polyurethanes waterborne compositions that comparative example 4～5,7 relates to respectively.

In addition, in table 1～3, the resinous principle in " carboxyl equivalent (meq/g) " expression silylated urethane waterborne compositions or the polyurethanes waterborne compositions: the equivalent of the carboxyl among the 1g.Resinous principle in " uncle's amino equivalent (meq/g) " expression silylated urethane waterborne compositions or the polyurethanes waterborne compositions: the equivalent of the uncle's amino among the 1g.Resinous principle in " uncle N/COOH (equivalence ratio) " expression silylated urethane waterborne compositions or the polyurethanes waterborne compositions: the ratio of the equivalent of the uncle's amino among the 1g and the equivalent of carboxyl.

In addition, the resinous principle in " silicon equivalent weight (meq/g) " expression silylated urethane waterborne compositions or the polyurethanes waterborne compositions: the equivalent of the Siliciumatom among the 1g.Resinous principle in " uncle N/Si (equivalence ratio) " expression silylated urethane waterborne compositions or the polyurethanes waterborne compositions: the ratio of the equivalent of the uncle's amino among the 1g and the equivalent of Siliciumatom.

Table 1

		Embodiment
										1		2	3	4	5	6	7
		Polyvalent alcohol (A1-a)		150		150	150	150	150									150
Polyvalent alcohol (A1-b)																	150
		Polyvalent alcohol (A1-c)
Polyvalent alcohol (A2-a)																20	20
		Polyvalent alcohol (A2-b)		20		20	20	20	20
Polyvalent alcohol (A3-a)										8		8	8	8	8	8	8
		Polyvalent alcohol (A3-b)
Polyvalent alcohol (A3-c)
		Polyisocyanates (A4-a)		75.2		75.2	75.2	75.2	75.2									78.7	78.3
Contain amino organoalkoxysilane (A5-a)										6.5
		Contain amino organoalkoxysilane (A5-b)				9.2
Contain amino organoalkoxysilane (A5-c)													20.8
		Contain amino organoalkoxysilane (A5-d)						16.7
Contain amino organoalkoxysilane (A5-e)															13.2	13.3	13.3
		Chainextender (A6-a)		5.7		5.7	5.7	5.7	5.7									5.8	5.8
Chainextender (A6-b)
		Triethylamine		13.6		13.6	13.6	13.6	13.6									15.1	15.1
Deionized water										496		501	522	514	508	517	516
		Add up to		775		782.7	815.3	803.2	793.7									807.9	806.5
Carboxyl equivalent (meq/g)										0.51		0.50	0.48	0.49	0.50	0.54	0.54
		Uncle's amino (meq/g)		0.25.		0.25	0.24	0.24	0.25									0.24	0.24
Uncle N/COOH base (equivalence ratio)										0.50		0.50	0.50	0.50	0.50	0.45	0.45
		Si equivalent (meq/g)		0.14		0.13	0.13	0.13	0.13									0.13	0.13
Uncle N/Si (equivalence ratio)										1.86		1.86	1.86	1.86	1.86	1.83	1.83
		The initial stage cementability	Placed 10 seconds	×		×	×	×	×									×	×
Placed 15 seconds	△									△	△	△	△	△	△
			Placed 20 seconds	○		○	○	○	○							○	○
Placed 25 seconds	○									○	○	○	○	○	○
			Placed 30 seconds	○		○	○	○	○							○	○
Placed 35 seconds	◎									◎	◎	◎	◎	◎	◎
			Placed 40 seconds	××		××	××	××	××							××	××
Placed 45 seconds
			Placed 50 seconds
Placed 55 seconds
			Placed 60 seconds
Placed 65 seconds
			Placed 70 seconds

Table 2

		Embodiment
								8	9	10	11	12	13
		Polyvalent alcohol (A1-a)		150	100	150	150							150	150
Polyvalent alcohol (A1-b)
		Polyvalent alcohol (A1-c)			5
Polyvalent alcohol (A2-a)
		Polyvalent alcohol (A2-b)		25	25	25	25							20	20
Polyvalent alcohol (A3-a)										12	16	5	15
		Polyvalent alcohol (A3-b)		12
Polyvalent alcohol (A3-c)									50
		Polyisocyanates (A4-a)		85.3	80.3	91.5	99.6							69.2	89.4
Contain amino organoalkoxysilane (A5-a)
		Contain amino organoalkoxysilane (A5-b)
Contain amino organoalkoxysilane (A5-c)								22.4	14.3	15.3	15.9	10.0	30.1
		Contain amino organoalkoxysilane (A5-d)
Contain amino organoalkoxysilane (A5-e)
		Chainextender (A6-a)		6.2	6.7	7.2								6.7	5.3
Chainextender (A6-b)											2.7
		Triethylamine		17.1	17.1	17.1	17.1							13.6	13.6
Deionized water								565	530	565	573	488	575
		Add up to		883	828.4	883.1	899.3							762.5	898.4
Carboxyl equivalent (meq/g)								0.56	0.60	0.56	0.55	0.52	0.44
		Uncle's amino (meq/g)		0.25	0.09	0.33	0.43							0.16	0.41
Uncle N/COOH base (equivalence ratio)								0.44	0.15	0.60	0.79	0.31	0.93
		Si equivalent (meq/g)		0.13	0.09	0.09	0.09							0.07	0.17
Uncle N/Si (equivalence ratio)								1.91	1.01	3.80	4.85	2.41	2.41
		The initial stage cementability	Placed 10 seconds	×	×	×	×							×	×
Placed 15 seconds	○							○	○	○	○	△
			Placed 20 seconds	○	○	○	◎						○	○
Placed 25 seconds	○							◎	◎	◎	○	○
			Placed 30 seconds	◎	◎	◎	××						◎	◎
Placed 35 seconds	××							××	××		××	××
			Placed 40 seconds
Placed 45 seconds
			Placed 50 seconds
Placed 55 seconds
			Placed 60 seconds
Placed 65 seconds
			Placed 70 seconds

Table 3

		Comparative example
									1	2	3	4	5	6	7
		Polyvalent alcohol (A1-a)		150	150	150	150	150								150	100
Polyvalent alcohol (A1-b)
		Polyvalent alcohol (A1-c)		6	6	6											5
Polyvalent alcohol (A2-a)
		Polyvalent alcohol (A2-b)		20	20	20	20	20								20	20
Polyvalent alcohol (A3-a)												6	6	6
		Polyvalent alcohol (A3-b)
Polyvalent alcohol (A3-c)															50
		Polyisocyanates (A4-a)		75.0	75.0	75.0	71.2	71.2								71.2	72.2
Contain amino organoalkoxysilane (A5-a)									6.4
		Contain amino organoalkoxysilane (A5-b)
Contain amino organoalkoxysilane (A5-c)										20.6	20.6
		Contain amino organoalkoxysilane (A5-d)					16.3
Contain amino organoalkoxysilane (A5-e)															12.8
		Chainextender (A6-a)		5.7	5.7											8.0
Chainextender (A6-b)
		1, the 4-butyleneglycol				3.0	3.0	4.2									3.0
Triethylamine									13.6	13.6	13.6	13.6	13.6	13.6	13.6
		Deionized water		492	517	507	493	464								478	486
Add up to									768.7	807.9	795.2	773.1	729	746.8	762.6
		Carboxyl equivalent (meq/g)		0.51	0.49	0.49	0.51	0.54								0.53	0.51
Uncle's amino (meq/g)									0.00	0.00	0.00	0.19	0.20	0.20	0.10
		Uncle N/COOH base (equivalence ratio)		0.00	0.00	0.00	0.37	0.37								0.37	0.19
Si equivalent (meq/g)									0.14	0.13	0.13	0.13	0.00	0.00	0.13
		Uncle N/Si (equivalence ratio)		0.00	0.00	0.00	1.43	-								-	0.71
The initial stage cementability	Placed 10 seconds								×	×	×	×	×	×	×
		Placed 15 seconds	×	×	×	×	×	×								×
	Placed 20 seconds								×	×	×	×	×	×	×
		Placed 25 seconds	×	×	×	×	×	×								×
	Placed 30 seconds								×	×	×	△	×	△	×
		Placed 35 seconds	△	△	△	△	△	△								△
	Placed 40 seconds								××	××	△	○	○	××	○
		Placed 45 seconds			○	○	○									○
	Placed 50 seconds										○	○	○		○
		Placed 55 seconds			○	○	○									○
	Placed 60 seconds										○	××	××		○
		Placed 65 seconds			××											××
	Placed 70 seconds

(evaluation)

Silylated urethane waterborne compositions that evaluation method by following initial stage cementability relates to embodiment 1～13 and comparative example 1～7 or caking agent are estimated the initial stage cementability of silylated urethane waterborne compositions etc.In addition, evaluation result is recorded in table 1～3 simultaneously.

[evaluation method of initial stage cementability]

Silylated urethane waterborne compositions or caking agent are coated (glue spread: about 80g/m on the sheet that olefine kind resin makes ²), 70 ℃ of following dryings after the specified time (being respectively the time shown in table 1～3) arbitrarily, MDF (porous matter wood materials) is fitted in coated face, close with the hand roll-in, with JIS K 6854-2 is that benchmark is measured at once and peeled off bonding strength (N/25mm), estimates the initial stage cementability by following judgement criteria.

(metewand)

◎: peel off bonding strength and be 10 (N/25mm) or more than 10 (N/25mm)

Zero: peel off bonding strength and be 7.5 (N/25mm) or more than 7.5 (N/25mm), less than 10 (N/25mm)

△: peel off bonding strength and be 5 (N/25mm) or more than 5 (N/25mm), less than 7.5 (N/25mm)

*: peel off bonding strength less than 5 (N/25mm)

* *: becomes inharmonious, can not fit

In addition, in the metewand of above-mentioned test (evaluation method of initial stage cementability), " ◎ " expression " excellent ", " zero " expression " very ", " △ " expression " qualified ", " * " expression " defective ".

Can be clear and definite from table 1～3, be equivalent to silylated urethane waterborne compositions that embodiments of the invention 1～13 relate to back 15 seconds in coating, show bonding force, even it is also extremely short to show the time water-based that clinging power needs.Therefore, when using the silylated urethane waterborne compositions that embodiment relates to, owing to be water-based, so safe, and, even water-based, also can obtain showing the needed time weak point of excellent bonding force, various treatment agents such as caking agent that the initial stage is excellent in adhesion or coating agent.

In addition, the silylated urethane waterborne compositions (or caking agent) for embodiment 10 relates to even about 20 quality % also can show good caking agent at this moment, shows convergency (receiving ま り) in the decrement (weight loss on heating) of 70 ℃ of dryings in the time of 20 seconds.On the other hand, the silylated urethane waterborne compositions (or caking agent) that relates to for comparative example 3, situation at the decrement (weight loss on heating) of 70 ℃ of dryings in the time of 20 seconds and embodiment 10 is about 20 quality % equally, but this moment or moisture state do not demonstrate convergency fully.Like this, the silylated urethane waterborne compositions that embodiment relates to is because the ratio of the decrement that evaporation of water causes is little, and, can not show the dry initial stage that contains too many moisture of bonding force in the past, also show good bonding force, show the time weak point that excellent bonding force needs, the initial stage is excellent in adhesion.

In addition, the silylated urethane waterborne compositions (or caking agent) that embodiment 3 is obtained is coated on the slabstone, and makes glue spread be about 300g/m ², after placing 5 minutes under the condition of 23 ℃ and 55%RH, when using the hand roller to be pressed together on the cork floor tile on the slabstone, can not confirm skew, grow dim (floating I), demonstrate good convergency.

Have, the silylated urethane waterborne compositions (or caking agent) that embodiment 3 is obtained is coated on the one side separately of soft core wood and plasterboard, and makes glue spread be about 200g/m again ², after placing 10 minutes under the condition of 23 ℃ and 55%RH, when the two is fitted, can not confirm skew, grow dim, demonstrate good convergency.

Have, the silylated urethane waterborne compositions (or caking agent) that embodiment 3 is obtained is coated on the one side separately of decorating calcium silicate board and plasterboard, and makes glue spread be about 200g/m again ², carry out forced drying in 15 minutes after, carry out the applying of the two and traction is at once peeled off, plasterboard destroys, and demonstrates good convergency.

Have again, the silylated urethane waterborne compositions that use embodiment 3 obtains is as caking agent, in addition, as sealing machine using appts trade(brand)name " pattern laminating machine (プ ロ Off ア イ Le ラ ミ ネ one one) PL-300CE " [Marunaka Tekkosho Inc.'s system], with surface printing the polyolefins sheet of grain pattern (thickness: 50 μ m; Carried out using the surface treatment of priming paint) under following laminating condition, be fitted in the MDF (length: surface 2.5m) of the section form of Fig. 1～shown in Figure 3, and when making it to become respectively the form of Fig. 4～shown in Figure 6, under the same linear velocity with the 2 liquid type solvent based polyurethane type resin caking agents that used as adhesives for wrapping in the past time the (about 15m/ divide or more than the 15m/ branch), can be not growing dim on the sheet, fit along the state of the shape driving fit of MDF.Particularly, for example in MDF shown in Figure 1, the A part that is called as what is called " contrary radius " is arranged, but as shown in Figure 4,, can fit no problemly even, also do not produce on the sheet and grow dim for this part against radius A.In addition,, as shown in Figure 5,, seal end, the place of the about 3mm of elongation portion as sheet for MDF shown in Figure 2, even but the seam width of the weak point of about 3mm so do not produce on the sheet yet and grow dim, can fit no problemly.Have again, in MDF shown in Figure 3, the B part as little protuberance is arranged, but as shown in Figure 6,, can fit no problemly even, also do not produce on the sheet and grow dim for the part of this protuberance B.

(laminating condition)

(1) situation of the MDF of shape shown in Figure 1

Glue spread: 80 μ m are (wet thick; 80g/m ²)

Linear velocity: 15m/ minute

The temperature of drying oven: 60 ℃

(2) situation of the MDF of shape shown in Figure 2

Glue spread: 80 μ m are (wet thick; 80g/m ²)

Linear velocity: 18m/ minute

The temperature of drying oven: 65 ℃

(3) situation of the MDF of shape shown in Figure 3

Glue spread: 80 μ m are (wet thick; 80g/m ²)

Linear velocity: 18m/ minute

The temperature of drying oven: 65 ℃

Fig. 1～Fig. 3 is the broad cross-section map that the section form of the MDF by sealing machine applying polyolefins sheet is shown respectively.Fig. 4～Fig. 6 is illustrated in MDF that the section of Fig. 1～shown in Figure 3 forms respectively to go up broad cross-section map by the state of sealing machine applying polyolefins sheet.In addition, in Fig. 4～Fig. 6, for convenience of explanation, have living space between polyolefins sheet and the MDF, but in fact the polyolefins sheet closely fits on the MDF.In addition, in Fig. 1～Fig. 6, A is contrary radius, and B is a protuberance.

In addition, for adopting above-mentioned fit that obtain, the processed goods of sealing shown in Figure 4 sealed, when carrying out the heat-resisting creep test shown in following, the strip length after 24 hours is 0mm.Therefore, do not peel off, confirmed to have good performance even do not produce fully after 24 hours yet.That is, even the aqueous adhesive of single-liquid type also can obtain and the equal adhesiveproperties of binary liquid shape solvent based caking agent that used in the past.

[heat-resisting creep test]

Adopting above-mentioned obtain, shown in Figure 4 the sealing on the processed goods of fitting of sealing, in advance with the width of 25mm after making the crack on the long direction, put into 60 ℃ ambiance, the end of the direction of the fissured length of the 25mm width of the polyolefin piece in sealing processed goods, with the quiet heavy burden of 90 ° of angle load 500gf/25mm wide (4.9N/25mm is wide), measure the strip length after 24 hours.

Industrial applicibility

As mentioned above, silylated urethane waterborne compositions of the present invention is safe, in addition, shows the time weak point that excellent bonding force needs, and the initial stage cementability is high. Have again, can bring into play productivity equal when using the solvent based bonding agent. Therefore, silylated urethane waterborne compositions of the present invention is extremely useful as water-based adhesives for wrapping or water-based contact adhesives.

Claims (15)

1. a silylated urethane waterborne compositions is characterized in that, said composition contains following (A) composition, (B) composition and (C) composition:

(A) do not contain the terminal polyurethane prepolymer of the alkoxysilyl that contains anionic property group and uncle's amino that the polyol compound (A1) of anionic property group, the polyol compound (A2) that contains the anionic property group, the compound (A3) that contains uncle's amino and isocyanate-reactive group, polyisocyanate compound (A4), the alkoxysilane compound containing trialkylsilyl group in molecular structure (A5) that contains isocyanate-reactive group and amine chain extender (A6) reaction obtain

(B) basic cpd

(C) water.

2. according to the silylated urethane waterborne compositions of claim 1 record, wherein, the terminal polyurethane prepolymer (A) of alkoxysilyl that contains anionic property group and uncle's amino, it is the polyurethane prepolymer that contains anionic property group and uncle's amino with the alkoxyl silicone alkanisation of terminal portions, further by amine chain extender (A6), make residual isocyanate group in the polyurethane prepolymer that contains anionic property group and uncle's amino of alkoxyl silicone alkanisation of above-mentioned end part, with the reaction of the amino of above-mentioned amine chain extender (A6) chain extension the polyurethane prepolymer that contains anionic property group and uncle's amino of alkoxyl silicone alkanisation, the polyurethane prepolymer that contains anionic property group and uncle's amino of the alkoxyl silicone alkanisation of described terminal portions, be by by the polyol compound that does not contain the anionic property group (A1), the polyol compound (A2) that contains the anionic property group, the compound (A3) that contains uncle's amino and isocyanate-reactive group, and the reaction of polyisocyanate compound (A4) and the polyurethane prepolymer that contains anionic property group and uncle's amino that obtains, with the reaction of the alkoxysilane compound containing trialkylsilyl group in molecular structure that contains isocyanate-reactive group (A5), the isocyanate group of the end of the polyurethane prepolymer that contains anionic property group and uncle's amino is obtained by alkoxyl silicone alkanisation partly.

3. according to claim 1 or the 2 silylated urethane waterborne compositions of putting down in writing, wherein, the silylated urethane waterborne compositions, be anionic property group in the polyurethane prepolymer (A) of the alkoxysilyl end by containing anionic property group and uncle's amino by basic cpd (B) neutralization, and the aqueous silane alcoholization polyurethane prepolymer compositions that obtained by water (C) hydrolysis of terminal alkoxysilyl.

4. according to the silylated urethane waterborne compositions of any record in the claim 1～3, wherein, the anionic property group that contains in the polyol compound (A2) of anionic property group is a carboxyl.

5. according to the silylated urethane waterborne compositions of any record in the claim 1～4, wherein, the polyol compound (A2) that contains the anionic property group is the dihydroxymethyl paraffinic acid.

6. according to the silylated urethane waterborne compositions of any record in the claim 1～5, wherein, containing uncle's compound (A3) amino and isocyanate-reactive group is the tertiary amine compounds that contains a plurality of isocyanate-reactive groups.

7. according to the silylated urethane waterborne compositions of any record in the claim 1～6, wherein, containing uncle's compound (A3) amino and isocyanate-reactive group is N, two (hydroxyl-organic group)-N-alkylamines of N-.

8. according to the silylated urethane waterborne compositions of any record in the claim 1～7, wherein, the alkoxysilane compound containing trialkylsilyl group in molecular structure (A5) that contains isocyanate-reactive group is the alkoxysilane compound containing trialkylsilyl group in molecular structure that contains secondary amino group that alkoxysilane compound containing trialkylsilyl group in molecular structure by containing primary amino at least and esters of unsaturated carboxylic acids reaction obtain.

9. according to the silylated urethane waterborne compositions of any record in the claim 1～8, wherein, the alkoxysilane compound containing trialkylsilyl group in molecular structure (A5) that contains isocyanate-reactive group is by containing the alkoxysilane compound containing trialkylsilyl group in molecular structure of primary amino and secondary amino group, reacting the alkoxysilane compound containing trialkylsilyl group in molecular structure that contains secondary amino group that obtains with esters of unsaturated carboxylic acids.

10. according to the silylated urethane waterborne compositions of any record in the claim 1～9, wherein, the content that contains the anionic property group in the terminal polyurethane prepolymer of alkoxysilyl (A) of anionic property group and uncle's amino is 0.4meq/g or more than the 0.4meq/g.

11. silylated urethane waterborne compositions according to any record in the claim 1～10, wherein, the content that contains the uncle's amino in the terminal polyurethane prepolymer of alkoxysilyl (A) of anionic property group and uncle's amino is 0.15meq/g or more than the 0.15meq/g.

12. silylated urethane waterborne compositions according to any record in the claim 1～11, wherein, containing the anionic property group in the terminal polyurethane prepolymer of alkoxysilyl (A) of anionic property group and uncle's amino and the ratio of uncle's amino is uncle's amino/anionic property group (mol ratio)=0.2～1.

13. silylated urethane waterborne compositions according to any record in the claim 1～12, wherein, the uncle's ratio amino and alkoxysilyl that contains in the terminal polyurethane prepolymer of alkoxysilyl (A) of anionic property group and uncle's amino is uncle's amino/alkoxysilyl (mol ratio)=1.0～5.5.

14. a water-based adhesives for wrapping is characterized in that, this caking agent contains the silylated urethane waterborne compositions of any record in the aforesaid right requirement 1～13.

15. a water-based contact adhesives is characterized in that, this caking agent contains the silylated urethane waterborne compositions of any record in the aforesaid right requirement 1～13.