CN1286936C

CN1286936C - Nonaqueous series laminated adhesive

Info

Publication number: CN1286936C
Application number: CN 01121923
Authority: CN
Inventors: 森川幸弘; 东久保一郎; 吉田孝治; 笹原俊昭
Original assignee: Nippon Polyurethane Industry Co Ltd
Current assignee: Nippon Polyurethane Industry Co Ltd
Priority date: 2001-06-21
Filing date: 2001-06-21
Publication date: 2006-11-29
Anticipated expiration: 2021-06-21
Also published as: CN1393499A

Abstract

The present invention relates to nonaqueous laminated adhesive containing polyurethane resin (A) with tertiary amine groups or polyurethane resin (B) with tertiary amine groups and carboxyl groups and polyisocyanate curing agents, wherein the resin (A) is prepared from a compound containing active hydrogen groups and from organic polyisocyanate, and the compound containing active hydrogen groups at least contains compounds with tertiary amine groups and hydroxy groups; the resin (B) is prepared from a compound containing active hydrogen groups and from organic polyisocyanate, and the compound containing active hydrogen groups at least contains compounds with tertiary amine groups and hydroxy groups and compounds with carboxyl groups and hydroxy groups; both the content of the tertiary amine groups of the resin (A) and the content of the tertiary amine groups and carboxy groups of the resin (B) are 0.001 to 1 mmol/g. The laminated adhesive has the advantages of short aging time, long storage period and favorable storage stability. The laminated adhesive can solve the problems insoluble to the existing laminated adhesive.

Description

Nonaqueous series laminated adhesive

The present invention relates to a kind of nonaqueous series laminated adhesive of making laminated film that is applicable to.

Recently, as Packaging Method, the operational suitability during owing to packaging intensity, commodity protectiveness, packing, a large amount of and cheap supply of the effect of publicity, film due to the packing make reasons such as packing cost reduction, and composite soft packaging grows up significantly.As the laminated tackiness agent that is used for this film and sheet material, from the viewpoint of adhesiveproperties and cold-resistant, excellent heat resistance and so that wide etc. the viewpoint of the subject range of base materials such as various plastics, tinsel is considered, generally the dual-component polyurethane that constitutes based on host with reactive hydrogen base and solidifying agent with isocyanate group is a tackiness agent.

As this laminating adhesive, the spy opens and discloses a kind of laminated binder composition of using in the clear 63-110272 communique, and this binder composition is to be made of polyvalent alcohol more than a kind or 2 kinds in polyether glycol, polyester polyol, polyether(poly)urethane polyvalent alcohol and the PAUR polyvalent alcohol and the silane coupling agent, the polyisocyanate curing agent that contain isocyanate group.

But,, seldom consider the reactivity of laminating adhesive in the past with solidifying agent and host though require to shorten the set time of the binder layer in the lamination.That is to say that the curing reaction of the tackiness agent after the coating is very slow, therefore need the so-called aged curing promotion operation that is called.Particularly, film that must lamination process is good was taken care of about 3～5 days in 35～60 ℃ moist closet, carried out ageing, and tackiness agent is solidified.At this moment, according to different ageing conditions, the state of cure of tackiness agent changes, and is therefore influential to the bonding strength of laminated film, and under the insufficient occasion of ageing, the curing of tackiness agent is bad to cause layering (layer is peeled off).Especially, aliphatic polyurethane is in the tackiness agent, and this curing reaction needs considerable time.Therefore, this ageing operation is integral in the dry lamination operation, is difficult to tackle the short delivery goods date.And, also need to be used for ageing with the facility investment of moist closet equipment be used to the expense of practical application of being incubated etc. thereafter.Adopt the spy to open the technology of putting down in writing in the clear 63-110272 communique, can seek to improve cementability, resistance to chemical reagents and the thermotolerance of laminating adhesive, but to shortening digestion time without any consideration.

In order to shorten digestion time, effective means generally is to add catalyzer.As this technology, can enumerate the spy and open the technology of putting down in writing in the flat 9-316422 communique.But, because the special technology of opening in the flat 9-316422 communique just cooperates catalyzer to urethane resin (solution) in, though digestion time has shortened the new problem of shortening storage period (serviceable time) after having produced host specifically again and solidifying agent cooperating.If storage period is short, then not only loss appears in tackiness agent, and tackiness agent tends to solidify, and apparatus for coating is broken down.

So, because dual-component polyurethane in the past is that the tackiness agent curing reaction of laminating adhesive after coating is very slow, therefore must prolong digestion time, this point wishes to improve.

In order to improve these shortcomings, effective means is to cooperate tertiary amine in tackiness agent.For example, the spy opens and has proposed a kind of pair of component dry lamination binder composition in the flat 11-50036 communique, it is characterized in that polyhydroxy reactant is made of carboxylic polyvalent alcohol, and at least a portion of this carboxyl neutralizes with alkali.In addition, the spy opens in the flat 11-181394 communique, discloses the film tackiness agent that a kind of use has the waterborne polyurethane resin of anionic group and two kinds of groups of cation group.

Also known in addition, if cooperate silane coupling agent in tackiness agent, then performances such as cementability, thermotolerance, resistance to chemical reagents improve.When carrying out film laminating, can cause mismatch error complicated three kinds of composition mixing with device, therefore, require coupler is coupled among the either party of host or solidifying agent in advance.But,, then can As time goes on cause painted and tackify if silane coupling agent is coupled to host in advance, particularly has in the host of functional groups such as amino or epoxy group(ing).Think that this is because the functional group in the host and the organoalkoxysilane of silane coupling agent partly wait the cause that reacts.And, because silane coupling agent has functional groups such as amino, epoxy group(ing) usually, therefore, in case polyisocyanate curing agent and silane coupling agent are combined together, similarly, isocyanate group and the functional group in the silane coupling agent in the solidifying agent will react, and can As time goes on cause tackify.

But, cooperated the tackiness agent of tertiary amine, tertiary amine plays a part catalyzer, easily and ester series solvent generation transesterification reaction such as acetic ester or cause hydrolysis by the moisture that contains in the solvent, therefore, exist the viscosity of tackiness agent and the problem that rerum naturas such as molecular weight reduction, bonding strength reduce.Therefore, tackiness agent is the stock for a long time, and this point wishes to improve.In addition, aqueous adhesive needs big energy when lamination, and the processing of waste liquid is also difficult.

Further, in order to improve the ageing stability of the laminating adhesive that uses silane coupling agent, as long as with the separately keeping of each composition, and before using, each components matching get final product together, but wish to have a kind of laminating adhesive problems such as site of storage and each components matching take a lot of trouble, that constitute by two kinds of compositions that do not have.

The objective of the invention is to, provide a kind of and not only can shorten digestion time, and storage period is long, and the good nonaqueous series laminated adhesive of storage stability, productivity and operability.

The inventor etc. have carried out deep research for this problem of the known technology of solving over, found that, in the main constituent of the host of nonaqueous series laminated adhesive, employing has the urethane resin of uncle's amino and reactive hydrogen base or has the urethane resin of uncle's amino, carboxyl and reactive hydrogen base, just can solve above-mentioned problem, thereby finish the present invention.

That is, the present invention is following (1)～(4).

(1) above-mentioned nonaqueous series laminated adhesive, it is a kind of urethane resin (A) with uncle's amino and nonaqueous series laminated adhesive of polyisocyanate curing agent of containing, the urethane resin of the wherein said uncle's of having amino (A) is to make to contain the what is called of selecting of compound more than a kind or 2 kinds at least contain the reactive hydrogen based compound from the compound that formula (1), (2), (3) and (4) are represented respectively, reacts under the condition of reactive hydrogen base surplus with organic polymeric polyisocyanate and obtains; It is characterized in that uncle's amino content of the urethane resin of the above-mentioned uncle's of having amino (A) is 0.001～1mmol/g.

(in the formula, R ₁1 valency alkyl for carbonatoms 1～10.R ₂, R ₃Can be identical or different separately, be the divalent alkyl of carbonatoms 1～10.)

(in the formula, R ₁1 valency alkyl for carbonatoms 1～10.R ₂, R ₃Can be identical or different separately, be the divalent alkyl of carbonatoms 1～10.R ₄, R ₅Can be identical or different separately, be the divalent organic group of carbonatoms 1～10.A, b are respectively and make the number-average molecular weight of formula (2) compound reach 300～10,000 the integer more than 0.)

(in the formula, R ₆3 valency alkyl for carbonatoms 1～10.R ₇, R ₈Can be identical or different separately, be 1 valency alkyl of carbonatoms 1～10.)

(in the formula, R ₆3 valency alkyl for carbonatoms 1～10.R ₇, R ₈Can be identical or different separately, be 1 valency alkyl of carbonatoms 1～10.R ₉, R ₁₀Can be identical or different separately, be the divalent organic group of carbonatoms 1～10.C, d are respectively and make the number-average molecular weight of formula (4) compound reach 300～10,000 the integer more than 0.)

(2) above-mentioned nonaqueous series laminated adhesive, it is a kind of nonaqueous series laminated adhesive that contains silane coupling agent shown in urethane resin (A), polyisocyanate curing agent and the formula (7) with uncle's amino, the urethane resin of the wherein said uncle's of having amino (A) is to make to contain the what is called of selecting of compound more than a kind or 2 kinds at least contain the reactive hydrogen based compound from the compound that formula (1), (2), (3) and (4) are represented respectively, reacts under the condition of reactive hydrogen base surplus with organic polymeric polyisocyanate and obtains; It is characterized in that uncle's amino content of the urethane resin of the above-mentioned uncle's of having amino (A) is 0.001～1mmol/g.

OCN-(CH ₂) _m-Si(OR) ₃ (7)

(in the formula, R is methyl or ethyl.M is 1～5 integer.)

(3) above-mentioned nonaqueous series laminated adhesive, it is a kind of containing to have uncle amino and the urethane resin (B) of carboxyl and the nonaqueous series laminated adhesive of polyisocyanate curing agent, the wherein said uncle of having urethane resin (B) amino and carboxyl is to make to contain at least from formula (1), (2), (3) and the what is called of compound of selecting in (4) compound of representing respectively more than a kind or 2 kinds and a kind or 2 kinds compound from the compound that formula (5) and (6) are represented respectively, selecting contain the reactive hydrogen based compound, react under the condition of reactive hydrogen base surplus with organic polymeric polyisocyanate and obtain; It is characterized in that the uncle's amino content and the carboxyl-content of the urethane resin (B) of the above-mentioned uncle's of having amino and carboxyl are respectively 0.001～1mmol/g.

(in the formula, R ₁₁1 valency alkyl for carbonatoms 1～10.R ₁₂, R ₁₃Can be identical or different separately, be the divalent alkyl of carbonatoms 1～10.)

(in the formula, R ₁₁1 valency alkyl for carbonatoms 1～10.R ₁₂, R ₁₃Can be identical or different separately, be the divalent alkyl of carbonatoms 1～10.R ₁₄, R ₁₅Can be identical or different separately, be the divalent organic group of carbonatoms 1～10.E, f are respectively and make the number-average molecular weight of formula (6) compound reach 300～10,000 the integer more than 0.)

(4) above-mentioned nonaqueous series laminated adhesive, it is a kind of urethane resin (B) with uncle's amino and carboxyl that contains, the nonaqueous series laminated adhesive of silane coupling agent shown in polyisocyanate curing agent and the formula (7), the wherein said uncle of having urethane resin (B) amino and carboxyl is to make to contain at least from formula (1), (2), (3) and the what is called of compound of selecting in (4) compound of representing respectively more than a kind or 2 kinds and a kind or 2 kinds compound from the compound that formula (5) and (6) are represented respectively, selecting contain the reactive hydrogen based compound, react under the condition of reactive hydrogen base surplus with organic polymeric polyisocyanate and obtain; It is characterized in that the uncle's amino content and the carboxyl-content of the urethane resin (B) of the above-mentioned uncle's of having amino and carboxyl are respectively 0.001～1mmol/g.

OCN-(CH ₂) _m-Si(OR) ₃ (7)

(in the formula, R is methyl or ethyl.M is 1～5 integer.)

Below explain the present invention.

At first narrate the urethane resin with uncle's amino (A) among the present invention and have the urethane resin (B) of the amino and carboxyl of uncle.

Laminating adhesive is required to have to the diversified plastics film that is used for base material and the cementability of tinsel with urethane resin, and, also require to utilize the laminated film of the tackiness agent manufacturing that contains urethane resin to have bendability, winter hardiness, thermotolerance etc.

The urethane resin with uncle's amino (A) among the present invention is to make the what is called that contains the compound with the amino and reactive hydrogen base of uncle at least contain reactive hydrogen based compound and organic polymeric polyisocyanate to react under the condition of reactive hydrogen base surplus and obtain.Therefore, the urethane resin (A) with uncle's amino will have the reactive hydrogen base in molecular end.(A) the reactive hydrogen base in preferably on average has more than 1 in molecular resin, especially preferably has more than 2.(A) do not exist under the occasion of reactive hydrogen base, can not react, so the performances such as bonding strength of film reduce with polyisocyanate curing agent.

Urethane resin (A) with uncle's amino must have uncle's amino, and the content of this uncle's amino is 0.001～1mmol/g, is preferably 0.01～0.9mmol/g, more preferably 0.03～0.8mmol/g.Under the occasion of the not enough lower limit of uncle's amino content, the digestion time behind the attaching film is elongated easily.And surpass under the occasion of the upper limit, cooperate solidifying agent to shorten easily storage period afterwards.

Number-average molecular weight with urethane resin (A) of uncle's amino is preferably 3,000～60, and 000, be preferably 5,000～40,000 especially.Under the occasion of the not enough lower limit of number-average molecular weight, easily make the bonding strength deficiency.And surpass under the occasion of the upper limit, in the adhesive coated operation, the viscosity of tackiness agent improves, and operability is reduced.

Urethane resin (B) among the present invention with uncle's amino and carboxyl, be make to contain compound at least and have carboxyl and the what is called of the compound of reactive hydrogen base contains the reactive hydrogen based compound, react under the condition of reactive hydrogen base surplus with organic polymeric polyisocyanate and obtain with the amino and reactive hydrogen base of uncle.Therefore, have uncle's urethane resin (B) amino and carboxyl and will have the reactive hydrogen base in molecular end.This reactive hydrogen base preferably on average has more than 1 in each (B) molecule, especially preferably has more than 2.(B) do not exist under the occasion of reactive hydrogen base, can not react with polyisocyanate curing agent, therefore, performances such as the bonding strength of film reduce.

Have uncle's urethane resin (B) amino and carboxyl and must contain uncle's amino and carboxyl, this uncle content amino and carboxyl is respectively 0.001～1mmol/g, is preferably 0.01～0.9mmol/g, more preferably 0.03～0.8mmol/g.Under the occasion of the not enough lower limit of uncle's amino content, digestion time is elongated easily, and surpasses under the occasion of the upper limit, cooperates solidifying agent to shorten easily storage period afterwards.Under the occasion of the not enough lower limit of carboxyl-content, the cementability cementability of aluminium foil (particularly to) deficiency, and surpass under the occasion of the upper limit, digestion time is elongated easily.

In addition, have the ratio (mol ratio) of the amino and carboxyl of uncle in the urethane resin (B) of the amino and carboxyl of uncle, be preferably uncle's amino/carboxyl=1/9～6/4, more preferably 3/7～5/5.Under the occasion of uncle's amino more than this ratio, cooperate shorten easily the storage period after the polyisocyanate curing agent, and under the amino few occasion of uncle, digestion time is elongated easily.

Number-average molecular weight with urethane resin (B) of uncle's amino and carboxyl is preferably 3,000～60, and 000, be preferably 5,000～40,000 especially.Under the occasion of the not enough lower limit of number-average molecular weight, easily make the bonding strength deficiency.And surpass under the occasion of the upper limit, in the adhesive coated operation, the viscosity of tackiness agent improves, and operability is reduced.

To have the urethane resin (A) of uncle's amino or have uncle's urethane resin (B) amino and carboxyl and be dissolved under the occasion of using in the organic solvent, its solid concentration is preferably 10～90 weight %, more preferably 15～85 weight %.In addition, the viscosity of the resin solution under 25 ℃ is preferably 10, below the 000mPas, more preferably 8, below the 000mPas.

What be used for making urethane resin (A) with uncle's amino contains the reactive hydrogen based compound, except containing the compound of from the compound that formula (1), (2), (3) and (4) are represented respectively, selecting more than a kind or 2 kinds, can also contain number-average molecular weight 300～10 according to different occasions, (in fact not tertiary-amino-containing or carboxyl) chain propagation agent of (in fact not tertiary-amino-containing or carboxyl) pure and mild molecular weight less than 300 of macromolecular multi-component of 000.What be used for making urethane resin (B) with the amino and carboxyl of uncle contains the reactive hydrogen based compound, except containing the compound more than a kind or 2 kinds from the compound that formula (1), (2), (3) and (4) are represented respectively, selected and a kind of from the compound that formula (5) and (6) are represented respectively, selecting or 2 kinds of compounds, can also contain number-average molecular weight 300～10 according to different occasions, (in fact not tertiary-amino-containing or carboxyl) chain propagation agent of (in fact not tertiary-amino-containing or carboxyl) pure and mild molecular weight less than 300 of macromolecular multi-component of 000.

As the compound shown in the formula (1), can enumerate N-methyl-N, N-dihydroxymethyl amine, N-ethyl-N, N-dihydroxymethyl amine, N-propyl group-N, N-dihydroxymethyl amine, N-phenyl-N, N-dihydroxymethyl amine, N-methyl-N, N-diethanolamine, N-ethyl-N, N-diethanolamine, N-propyl group-N, N-diethanolamine, N-phenyl-N, N-diethanolamine, N-methyl-N, N-dipropanolamine, N-ethyl-N, N-dipropanolamine, N-propyl group-N, N-dipropanolamine, N-phenyl-N, N-dipropanolamine etc.Among the present invention, R in the formula (1) preferably ₁Alkyl, R for carbonatoms 1～6 ₂And R ₃Be respectively the compound of the alkylidene group of carbonatoms 1～6.

As the compound shown in the formula (2), can enumerate cyclic esters such as addition 6-caprolactone, γ-Wu Neizhi in the compound shown in the formula (1), perhaps epoxide such as oxyethane, propylene oxide and the compound that forms.Among the present invention, R in the formula (2) preferably ₁Alkyl, R for carbonatoms 1～6 ₂And R ₃Be respectively alkylidene group, the R of carbonatoms 1～6 ₄And R ₅Be respectively general formula: (in the formula, R ' is the alkylidene group of carbonatoms 1～10 to-R '-CO-.) shown in compound.In addition, the preferred number average molecular weight of compound is 500～5,000 shown in the formula (2).

As the compound shown in the formula (3), can enumerate 2-(N, the N-dimethylamino)-1, ammediol, 2-(N, N-diethylin)-1, ammediol, 2-(N-methyl-N-ethylamino)-1, ammediol, 5-(N, N-Dimethylaminobenzene)-1,3-dimethanol, 2-(N, the N-dimethylamino methyl)-1, ammediol etc.Among the present invention, R in the formula (3) preferably ₆3 valency representative examples of saturated aliphatic alkyl, R for carbonatoms 1～6 ₇And R ₈Be respectively the compound of the alkyl of carbonatoms 1～6.

As the compound shown in the formula (4), can enumerate cyclic esters such as addition 6-caprolactone, γ-Wu Neizhi in the compound shown in the formula (3), or the compound that forms of epoxide such as oxyethane, propylene oxide.Among the present invention, R in the formula (4) preferably ₆3 valency representative examples of saturated aliphatic alkyl, R for carbonatoms 1～6 ₇And R ₈Be respectively alkyl, the R of carbonatoms 1～6 ₉And R ₁₀Be respectively general formula: (in the formula, R ' is the alkylidene group of carbonatoms 1～10 to-R '-CO-.) shown in compound.In addition, the preferred number average molecular weight of compound is 500～5,000 shown in the formula (4).

As the compound shown in the formula (5), can enumerate 2,2-dimethylol propionic acid, 2,2-dimethylolpropionic acid, 2-methylol-2-hydroxyethyl propionic acid, 2-methylol-2-hydroxyethyl butyric acid etc.Among the present invention, preferably R11 is the compound that alkyl, R12 and the R13 of carbonatoms 1～6 is respectively the alkylidene group of carbonatoms 1～6 in the formula (5).

As the compound shown in the formula (6), can enumerate the compound that epoxide such as cyclic ester, oxyethane, propylene oxide such as addition 6-caprolactone, γ-Wu Neizhi form in the compound shown in the formula (5).Among the present invention, preferably R11 is that alkylidene group, R14 and the R15 that alkyl, R12 and the R13 of carbonatoms 1～6 is respectively carbonatoms 1～6 is respectively general formula in the formula (6): (in the formula, R ' is the alkylidene group of carbonatoms 1～10 to-R '-CO-.) shown in compound.In addition, the preferred number average molecular weight of compound is 500～5,000 shown in the formula (6).

As (in fact not tertiary-amino-containing or carboxyl) macromolecule polyol, can enumerate polyester polyol, polyesteramide polyvalent alcohol, polycarbonate polyol, polyether glycol, polyolefin polyhydric alcohol, animals and plants is polyvalent alcohol or their polyol etc.These macromolecule polyols may be used alone, can also be two or more kinds in combination.The number-average molecular weight of macromolecule polyol is preferably 300～10, and 000, be preferably 500～5,000 especially.

As polyester polyol, the polyesteramide polyvalent alcohol, can enumerate succsinic acid, hexanodioic acid, sebacic acid, nonane diacid, terephthalic acid, m-phthalic acid, phthalic acid, hexahydroterephthalic acid, the hexahydro-m-phthalic acid, hexahydro-phthalic acid, naphthalic acid, polyprotonic acids such as trimellitic acid, acid esters, or more than a kind of acid anhydrides etc., with ethylene glycol, 1, the 2-propylene glycol, 1, ammediol, 1, the 2-butyleneglycol, 1, the 3-butyleneglycol, 1, the 4-butyleneglycol, 1, the 5-pentanediol, the 2-methyl isophthalic acid, the 5-pentanediol, the 3-methyl isophthalic acid, the 5-pentanediol, 1, the 6-hexylene glycol, the 3-methyl isophthalic acid, the 5-pentanediol, neopentyl glycol, 1, the 8-ethohexadiol, 1, the 9-nonanediol, 2,2-diethyl-1, ammediol, 2-normal-butyl-2-ethyl-1, ammediol, 2,2,4-trimethylammonium-1, the 3-pentanediol, 2-ethyl-1, the 3-hexylene glycol, 2-n-hexadecane-1,2-NSC 62789-1,2-positive octacosane-1,2-ethylene glycol, Diethylene Glycol, dipropylene glycol, 1, the 4-cyclohexane diol, the perhaps oxyethane of dihydroxyphenyl propane or propylene oxide adduct, the hydrogenation dihydroxyphenyl propane, 3-hydroxyl-2,2-dimethyl propyl-3-hydroxyl-2,2-dimethyl propylene acid esters, TriMethylolPropane(TMP), glycerine, the product that carries out the dehydration condensation acquisition more than a kind of low molecular polylol classes such as tetramethylolmethane.In addition, can also enumerate with the low molecular polylol is starting raw material, and the lactone that makes cyclic ester (lactone) monomers such as 6-caprolactone, γ-Wu Neizhi carry out the ring-opening polymerization acquisition is a polyester polyol.

As polycarbonate polyol, can enumerate the low molecular polylol that is used for synthetic above-mentioned polyester polyol carries out acquisitions such as dealcoholization, dephenolize reaction with carbonic acid diethylidene ester, methylcarbonate, diethyl carbonate, diphenyl carbonate etc. product.

As polyether glycol, can enumerate with the low molecular polylol that is used for synthetic above-mentioned polyester polyol, low molecule polyamine, low molecule amino alcohol is starting raw material, the polyether glycol that the polyoxyethylene glycol that makes oxyethane, propylene oxide, tetrahydrofuran (THF) etc. carry out ring-opening polymerization to form, polypropylene glycol, polytetramethylene ether diol etc. or their copolymerization form, further also having with above-mentioned polyester polyol, polycarbonate polyol is the polyester ether polyvalent alcohol of starting raw material.

As polyolefin polyhydric alcohol, can enumerate the polyhutadiene with hydroxyl, the polyhutadiene with hydroxyl of hydrogenation, polyisoprene, hydrogenation with hydroxyl the polyisoprene with hydroxyl, have hydroxyl Chlorinated Polypropylene III, have the chlorinatedpolyethylene of hydroxyl etc.

As animals and plants is polyvalent alcohol, and can enumerate Viscotrol C is polyvalent alcohol, spun silk albumen etc.

Should illustrate, if urea resin, melmac, Resins, epoxy, vibrin, acrylic resin, polyvinyl alcohol, Gum Rosin etc. contain more than 1, preferred more than 2 can with the functional groups such as reactive hydrogen base of isocyanic ester radical reaction, just can be used as a part that contains the reactive hydrogen based compound and use.

Consider that as macromolecule polyol, the polyester polyol that uses terephthalic acid, m-phthalic acid, hexanodioic acid, nonane diacid or sebacic acid to obtain is suitable under the occasion with the adhesiveproperties of base material film.

As chain propagation agent, can enumerate low molecular polylol into above-mentioned polyester polyols raw polyol, water, urea etc.

As being used to make urethane resin (A) or having organic polymeric polyisocyanate of the urethane resin (B) of the amino and carboxyl of uncle with uncle's amino, for example can enumerate 2,4-Ben Yajiaji vulcabond, 2,6-Ben Yajiaji vulcabond, dimethylbenzene-1, the 4-vulcabond, dimethylbenzene-1, the 3-vulcabond, 4,4 '-diphenylmethanediisocyanate, 2,4 '-diphenylmethanediisocyanate, 4,4 '-diphenyl ether vulcabond, 2-nitro phenylbenzene-4,4 '-vulcabond, 2,2 '-diphenyl propane-4,4 '-vulcabond, 3,3 '-dimethyl diphenylmethane-4,4 '-vulcabond, 4,4 '-diphenyl propane vulcabond, the m-phenylene vulcabond, the p-phenylene vulcabond, naphthylidene-1, the 4-vulcabond, naphthylidene-1, the 5-vulcabond, 3,3 '-dimethoxy-biphenyl-4, aromatic diisocyanates such as 4 '-vulcabond, polyphenylene polymethylene polyisocyanates, aromatic polyisocyanates such as Network Le one De Ben Yajiaji vulcabond, tetramethylene diisocyanate, hexamethylene diisocyanate, the decamethylene vulcabond, aliphatic diisocyanates such as lysinediisocyanate, isophorone diisocyanate, hydrogenation Ben Yajiaji vulcabond, the hydrogenation Xylene Diisocyanate, the hydrogenation diphenylmethanediisocyanate, polyisocyanates such as alicyclic diisocyanate such as tetramethylxylene diisocyanate, and the biuret modified body of above-mentioned polyisocyanates, ウレトジオ Application modification body, the ester modified body of cyamelide, the ester modified body of ウレトジオ Application cyamelide, the polyvalent alcohols that ウレト Application イミ Application modification body and 2 functional groups are above etc. and above-mentioned polyisocyanates or this modified polyisocyanate body react the adducts of the polyisocyanates of acquisition.

As being used to make above-mentioned urethane resin (A) or reaction unit (B), get final product so long as can reach any device of above-mentioned reaction, can enumerate the mixed milling devices such as reactor, kneader, single screw rod or multiscrew extrusion reaction machine that for example have whipping appts.As being used to promote catalyst for reaction, also can use tertiary amine catalysts such as metal catalysts such as making dioctyl tin dilaurate that urethane and polyureas be used often and triethylamine etc.

Above-mentioned urethane resin (A) or (B) can be the non-solvent state or use as the solution that is dissolved in the organic solvent with non-water system.Wherein, preferably resin dissolves is used as solution in organic solvent.Adopt in the tackiness agent of aqueous polyurethane resin, exist when coating adhesive the wettability to base material bad, when tackiness agent is dry, need problem such as a large amount of heat energy.

As organic solvent, needing only isocyanate group is the inert solvent, just has no particular limits, and can use, and can enumerate for example aromatic hydrocarbons such as toluene, dimethylbenzene series solvent; Ester such as vinyl acetic monomer, N-BUTYL ACETATE series solvent; Ketone such as methylethylketone, pimelinketone series solvent, ethyl cellosolve acetate, propylene glycol methyl ether acetate, ethyl-glycol ether-ether series solvents such as 3-ethoxy-c acid esters; Ether such as tetrahydrofuran (THF), dioxane series solvent; In dimethyl formamide, N,N-DIMETHYLACETAMIDE, N-Methyl pyrrolidone, the furfural isopolarity solvent more than a kind or 2 kinds.In addition, also can use these organic solvents, below 100 ℃, in above-mentioned matching requirements scope, each composition uniform mixing be made its reaction, make above-mentioned urethane resin (A) or (B) preferred.

Above-mentioned urethane resin (A) or (B) in, also can cooperate additives such as pigment, dyestuff, thixotropic agent, antioxidant, UV light absorber, defoamer, tackifier, dispersion agent, tensio-active agent, mould inhibitor, antiseptic-germicide, sanitas, catalyzer, weighting agent as required.

As the polyisocyanate curing agent among the present invention, can enumerate and be used to make above-mentioned urethane resin (A) or organic polymeric polyisocyanate (B) etc.As preferred organic polymeric polyisocyanate, can enumerate コロネ-ト (registered trademark)-L ,-3041 that Japanese polyurethane industry (strain) produces ,-HL ,-the ester modified body of polyisocyanates such as HX.Particularly preferred organic polymeric polyisocyanate is the ester modified body of polyisocyanate of being derived and being formed by hexamethylene diisocyanate, is コロネ-ト HL and コロネ-ト HX that Japanese polyurethane industry (strain) is produced.

Above-mentioned urethane resin (A) or (B) and the proportioning of polyisocyanate curing agent, the ratio of the mole number of total isocyanate group in the mole number of total reactive hydrogen base and the polyisocyanate curing agent by above-mentioned urethane resin (A) or (B), be preferably 1: 20～20: 1, more preferably 1: 15～15: 1.Proportioning is difficult to realize (high) bonding strength beyond this scope the time.

Nonaqueous series laminated adhesive among the present invention, if also with the silane coupling agent shown in the formula (7), the bonding strength after then high temperature steaming is handled becomes very strong, is preferred therefore.

OCN-(CH ₂) _m-Si(OR) ₃ (7)

(in the formula, R is methyl or ethyl.M is 1～5 integer.)

As this silane coupling agent, can enumerate γ-isocyanato-propyl trimethoxy silicane, γ-isocyanato-propyl-triethoxysilicane etc.

This silane coupling agent since functional group be-(in the formula, R is methyl or ethyl for NCO and Si-OR.), therefore under common maintaining requirement, can not react with polyisocyanate curing agent.Therefore, even polyisocyanate curing agent is mixed use with silane coupling agent, it is also fine to last stability.

Cooperate under the occasion of silane coupling agent use in polyisocyanate curing agent, the use level of silane coupling agent is preferably below the 10 weight % of polyisocyanate curing agent, more preferably below the 8 weight %.Under the too much occasion of the use level of silane coupling agent, cementability reduces, and the operability when making laminate adhesive reduces.Use level shown here has considered that base material film lining area and the lining efficient and the adhesiveproperties etc. of silane coupling agent calculate.

Nonaqueous series laminated adhesive of the present invention is at the film with plastics such as oriented polypropylene, un-stretched polypropylene, polyester, nylon, new LDPE (film grade), high density polyethylene(HDPE), ethylene-vinyl acetate copolymer, polyvinyl alcohol, ethylene-vinyl alcohol copolymer, polystyrene, polycarbonate, polyvinylidene chloride, polyvinyl chloride; The tinsel of aluminium, copper etc.; Paper etc., and to use the film of implementing polymer-coated, aluminum oxide evaporation, silica steam plating etc. on these materials to make laminated film be only.

It is carried out suitable surface treatments such as Corona discharge Treatment before these films are carried out lamination, this is being preferred aspect bonding force that improves between film.

The laminating condition of nonaqueous series laminated adhesive of the present invention is 10～180 ℃, 0.1～1MPa, more preferably 20～150 ℃, 0.2～0.8MPa.

Nonaqueous series laminated adhesive of the present invention can adopt dry lamination, hot melt lamination, extrude known laminating methods such as lamination.Can be carried out ageing by laminated film finishes curing reaction.

Adopt this method not only 2 films can be made laminated film, also the film more than 3 can be made laminated film.

Carry out ageing condition optimization behind the lamination for 20～70 ℃ of following ageings 10～60 hours, more preferably 25～50 ℃ of following ageings 50 hours with nonaqueous series laminated adhesive of the present invention.Should illustrate,, need more than 72 hours under this temperature condition with the ageing of laminating adhesive in the past.

As described above, laminating adhesive of the present invention, digestion time is short, and storage period is long, has good storage stability simultaneously, can solve the problem that laminating adhesive in the past cann't be solved.

Below describe embodiments of the invention in detail, but the present invention is not subjected to any qualification and the explanation of these embodiment.Unless otherwise specified, " % " in embodiment and the comparative example just means " weight % ".

Manufacturing with urethane resin of uncle's amino

Embodiment 1

In the reactor of the capacity 2L that has stirrer, thermometer, nitrogen-sealed pipe and water cooler, add polyvalent alcohol A 400g, polyvalent alcohol B 50g, vinyl acetic monomer 333g, under 60 ℃, make its dissolving.Then, add MDI 50g, DOTDL 0.1g, under 70 ℃, make its reaction 4 hours.When the absorption peak of the isocyanate group of measuring when the infrared rays absorptiometric analysis disappears, add vinyl acetic monomer 167g again and dilute, obtain polyurethane resin solution PU-1.

Embodiment 2

In reactor similarly to Example 1, add polyvalent alcohol A 463g, MDEA 0.3g, vinyl acetic monomer 125g, under 60 ℃, make its dissolving.Then, add HDI 36g, DOTDL0.1g, under 70 ℃, make its reaction 5 hours.When the absorption peak of the isocyanate group of measuring when the infrared rays absorptiometric analysis disappears, add vinyl acetic monomer 375g again and dilute, obtain polyurethane resin solution PU-2.

Embodiment 3

In reactor similarly to Example 1, add polyvalent alcohol A 457g, MDEA 2.4g, vinyl acetic monomer 125g, under 60 ℃, make its dissolving.Then, add HDI 41g, DOTDL0.1g, under 70 ℃, make its reaction 5 hours.When the absorption peak of the isocyanate group of measuring when the infrared rays absorptiometric analysis disappears, add vinyl acetic monomer 375g again and dilute, obtain polyurethane resin solution PU-3.

Embodiment 4

In reactor similarly to Example 1, add polyvalent alcohol A 458g, MDEA 3.0g, vinyl acetic monomer 125g, under 60 ℃, make its dissolving.Then, add HDI 39g, DOTDL0.1g, under 70 ℃, make its reaction 5 hours.When the absorption peak of the isocyanate group of measuring when the infrared rays absorptiometric analysis disappears, add vinyl acetic monomer 375g again and dilute, obtain polyurethane resin solution PU-4.

Embodiment 5

In reactor similarly to Example 1, add polyvalent alcohol A 370g, MDEA 48g, vinyl acetic monomer 333g, under 60 ℃, make its dissolving.Then, add TDI 82g, DOTDL0.1g, under 70 ℃, make its reaction 5 hours.When the absorption peak of the isocyanate group of measuring when the infrared rays absorptiometric analysis disappears, add vinyl acetic monomer 167g again and dilute, obtain polyurethane resin solution PU-5.

Embodiment 6

In reactor similarly to Example 1, add polyvalent alcohol A 443g, DEAPD 4.4g, vinyl acetic monomer 125g, under 60 ℃, make its dissolving.Then, add IPDI 52g, DOTDL 0.1g, under 70 ℃, make its reaction 8 hours.When the absorption peak of the isocyanate group of measuring when the infrared rays absorptiometric analysis disappears, add vinyl acetic monomer 375g again and dilute, obtain polyurethane resin solution PU-6.

Embodiment 7

In reactor similarly to Example 1, add polyvalent alcohol A 400g, polyvalent alcohol C 50g, vinyl acetic monomer 333g, under 60 ℃, make its dissolving.Then, add MDI 50g, DOTDL0.1g, under 70 ℃, make its reaction 4 hours.When the absorption peak of the isocyanate group of measuring when the infrared rays absorptiometric analysis disappears, add vinyl acetic monomer 167g again and dilute, obtain polyurethane resin solution PU-7.

Comparative example 1

In reactor similarly to Example 1, add polyvalent alcohol A 449g, vinyl acetic monomer 333g, under 60 ℃, make its dissolving.Then, add MDI 48g, DOTDL 0.1g, under 70 ℃, make its reaction 4 hours.When the absorption peak of the isocyanate group of measuring when the infrared rays absorptiometric analysis disappears, add vinyl acetic monomer 167g and dilute, add A-1310 1.0g, TEA 2.5g again, obtain polyurethane resin solution PU-8.

Comparative example 2

In reactor similarly to Example 1, add polyvalent alcohol A 469g, vinyl acetic monomer 125g, under 60 ℃, make its dissolving.Then, add HDI 30g, DOTDL 0.1g, under 70 ℃, make its reaction 5 hours.When the absorption peak of the isocyanate group of measuring when the infrared rays absorptiometric analysis disappears, add vinyl acetic monomer 375g again and dilute, obtain polyurethane resin solution PU-9.

Comparative example 3

In reactor similarly to Example 1, add polyvalent alcohol A 278g, MDEA 71g, vinyl acetic monomer 125g, under 60 ℃, make its dissolving.Then, add MDI 148g, DOTDL 0.1g, under 70 ℃, make its reaction 4 hours.When the absorption peak of the isocyanate group of measuring when the infrared rays absorptiometric analysis disappears, add vinyl acetic monomer 375g again and dilute, obtain polyurethane resin solution PU-10.

Comparative example 4

In reactor similarly to Example 1, add polyvalent alcohol A 459g, MDEA 3.1g, vinyl acetic monomer 125g, under 60 ℃, make its dissolving.Then, add HDI 38g, DOTDL0.1g, under 70 ℃, make its reaction 5 hours.When the absorption peak of the isocyanate group of measuring when the infrared rays absorptiometric analysis disappears, add vinyl acetic monomer 375g and dilute, add A-187 0.4g again, obtain polyurethane resin solution PU-11.

Manufacturing with urethane resin of uncle's amino and carboxyl

Embodiment 8

In reactor similarly to Example 1, add polyvalent alcohol A 448.1g, MDEA2.4g, DMBA 4.4g, vinyl acetic monomer 125g, under 60 ℃, make its dissolving.Then, add IPDI 49.7g, DOTDL 0.1g, under 70 ℃, make its reaction 6 hours.When the absorption peak of the isocyanate group of measuring when the infrared rays absorptiometric analysis disappears, add vinyl acetic monomer 375g again and dilute, obtain polyurethane resin solution PU-12.

Embodiment 9

In reactor similarly to Example 1, add polyvalent alcohol B 423.9g, DEAPD2.9g, DMBA 4.4g, vinyl acetic monomer 125g, under 60 ℃, make its dissolving.Then, add HDI 71.2g, DOTDL 0.1g, under 70 ℃, make its reaction 6 hours.When the absorption peak of the isocyanate group of measuring when the infrared rays absorptiometric analysis disappears, add vinyl acetic monomer 375g again and dilute, obtain polyurethane resin solution PU-13.

Embodiment 10

In reactor similarly to Example 1, add polyvalent alcohol B 393.1g, polyvalent alcohol C 20.0g, DMBA 8.9g, vinyl acetic monomer 125g, under 60 ℃, make its dissolving.Then, add IPDI 87.3g, DOTDL 0.1g, under 70 ℃, make its reaction 6 hours.When the absorption peak of the isocyanate group of measuring when the infrared rays absorptiometric analysis disappears, add vinyl acetic monomer 375g again and dilute, obtain polyurethane resin solution PU-14.

Embodiment 11

In reactor similarly to Example 1, add polyvalent alcohol A 358.7g, MDEA11.9g, polyol E 100.0g, vinyl acetic monomer 333g, under 60 ℃, make its dissolving.Then, add TDI 31.2g, DOTDL 0.1g, under 70 ℃, make its reaction 5 hours.When the absorption peak of the isocyanate group of measuring when the infrared rays absorptiometric analysis disappears, add vinyl acetic monomer 167g again and dilute, obtain polyurethane resin solution PU-15.

Embodiment 12

In reactor similarly to Example 1, add polyvalent alcohol A 265.2g, DEAPD7.3g, polyol E 200.0g, vinyl acetic monomer 125g, under 60 ℃, make its dissolving.Then, add IPDI 29.4g, DOTDL 0.1g, under 70 ℃, make its reaction 6 hours.When the absorption peak of the isocyanate group of measuring when the infrared rays absorptiometric analysis disappears, add vinyl acetic monomer 375g again and dilute, obtain polyurethane resin solution PU-16.

Embodiment 13

In reactor similarly to Example 1, add polyvalent alcohol A 440.5g, NPG 2.3g, polyvalent alcohol D 5.0g, polyol E 10.0g, vinyl acetic monomer 333g, under 60 ℃, make its dissolving.Then, add MDI 55.1g, DOTDL 0.1g, under 70 ℃, make its reaction 5 hours.When the absorption peak of the isocyanate group of measuring when the infrared rays absorptiometric analysis disappears, add vinyl acetic monomer 167g again and dilute, obtain polyurethane resin solution PU-17.

Embodiment 14

In reactor similarly to Example 1, add polyvalent alcohol A 444.1g, MDEA1.2g, DEAPD 1.5g, DMBA 4.4g, vinyl acetic monomer 125g, under 60 ℃, make its dissolving.Then, add IPDI 49.3g, DOTDL 0.1g, under 70 ℃, make its reaction 6 hours.When the absorption peak of the isocyanate group of measuring when the infrared rays absorptiometric analysis disappears, add vinyl acetic monomer 375g again and dilute, obtain polyurethane resin solution PU-18.

Comparative example 5

In reactor similarly to Example 1, add polyvalent alcohol A 460.6g, DMBA4.4g, vinyl acetic monomer 125g, under 60 ℃, make its dissolving.Then, add HDI 38.7g, DOTDL 0.1g, under 70 ℃, make its reaction 6 hours.When the absorption peak of the isocyanate group of measuring when the infrared rays absorptiometric analysis disappears, add vinyl acetic monomer 375g again and dilute, obtain polyurethane resin solution PU-19.

Comparative example 6

In reactor similarly to Example 1, add polyvalent alcohol A 358.3g, MDEA23.8g, DMBA 88.8g, vinyl acetic monomer 125g, under 60 ℃, make its dissolving.Then, add HDI 30.1g, DOTDL 0.1g, under 70 ℃, make its reaction 6 hours.When the absorption peak of the isocyanate group of measuring when the infrared rays absorptiometric analysis disappears, add vinyl acetic monomer 375g again and dilute, obtain polyurethane resin solution PU-20.

Comparative example 7

In reactor similarly to Example 1, add polyvalent alcohol A 355.3g, MDEA71.4g, DMBA 44.4g, vinyl acetic monomer 125g, under 60 ℃, make its dissolving.Then, add HDI 29.8g, DOTDL 0.1g, under 70 ℃, make its reaction 6 hours.When the absorption peak of the isocyanate group of measuring when the infrared rays absorptiometric analysis disappears, add vinyl acetic monomer 375g again and dilute, obtain polyurethane resin solution PU-21.

Comparative example 8

In reactor similarly to Example 1, add polyvalent alcohol A 465.1g, vinyl acetic monomer 125g, under 60 ℃, make its dissolving.Then, add HDI 39.1g, DOTDL 0.1g, under 70 ℃, make its reaction 6 hours.When the absorption peak of the isocyanate group of measuring when the infrared rays absorptiometric analysis disappears, add vinyl acetic monomer 375g again and dilute, obtain polyurethane resin solution PU-22.

Comparative example 9

In reactor similarly to Example 1, add polyvalent alcohol A 460.6g, DMBA4.4g, vinyl acetic monomer 125g, under 60 ℃, make its dissolving.Then, add HDI 38.7g, DOTDL 0.1g, under 70 ℃, make its reaction 6 hours.When the absorption peak of the isocyanate group of measuring when the infrared rays absorptiometric analysis disappears, add vinyl acetic monomer 375g again and dilute.Then, be cooled to below 50 ℃ after, add TEA 1.5g, under 40～50 ℃, carry out 1 hour neutralization reaction, obtain polyurethane resin solution PU-23.

The storage stability test

PU-1～23 are added in the 200ml sample bottle, and sealing is placed after 24 hours in 25 ℃ Water Tank with Temp.-controlled and is taken out, and under 25 ℃ * 50%RH ambiance, measures viscosity with Brookfield viscometer (sesame Pu システ system (strain) system).Sealing once more after the mensuration is similarly measured viscosity in storage under 40 ℃ after 3 months.The results are shown in table 1～4.

[table 1]

	Embodiment
	Embodiment							1	2	3	4	5	6	7
	Macromolecule polyol (g) polyvalent alcohol A	400	463	457	458	370	443	1	2	3	4	5	6	7	400
Compound (g) polyvalent alcohol B polyvalent alcohol C MDEA DEAPD with uncle's amino and reactive hydrogen base	Macromolecule polyol (g) polyvalent alcohol A	400	463	457	458	370	443	50	0.3	2.4	3.0	48	4.4	50	400
	Organic polymeric polyisocyanate (g) MDI HDT TDI IPDI	50	36	41	39	82	52	50	0.3	2.4	3.0	48	4.4	50	50
Catalyzer (g) DOTDL	Organic polymeric polyisocyanate (g) MDI HDT TDI IPDI	50	36	41	39	82	52	0.1	0.1	0.1	0.1	0.1	0.1	0.1	50
Catalyzer (g) DOTDL	Organic solvent (g) vinyl acetic monomer	500	500	500	500	500	500	0.1	0.1	0.1	0.1	0.1	0.1	0.1	500
Polyurethane resin solution uncle amino content (mmol/g) solid concentration (%) viscosity (mPas/25 ℃) number-average molecular weight	Organic solvent (g) vinyl acetic monomer	500	500	500	500	500	500	PU-1 0.1 50.1 1,590 19,000	PU-2 0.005 50.0 1,000 18,000	PU-3 0.04 50.2 3,300 35,000	PU-4 0.05 49.8 1,070 20,000	PU-5 0.8 50.1 550 7,000	PU-6 0.06 50.1 1,200 21,000	PU-7 0.1 50.0 1,570 19,000	500
	Package stability through the time after viscosity (mPas/25 ℃) viscosity conservation rate (%)	1,550 97.5	940 94.0	3,210 97.3	1,020 95.3	510 92.7	1,130 94.2	PU-1 0.1 50.1 1,590 19,000	PU-2 0.005 50.0 1,000 18,000	PU-3 0.04 50.2 3,300 35,000	PU-4 0.05 49.8 1,070 20,000	PU-5 0.8 50.1 550 7,000	PU-6 0.06 50.1 1,200 21,000	PU-7 0.1 50.0 1,570 19,000	1,540 98.1

[table 2]

	Comparative example
	Comparative example				1	2	3	4
	Macromolecule polyol (g) polyvalent alcohol A	449	469	278	1	2	3	4	459
Compound (g) MDEA with uncle's amino and reactive hydrogen base	Macromolecule polyol (g) polyvalent alcohol A	449	469	278			71	3.1	459
	Has uncle's aminocompound (g) TEA	2.5					71	3.1
Organic polymeric polyisocyanate (g) MDI HDI	Has uncle's aminocompound (g) TEA	2.5			48	30	148	38
Organic polymeric polyisocyanate (g) MDI HDI	Catalyzer (g) DOTDL	0.1	0.1	0.1	48	30	148	38	0.1
Silane coupling agent (g) A-1310 A-187	Catalyzer (g) DOTDL	0.1	0.1	0.1	1.0			0.4	0.1
Silane coupling agent (g) A-1310 A-187	Organic solvent (g) vinyl acetic monomer	500	500	500	1.0			0.4	500
Polyurethane resin solution uncle amino content (mmol/g) solid concentration (%) viscosity (mPas/25 ℃) number-average molecular weight	Organic solvent (g) vinyl acetic monomer	500	500	500	PU-8 0.05 49.9 3,000 30,000	PU-9 50.2 620 8,000	PU-10 1.2 50.1 980 13,000	PU-11 0.05 49.9 1,650 20,000	500
	Package stability through the time after viscosity (mPas/25 ℃) viscosity conservation rate (%)	1,400 46.7	650 104.9	950 96.9	PU-8 0.05 49.9 3,000 30,000	PU-9 50.2 620 8,000	PU-10 1.2 50.1 980 13,000	PU-11 0.05 49.9 1,650 20,000	6,380 204.8

[table 3]

	Embodiment
	Embodiment							8	9	10	11	12	13	14
	Macromolecule polyol (g) polyvalent alcohol A polyvalent alcohol B	448.1	423.9	393.1	358.7	265.2	440.5	8	9	10	11	12	13	14	444.1
Chain propagation agent (g) NPG		448.1	423.9	393.1	358.7	265.2	440.5						2.3		444.1
Chain propagation agent (g) NPG	Compound (g) MDEA DEAPD polyvalent alcohol C polyvalent alcohol D with uncle's amino and reactive hydrogen base	2.4	2.9	20.0	11.9	7.3	5.0						2.3		1.2 1.5
Compound (g) the DMBA polyol E that contains carboxyl and reactive hydrogen base		2.4	2.9	20.0	11.9	7.3	5.0	4.4	4.4	8.9	100.0	200.0	10.0	4.4	1.2 1.5
	Organic polymeric polyisocyanate (g) IPDI HDI TDI MDI	49.7	71.2	87.3	31.2	29.4	55.1	4.4	4.4	8.9	100.0	200.0	10.0	4.4	49.3
Catalyzer (g) DOTDL	Organic polymeric polyisocyanate (g) IPDI HDI TDI MDI	49.7	71.2	87.3	31.2	29.4	55.1	0.1	0.1	0.1	0.1	0.1	0.1	0.1	49.3
Catalyzer (g) DOTDL	Organic solvent (g) vinyl acetic monomer	500	500	500	500	500	500	0.1	0.1	0.1	0.1	0.1	0.1	0.1	500
Polyurethane resin solution uncle amino content, (mmol/g) carboxyl-content, (mmol/g) solid concentration, (%) viscosity, (mPas/25 ℃) number-average molecular weight	Organic solvent (g) vinyl acetic monomer	500	500	500	500	500	500	PU-12 0.04 0.06 50.2 2,200 21,000	PU-13 0.04 0.06 50.1 2,100 32,000	PU-14 0.08 0.12 49.8 800 11,000	PU-15 0.2 0.4 49.9 2,000 20,000	PU-16 0.1 0.8 50.0 1,900 16,000	PU-17 0.02 0.04 50.1 600 8,000	PU-18 0.04 0.06 50.0 2,000 20,000	500
	Package stability through the time after viscosity (mPas/25 ℃) viscosity increment rate (%)	2,250 2.3	2,150 2.4	830 3.8	2,050 2.5	1.900 0.0	650 8.3	PU-12 0.04 0.06 50.2 2,200 21,000	PU-13 0.04 0.06 50.1 2,100 32,000	PU-14 0.08 0.12 49.8 800 11,000	PU-15 0.2 0.4 49.9 2,000 20,000	PU-16 0.1 0.8 50.0 1,900 16,000	PU-17 0.02 0.04 50.1 600 8,000	PU-18 0.04 0.06 50.0 2,000 20,000	2,070 3.5

[table 4]

	Comparative example
	Comparative example					5	6	7	8	9
	Macromolecule polyol (g) polyvalent alcohol A	460.6	358.3	355.3	465.1	5	6	7	8	9	460.6
Compound (g) MDEA with uncle's amino and reactive hydrogen base	Macromolecule polyol (g) polyvalent alcohol A	460.6	358.3	355.3	465.1		23.8	71.4			460.6
	Compound (g) DMBA that contains carboxyl and reactive hydrogen base	4.4	88.8	44.4			23.8	71.4			4.4
Organic polymeric polyisocyanate (g) HDI		4.4	88.8	44.4		38.7	30.1	29.8	39.1	38.7	4.4
Organic polymeric polyisocyanate (g) HDI	Catalyzer (g) DOTDL	0.1	0.1	0.1	0.1	38.7	30.1	29.8	39.1	38.7	0.1
Compound (g) TEA with uncle's amino	Catalyzer (g) DOTDL	0.1	0.1	0.1	0.1					1.5	0.1
Compound (g) TEA with uncle's amino	Organic solvent (g) vinyl acetic monomer	500	500	500	500					1.5	500
Polyurethane resin solution uncle amino content, (mmol/g) carboxyl-content, (mmol/g) solid concentration, (%) viscosity, (mPas/25 ℃) number-average molecular weight	Organic solvent (g) vinyl acetic monomer	500	500	500	500	PU-19 0.06 50.1 1,900 20,000	PU-20 0.4 1.2 50.3 3,200 21,000	PU-21 1.2 0.6 49.8 2,800 19,000	PU-22 49.8 1,480 18,000	PU-23 0.03 0.06 50.2 1,500 22,000	500
	Package stability through the time after viscosity (mPas/25 ℃) viscosity increment rate (%)	1,950 2.6	3,200 0.0	2,830 1.1	1,500 1.4	PU-19 0.06 50.1 1,900 20,000	PU-20 0.4 1.2 50.3 3,200 21,000	PU-21 1.2 0.6 49.8 2,800 19,000	PU-22 49.8 1,480 18,000	PU-23 0.03 0.06 50.2 1,500 22,000	900 -40.0

In embodiment 1～14, comparative example 1～9 and table 1～4:

Polyvalent alcohol A: by ethylene glycol/neopentyl glycol=1/1 (mol ratio) polyester glycol with sebacic acid/m-phthalic acid=1/1 (mol ratio) acquisition

Number-average molecular weight=2,000

Polyvalent alcohol B: by ethylene glycol/neopentyl glycol=1/1 (mol ratio) polyester glycol with sebacic acid/m-phthalic acid=1/1 (mol ratio) acquisition

Number-average molecular weight=1,000

Polyvalent alcohol C: at N-methyl-N, addition 6-caprolactone in the N-diethanolamine and the lactone with uncle's amino that forms is a polyvalent alcohol

Number-average molecular weight=500

Polyvalent alcohol D: at 2-(N, N-diethylin)-1, addition 6-caprolactone in the ammediol and the lactone with uncle's amino that forms is a polyvalent alcohol

Number-average molecular weight=500

Polyol E: dimethylol propionic acid (methylol) go up the addition 6-caprolactone and form contain carboxylic diol

Number-average molecular weight=500

NPG: neopentyl glycol

MDEA:N-methyl-N, the N-diethanolamine

DEAPD:2-(N, N-diethylin)-1, ammediol

DMBA:2, the 2-dimethylolpropionic acid

IPDI: isophorone diisocyanate

HDI: hexamethylene diisocyanate

TDI:2,4-Ben Yajiaji vulcabond

MDI:4,4 '-diphenylmethanediisocyanate

DOTDL: dioctyl tin dilaurate

TEA: triethylamine

A-187: Japanese ュニカ-(strain) system silane coupling agent

γ-glycidoxypropyltrime,hoxysilane

A-1310: Japanese ユニカ-(strain) system silane coupling agent

γ-isocyanato-propyl-triethoxysilicane

The viscosity conservation rate of the polyurethane resin solution of embodiment 1～7 (=25 ℃ of 40 ℃ of viscosity * 100 of preserving down after 3 months of viscosity ÷ of preserving down after 24 hours) is all 90～100%, in addition, (=40 ℃ of 25 ℃ of viscosity ÷ that preserve down after 3 months preserve viscosity after 24 hours * 100-100) down all greatly in 10 to the viscosity increment rate of the polyurethane resin solution of embodiment 8～14, and storage stability is good.But the viscosity of the polyurethane resin solution of comparative example 1,9 reduces very big.Think that this is that urethane resin is by the cause of free tertiary amine hydrolysis.In addition, the viscosity of the polyurethane resin solution of comparative example 4 increases a lot.Think that this is the cause that silane coupling agent causes crosslinking reaction.

The cooperation of solidifying agent

Formulation example 1～6

Press cooperation preparation polyisocyanate curing agent CA-1～6 shown in the table 5.The polyisocyanate curing agent for preparing after 1 month, is carried out the test of storage stability in the keeping of sombre dark place.The results are shown in the table 5.

[table 5]

	Formulation example
	Formulation example						1	2	3	4	5	6
	Organic polymeric polyisocyanate (g) C-HL C-L NCO-1	100	100	100	100	100	1	2	3	4	5	6	100
Silane coupling agent (g) A-1310 A-187	Organic polymeric polyisocyanate (g) C-HL C-L NCO-1	100	100	100	100	100	0.2	0.4	0.05		5.0	0.2	100
Silane coupling agent (g) A-1310 A-187	The polyisocyanate curing agent package stability	CA-1 ○	CA-2 ○	CA-3 ○	CA-4 ○	CA-5 ○	0.2	0.4	0.05		5.0	0.2	CA-6 ×

In the table 5:

C-HL: Japanese polyurethane industry (strain) system

The urethane modification body of hexamethylene diisocyanate

Isocyanate group content=12.8%

(trade(brand)name: コロネ-ト HL, solid concentration=75%)

C-L: Japanese polyurethane industry (strain) system

The urethane modification body of Ben Yajiaji vulcabond

Isocyanate group content=13.2%

(trade(brand)name: コロネ-ト L, solid concentration=75%)

NCO-1: Japanese polyurethane industry (strain) system

Import the ester modified body of polyisocyanate of nonionic hydrophilic radical in by the polymeric polyisocyanate of isocyanuric acid esterification to hexamethylene diisocyanate

Isocyanate group content=16.5%, solid concentration=100%

A-1310: Japanese ユニカ-(strain) system silane coupling agent

γ-isocyanato-propyl-triethoxysilicane

A-187: Japanese ユニカ-(strain) system silane coupling agent

γ-glycidoxypropyltrime,hoxysilane

The evaluation of storage stability: estimate with the viscosity increment rate.

Zero: unconfirmed have phenomenons such as viscosity increase, bad order.

*: assert has phenomenons such as viscosity increase, bad order.

Find out that by table 5 storage stability of polyisocyanate curing agent that has added epoxy and be coupler is bad.

The cooperation of tackiness agent

Embodiment 15～29, comparative example 10～15

In the ratio shown in table 6～9, cooperate polyurethane resin solution, polyisocyanate curing agent and organic solvent, the preparation laminating adhesive.Should illustrate that PU-8,11,23 storage stability are bad, therefore do not carry out the evaluation as tackiness agent.

Stability, curing speed, the bonding strength of the laminating adhesive that measure to obtain, last the bonding strength after bonding strength and high temperature steaming are handled.

The results are shown in table 6～9.

Should illustrate that the bonding strength after high temperature steaming is handled is only estimated the tackiness agent that uses coupler.The tackiness agent stability (storage period) of PU-21 is bad, does not therefore carry out the mensuration of various bonding strengths.

The stability test of tackiness agent

Behind preparation laminating adhesive under the ambiance of 25 ℃ * 50%RH, put into the 200ml sample bottle, sealing.It is placed in 25 ℃ Water Tank with Temp.-controlled after 1 hour take out, under the ambiance of 25 ℃ * 50%RH, with Brookfield viscometer (sesame Pu システ system (strain) system) mensuration (viscosity).Viscosity at this moment as initial value, is put into 25 ℃ Water Tank with Temp.-controlled once more.With time to start with time of measuring initial value, begin after 8 hours and after 24 hours, similarly measure viscosity from this time.

The mensuration of curing speed

Behind preparation laminating adhesive under the ambiance of 25 ℃ * 50%RH, put into the 200ml sample bottle, sealing.It is placed in 25 ℃ Water Tank with Temp.-controlled after 1 hour take out, carry out infrared absorbency analysis (IR analysis).After the mensuration, put into 25 ℃ Water Tank with Temp.-controlled once more.Beginning similarly to carry out after 8 hours and after 24 hours IR from this time analyzes.

Curing speed is to utilize in the infrared absorbency analysis (IR analysis) 2,240～2,300cm ^-1Peak (isocyanate group) and 2,900～2,960cm ^-1The peak intensity ratio at peak (methylene radical), calculate the isocyanate group survival rate by following formula (1) and (2), obtain the reactivity (=100%-isocyanate group survival rate) of laminating adhesive more thus.

Wherein, A: cooperate solidifying agent peak intensity ratio afterwards

B: the peak intensity ratio behind the certain hour

Wherein, in the C:IR spectrogram, by the baseline of isocyanic ester base peak length to summit

In the D:IR spectrogram, by the baseline of methylene peak length to summit

Should illustrate that the longitudinal axis of spectrogram is transmitance (%).

Through the time bonding strength mensuration-1

15 μ m) and LLDPE film (film thickness: 130 μ m) place dry laminating machine with laminating adhesive AD 1～9, NY film (film thickness:.Then, with grooved roll laminating adhesive is applied on the corona treatment face of NY film, so that glue spread is counted 3.5g/m by drying ²Coating adhesive, make its drying oven that passes through 80 ℃ after, make itself and LLDPE together film adhered with the nip rolls of 80 ℃ * 0.3MPa, obtain laminated film.Should illustrate that film speed is the 50m/ branch.It is wide that this laminated film is cut into 15mm, carries out the stripping test of T type.Bonding strength at this moment as initial value, is carried out ageing with the laminated film that obtains under 35 ℃,, similarly measure bonding strength taking a sample after 8 hours and after 48 hours from the beginning of fitting.

The mensuration of bonding strength-1

15 μ m) and CPP film (film thickness: 70 μ m) place dry laminating machine with laminating adhesive AD 1～9, NY film (film thickness:.Then, with grooved roll laminating adhesive is applied on the corona treatment face of NY film, so that glue spread is counted 3.5g/m by drying ²Coating adhesive, make its drying oven that passes through 80 ℃ after, make itself and CPP together film adhered with the nip rolls of 80 ℃ * 0.3MPa.Should illustrate that film speed is the 50m/ branch.After the applying,, obtain laminated film 35 ℃ of following ageings 48 hours.It is wide that this laminated film is cut into 15mm, carries out the stripping test of T type, measures bonding strength (normality).

In addition, after the applying, with 35 ℃ of following ageings 16 hours laminated film be cut into the rectangle of 25cm * 30cm, with the NY pellicular front as the outside, under 180 ℃, 0.3MPa, 1 second condition,, make packing bag with three limits heat-sealings except that a minor face, the mixture of tomato-sauce/salad oil/vinegar=1/1/1 (weight ratio) of packing into therein seals unencapsulated limit under 180 ℃, 0.3MPa, 1 second condition.After carrying out boiling in 30 minutes under 120 ℃ and handling, it is wide that laminated film is cut into 15mm, carries out T type Film test, measures the bonding strength after boiling is handled with it.

The mensuration of bonding strength-2

15 μ m) and LLDPE film (film thickness: 130 μ m) place dry laminating machine with laminating adhesive AD 10～21, NY film (film thickness:.Then, with grooved roll laminating adhesive is applied on the corona treatment face of NY film, so that glue spread is counted 3.5g/m by drying ²Coating adhesive, make its drying oven that passes through 80 ℃ after, make itself and LLDPE together film adhered with the nip rolls of 80 ℃ * 0.3MPa, obtain laminated film.Should illustrate that film speed is the 50m/ branch.Behind the lamination,, obtain laminated film 35 ℃ of following ageings 48 hours.It is wide that this laminated film is cut into 15mm, carries out the stripping test of T type, measures bonding strength.

Through the time bonding strength mensuration-2

12 μ m), aluminium foil (film thickness: 9 μ m) and CPP film (film thickness: 70 μ m) place dry laminating machine with laminating adhesive AD 10～21, PET film (film thickness:.Then, with grooved roll laminating adhesive is applied on the corona treatment face of PET film, so that glue spread is counted 3.5g/m by drying ²Coating adhesive, make its drying oven that passes through 80 ℃ after, with the nip rolls of 80 ℃ * 0.3MPa itself and aluminium foil are fit together.Then, on aluminium foil surface, be coated with laminating adhesive, make glue spread count 3.5g/m by drying with grooved roll ², make its drying oven that passes through 80 ℃ after, with the nip rolls of 80 ℃ * 0.3MPa the corona treatment face of itself and CPP film is fit together, obtain laminated film.Should illustrate that film speed is the 50m/ branch.It is wide that this laminated film is cut into 15mm, carries out the stripping test of T type.The bonding strength of this moment as initial value, 35 ℃ of following ageings, from fitting beginning after 8 hours and sampling after 48 hours, is similarly measured bonding strength with the laminated film that obtains.

The mensuration of the bonding strength after high temperature steaming is handled

12 μ m), aluminium foil (film thickness: 9 μ m) and CPP film (film thickness: 70 μ m) place dry laminating machine with laminating adhesive AD 10～21, PET film (film thickness:.Then, with grooved roll laminating adhesive is applied on the corona treatment face of PET film, so that glue spread is counted 3.5g/m by drying ²Coating adhesive, make its drying oven that passes through 80 ℃ after, with the nip rolls of 80 ℃ * 0.3MPa itself and aluminium foil are fit together.Then, on aluminium foil surface, be coated with laminating adhesive, make glue spread count 3.5g/m by drying with grooved roll ², make its drying oven that passes through 80 ℃ then, with the nip rolls of 80 ℃ * 0.3MPa the corona treatment face of itself and CPP film is fit together, obtain laminated film.Should illustrate that film speed is the 50m/ branch.

After the applying, the laminated film of 35 ℃ of following ageings after 48 hours is cut into the rectangle of 25cm * 30cm, with the PET pellicular front as the outside, under 180 ℃, 0.3MPa, 1 second condition, three limits except that a minor face are sealed, make packing bag, the mixture of the tomato-sauce/salad oil of packing into therein/vinegar=1/1/1 (weight ratio) seals unencapsulated limit under 180 ℃, 0.3MPa, 1 second condition.After carrying out boiling in 20 minutes under 135 ℃ and handling, it is wide that laminated film is cut into 15mm, carries out T type Film test with it.

Bonding strength, through the time bonding strength and the boiling bonding strength after handling mensuration in, the stripping conditions of T type stripping test is:

Draw speed: the 300mm/ branch, measure ambiance: 25 ℃, 50%RH

[table 6]

	Embodiment
	Embodiment							15	16	17	18	19	20	21
	Polyurethane resin solution (g) PU-1 PU-2 PU-3 PU-4 PU-5 PU-6 PU-7	1000	1000	1000	1000	1000	1000	15	16	17	18	19	20	21	1000
Polyisocyanate curing agent (g) CA-1 CA-2 CA-3 CA-4 CA-5		1000	1000	1000	1000	1000	1000	100	100	75	100	75	75	100	1000
Polyisocyanate curing agent (g) CA-1 CA-2 CA-3 CA-4 CA-5	Organic solvent (g) vinyl acetic monomer	1200	1200	1225	1200	1225	1225	100	100	75	100	75	75	100	1200
Laminating adhesive NCO/OH (mol ratio) ¹⁾After 24 hours afterreaction rates cooperated after 8 hours after viscosity (mPas/25 ℃) cooperated after 8 hours after 48 hours	Organic solvent (g) vinyl acetic monomer	1200	1200	1225	1200	1225	1225	AD-1 6.0/1 33 36 40 0 83 100	AD-2 5.5/1 30 31 33 0 62 100	AD-3 10.3/1 40 42 45 0 90 100	AD-4 6.1/1 33 35 36 0 63 100	AD-5 2.1/1 26 27 29 0 83 100	AD-6 6.2/1 28 29 31 0 74 100	AD-7 6.0/1 35 36 37 0 77 100	1200
	Through the time bonding strength (N/cm) cooperate after after 8 hours after 48 hours	0.8 12.7 13.0	0.7 9.7 9.8	0.7 9.9 10.0	0.7 8.5 9.1	0.8 11.5 11.5	0.7 10.8 10.9	AD-1 6.0/1 33 36 40 0 83 100	AD-2 5.5/1 30 31 33 0 62 100	AD-3 10.3/1 40 42 45 0 90 100	AD-4 6.1/1 33 35 36 0 63 100	AD-5 2.1/1 26 27 29 0 83 100	AD-6 6.2/1 28 29 31 0 74 100	AD-7 6.0/1 35 36 37 0 77 100	0.8 12.8 12.8
After the boiling of bonding strength (N/cm) normality is handled		0.8 12.7 13.0	0.7 9.7 9.8	0.7 9.9 10.0	0.7 8.5 9.1	0.8 11.5 11.5	0.7 10.8 10.9	11.0 11.8	8.5 7.9	7.3 7.7	8.9 7.6	7.2 7.0	7.6 8.3	7.5 7.6	0.8 12.8 12.8

Notes 1) in the calculating of the NCO/OH (mol ratio) of laminating adhesive, the OH mole number of urethane resin adopts its number-average molecular weight to calculate.

[table 7]

	Comparative example
	Comparative example		10	11
	Polyurethane resin solution (g) PU-9 PU-10	1000	10	11	1000
Polyisocyanate curing agent (g) CA-1 CA-4	Polyurethane resin solution (g) PU-9 PU-10	1000	100	100	1000
Polyisocyanate curing agent (g) CA-1 CA-4	Organic solvent (g) ritalin	1200	100	100	1200
Laminating adhesive NCO/OH (mol ratio) ¹⁾After 24 hours afterreaction rates cooperated after 8 hours after viscosity (mPas/25 ℃) cooperated after 8 hours after 48 hours	Organic solvent (g) ritalin	1200	AD-8 2.4/1 25 26 27 0 16 60	AD-9 4.2/1 31 145 gelation 0 77 100	1200
	Through the time bonding strength (N/cm) cooperate after after 8 hours after 48 hours	0.5 2.8 6.4	AD-8 2.4/1 25 26 27 0 16 60	AD-9 4.2/1 31 145 gelation 0 77 100	0.8 0.8 4.7
After the boiling of bonding strength (N/cm) normality is handled		0.5 2.8 6.4	3.0 4.2	7.0 7.2	0.8 0.8 4.7

[table 8]

2) PET film/aluminium foil of embodiment 22～29 through the time bonding strength mensuration in, the PET film breaks.

3) aluminium foil/CPP film through the time bonding strength mensuration in, under the occasion of embodiment 22～28, aluminium foil breaks, under the occasion of embodiment 29, the CPP film breaks.

[table 9]

In table 6～table 9:

NY film: corona treatment oriented nylon film, thickness: 15 μ m

Trade(brand)name: N-1102 ((strain) system is spun by Japan)

LLDPE film: the corona treatment low-density polyethylene film that do not stretch, thickness: 130 μ m

Trade(brand)name: TUX-FCS (eastern セロ (strain) system)

PET film: corona treatment pet film, thickness: 12 μ m

Trade(brand)name: E-5100 ((strain) system is spun by Japan)

Al paper tinsel: aluminium foil, thickness 9 μ m

Trade(brand)name: ア Le ミ Ha Network C (Japan ア Le ミニウ system (strain) system)

CPP film: corona treatment un-stretched polypropylene film, thickness: 70 μ m

Trade(brand)name: RXC-11 (eastern セロ (strain) system)

Laminating adhesive of the present invention, ageing condition be 35 ℃ following 48 hours, compare with the condition (35 ℃ are following more than 72 hours) in past, not only the time shortens, and, can realize enough bonding strengths.On the other hand, storage period is also long than the product in past.Further, storage stability is also good.

In addition, owing to do not import tertiary amine among the PU-9, therefore, though cooperate the tackiness agent stability (storage period) behind the polyisocyanate curing agent fine, curing speed is slow, and various bonding strength is also not enough.The amino import volume of the uncle of PU-10 is too much, though therefore curing speed, various bonding strength are fine, fall short of storage period.

Claims

1. nonaqueous series laminated adhesive, it is the nonaqueous series laminated adhesive that contains silane coupling agent shown in urethane resin (A), polyisocyanate curing agent and the formula (7) with uncle's amino, the urethane resin of the wherein said uncle's of having amino (A) is to make to contain the what is called of selecting of compound more than a kind or 2 kinds at least contain the reactive hydrogen based compound from the compound that formula (1), (2), (3) and (4) are represented respectively, reacts under the condition of reactive hydrogen base surplus with organic polymeric polyisocyanate and obtains;

It is characterized in that uncle's amino content of the urethane resin of the above-mentioned uncle's of having amino (A) is 0.005～0.8mmol/g,

In the formula, R ₁Be 1 valency alkyl of carbonatoms 1～10, R ₂, R ₃Identical or different separately, be the divalent alkyl of carbonatoms 1～10;

In the formula, R ₁Be 1 valency alkyl of carbonatoms 1～10, R ₂, R ₃Identical or different separately, be the divalent alkyl of carbonatoms 1～10, R ₄, R ₅Identical or different separately, be the divalent organic group of carbonatoms 1～10, a, b are respectively and make the number-average molecular weight of formula (2) compound reach 300～10,000 the integer more than 0;

In the formula, R ₆Be 3 valency alkyl of carbonatoms 1～10, R ₇, R ₈Identical or different separately, be 1 valency alkyl of carbonatoms 1～10;

In the formula, R ₆Be 3 valency alkyl of carbonatoms 1～10, R ₇, R ₈Identical or different separately, be 1 valency alkyl of carbonatoms 1～10, R ₉, R ₁₀Identical or different separately, be the divalent organic group of carbonatoms 1～10, c, d are respectively and make the number-average molecular weight of formula (4) compound reach 300～10,000 the integer more than 0;

OCN——(CH ₂) _m——Si(OR) ₃ (7)

In the formula, R is methyl or ethyl, and m is 1～5 integer.

2. the described nonaqueous series laminated adhesive of claim 1, wherein, in the urethane resin of the above-mentioned uncle's of having amino (A) in the mole number of total reactive hydrogen base and the above-mentioned polyisocyanate curing agent ratio of the mole number of total isocyanate group be 1: 2.1～1: 10.3.

3. nonaqueous series laminated adhesive, be to contain urethane resin (B) with uncle's amino and carboxyl, the nonaqueous series laminated adhesive of silane coupling agent shown in polyisocyanate curing agent and the formula (7), the wherein said uncle of having urethane resin (B) amino and carboxyl is to make to contain at least from formula (1), (2), (3) and the what is called of compound of selecting in (4) compound of representing respectively more than a kind or 2 kinds and a kind or 2 kinds compound from the compound that formula (5) and (6) are represented respectively, selecting contain the reactive hydrogen based compound, react under the condition of reactive hydrogen base surplus with organic polymeric polyisocyanate and obtain;

It is characterized in that uncle's amino content of the urethane resin (B) of the above-mentioned uncle's of having amino and carboxyl is that 0.02～0.2mmol/g, carboxyl-content are 0.04～0.8mmol/g;

In the formula, R ₁₁Be 1 valency alkyl of carbonatoms 1～10, R ₁₂, R ₁₃Identical or different separately, be the divalent alkyl of carbonatoms 1～10;

In the formula, R ₁₁Be 1 valency alkyl of carbonatoms 1～10, R ₁₂, R ₁₃Identical or different separately, be the divalent alkyl of carbonatoms 1～10, R ₁₄, R ₁₅Identical or different separately, be the divalent organic group of carbonatoms 1～10, e, f are respectively and make the number-average molecular weight of formula (6) compound reach 300～10,000 the integer more than 0;

OCN——(CH ₂) _m——Si(OR) ₃ (7)

In the formula, R is methyl or ethyl, and m is 1～5 integer.

4. the described nonaqueous series laminated adhesive of claim 3, wherein, in the urethane resin (B) of the amino and carboxyl of the above-mentioned uncle of having in the mole number of total reactive hydrogen base and the above-mentioned polyisocyanate curing agent always the ratio of the mole number of isocyanate group be 1: 2.4～1: 10.0.