CN1396210A - Polyisocyanate curing agent for laminated material adhesive and its preparation method - Google Patents

Abstract

A polyisocyanate as solidifying agent for laminating adhesive is prepared by reaction of organic polyisocyanate containing at least aromatic diisocyanate on a compound containing active hydrogen and diol compound whose number average molecular weight is 100-2000. Its advantages are short ageing time, high adhesion and high resistance to boiling or steaming.

Description

Polyisocyanate curing agent for laminated material adhesive and preparation method thereof

Invention field

The present invention relates to that the usage period can not shorten and ripe polyisocyanate curing agent for laminated material adhesive that the time can shorten and adhesive property is good and preparation method thereof.

Background of invention

Recently,, consider the intensity of packing, the protectiveness of commodity, the operability of packing, the advertising results of packing as wrapping material since film can be in a large number, provide at an easy rate, packing cost is descended, so composite soft packaging material obtains to develop rapidly.As used tackiness agent in the laminating material of this film of preparation and sheet material, consider and to possess excellent cohesiveness, cold-resistant, thermotolerance, can be widely used on the base materials such as various plastics and tinsel, in general, mainly use by by the host of reactive hydrogen with contain the two-pack type polyurethane binding that the solidifying agent of isocyanic ester is formed.

The tackiness agent of using as this laminating material, polyester resin mixture, ortho-phosphoric acid or its ester compound and the organic isocyanate compound that contain PAUR polyvalent alcohol, molecular end band carboxyl are disclosed in the Te Kaiping 5-51574 communique, also contain the binder composition that the organosilane coupler is formed in case of necessity, can use the modifier of carbamate of tolylene diisocyanate or the modifier of isocyanuric acid ester as the organic isocyanate compound.

In addition, the spy open also disclose in the clear 63-110272 communique by in polyether glycol, polyester polyol, polyether(poly)urethane polyvalent alcohol and the PAUR polyvalent alcohol one or more polyvalent alcohol and contain the organosilane coupler of isocyanic ester and binder composition that composite laminates that polyisocyanate curing agent is formed is used.

But, in the past,, and laminated material adhesive considered also less with the solidifying agent and the reactivity of host not only to considering fewly the set time of the shortening tackiness agent in the lamination.That is, because after the coating, the curing reaction of tackiness agent is very slow, so need so-called sophisticated curing to promote operation.Specifically, be the time that the film after the lamination process was placed in 35～60 ℃ thermostatic chamber about 3～5 days need be carried out maturation, tackiness agent is fully solidified.At this moment,,, influence the bond strength of laminated film sometimes because the state of cure of tackiness agent can change according to the difference of maturation condition, ripe when insufficient, solidify bad generation delamination because of tackiness agent sometimes.Particularly use aliphatic polyurethane class tackiness agent, this curing reaction needs long time.Therefore, so ripe operation is indispensable operation in the dry method lamination process, so be difficult to adapt with the reduction of erection time.In addition, also need the investment cost of the heat-preserving equipment used in the ripe operation and subsequent in order to be incubated the expense of required general facilities etc.Have, if adopt the special technology of opening in the clear 63-110272 communique, expectation can improve cohesiveness, resistance to chemical reagents, the thermotolerance of laminating adhesive, still, does not consider the shortening of maturation time again.

In order to shorten maturation time, in general, it is effective adding catalyst.As this technology, can enumerate the spy and open the technology of putting down in writing in the flat 9-316422 communique.But, if adopted the special technology of opening in the flat 9-316422 communique and since in urethane resin (solution) separately blending catalyst, so maturation time shortens, still, new problem has appearred but, that is, behind blending host and the solidifying agent, the usage period has shortened.Usage period one shortens, and the tackiness agent loss strengthens, and usually because of tackiness agent solidifies, apparatus for coating is easily broken down.

It is the polyisocyanate resin that the polyol reaction below 5000 makes that the spy opens modifier and the number-average molecular weight put down in writing in the clear 60-15419 communique by the isocyanuric acid ester of tolylene diisocyanate.The solidifying agent of putting down in writing in the Te Kaiping 5-51574 communique, as organic polyisocyanate curing agent, can enumerate the dimer of urethane isocyanic ester that low-molecular-weight isocyanate compound, this low-molecular-weight isocyanate compound and water or polyol reaction make, low-molecular-weight isocyanate compound and tripolymer etc.

Put down in writing the solidifying agent that this polyisocyanate resin can be used as coating in the clear 60-15419 communique though the spy opens, do not pointed out to do the solidifying agent of laminating adhesive.In addition, the spy opens and does not mention also in the flat 5-51574 communique that to make vulcabond and macromolecule polyol reaction end that make, that contain carbamate groups and isocyanuric acid ester group be the prepolymer of isocyanic ester.If use the spy to open the polyisocyanate curing agent of putting down in writing in the flat 5-51574 communique, though do not shorten working life,, it is still very difficult to solve the problem that shortens maturation time.

Summary of the invention

The purpose of this invention is to provide polyisocyanate curing agent that a kind of laminating adhesive uses and preparation method thereof, it is characterized in that, can not shorten working life and can shorten maturation time, and cohesiveness is good, particularly anti-distillation (Ha イ レ ト Le ト).

Summary of the invention

The inventor finds to adopt can be achieved the above object by specific polyisocyanates and specific polyvalent alcohol polyisocyanate curing agent that make, that contain special groups, until having finished the present invention through research with keen determination.

That is, the present invention includes the content of following (1)～(10).(1) polyisocyanate curing agent used of a kind of laminating adhesive, it is characterized in that, it contains the prepolymer that (A) has band isocyanate group isocyanuric acid ester group and carbamate groups and terminal, and this prepolymer is by the organic multiple isocyanate that contains (a1) aromatic diisocyanate at least and to contain (a2) number-average molecular weight at least be that the compound that contains reactive hydrogen of 100～2000 diatomic alcohol compounds reacts and makes.(2) polyisocyanate curing agent used of a kind of laminating adhesive, it is characterized in that, it contain (A) have isocyanuric acid ester group and carbamate groups end band isocyanate group prepolymer and (B) contain the prepolymer of the end band isocyanate group of carbamate groups, (A) be by the organic multiple isocyanate that contains (a1) aromatic diisocyanate at least and to contain (a2) number-average molecular weight at least be that the compound that contains reactive hydrogen of 100～2000 diatomic alcohol compounds reacts and makes.(3) polyisocyanate curing agent used of a kind of laminating adhesive, it is characterized in that, it contains prepolymer and (C) the represented organosilane coupler of following formula (1) that (A) has the end band isocyanate group of isocyanuric acid ester group and carbamate groups, (A) is by the organic multiple isocyanate that contains (a1) aromatic diisocyanate at least and to contain (a2) number-average molecular weight at least be that the compound that contains reactive hydrogen of 100～2000 diatomic alcohol compounds reacts and makes.

OCN-(CH ₂) _m-Si(OR) ₃???????????(1)

(here, R represents methyl or ethyl, and m is 1～5 integer.) polyisocyanate curing agent used of (4) a kind of laminating adhesive, it is characterized in that, it contains the prepolymer of prepolymer that (A) have the end band isocyanate group of isocyanuric acid ester group and carbamate groups, end band isocyanate group that (B) contains carbamate groups and (C) by the organosilane coupler shown in the following formula (1), (A) is by the organic multiple isocyanate that contains (a1) aromatic diisocyanate at least and to contain (a2) number-average molecular weight at least be that the compound that contains reactive hydrogen of 100～2000 diatomic alcohol compounds reacts and makes.

OCN-(CH ₂) _m-Si(OR) ₃????(1)

(here, R represents methyl or ethyl, and m is 1～5 integer.) (5) (1) laminating adhesive manufacture method of polyisocyanate curing agent, it is characterized in that containing following (イ) and operation (ロ).(イ): will contain the organic multiple isocyanate of (a1) aromatic diisocyanate at least and contain (a2) number-average molecular weight at least is that the active hydrogen compounds of 100～2000 diatomic alcohol compounds carries out the urethane reaction, prepares the operation of urethane-modified polymeric polyisocyanate.(ロ): this urethane-modified polymeric polyisocyanate is carried out isocyanuric acid esterification reaction, and preparation (A) contains the operation of prepolymer of the end band isocyanate group of isocyanuric acid ester group and carbamate groups.(6) (1) laminating adhesive is characterized in that containing following (Ha) and operation (ニ) with the manufacture method of polyisocyanate curing agent.(Ha): the organic multiple isocyanate that will contain (a1) aromatic diisocyanate at least carries out the isocyanuric acid esterification, prepares the operation of isocyanurate-modified polymeric polyisocyanate.(ニ): will this isocyanurate-modified polymeric polyisocyanate and to contain (a2) number-average molecular weight at least be that the compound that contains reactive hydrogen of 100～2000 diatomic alcohol compounds carries out the urethane reaction, preparation (A) contains the operation of prepolymer of the end band isocyanate group of isocyanuric acid ester group and carbamate groups.(7) (1) laminating adhesive is characterized in that comprising following (ホ) operation with the preparation method of polyisocyanate curing agent.(ホ): will contain the organic multiple isocyanate of (a1) aromatic diisocyanate at least and contain (a2) number-average molecular weight at least is that the compound that contains reactive hydrogen of 100～2000 diatomic alcohol compounds carries out urethane reaction and isocyanuric acid esterification reaction simultaneously, prepares the operation of prepolymer that (A) contains the end band isocyanate group of isocyanuric acid ester group and carbamate groups.(8) laminating adhesive of (2) is with the preparation method of polyisocyanate curing agent, it is characterized in that comprising following (イ), (ロ) and (ヘ) operation.(イ): will contain the organic multiple isocyanate of (a1) aromatic diisocyanate at least and contain (a2) number-average molecular weight at least is that the compound that contains reactive hydrogen of 100～2000 diatomic alcohol compounds carries out the urethane reaction, prepares the operation of urethane-modified polymeric polyisocyanate.(ロ): this urethane-modified polymeric polyisocyanate is carried out the isocyanuric acid esterification, and preparation (A) contains the operation of prepolymer of the end band isocyanate group of isocyanuric acid ester and carbamate groups.(ヘ): will be somebody's turn to do (A) and contain the prepolymer of end band isocyanate group of isocyanuric acid ester group and carbamate groups and the prepolymer that (B) contains the end band isocyanate group of carbamate groups carries out the blended operation.(9), following (Ha), (ニ) and operation (ト) have been it is characterized in that comprising about the laminating adhesive of (2) preparation method with polyisocyanate curing agent.(Ha): the organic multiple isocyanate that will contain (a1) aromatic diisocyanate at least carries out the isocyanuric acid esterification, prepares the operation of isocyanurate-modified polymeric polyisocyanate.(ニ): will this isocyanurate-modified polymeric polyisocyanate and to contain (a2) number-average molecular weight at least be that the compound that contains reactive hydrogen of 100～2000 diatomic alcohol compounds carries out the urethane reaction, preparation (A1) contains the operation of prepolymer of the end band isocyanate group of isocyanuric acid ester group and carbamate groups.(ト): will be somebody's turn to do the prepolymer that (A) contain the end band isocyanate group of isocyanuric acid ester group and carbamate groups and carry out the blended operation with the prepolymer that (B) contains the end band isocyanate group of carbamate groups.(10), following (ホ) and operation (チ) have been it is characterized in that comprising about the laminating adhesive of (2) preparation method with polyisocyanate curing agent.(ホ): will contain the organic multiple isocyanate of (a1) aromatic diisocyanate at least and contain (a2) number-average molecular weight at least is that the compound that contains reactive hydrogen of 100～2000 diatomic alcohol compounds carries out urethane reaction and isocyanuric acid esterification reaction simultaneously, and preparation (A) contains the operation of prepolymer of the end band isocyanate group of isocyanuric acid ester group and carbamate groups.(チ): will be somebody's turn to do the prepolymer that (A) contain the end band isocyanate group of isocyanuric acid ester group and carbamate groups and carry out the blended operation with the prepolymer that (B) contains the end band isocyanate group of carbamate groups.Detailed Description Of The Invention

Describe the present invention below in detail.

The raw material that uses among the present invention at first is described.

The prepolymer that (A) among the present invention contains the end band isocyanate group of isocyanuric acid ester group and carbamate groups is by the organic multiple isocyanate that contains (a1) aromatic diisocyanate at least and contains the compound that contains reactive hydrogen that (a2) number-average molecular weight is 100～2000 diatomic alcohol compounds at least, for reactive hydrogen, under the situation of isocyanuric acid ester group surplus, carry out urethane reaction and isocyanuric acid esterification reaction and make.

As this (a1) aromatic diisocyanate, can enumerate as: 2, (slightly note does 2 to the 4-tolylene diisocyanate later on, 4-TDI), 2,6-tolylene diisocyanate (later abbreviation 2,6-TDI), dimethylbenzene-1, (slightly note does 1 to the 4-vulcabond later on, 4-XDI), dimethylbenzene-1, (slightly note does 1 to the 3-vulcabond later on, 3-XDI), 4,4 '-'-diphenylmethane diisocyanate (later abbreviation MDI), 2,4 '-'-diphenylmethane diisocyanate, 2,2 '-'-diphenylmethane diisocyanate, 4,4 '-phenyl ether vulcabond, 2-nitro phenylbenzene-4,4 '-vulcabond, 2,2 '-diphenyl propane-4,4 '-vulcabond, 3,3 '-dimethyl diphenyl methane-4,4 '-vulcabond, 4,4 '-diphenyl propane vulcabond, the m-phenylene diisocyanate, the p-phenylene diisocyanate, naphthalene-1, the 4-vulcabond, naphthalene-1, the 5-vulcabond, 3,3 '-dimethoxy phenylbenzene 4,4 '-vulcabond, their urethane-modified thing (polyvalent alcohol that uses in here, urethane-modified is to remove the alcohol that (a2) described later number-average molecular weight is 100～2000 diatomic alcohol compounds), urea-modified thing, biuret modified thing, urea diketone modifier, isocyanurate-modified thing, the isocyanurate-modified thing of urea diketone, the carbodiimide modifier, urea acid amides modifier.They can use separately or with two or more mixtures.

Among the present invention, if consider and the productivity of the reactivity of host, solidifying agent, cohesiveness etc. that ideal (a1) aromatic diisocyanate is 2,4-TDI and/or 2,6-TDI it is desirable to 2 especially, 4-TDI.

Among the present invention, as required also can and with (a1) organic multiple isocyanate in addition, can enumerate as aliphatic diisocyanate, isophorone diisocyanate (later abbreviation IPDI), hydrogenation TDI, hydrogenation xylylene vulcabond (later abbreviation H such as aromatic polyisocyanate, tetramethylene diisocyanate, two isocyanic acids, six methylene esters (later abbreviation HDI), two isocyanic acids, ten methylene esters, Trimethyl glycine (リ ジ Application) vulcabond such as the poly-methylene support of polyphenyl polyisocyanates, crude product TDI ₆XDI), the vulcabond of alicyclic diisocyanates such as hydrogenation '-diphenylmethane diisocyanate, tetramethylxylene diisocyanate etc., their urethane-modified thing, urea-modified thing, biuret modified thing, urea diketone modifier, isocyanurate-modified thing, the isocyanurate-modified thing of urea diketone, carbodiimide modifier, urea acid amides modifier.

(a2) diatomic alcohol compounds is meant the compound that in fact has 2 hydroxyls in 1 molecule, with number-average molecular weight be 100～2000, particularly 500～1800 be ideal.

(a2) prescribe a time limit under the number-average molecular weight deficiency of diatomic alcohol compounds, the cohesiveness of tackiness agent easily descends.In addition, surpass last prescribing a time limit, tack time is easily elongated.

So-called " in fact having 2 hydroxyls " is meant and approximately contains 2 hydroxyls in a molecule.For example during polyester diol, strictly speaking, its terminal part is a carboxyl, and still, usually, carboxyl is about 1% when following of hydroxyl mole number, in fact there is no harm in to regard diatomic alcohol compounds completely as.

(a2) hydroxyl that contains in the diatomic alcohol compounds when in fact surpassing 2, then in the process of preparation polyisocyanate curing agent, produces gelling sometimes.2 of less thaies, the rerum natura of laminating adhesive descends sometimes.

Such diatomic alcohol compounds can be enumerated as polyester diol, polyesteramide dibasic alcohol, polyether Glycols, polyester ether dibasic alcohol, PCDL, polycarbonate polyester dibasic alcohol, polycarbonate polyether Glycols, polyolefine dibasic alcohol.They can use separately or with two or more mixing.

As polyester diol, the polyesteramide dibasic alcohol, can enumerate by known Succinic Acid, hexanodioic acid, sebacic acid, nonane diacid, terephthalic acid, m-phthalic acid, phthalic acid, hexahydroterephthalic acid, the hexahydro-m-phthalic acid, hexahydro-phthalic acid, dicarboxylic acid such as naphthalene dicarboxylic acids, more than one and ethylene glycol such as acid esters or acid anhydrides, 1, the 2-propylene glycol, 1, ammediol, the 2-methyl isophthalic acid, 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, 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-ethylene glycol, 2-NSC 62789-1,2-ethylene glycol, 2-positive octacosane-1,2-ethylene glycol, glycol ether, dipropylene glycol, 1, the 4-cyclohexanedimethanol, the epoxide affixture of dihydroxyphenyl propane, the hydrogenation dihydroxyphenyl propane, low-molecular-weight diols such as the epoxide affixture of hydrogenation dihydroxyphenyl propane, hexanediamine, the xylylene diamines, low molecule diamines such as isophorone diamine, Monoethanolamine MEA BASF, low molecule amino alcohols (here, hydroxyl that has in 1 molecule and amino sum are 2) such as N-Mono Methyl Ethanol Amine wait more than one to carry out dehydration condensation and make.Also can enumerate, make initiator, cyclic esters such as 6-caprolactone, γ-Wu Neizhi (lactone) monomer be carried out ring-opening polymerization and the lactone polyester diol that makes etc. with low-molecular-weight diol, low molecule diamines or low molecule amino alcohol.

As PCDL, polycarbonate polyester dibasic alcohol, can enumerate as: have the low molecular compound of 1 carbonate group to carry out dealcoholysis in used low-molecular-weight diol and carbonic acid two ethyls (diethylenecarbonate), methylcarbonate, diethyl carbonate, the diphenyl carbonate equimolecular in synthetic aforesaid polyester diol or its, dephenolize is reacted and the compound that makes.

As polyether Glycols can enumerate as: with aforesaid polyester diol in synthetic used low-molecular-weight diol, low molecule diamines or low molecule amino alcohol as initiator, poly-(ethylene oxide) dibasic alcohol that makes oxyethane, propylene oxide, tetrahydrofuran (THF) etc. carry out ring-opening polymerization and obtain, poly-(propylene oxide) dibasic alcohol, poly-(oxidation tetramethylene) dibasic alcohol etc. and the polyether Glycols that their copolymerization are obtained, also having, is polyester ether dibasic alcohol, the polycarbonate polyether Glycols of initiator preparation with aforesaid polyester diol, PCDL.

Can enumerate as polyhutadiene, hydrogenation polyhutadiene, polyisoprene, hydrogenation polyisoprene, Chlorinated Polypropylene III, chlorinatedpolyethylene that in fact 2 hydroxyls are arranged in 1 molecule as the polyolefine dibasic alcohol.

Also have,, can enumerate as used aforesaid low-molecular-weight diol during polyester diol is synthetic as (a2) diatomic alcohol compounds.

If consider performances such as cohesiveness, ideal among the present invention (a2) diatomic alcohol compounds is the compound that the side chain alkyl is arranged.Can enumerate as the PCDL that makes through dealcoholization, dephenolize reaction etc. by the low-molecular-weight diol of band side chain and polyester diol that dicarboxylic acid makes, by the low-molecular-weight diol of band side chain and carbonic acid two ethyls, methylcarbonate, diethyl carbonate, diphenyl carbonate etc. as this diatomic alcohol compounds, be the polyether Glycols that oxirane more than 3 and the dual functional compound generation addition reaction that contains reactive hydrogen make with carbon atom quantity.Special ideal diatomic alcohol compounds is by the 3-methyl isophthalic acid, the polyester diol that 5-pentanediol and hexanodioic acid make, poly-(propylene oxide) dibasic alcohol.

In addition, in order to improve the intermiscibility of cohesiveness, improvement and host, can and be the compound that contains reactive hydrogen beyond 100～2000 the diatomic alcohol compounds also as required with (a2) number-average molecular weight, as except aforesaid low molecule diamines, low molecule amino alcohol, with low molecular polylols such as glycerol, TriMethylolPropane(TMP) (later abbreviation TMP), tetramethylolmethanes is that the polyvalent alcohol, number-average molecular weight of feedstock production surpasses 2000 macromolecule polyol, low molecule monohydroxy-alcohols such as polyethers monohydroxy-alcohol.

This (A) contains the prepolymer of the end band isocyanate group of isocyanuric acid ester group and carbamate groups, and the content of its isocyanuric acid ester group in solids constituent, for well, serves as better with 6～23 weight % with 5～25 weight %.Isocyanuric acid ester group content is very little the time, and the tackiness agent curing speed is slow, and maturation time is easily elongated.In addition, when too many, it is big that the viscosity of polyisocyanate curing agent becomes, and operability easily descends.

Contain in the prepolymer of end band isocyanate group of isocyanuric acid ester group and carbamate groups at (A), (a2) content of diatomic alcohol compounds in solids constituent, is 10～90 weight %, is preferably 15～85 weight %.(a2) content is beyond this scope the time, and cohesive strength easily descends.

Contain in the prepolymer of end band isocyanate group of isocyanuric acid ester group and carbamate groups at (A), the content of its isocyanate group in solids constituent, for well, serves as better with 3～10 weight % with 3～15 weight %.Isocyanate content is very little the time, and cohesive strength is not enough.When isocyanate content was too big, the flexibility of cure adhesive descended, and the tackiness agent curing speed is slack-off.

Used (B) contains the prepolymer of the end band isocyanate group of carbamate groups among the present invention, with (b1) organic diisocyanate and (b2) prepolymer that makes through urethane reaction of polyvalent alcohol for well.(B) be not with the isocyanuric acid ester group.

As (b1) organic diisocyanate, can enumerate as, except that aforesaid (a1) aromatic diisocyanate, also have aliphatic diisocyanate, alicyclic diisocyanate and their urea-modified thing, biuret modified thing, carbodiimide modifier, urea acid amides modifier.If consider its reactive words, ideal among the present invention (b1) organic diisocyanate is an aromatic diisocyanate, it is desirable to TDI especially.

As (b2) polyvalent alcohol, can enumerate as, except that aforesaid (a2) diatomic alcohol compounds, also have low molecular polylols such as glycerol, TMP, tetramethylolmethane, be polyester polyol, polycarbonate polyol, the polyether glycol of feedstock production with these low molecular polylols.If consider cross-linking efficiency etc., ideal among the present invention (b2) polyvalent alcohol be in fact have 2～5 hydroxyls, molecular weight is 62～300 compound.

Contain in the prepolymer of end band isocyanate group of carbamate groups at (B), the content of isocyanate group, in solids constituent, with 5～30 weight % for well, serve as better with 7～25 weight %.Isocyanate group content is very little the time, the cohesive strength deficiency, and when isocyanate group content was too big, the flexibility after tackiness agent solidifies easily reduced.

Contain the prepolymer of the end band isocyanate group of carbamate groups as (B), can enumerate compound shown below particularly.

With TMP TDI is carried out urethane-modified polymeric polyisocyanate:

コ ロ ネ-ト (registered trademark) L of Japanese polyurethane industrial system

ス ミ ジ ユ-Le (registered trademark) L-75 of Sumitomo バ イ エ Le ウ レ Application corporate system

The ケ ネ-ト of military field pharmaceutical industries corporate system ^D-102

With TMP HDI is carried out urethane-modified polymeric polyisocyanate:

The system コ ロ ネ of Japanese polyurethane industrial-ト HL

Sumitomo バ イ エ Le ウ レ Application system ス ミ ジ ユ-Le HT

The ケ ネ-ト D-160N of military field pharmaceutical industries corporate system

With TMP IPDI is carried out urethane-modified polymeric polyisocyanate:

The ケ ネ-ト D-140N of military field pharmaceutical industries corporate system

マ イ テ Star Network (registered trademark) NY215A of Mitsubishi Chemical Ind's system

With TMP XDI is carried out urethane-modified polymeric polyisocyanate:

The ケ ネ-ト D-110N of military field pharmaceutical industries corporate system

With TMP to H ₆XDI carries out urethane-modified polymeric polyisocyanate:

The ケ ネ-ト D-120N of military field pharmaceutical industries corporate system

Laminating adhesive of the present invention contains the ratio of mixture (being converted into solids constituent) of prepolymer and the prepolymer of the end band isocyanate group that (B) contains carbamate groups of end band isocyanate group of isocyanuric acid ester group and carbamate groups in weight ratio with (A) in the polyisocyanate curing agent, for well, serves as better with (A)/(B)=100/5～100/100 with (A)/(B)=100/0～100/100.If (B) too many, maturation time will be elongated sometimes.

Of the present invention containing (A) and laminating adhesive (B) in solids constituent, for well, serve as better with 7～18 weight % with 5～20 weight % with the content of isocyanate group in the polyisocyanate curing agent.

Used (C) organosilane coupler is the material of representing with (1) formula among the present invention.

OCN-(CH ₂) _m-Si(OR) ₃????????????????(1)

(here, R represents methyl or ethyl in the formula, and m is 1～5 integer.)

As everyone knows, by using the organosilane coupler can improve the performances such as cohesiveness, thermotolerance, resistance to chemical reagents of tackiness agent.But, if in advance in host, particularly in host, cooperate organic silane coupling agent with functional groups such as amino or epoxide groups, As time goes on, cause painted or tackify sometimes.This can think the result that functional group in the host and the alkoxysilyl in the organosilane coupler etc. react.In addition, because the organosilane coupler contains functional groups such as amino, epoxy group(ing) usually, so in case words that polyisocyanate curing agent and organosilane coupler are cooperated, equally, because the functional group in isocyanate group in the solidifying agent and the organosilane coupler can react, so, As time goes on, also can cause tackified phenomenon.

Therefore, consider the stability in storage of laminating adhesive, each component is preserved respectively, again each set of dispense is combined into before the use.But, owing to need place, each set of dispense of preservation fashionable pretty troublesome again, so hope can work out a kind of laminating adhesive of two-component-type.If without the organosilane coupler, can be made into the tackiness agent of two-component-type certainly, still, make the laminated film that boiling is used, cohesiveness is good inadequately.For this reason, make the laminating adhesive that the energy boiling is used, the organosilane coupler must be arranged.

The functional group of (C) organosilane coupler that uses among the present invention owing to be-NCO and-Si-(OR) ₃(here, R is methyl or ethyl in the formula) be not so under common preservation condition, the prepolymer with end band isocyanate group reacts.Therefore, polyisocyanate curing agent storage stability of the present invention is good.

Among the present invention, (C) addition of organosilane coupler, for the gross weight of the prepolymer of end band isocyanate group, to be good below the 10 weight %, with 0.1～8 weight % for better.When addition (C) was too many, cohesiveness descended, and the operability during laminated bonding descends.

With in the polyisocyanate curing agent, as required, also can cooperate various additives at laminating adhesive of the present invention.Can enumerate as pigment, dyestuff, solvent, thixotropic agent, antioxidant, UV light absorber, defoamer, tackifier, dispersion agent, tensio-active agent, rust-preventive agent, antiseptic-germicide, sanitas, catalyst, weighting agent as additive.Fitting method is not particularly limited, available known method.

Introduce each operation among the preparation method of polyisocyanate curing agent of the present invention below.

The reaction process of (イ) urethane in the invention is that to instigate at least the organic multiple isocyanate that contains (a1) aromatic diisocyanate and contain (a2) number-average molecular weight at least be the operation that the compound that contains reactive hydrogen of 100～2000 diatomic alcohol compounds reacts.At this moment, though can be with the catalyst of known urethane,, among the present invention, it is reacted.This is because urethane when reaction, and isocyanate group is more excessive than reactive hydrogen, and this isocyanate group directly links to each other with aromatic nucleus, the cause that reactivity is high.The urethane temperature is 0～120 ℃, serves as special good with 20～100 ℃.

(ロ) isocyanuric acid esterification reaction process is to add isocyanuric acid esterification catalyst to carry out in the urethane-modified polymeric polyisocyanate that makes with (イ) operation.

As this isocyanuric acid esterification catalyst, as: Tetramethylammonium hydroxide, tetraethyl ammonium hydroxide, tetra-alkyl ammonium hydroxides such as TBAH, the tetramethyl-ammonium acetate, the tetraethyl-ammonium acetate, organic monoacid salt such as tetrabutylammonium acetate ammonium, trimethylammonium hydroxypropyl ammonium hydroxide, trimethyl hydroxyethylammoniumhydroxide hydroxide, triethyl hydroxypropyl ammonium hydroxide, trialkyl hydroxyalkyl ammonium hydroxide such as triethyl hydroxyethylammoniumhydroxide hydroxide, trimethylammonium hydroxypropyl ammonium acetate, trimethylammonium hydroxyethyl ammonium acetate, triethyl hydroxypropyl ammonium acetate, organic monoacid salt such as triethyl hydroxyethyl ammonium acetate, triethylamine, triethylenediamine, 1,5-phenodiazine-dicyclo [4.3.0] nonene-5,1,8-diaza-bicyclo [5.4.0]-hendecene-7,2,4, tertiary amines such as 6-three (dimethylamino methyl) phenol, acetic acid, caproic acid, capric acid, sad, TETRADECONIC ACID, the well-known compounds such as metal-salt of alkyl carboxylic acids such as naphthenic acid can use entirely.

With 10-10, the scope of 000ppm is for well in reaction system for the addition of isocyanuric acid esterification catalyst.As the addition means of this catalyst, except can once adding, also can add in batches.During portion-wise addition, the addition of each time of catalyst both can be the same or different.The temperature of reaction of isocyanuric acid esterification reaction is 0～120 ℃, serves as special good with 20～100 ℃.

When the content of isocyanate group reaches target value, add isocyanuric acid esterification reaction terminating agent, make reaction terminating.As this terminator, as mineral acids such as phosphoric acid, hydrochloric acid, having well-known compounds such as the organic acid of sulfonic group, sulfamide groups etc. and their ester class, acetyl halide compound can use.

The addition of isocyanuric acid esterification reaction terminating agent for isocyanuric acid esterification catalyst, is 0.5～2 times of molar weight, serves as better with 0.8～1.8 times of molar weight.The addition of this terminator can not make isocyanuric acid esterification reaction terminating very little the time, the content of the isocyanate group in the polyisocyanate curing agent of the present invention is descended or causes gelationization.In addition, when too many, make polyisocyanate curing agent dirt of the present invention sometimes, cause the decline of cohesive strength.

(Ha) isocyanuric acid esterification reaction process in the inventive method is to add isocyanuric acid esterification catalyst to carry out in the organic multiple isocyanate that contains (a1) aromatic diisocyanate at least.

The interpolation time of the kind of isocyanuric acid esterification catalyst and addition, isocyanuric acid esterification reaction terminating agent and addition etc. are the same with aforesaid (ロ).

(ニ) the urethane reaction process is the isocyanurate-modified polymeric polyisocyanate that will make in (Ha) and to contain (a2) number-average molecular weight at least be the operation that the compound that contains reactive hydrogen of 100～2,000 diatomic alcohol compounds carries out the urethane reaction.

Though the reaction of this urethane can be with well-known urethane catalyst,, in the present invention, special is also can without catalyst.

(ホ) operation among the present invention is meant that with containing the organic multiple isocyanate of (a1) aromatic diisocyanate at least and containing (a2) number-average molecular weight at least be 100～2, after the compound that contains reactive hydrogen of 000 diatomic alcohol compounds adds, add isocyanuric acid esterification catalyst again and make the operation of its reaction, as previously mentioned, because this operation also can be carried out under the non-existent situation of urethane catalyst, so isocyanuric acid esterification reaction and urethane reaction can take place simultaneously.

The interpolation time of the kind of isocyanuric acid esterification catalyst and addition, terminator and addition etc. are the same with aforesaid (ロ).

In aforementioned various preparation methods of the present invention, at least containing the organic multiple isocyanate of (a1) aromatic diisocyanate and contain the adding mol ratio of the compound that contains reactive hydrogen of (a2) diatomic alcohol compounds at least, organic multiple isocyanate/contain compound=2/1～100/1 of reactive hydrogen, serves as special good with 3/1～50/1.Contain the compound of reactive hydrogen when too many, it is too big that the viscosity of solidifying agent easily becomes.In addition, compound that can reactive hydrogen is very little the time, and the cohesiveness of tackiness agent descends easily.

(ヘ) mixed processes in the inventive method be meant with through (イ) operation and (ロ) operation (A) that make contain the prepolymer of end band isocyanate group of isocyanuric acid ester group and carbamate groups and the prepolymer that (B) contains the end band isocyanate group of carbamate groups carries out the blended operation.Though mixing condition is not particularly limited, still, if mixing temperature is 30～80 ℃, the mixed system viscosity degradation, because the mixing efficiency raising, so relatively good.

(ト) operation and (チ) operation can with the same the carrying out of aforesaid (ヘ) operation.

In aforementioned various preparation methods of the present invention, isocyanuric acid esterification reaction is carried out to good with organic solvent.This is because in isocyanuric acid esterification reaction, resultant of reaction forms three-dimensional arrangement, is difficult to be dissolved in the cause in the solvent.

As this organic solvent, as long as is inactive all passable, can enumerate as independent or two or more mixtures of aprotic polar solvent such as ether solvent, dimethyl formamide, N,N-DIMETHYLACETAMIDE, N-Methyl pyrrolidone, furfural such as the glycol ether esters solvent of ketones solvents such as esters solvents such as aromatic hydrocarbon solvents such as toluene, dimethylbenzene, vinyl acetic monomer, N-BUTYL ACETATE, butanone, pimelinketone, ethylene glycol ether acetate, 1-Methoxy-2-propyl acetate, ethyl-3-ethoxy-c acid esters etc., tetrahydrofuran (THF), dioxane to isocyanate group.In addition, solid ingredient is at 10～90 weight %, particularly react in the scope of 20～80 weight % for well.Solid ingredient is very little the time, and the reaction times is elongated easily.When solid ingredient was too many, resultant of reaction solidified easily, and operability descends.In the present invention, residual solvent is few behind the lamination, uses esters solvent, particularly uses the acetates solvent for well.

The content of the aromatic diisocyanate of free (unreacted) is below the 1 weight % in the preferred polyisocyanate curing agent that makes like this.When the content of free aromatic diisocyanate was too many, because the influence of foul smell, operating environment can worsen.

In aforesaid each operation, no matter be after the reaction or before the reaction, cooperate the aforesaid various additive can.Its fitting method does not have special restriction, can adopt well-known method.

As required, (C) organosilane coupler can be sneaked into aforementioned (A) that makes and contain in the prepolymer of end band isocyanate group of isocyanuric acid ester group and carbamate groups or sneak into (A) and contain in the prepolymer of prepolymer and the end band isocyanate group that (B) contains carbamate groups of end band isocyanate group of isocyanuric acid ester group and carbamate groups, can make desired laminating adhesive polyisocyanate curing agent.

Polyisocyanate curing agent of the present invention is sneaked in the resin of using as host that contains reactive hydrogen, then is coated on the adherend, is used for bonding.Resin as this host is used so long as contain the resin of reactive hydrogen, does not just have special restriction.Concrete enumerating as: urethane resin, polyamide resin, saturated or unsaturated polyester resin, Synolac, acrylic resin, fluoro-resin, Resins, epoxy, celluosic resin etc. with saturated fatty acid or unsaturated fatty acids modification.Ideal host resin is a urethane resin, and it is good to the cohesiveness between the adherend not of the same race, weather resistance is also excellent.

As such urethane resin, more particularly, to be dissolved in polyester urethane resin in the organic solvent for well.In addition, this urethane resin, during lamination, if consider the difficulty or ease of coating and cohesive strength etc., before coating, with number-average molecular weight be 1,000～100,000, solid is divided into 5～80 weight %, 25 ℃ of following viscosity are 10,000mPas following for well.

The ratio of mixture of host and solidifying agent is scaled the mol ratio of reactive hydrogen and isocyanate group in the system, is 9 with reactive hydrogen/isocyanate group: 1-1: 9 scope is for well.

As the apparatus for coating of the tackiness agent that has mixed polyisocyanate curing agent of the present invention, can enumerate well-known device such as vacuum spray painting machine, aerial spraying machine, dip coater, roller coating machine, hairbrush etc.

The tackiness agent that has mixed polyisocyanate curing agent of the present invention, its laminating condition for well, serve as special good with 20～150 ℃, 0.2～0.8MPa with 10～180 ℃, 0.1～1MPa.

When usefulness has been mixed the tackiness agent prepared layer press mold of polyisocyanate curing agent of the present invention, used film and without particular limitation can be enumerated as: tinsels such as polyamide-based film such as polyolefins film, nylon, aluminium foil or Copper Foil such as polyester film, polyethylene or polypropylene such as polyethylene terephthalate, ethylene-vinyl acetate copolymer and saponified, glassine paper thereof, polyvinyl chloride, polyvinylidene chloride, polystyrene, paper etc.In addition, also be fit to after the surface treatments such as these film drawn processing, corona discharge or various coating processing use.

Also have, mixed the tackiness agent of polyisocyanate curing agent of the present invention, not only can be used for bonding between two membranes, and as the tackiness agent between the multilayer film more than three layers or three layers also particularly suitable.

The tackiness agent that has mixed polyisocyanate curing agent of the present invention, the maturation condition behind its lamination under 20～70 ℃ of conditions, for well, under 25～50 ℃ condition, is special good more than 10 hours more than 5 hours.With well-known laminating adhesive in the past, its maturation condition, under uniform temp, need more than 48 hours.

Illustrate in greater detail the present invention by embodiment and comparative example, still, the present invention never is limited to these." % " in embodiment and the comparative example all refers to " weight % ".

The code name that contains the raw material that uses in the preparation synthesis example 1～11 of prepolymer of end band isocyanate group of isocyanuric acid ester group and carbamate groups is as follows.TDI (1): 2,4-TDITDI (2): 2,4-TDI/2, the mixture polyvalent alcohol A of 6-TDI=80/20 (weight ratio): propylene oxide and 1, the generation addition reaction of 2-propylene glycol and the polyether Glycols that generates

Number-average molecular weight=500 polyvalent alcohol B: propylene oxide and 1, the generation addition reaction of 2-propylene glycol and the polyether Glycols that generates

Number-average molecular weight=1,000 polyvalent alcohol C: propylene oxide and 1, the generation addition reaction of 2-propylene glycol and the polyether Glycols that generates

Number-average molecular weight=1,500 polyvalent alcohol D: by the 3-methyl isophthalic acid, the polyester diol that 5-pentanediol and hexanodioic acid reaction make

Number-average molecular weight=1,000 polyol E: by the 3-methyl isophthalic acid, the polyester diol that 5-pentanediol and hexanodioic acid reaction make

Number-average molecular weight=3,000 monohydroxy-alcohol A: oxyethane and methyl alcohol generation addition reaction and the polyethers monohydroxy-alcohol that generates

Number-average molecular weight=400 synthesis examples 1

The capacity that agitator, thermometer, nitrogen tube sealing, condenser are housed with nitrogen replacement is the air of 1 liter inside reactor.Then, add 100gTDI (1), 140g vinyl acetic monomer, stir.Toward wherein adding 0.5g naphthenic acid magnesium, under 75 ℃, make its isocyanuric acid esterification of carrying out 5 hours reaction again., add 0.05g phosphoric acid, under 60 ℃, stirred 1 hour, make isocyanuric acid esterification reaction terminating thereafter.Analyze by infrared absorption spectrum (IR), can confirm in resultant of reaction, to have isocyanate group and isocyanuric acid ester group.In this resultant of reaction, contain isocyanate group 9.2%, contain isocyanuric acid ester group 10.7%.

Then,, make its reaction 3 hours under 75 ℃, make the prepolymer NCO-A1 of terminal band isocyanate group toward the polyvalent alcohol A that wherein adds 37.8g again.When analyzing NCO-A1 with IR, though have isocyanate group, isocyanuric acid ester group, carbamate groups to exist as can be known, hydroxyl does not exist.Contain isocyanate group 5.7% among the NCO-A1, isocyanuric acid ester group 9.3%.Solid is divided into 50.0%.In addition, analyzed as can be known by gel permeation chromatography (GPC), the content of free TDI (1) is 0.2%.Synthesis example 2

Behind the identical inside reactor of nitrogen replacement and synthesis example 1, add TDI (1), the 175g vinyl acetic monomer of 100g, stir.Toward wherein adding 0.5g naphthenic acid magnesium, under 75 ℃, carry out 5 hours isocyanuric acid esterification reaction.Then, add 0.05g phosphoric acid, stir down in 60 ℃ and made isocyanuric acid esterification reaction terminating in 1 hour.Analyze by IR, confirm in resultant of reaction, to have isocyanate group and isocyanuric acid ester group to exist.The content of isocyanate group is 7.6% in this resultant, the content of isocyanuric acid ester group is 9.9%.

Then,, under 75 ℃, make its reaction 3 hours, make the prepolymer NCO-A2 of terminal band isocyanate group toward the polyvalent alcohol B that wherein adds 73.9g again.When analyzing NCO-A2, can confirm that isocyanate group is arranged with IR, the existence of isocyanuric acid ester group, carbamate groups, still, can't see the existence of hydroxyl.The content of isocyanate group is 4.2% among the NCO-A2, the content of isocyanuric acid ester group is 7.8%.Solid is divided into 49.9%.In addition, according to the analysis of GPC, the content of free TDI (1) is 0.3%.Synthesis example 3

Inside with the same reactor of nitrogen replacement and synthesis example 1 adds the TDI (1) of 100g, the vinyl acetic monomer of 214g then, stirs.Toward wherein adding 113.5g polyvalent alcohol C, reacted 3 hours down again in 75 ℃.In resultant of reaction, there are isocyanate group and carbamate groups to exist by the IR analysis confirmation, but do not have hydroxyl to exist.The content of isocyanate group is 9.8% in this resultant of reaction.

Then, toward the naphthenic acid magnesium that wherein adds 0.5g again, under 75 ℃, carry out 5 hours isocyanuric acid esterification reaction., add 0.05g phosphoric acid, stirred 1 hour down, make isocyanuric acid esterification reaction terminating, make the prepolymer NCO-A3 of terminal band isocyanate group in 60 ℃ thereafter.When analyzing NCO-A3, confirmed that isocyanate group is arranged with IR, the existence of isocyanuric acid ester group, carbamate groups, still, hydroxyl does not exist.The content of isocyanate group is 3.7% among the NCO-A3, the content of isocyanuric acid ester group is 6.1%.Solid is divided into 50.0%, in addition, by gpc analysis as can be known the content of free TDI (1) be 0.3%.Synthesis example 4

Inside with the identical reactor of nitrogen replacement and synthesis example 1 then, adds the TDI (1) of 100g, the vinyl acetic monomer of 176g, stirs.Toward the naphthenic acid magnesium that wherein adds polyvalent alcohol D, the 0.5g of 73.9g, under 75 ℃, carry out 5 hours isocyanuric acid esterification reaction and urethane reaction again., add the phosphoric acid of 0.05g,, make isocyanuric acid esterification reaction terminating, make the prepolymer NCO-A4 of terminal band isocyanate group in 60 ℃ of stirrings 1 hour thereafter.Analyze NCO-A4 as can be known by IR, have isocyanate group, isocyanuric acid ester group, carbamate groups to exist, still, hydroxyl does not exist.Isocyanate group content is 4.2% among the NCO-A4, and isocyanuric acid ester group content is 7.8%.Solid is divided into 50.0%.In addition, by gpc analysis as can be known, free TDI (1) content is 0.4%.Synthesis example 5

Inside with the identical reactor of nitrogen replacement and synthesis example 1 then, adds 100gTDI (1), 172g vinyl acetic monomer, stirs.Again toward wherein adding 0.5g naphthenic acid magnesium, in 75 ℃ of isocyanuric acid esterification reactions of carrying out 5 hours., add 0.05g phosphoric acid,, make isocyanuric acid esterification reaction terminating in 60 ℃ of stirrings 1 hour thereafter.By the IR analysis confirmation in resultant of reaction, have isocyanate group and isocyanuric acid ester group to exist.In this resultant of reaction, the content of isocyanate group is 7.6%, the content of isocyanuric acid ester group is 10.1%.

Then,, under 75 ℃, make its reaction 3 hours, make the prepolymer NCO-A5 of terminal band isocyanate group toward wherein adding 61.6g polyvalent alcohol B, 10.0g monohydroxy-alcohol A again.When analyzing NCO-A5, confirmed that isocyanate group is arranged by IR, the existence of isocyanuric acid ester group, carbamate groups.But, do not have hydroxyl to exist.Among the NCO-A5, the content of isocyanate group is 4.2%, the content of isocyanuric acid ester group is 8.0%.Solid is divided into 50.0%.In addition, by gpc analysis as can be known, the content of free TDI (1) is 0.3%.Synthesis example 6

Inside with the identical reactor of nitrogen replacement and synthesis example 1 then, adds 100gTDI (2), 176g vinyl acetic monomer, stirs.Toward wherein adding 0.5g naphthenic acid magnesium, under 75 ℃, carry out 5 hours isocyanuric acid esterification reaction again., add 0.05g phosphoric acid, stirred 1 hour down, make isocyanuric acid esterification reaction terminating in 60 ℃ thereafter.Can confirm to have in the resultant of reaction isocyanate group and isocyanuric acid ester group to exist by the IR analysis.In this resultant of reaction, the content of isocyanate group is 7.5%, the content of isocyanuric acid ester group is 9.8%.

Then,, reacted 3 hours down, make the prepolymer NCO-A6 of terminal band isocyanate group in 75 ℃ toward wherein adding 73.9g polyvalent alcohol B again.NCO-A6 is analyzed with IR, can confirm that isocyanate group is arranged, the existence of isocyanuric acid ester group, carbamate groups, exist and there is hydroxyl.The content of isocyanate group is 4.2% among the NCO-A6, isocyanuric acid ester group content is 7.8%.Solid is divided into 50.0%.In addition, by gpc analysis as can be known, the content of free TDI (2) is 0.4%.Synthesis example 7

Inside with the identical reactor of nitrogen replacement and synthesis example 1 then, adds 100gTDI (1), 199g vinyl acetic monomer, stirs.Toward wherein adding 0.5g naphthenic acid magnesium, under 75 ℃, carry out 5 hours isocyanuric acid esterification reaction again., add 0.05g phosphoric acid, stirred 1 hour down, make isocyanuric acid esterification reaction terminating in 60 ℃ thereafter.Can confirm in resultant of reaction, to have isocyanate group and isocyanuric acid ester group to exist by the IR analysis.In this resultant of reaction, isocyanate group content is 8.0%, isocyanuric acid ester group content is 8.2%.

Then,, reacted 3 hours down, make the prepolymer NCO-A7 of terminal band isocyanate group in 75 ℃ toward the polyvalent alcohol B that wherein adds 98.8g again.NCO-A7 is analyzed with IR, can confirm that isocyanate group is arranged, the existence of isocyanuric acid ester group, carbamate groups, and do not have hydroxyl to exist.The content of isocyanate group is 3.9% among the NCO-A7, isocyanuric acid ester group content is 6.1%.Solid is divided into 50.0%.In addition, by gpc analysis as can be known, free TDI (1) content is 0.2%.Synthesis example 8

Inside with the identical reactor of nitrogen replacement and synthesis example 1 then, adds 100gTDI (1), 106g vinyl acetic monomer, stirs.Toward wherein adding 0.5g naphthenic acid magnesium, under 75 ℃, carry out 5 hours isocyanuric acid esterification reaction again., add 0.05g phosphoric acid, stirred 1 hour down, make isocyanuric acid esterification reaction terminating in 60 ℃ thereafter.Analyze the existence that to confirm to have in the resultant of reaction isocyanate group and isocyanuric acid ester group by IR.In this resultant of reaction, isocyanate group content is 10.7%, isocyanuric acid ester group content is 12.7%.

Then, toward wherein adding 5.8g1 again, the 2-propylene glycol reacted 3 hours down in 75 ℃, made polyisocyanate curing agent NCO-B1.NCO-B1 is analyzed with IR, can confirm that isocyanate group is arranged, the existence of isocyanuric acid ester group, carbamate groups, and do not have hydroxyl to exist.Among the NCO-B1, the content of isocyanate group is 7.4%, isocyanuric acid ester group content is 12.3%.Solid is divided into 50.1%.In addition, by gpc analysis as can be known, the content of free TDI (1) is 0.2%.Synthesis example 9

Inside with the identical reactor of nitrogen replacement and synthesis example 1 then, adds 100gTDI (1), 329g vinyl acetic monomer, stirs.Toward wherein adding the 227.1g polyol E, reacted 3 hours down again in 75 ℃.Can confirm to have in the resultant of reaction existence of isocyanate group and carbamate groups by the IR analysis, and not have hydroxyl to exist.In this resultant of reaction, the content of isocyanate group is 7.4%.

Then, toward wherein adding 0.5g naphthenic acid magnesium again, under 75 ℃, carry out 5 hours isocyanuric acid esterification reaction., add 0.05g phosphoric acid, stirred 1 hour down, make isocyanuric acid esterification reaction terminating, make polyisocyanate curing agent NCO-B2 in 60 ℃ thereafter.NCO-B2 is analyzed with IR, can confirm that isocyanate group is arranged, the existence of isocyanuric acid ester group, carbamate groups, and do not have hydroxyl to exist.The content of isocyanate group is 2.4% among the NCO-B2, isocyanuric acid ester group content is 4.0%.Solid is divided into 50.0%.In addition, by gpc analysis as can be known, the content of free TDI (1) is 0.4%.Synthesis example 10

Inside with the identical reactor of nitrogen replacement and synthesis example 1 then, adds the polyvalent alcohol B of HDI, the 98.8g of 200g, in 75 ℃ of reactions 3 hours down.Analyze the existence that to confirm in resultant of reaction, to have isocyanate group and carbamate groups by IR, but do not have hydroxyl to exist.In this resultant of reaction, isocyanate group content is 30.7%.

Then, toward wherein adding the Potassium n-decanoate of 0.22g, the phenol of 0.03g again, under 50 ℃, carry out 5 hours isocyanuric acid esterification reaction., add 0.3g phosphoric acid, stirred 1 hour down, make isocyanuric acid esterification reaction terminating in 60 ℃ thereafter.At this moment isocyanate group content is 26.1%., under 120 ℃, the condition of 13kPa, carry out thin film distillation, remove free HDI, make polyisocyanate curing agent NCO-B3 thereafter.Yield is 55%.NCO-B3 is analyzed with IR, can confirm that isocyanate group is arranged, the existence of isocyanuric acid ester group, carbamate groups, but do not have hydroxyl to exist.The isocyanate group content of NCO-B3 is 5.2%, isocyanuric acid ester group content is 9.7%.Solid is divided into 100.0%.In addition by gpc analysis as can be known, free HDI content is 0.4%.Synthesis example 11

Inside with the identical reactor of nitrogen replacement and synthesis example 1 then, adds the TDI (1) of 100g, the vinyl acetic monomer of 101g, stirs.Toward the naphthenic acid magnesium that wherein adds 0.5g, under 75 ℃, carry out 5 hours isocyanuric acid esterification reaction again.Thereafter the phosphoric acid that adds 0.05g stirred 1 hour down in 60 ℃, made isocyanuric acid esterification reaction terminating, made polyisocyanate curing agent NCO-B4.NCO-B4 is analyzed with IR, can confirm that isocyanate group is arranged, the existence of isocyanuric acid ester group.Among the NCO-B4, the content of isocyanate group is 8.5%, isocyanuric acid ester group content is 15.5%.Solid is divided into 49.9%.In addition, by gpc analysis as can be known, the content of free TDI (1) is 0.3%.The preparation of polyisocyanate curing agent

(be converted into solids component, g) mix, the preparation polyisocyanate curing agent with the component shown in table 1～10.Stability in storage

With the polyisocyanate curing agent that is mixed with coupler that makes in the dark, preserved 1 month down, judge stability in storage by visual method in 25 ℃.

Judgment standard

Zero: the outward appearance no change

(not seeing the generation of curing or throw out or seston)

*: outward appearance changes

(generation of curing or throw out or seston is arranged) host is as follows with the code name of the raw material that uses in the synthetic synthesis example 12 of resin.Polyvalent alcohol F: by ethylene glycol/neopentyl glycol=1/1 and sebacic acid/m-phthalic acid=1/1

The polyester diol that (being respectively mol ratio) makes,

Number-average molecular weight=2,000 polyvalent alcohol G: with 6-caprolactone and 2,2-dimethylolpropionic acid generation addition reaction system

The dibasic alcohol that gets

Number-average molecular weight=500DBTDL: dibutyltin dilaurate synthesis example 12

Inside with the identical reactor of nitrogen replacement and synthesis example 1 then, adds polyvalent alcohol F, 75g polyvalent alcohol G, the 215g vinyl acetic monomer of 350g, stirs.Then, again toward wherein adding 75gMDI, 0.1gDBTDL, in 75 ℃ of reactions down.During by IR analysis confirmation isocyanate-free base, add the 285g vinyl acetic monomer, stir, make urethane resin PU-1.Solid is divided into 50.0%.The evaluation embodiment 1～40 of tackiness agent, comparative example 1～28

With the ratio shown in table 1～10, host and solidifying agent to be mixed, various tests are carried out in preparation laminating adhesive AD-1～68.Result's conclusion is shown in table 1～10.The mensuration of softening temperature

The laminating adhesive of preparation is cast on the release paper, make it under drying regime, thickness is about 100 μ m, 25 ℃ leave standstill 2 hours after, the hot air dryer of putting into 80 ℃ kept 5 minutes, after the taking-up, left standstill under 35 ℃ 16 hours, made laminated film.No. 2 shapes that this film is die-cut among the JIS K6301 are dumbbell shape, as test piece.In this test piece, hang up the loading of 49kPa, heat up, measure softening temperature with 10 ℃/minute speed.Softening temperature is temperature when extending rapidly or the temperature when cutting off.The mensuration of viscosity increment rate

Put into sample bottle after tackiness agent is made into, it was kept in 25 ℃ the Water Tank with Temp.-controlled after 1 hour, measure its viscosity with Brookfield viscometer, as initial viscosity., again in 25 ℃ Water Tank with Temp.-controlled preserve 24 hour after, measure its viscosity with Brookfield viscometer thereafter.Estimate with the increment rate (%) of depositing the relative initial viscosity of viscosity of tackiness agent after 24 hours.

◎: the viscosity increment rate is discontented with 10%,

Zero: the viscosity increment rate is 10～30%,

△: the viscosity increment rate is 30～100%,

*: the viscosity increment rate surpasses 100% or gelationization viscosity increment rate (%)=laminated test (1) method in (depositing the viscosity-initial viscosity after 24 hours)/initial viscosity * 100

New LDPE (film grade) (LLDPE) film crossed of the nylon that laminating adhesive AD-1～13, corona treatment are crossed (NY) film, corona treatment is contained on the dry lamination device respectively.Then, with recessed roller with adhesive coated to the NY film on the face that corona treatment is crossed.The glue spread of tackiness agent under the dry type state, is 3.5g/m ²The NY film that has been coated with tackiness agent is by in 80 ℃ the hot air dryer, and is bonding with the face that pressure roller is crossed the corona treatment of itself and LLDPE film.The condition of pressing is 100 ℃, 0.3MPa.35 ℃ following maintenances 16 hour, make laminate film thereafter.

It is wide that the laminate film that makes is cut into 15mm, carries out the stripping test of T type.Stripping conditions is a draw speed 300mm/ branch, measures environment: 25 ℃, 50%RH.

In addition, with the laminate film that makes, be cut into the rectangle of 25cm * 30cm, the NY face is made outer side, under 220 ℃, 0.3MPa, 1 second condition, other three limit except that a minor face is sealed, make pocket, toward wherein putting into commercially available family expenses weakly alkaline dress material liquid synthetic detergent (trade(brand)name: ア Star Network (registered trademark), KAO. Corp. SA's system), the one side that to not seal again seals under 220 ℃, 0.3MPa, 1 second condition.It after preserving for 2 weeks under 50 ℃, is observed outward appearance.Again laminate film is cut into the width of 15mm, carries out the stripping test of T type.Stripping conditions, draw speed: the 300mm/ branch, measure environment: 25 ℃, 50%RH.

The film that uses

The NY film: corporate system N-1102 (thickness: 15 μ m) spins in Japan

LLDPE film: eastern セ ロ corporate system TUX-FCD (thickness: (2) method 130 μ m)

Un-stretched polypropylene (CPP) film crossed of the polyethylene terephthalate that laminating adhesive AD-14～68, corona treatment are crossed (PET) film, aluminium (Al) paper tinsel, corona treatment is contained on the dry type laminator respectively.Then, on the face of adhesive coated being crossed to the corona treatment of PET film with recessed roller.The glue spread of tackiness agent is 3.5g/m under the dry type state ²With being coated with the PET film of tackiness agent, in 80 ℃ hot air dryer, make itself and Al paper tinsel bonding with pressure roller.The pressing condition: 100 ℃, 0.3MPa.Then, with recessed roller with adhesive coated to Al paper tinsel face.The glue spread of tackiness agent is 3.5g/m under the dry type state ²With being coated with the PET film/laminated film of Al paper tinsel of tackiness agent, in 80 ℃ hot air dryer, bonding with the face that pressure roller is crossed the corona treatment of itself and CPP film.Pressing condition: 100 ℃, 0.3MPa.35 ℃ following maintenances 16 hour, make laminate film thereafter.

It is wide that the laminate film that makes is cut into 15mm, carries out the stripping test of T type.Stripping conditions is draw speed: the 300mm/ branch, measure environment: 25 ℃, 50%RH.

In addition, the laminate film that makes is cut into the rectangle of 25cm * 30cm, the PET face is made outer side, under 180 ℃, 0.3MPa, 1 second condition, pocket is made in other three limit heat-sealings except that a minor face, toward the mixture that wherein adds tomato ketchup/salad oil/vinegar=1/1/1 (weight ratio), one side of envelope is not sealed under 180 ℃, 0.3MPa, 1 second condition.Under 120 ℃, boiling is after 30 minutes with it, and it is wide that laminate film is cut into 15mm, carries out the stripping test of T type.Stripping conditions is draw speed: the 300mm/ branch, measure environment: 25 ℃, 50%RH.

Used film

The PET film: corporate system E-5100 (thickness: 12 μ m) spins in Japan

Al paper tinsel: Japan's aluminium corporate system, ア Le ミ Ha Network C (thickness: 9 μ m)

CPP film: eastern セ ロ corporate system CP RXC-11 (thickness 70 μ m)

[table 1]

	Embodiment
								1	?2	?3	?4	?5	?6	?7
	Laminating adhesive (title) host: polyurethane resin (being scaled solid branch, g) PU-1 curing agent: end is with prepolymer (being scaled solid branch, g) the NCO-A1 NCO-A2 NCO-A3 NCO-A4 NCO-A5 NCO-A6 NCO-A7 of NCO base	AD-1 ? 100 ? ? 25	?AD-2 ? ?100 ? ? ? ?25	?AD-3 ? ?100 ? ? ? ? ?25	?AD-4 ? ?100 ? ? ? ? ? ?25	?AD-5 ? ?100 ? ? ? ? ? ? ?25	?AD-6 ? ?100 ? ? ? ? ? ? ? ?25								?AD-7 ? ?100 ? ? ? ? ? ? ? ? ?25
Softening temperature (℃)								246	?230	?217	?234	?210	?229	?230
	The viscosity increment rate	? ○	? ?○	? ?○	? ?○	? ?○	? ?○								? ?○
Bond strength (N/cm) NY/LLDPE 1)								7.0	?8.5	?7.0	?8.5	?9.1	?8.1	?9.5
	Resistance to detergents can outward appearance bond strength (N/cm) NY/LLDPE 1)	Good 6.9	Good 8.4	Good 6.7	Good 8.2	Good 8.9	Good 7.7								Good 9.4

Notes 1) in the mensuration of the bond strength of the NY/LLDPE of embodiment 2,1～7, the LLDPE film is what to be stretched.

[table 2]

	Comparative example
							1	?2	3	?4	?5	?6
	Laminating adhesive (title) host: polyurethane resin (being scaled solid branch, g) PU-1 curing agent: end is with prepolymer (being scaled solid branch, g) the NCO-B1 NCO-B2 NCO-B3 NCO-B4 C-L of NCO base	AD-8 ? 100 ? ? 25	?AD-9 ? ?100 ? ? ? ?25	AD-10 ? 100 ? ? ? ? 10	?AD-11 ? ?100 ? ? ? ? ? ?25	?AD-12 ? ?100 ? ? ? ? ? ? ?15							?AD-13 ? ?100 ? ? ? ? ? ? ?15
Isocyanuric acid esterification catalyst (g) TEA												? ?0.05
	Softening temperature (℃)	250	?237	33	?238	?35							?214
The viscosity increment rate							? ○	? ?○	? ◎	? ?○	? ?◎	? ?×
	Bond strength (N/cm) NY/LLDPE	3.5	?3.7	6.5	?3.0	?7.0							?7.8
Resistance to detergents can outward appearance bond strength (N/cm) NY/LLDPE							Good 3.4	Good 3.2	Part peels off 3.7	Good 3.1	Part peels off 6.5	Good 7.9

[table 3]

	Embodiment
											?8	?9	?10	??11	??12	??13	??14	??15	??16	??17
	Laminating adhesive (title) host: polyurethane resin (being scaled solid branch, g) PU-1 curing agent: end is with prepolymer (being scaled solid branch, g) the NCO-A1 NCO-A2 NCO-A3 NCO-A4 C-L C-HL NY215A D-110N D-120N of NCO base	?AD-14 ? ? ?100 ? ? ? ? ?22.5 ? ? ?2.5	?AD-15 ? ? ?100 ? ? ? ? ?20 ? ? ?5	?AD-16 ? ? ?100 ? ? ? ? ?12.5 ? ? ?12.5	??AD-17 ? ? ??100 ? ? ? ? ??20 ? ? ? ??5	??AD-18 ? ? ??100 ? ? ? ? ??20 ? ? ? ? ??5	??AD-19 ? ? ??100 ? ? ? ? ??20 ? ? ? ? ? ??5	??AD-20 ? ? ??100 ? ? ? ? ??20 ? ? ? ? ? ? ??5	??AD-21 ? ? ??100 ? ? ? ??20 ? ? ? ??5	??AD-22 ? ? ??100 ? ? ? ? ? ??20 ? ??5											??AD-23 ? ? ??100 ? ? ? ? ? ? ??20 ??5
Softening temperature (℃)											?246	??232	??217	??234	??232	??236	??234	??234	??215	??234
	The viscosity increment rate	?○	??○	??○	??○	??○	??○	??○	??○	??○											??○
Bond strength (N/cm) PET/AL 1)??????????????AL/CPP											? ?2.6 ?6.0	? ??2.9 ??6.7	? ??2.6 ??6.0	? ??2.9 ??6.6	? ??3.2 ??6.8	? ??3.0 ??6.7	? ??3.0 ??6.7	? ??2.4 ??6.6	? ??3.0 ??5.9	? ??2.9 ??6.8
	Bond strength (N/cm); Back PET/AL AL/CPP is handled in destructive distillation (retort)	Can not measure
?6.2												??6.5	??6.2	??6.3	??6.5	??6.3	??6.3	??6.2	??6.0	??6.5

Annotate 1) in the bond strength of the PET/AL that measures embodiment 8-17, the PET film rupture.

[table 4]

	Embodiment			Comparative example
										??18	??19	??20	??7	??8	??9	??10	??11	??12
	Laminating adhesive (title) host: polyurethane resin (being scaled solid branch, g) PU-1 curing agent: end is with prepolymer (being scaled solid branch, g) the NCO-A5 NCO-A6 NCO-A7 NCO-B1 NCO-B2 NCO-B3 NCO-B4 C-L of NCO base	??AD-24 ? ? ??100 ? ? ? ??20 ? ? ? ? ? ? ??5	??AD-25 ? ? ??100 ? ? ? ? ??20 ? ? ? ? ? ??5	??AD-26 ? ? ??100 ? ? ? ? ? ??20 ? ? ? ? ??5	??AD-27 ? ? ??100 ? ? ? ? ? ? ??20 ? ? ? ??5	??AD-28 ? ? ??100 ? ? ? ? ? ? ? ??20 ? ? ??5	??AD-29 ? ? ??100 ? ? ? ? ? ? ? ? ??20 ? ??5	??AD?30 ? ? ??100 ? ? ? ? ? ? ? ? ? ??20 ??5	??AD-31 ? ? ??100 ? ? ? ? ? ? ? ? ? ? ??25										??AD-32 ? ? ??100 ? ? ? ? ? ? ? ? ? ? ??25
Isocyanuric acid esterification catalyst (g) TEA																		? ??0.0125
	Softening temperature (℃)	??227	??230	??230	??250	??220	??35	??238	??35										??214
The viscosity increment rate										??○	??○	??○	??○	??○	??◎	??○	??◎	??×
	Bond strength (N/cm) PET/AL 1)??????????????AL/CPP	? ??3.4 ??7.2	? ??2.6 ??6.2	? ??3.0 ??6.8	? ??1.4 ??3.0	? ??1.8 ??3.4	? ??3.1 ??4.5	? ??1.4 ??2.8	? ??3.6 ??5.0										? ??3.2 ??6.6
Bond strength (N/cm); Back PET/AL is handled in destructive distillation 2)??????????????AL/CPP 2)										Can not measure			? ? ??1.2 ??2.8	? ? ??2.8 ??3.5	? ? ??2.4 ??3.3	? ? ??1.2 ??2.7	? ? ??2.7 ??4.2	Can not measure 6.2
	??7.0	??6.1	??6.5

Annotate 1) in the bond strength of the PET/AL that measures embodiment 18-20, the PET film rupture.

Annotate 2) bonding after the destructive distillation of the PET/AL of comparative example 9 and 11 and AL/CPP is handled

In the strength detection, the part delamination takes place.

[table 5]

	Embodiment
								??21	??22	??23	??24	??25	??26	??27
	Laminating adhesive (title) host: polyurethane resin (being scaled solid branch, g) PU-1 curing agent: end is with prepolymer (being scaled solid branch, g) NCO-A1 NCO-A2 NCO-A3 NCO-A4 NCO-A5 NCO-A6 NCO-A7 organosilan coupling agent (g) the SC-1 SC-2 of NCO base	??AD-33 ? ? ??100 ? ? ? ??25 ? ? ? ? ? ? ? ??0.25	??AD-34 ? ? ??100 ? ? ? ? ??25 ? ? ? ? ? ? ? ??0.25	??AD-35 ? ? ??100 ? ? ? ? ? ??25 ? ? ? ? ? ??0.125	??AD-36 ? ? ??100 ? ? ? ? ? ? ??25 ? ? ? ? ? ??0.5	??AD-37 ? ? ??100 ? ? ? ? ? ? ? ??25 ? ? ? ??0.75	??AD-38 ? ? ??100 ? ? ? ? ? ? ? ? ??25 ? ? ? ??1.25								??AD-39 ? ? ??100 ? ? ? ? ? ? ? ? ? ??25 ? ??0.25
Be mixed with the stability in storage of the solidifying agent of coupler								? ??○	? ??○	? ??○	? ??○	? ??○	? ??○	? ??○
	Softening temperature (℃)	??246	??230	??215	??232	??210	??230								??230
The viscosity increment rate								??○	??○	??○	??○	??○	??○	??○
	Bond strength (N/cm) PET/AL 1)????????????AL/CPP	? ??2.7 ??6.8	? ??3.1 ??7.0	? ??3.0 ??6.4	? ??3.1 ??6.9	? ??3.5 ??7.8	? ??3.2 ??6.6								? ??3.3 ??7.0
Bond strength (N/cm); Back PET/AL AL/CPP is handled in destructive distillation								Can not measure
	??6.2	??6.3	??6.3	??7.6	??7.0	??6.5	??6.7?

Annotate 1) in the bond strength of the PET/AL that measures embodiment 21-27, the PET film rupture.

[table 6]

	Embodiment
								28	?29	?30	?31	?32	?33	?34
	Laminating adhesive (title) host: polyurethane resin (being scaled solid branch, g) PU-1 curing agent: end is with prepolymer (being scaled solid branch, g) NCO-A2 C-L C-HL NY215A D-110N D-120N organosilan coupling agent (g) the SC-1 SC-2 of NCO base	AD-40 ? ? 100 ? ? ? 22.5 2.5 ? ? ? ? ? 0.25	?AD-41 ? ? ?100 ? ? ? ?20 ?5 ? ? ? ? ? ? ?0.25	?AD-42 ? ? ?100 ? ? ? ?12.5 ?12.5 ? ? ? ? ? ?0.5	?AD-43 ? ? ?100 ? ? ? ?20 ? ?5 ? ? ? ? ? ?0.125	?AD-44 ? ? ?100 ? ? ? ?20 ? ? ?5 ? ? ? ?0.25	?AD-45 ? ? ?100 ? ? ? ?20 ? ? ? ?5 ? ? ? ?0.75								?AD-46 ? ? ?100 ? ? ? ?20 ? ? ? ? ?5 ? ?1.25
Be mixed with the stability in storage of the solidifying agent of coupler								? ○	? ?○	? ?○	? ?○	? ?○	? ?○	? ?○
	Softening temperature (℃)	245	?230	?217	?231	?235	?235								?234
The viscosity increment rate								○	?○	?○	?○	?○	?○	?○
	Bond strength (N/cm) PET/AL 1)????????????AL/CPP	? 3.0 6.2	? ?3.3 ?7.0	? ?3.0 ?6.4	? ?3.2 ?6.9	? ?3.8 ?7.8	? ?3.4 ?7.2								? ?3.4 ?7.2
Bond strength (N/cm); Back PET/AL AL/CPP is handled in destructive distillation								Can not measure
	6.2	?7.1	?6.2	?7.0	?7.7	?7.0	?7.2

Annotate 1) in the bond strength of the PET/AL that measures embodiment 28-34, the PET film rupture.

[table 7]

	Embodiment
							?35	?36	?37	?38	?39	?40
	Laminating adhesive (title) host: polyurethane resin (being scaled solid branch, g) PU-1 curing agent: end is with prepolymer (being scaled solid branch, g) NCO-A1 NCO-A3 NCO-A4 NCO-A5 NCO-A6 NCO-A7 C-L organosilan coupling agent (g) the SC-1 SC-2 of NCO base	?AD-47 ? ? ?100 ? ? ? ?20 ? ? ? ? ? ?5 ? ?0.25	?AD-48 ? ? ?100 ? ? ? ? ?20 ? ? ? ? ?5 ? ? ?0.25	?AD-49 ? ? ?100 ? ? ? ? ? ?20 ? ? ? ?5 ? ?0.5	?AD-50 ? ? ?100 ? ? ? ? ? ? ?20 ? ? ?5 ? ? ?0.125	?AD-51 ? ? ?100 ? ? ? ? ? ? ? ?20 ? ?5 ? ?1.25							?AD-52 ? ? ?100 ? ? ? ? ? ? ? ? ?20 ?5 ? ? ?0.25
Be mixed with the stability in storage of the solidifying agent of coupler							? ?○	? ?○	? ?○	? ?○	? ?○	? ?○
	Softening temperature (℃)	?230	?215	?232	?227	?230							?228
The viscosity increment rate							?○	?○	?○	?○	?○	?○
	Bond strength (N/cm) PET/AL 1)????????????AL/CPP	? ?2.8 ?7.2	? ?3.2 ?6.5	? ?3.0 ?7.1	? ?3.7 ?8.0	? ?3.0 ?6.7							? ?3.4 ?7.1
Bond strength (N/cm); Back PET/AL AL/CPP is handled in destructive distillation							Can not measure
	?6.7	?6.4	?7.0	?7.2	?6.7	?6.9

Annotate 1) in the mensuration of the bond strength of the PET/AL of embodiment 35-40, the PET film rupture.

[table 8]

	Comparative example
							??13	??14	??15	??16	??17	??18
	Laminating adhesive (title) host: polyurethane resin (being scaled solid branch, g) PU-1 curing agent: end is with prepolymer (being scaled solid branch, g) NCO-A2 NCO-B1 NCO-B2 NCO-B3 NCO-B4 organosilan coupling agent (g) the SC-1 SC-3 of NCO base	??AD-53 ? ? ??100 ? ? ? ??25 ? ? ? ? ? ? ??0.25	??AD-54 ? ? ??100 ? ? ? ? ??25 ? ? ? ? ??0.25	??AD-55 ? ? ??100 ? ? ? ? ? ??25 ? ? ? ??0.25	??AD-56 ? ? ??100 ? ? ? ? ? ? ??25 ? ? ??0.25	??AD-57 ? ? ??100 ? ? ? ? ? ? ? ??25 ? ??0.25							??AD-58 ? ? ??100 ? ? ? ??25
Be mixed with the stability in storage of the solidifying agent of coupler							? ??×	? ??○	? ??○	? ??○	? ??○	? ??○
	Softening temperature (℃)	??230	??247	??237	??33	??240							??230
The viscosity increment rate							??○	??○	??○	??◎	??○	??◎
	Bond strength (N/cm) PET/AL 1)??????????????AL/CPP	? ??3.0 ??6.5	? ??1.2 ??3.0	? ??1.8 ??3.1	? ??3.0 ??4.2	? ??1.1 ??2.8							? ??2.9 ??6.1
Bond strength (N/cm); Back PET/AL is handled in destructive distillation 2)??????????????AL/CPP 2)							Can not measure 7.0	? ? ??1.2 ??2.8	? ? ??2.7 ??3.5	? ? ??2.1 ??3.4	? ? ??1.0 ??2.6	? ? ??2.1 ??3.2

Annotate 1) in the mensuration of the bond strength of the PET/AL of comparative example 13 and 18, the PET film rupture.Annotate 2) survey of bond strength after the destructive distillation of the PET/AL of comparative example 16 and AL/CPP is handled

In fixed, delamination takes place in part.

[table 9]

	Comparative example
						?19	?20	?21	?22	?23
	Laminating adhesive (title) host: polyurethane resin (being scaled solid branch, g) PU-1 curing agent: end is with prepolymer (being scaled solid branch, g) NCO-A2 NCO-B1 NCO-B2 NCO-B3 NCO-B4 C-L organosilan coupling agent (g) the SC-1 SC-3 of NCO base	?AD-59 ? ? ?100 ? ? ? ?20 ? ? ? ? ?5 ? ? ?0.25	?AD-60 ? ? ?100 ? ? ? ? ?20 ? ? ? ?5 ? ?0.25	?AD-61 ? ? ?100 ? ? ? ? ? ?20 ? ? ?5 ? ?0.25	?AD-62 ? ? ?100 ? ? ? ? ? ? ?20 ? ?5 ? ?0.25						?AD-63 ? ? ?100 ? ? ? ? ? ? ? ?20 ?5 ? ?0.25
Be mixed with the stability in storage of the solidifying agent of coupler						? ?×	? ?○	? ?○	? ?○	? ?○
	Softening temperature (℃)	?230	?250	?218	?33						?235
The viscosity increment rate						?○	?○	?○	?◎	?○
	Bond strength (N/cm) PET/AL 1)????????????AL/CPP	? ?3.2 ?7.0	? ?1.4 ?3.3	? ?2.0 ?3.5	? ?3.3 ?4.7						? ?1.4 ?3.0
Bond strength (N/cm); Back PET/AL is handled in destructive distillation 2)????????????AL/CPP 2)						Can't measure 7.2	? ? ?1.4 ?3.0	? ? ?2.8 ?3.6	? ? ?2.2 ?3.4	? ? ?1.2 ?2.8

Annotate 1) in the mensuration of the bond strength of the PET/AL of comparative example 19, the PET film rupture.Annotate 2) in the mensuration of bond strength after the destructive distillation of the PET/AL of comparative example 22 and AL/CPP is handled, delamination takes place in part.

[table 10]

	Comparative example
						??24	?25	?26	??27	?28
	Laminating adhesive (title) host: polyurethane resin (being scaled solid branch, g) PU-1 curing agent: end is with prepolymer (being scaled solid branch, g) NCO-A2 C-L organosilan coupling agent (g) the SC-1 SC-3 of NCO base	??AD-64 ? ? ??100 ? ? ? ? ??25 ? ? ??0.25	?AD-65 ? ? ?100 ? ? ? ? ?25 ? ?0.25	?AD-66 ? ? ?100 ? ? ? ? ?25 ? ? ?0.25	?AD-67 ? ? ?100 ? ? ? ? ?25 ? ?0.25						?AD-68 ? ? ?100 ? ? ? ?20 ?5 ? ? ?
Isocyanuric acid esterification catalyst (g) TEA								? ?0.0125	? ?0.0125
	Be mixed with the stability in storage of the solidifying agent of coupler	? ??×	? ?○	? ?×	? ?×						? ?○
Softening temperature (℃)						??38	?40	?217	?215	?230
	The viscosity increment rate	??◎	?◎	?×	?×						?◎
Bond strength (N/cm) PET/AL AL/CPP						? ??3.6 ??5.2	? ?3.4 ?5.4	? ?3.4 ?7.0	? ?3.2 ?7.0	? ?3.1 ?7.0
	Bond strength (N/cm); Back PET/AL is handled in destructive distillation 1)????????????AL/CPP 1)	? ? ??2.9 ??5.0	? ? ?2.7 ?5.1	Can not measure 6.9	Can not measure 7.1						? ? ?2.9 ?3.8

Annotate 1) bond strength after the destructive distillation of the PET/AL of comparative example 25 and 24 and AL/CPP is handled

Mensuration in, delamination takes place in part.In table 1～10, C-L: コ ロ ネ-ト (registered trademark) L

Japanese polyurethane industrial system is carried out TDI with TMP

Urethane-modified polymeric polyisocyanate

The content of isocyanate group=13.2%, solids constituent=75%, vinyl acetic monomer solution C-HL: コ ロ ネ-ト HL

Japanese polyurethane industrial system is carried out amino with HDI with TMP

The polymeric polyisocyanate of manthanoate modification

Isocyanate group content=12.8%, solids constituent=75%, vinyl acetic monomer solution NY215A: マ イ テ Star Network (registered trademark) NY215A

Mitsubishi Chemical Ind's system.Carry out urethane-modified with TMP IPDI

Polymeric polyisocyanate

Isocyanate group content=10.5%, solids constituent=75%, vinyl acetic monomer solution D-110N: ケ ネ-ト (registered trademark) D-110N

Military field pharmaceutical industries corporate system is carried out urethane-modified with TMP XDI

Polymeric polyisocyanate

Isocyanate group content=11.5%, solids constituent=75%, vinyl acetic monomer solution D-120N: ケ ネ-ト D-120N

Military field pharmaceutical industries corporate system is with H ₆XDI carries out carbamate with TMP

The polymeric polyisocyanate of modification

Isocyanate group content=11.0%, solids constituent=75%, vinyl acetic monomer solution TEA: triethylamine SC-1: γ-propyl isocyanate base Trimethoxy silane SC-2: γ-propyl isocyanate ethyl triethoxy silicane alkane SC-3: gamma-amino propyl trimethoxy silicane

By table 1,3 and 4 as can be known, laminating adhesive AD1～7,14～26 among the embodiment 1～20, even with after host and the solidifying agent mixing, the viscosity increment rate is also little, validity period is enough.Moreover, and softening temperature height, reactive behavior are also high, so under the condition (25 ℃ * 2 hours+80 ℃ * 5 minutes+35 ℃ * 16 hours) of making film, crosslinking reaction also can be carried out fully.In the laminate adhesive process of reality, with 16 hours so short maturation time (for below 1/3 of former maturation time) just can give full play to binding property.

As shown in Table 2, the solidifying agent AD-8,9 of comparative example 1,2 is because the softening temperature height, so can think that its crosslinking reaction carries out fully.But, because the molecular weight of polyvalent alcohol is inappropriate, so binding property is low.In addition, the comparative example 4 without polyvalent alcohol also has same trend with comparative example 1,2.In the comparative example 3,5, because softening temperature is low, so under the condition of aforementioned making film, crosslinking reaction can not fully be carried out.In addition, though cohesive strength is good, because inreal curing, so washing fastness is not enough.Comparative example 6 is with the solidifying agent AD-13 of comparative example 5 and the example of catalyst and usefulness, though the reactivity of host and solidifying agent be improved because validity period is short, so, if consider actual adhesive coated operation, also have any problem in the use.

Have again, as shown in Table 4, the solidifying agent AD-27,28 of comparative example 7,8, because the softening temperature height, so crosslinking reaction is carried out fully.But, because the molecular weight of polyvalent alcohol is inappropriate, so bad adhesion.In addition, do not use the comparative example 10 of polyvalent alcohol to have same trend with comparative example 7,8 yet.In comparative example 9,11, because softening temperature is low, so under aforesaid film manufacturing conditions, can think that crosslinking reaction can not fully carry out.Though cohesive strength is good, because inreal curing, so after boiling was handled, cohesive strength was not enough.Comparative example 12 is with the solidifying agent AD-31 of comparative example 11 and the example of catalyst and usefulness, though can improve reactivity, validity period is short, if consider actual adhesive coated operation, also has any problem in the use.

By table 5～10 as can be known, added polyisocyanate curing agent with amino organosilane coupler, its poor storage stability, in addition, validity period and maturation time are also incompatible.The effect of invention

As mentioned above, polyisocyanate curing agent of the present invention shortens maturation time owing to can not shortening validity period, so, can improve the production efficiency of laminate film significantly.Use the laminating adhesive of polyisocyanate curing agent of the present invention, its binding property is good, in addition, and the anti-boiling of the laminate film that makes.Polyisocyanate curing agent of the present invention not only can be used for laminating adhesive, also is applicable to common two-pack type tackiness agent, coating, magnetic recording media, coating agent, priming paint, printing-ink, sealing material etc.

Claims (25)

1. laminating adhesive polyisocyanate curing agent, it is characterized in that, contain the prepolymer that (A) has the end band isocyanate group of isocyanuric acid ester group and carbamate groups, described (A) is by the organic multiple isocyanate that contains (a1) aromatic diisocyanate at least and to contain (a2) number-average molecular weight at least be that the compound reaction with reactive hydrogen of 100～2000 diatomic alcohol compounds makes.

2. the laminating adhesive polyisocyanate curing agent of claim 1, aforesaid organic multiple isocyanate is (a1) aromatic diisocyanate, and the aforesaid compound that contains reactive hydrogen is that (a2) number-average molecular weight is 100～2000 diatomic alcohol compounds.

3. laminating adhesive polyisocyanate curing agent, it is characterized in that, contain (A) have isocyanuric acid ester group and carbamate groups end band isocyanate group prepolymer and (B) have a prepolymer of the end band isocyanate group of carbamate groups, described (A) is by the organic multiple isocyanate that contains (a1) aromatic diisocyanate at least and to contain (a2) number-average molecular weight at least be that the compound with reactive hydrogen of 100～2000 diatomic alcohol compounds reacts and makes.

4. the laminating adhesive polyisocyanate curing agent of claim 3, aforesaid organic multiple isocyanate is (a1) aromatic diisocyanate, and the aforesaid compound that contains reactive hydrogen is that (a2) number-average molecular weight is 100～2000 diatomic alcohol compounds.

5. the laminating adhesive polyisocyanate curing agent of claim 3, aforementioned composition (B) is the prepolymer with end band isocyanate group of carbamate groups, this prepolymer by (b1) organic diisocyanate and (b2) polyol reaction make.

6. laminating adhesive polyisocyanate curing agent, it is characterized in that, contain (A) and (C), (A) be prepolymer with end band isocyanate group of isocyanuric acid ester group and carbamate groups, by the organic multiple isocyanate that contains (a1) aromatic diisocyanate at least with to contain (2) number-average molecular weight at least be 100～2, the active hydrogen compounds reaction of 000 diatomic alcohol compounds makes, and (C) is by the represented organosilane coupler of following formula (1).

OCN-(CH ₂) _m-Si(OR) ₃????(1)

(here, in the formula, R represents methyl or ethyl, and m is 1～5 integer)

7. the laminating adhesive polyisocyanate curing agent of claim 6, aforesaid organic multiple isocyanate is (a1) aromatic diisocyanate, and the aforesaid compound that contains reactive hydrogen is that (a2) number-average molecular weight is 100～2,000 diatomic alcohol compounds.

8. laminating adhesive polyisocyanate curing agent, it is characterized in that, it contains (A), (B) and (C) component, (A) be prepolymer with end band isocyanate group of isocyanuric acid ester group and carbamate groups, by the organic multiple isocyanate that contains (a1) aromatic diisocyanate at least with to contain (a2) number-average molecular weight at least be that the compound reaction that contains reactive hydrogen of 100～2000 diatomic alcohol compounds makes, (B) being the prepolymer with end band isocyanate group of carbamate groups, (C) is with the represented organosilane coupler of following formula (1).

OCN-(CH ₂) _m-Si(OR) ₃???????????(1)

(here, in the formula, R represents methyl or ethyl, and m represents 1～5 integer)

9. the laminating adhesive polyisocyanate curing agent of claim 8, aforesaid organic multiple isocyanate is (a1) aromatic diisocyanate, and the aforesaid compound that contains reactive hydrogen is that (a2) number-average molecular weight is 100～2000 diatomic alcohol compounds.

10. the laminating adhesive polyisocyanate curing agent of claim 8, aforementioned composition (B) is the prepolymer with end band isocyanate group of carbamate groups, by (b1) organic diisocyanate and (b2) polyol reaction make.

11. the laminating adhesive of claim 1 preparation method of polyisocyanate curing agent, (イ) reaches (ロ) operation below it is characterized in that comprising, (イ): will contain the organic multiple isocyanate of (a1) aromatic diisocyanate at least and contain (a2) number-average molecular weight at least is the operation that the compound with reactive hydrogen of 100～2000 diatomic alcohol compounds carries out the urethane-modified polymeric polyisocyanate of urethane prepared in reaction, (ロ): this urethane-modified polymeric polyisocyanate is carried out isocyanuric acid esterification reaction, and preparation (A) has the operation of prepolymer of the end band isocyanate group of isocyanuric acid ester group and carbamate groups.

12. the laminating adhesive of claim 11 preparation method of polyisocyanate curing agent, wherein, aforesaid organic multiple isocyanate is (a1) aromatic diisocyanate, and the aforesaid compound that contains reactive hydrogen is that (a2) number-average molecular weight is 100～2000 diatomic alcohol compounds.

13. the laminating adhesive of claim 1 preparation method of polyisocyanate curing agent, it is characterized in that comprising that following (Ha) reaches (ニ) operation, (Ha): the organic multiple isocyanate that will contain (a1) aromatic diisocyanate at least carries out isocyanuric acid esterification reaction, the operation for preparing isocyanurate-modified polymeric polyisocyanate, (ニ): will this isocyanurate-modified polymeric polyisocyanate and to contain (a2) number-average molecular weight at least be that the compound with reactive hydrogen of 100～2000 diatomic alcohol compounds carries out the urethane reaction, preparation (A) has the operation of prepolymer of the end band isocyanate group of isocyanuric acid ester group and carbamate groups.

14. the laminating adhesive of claim 13 preparation method of polyisocyanate curing agent, aforesaid organic multiple isocyanate is (a1) aromatic diisocyanate, and the aforesaid compound that contains reactive hydrogen is that (a2) number-average molecular weight is 100～2000 diatomic alcohol compounds.

15. the laminating adhesive of claim 1 preparation method of polyisocyanate curing agent, it is characterized in that comprising following (ホ) operation, (ホ): will contain the organic multiple isocyanate of (a1) aromatic diisocyanate at least and contain (a2) number-average molecular weight at least is that the compound with reactive hydrogen of 100～2000 diatomic alcohol compounds carries out urethane reaction and isocyanuric acid esterification reaction simultaneously, and preparation (A) has the operation of prepolymer of the end band isocyanate group of isocyanuric acid ester group and carbamate groups.

16. the laminating adhesive of claim 15 preparation method of polyisocyanate curing agent, described organic multiple isocyanate is (a1) aromatic diisocyanate, and aforesaid active hydrogen compounds is that (a2) number-average molecular weight is 100～2000 diatomic alcohol compounds.

17. the laminating adhesive of claim 3 preparation method of polyisocyanate curing agent, it is characterized in that comprising following (イ), (ロ) reach (ヘ) operation, (イ): will contain the organic multiple isocyanate of (a1) aromatic diisocyanate at least and contain (a2) number-average molecular weight at least is that the compound with reactive hydrogen of 100～2000 diatomic alcohol compounds carries out the urethane reaction, the operation for preparing urethane-modified polymeric polyisocyanate, (ロ): this urethane-modified polymeric polyisocyanate is carried out isocyanuric acid esterification reaction, preparation (A) has the operation of prepolymer of the end band isocyanate group of isocyanuric acid ester group and carbamate groups, (ヘ): should (A) and (B) carry out the blended operation, (A) being the prepolymer with end band isocyanate group of isocyanuric acid ester group and carbamate groups, (B) is the prepolymer with end band isocyanate group of carbamate groups.

18. the laminating adhesive of claim 17 preparation method of polyisocyanate curing agent, aforesaid organic multiple isocyanate is (a1) aromatic diisocyanate, and the aforesaid compound that contains reactive hydrogen is that (a2) number-average molecular weight is 100～2000 diatomic alcohol compounds.

19. the laminating adhesive of claim 17 is with the preparation method of polyisocyanate curing agent, aforementioned component (B) by (b1) organic diisocyanate and (b2) polyol reaction make, contain the prepolymer of the end band isocyanate group of carbamate groups.

20. the laminating adhesive of claim 3 preparation method of polyisocyanate curing agent, it is characterized in that containing following (Ha), (ニ) reach (ト) operation, (Ha): the organic multiple isocyanate that will contain (a1) aromatic diisocyanate at least carries out isocyanuric acid esterification reaction, the operation for preparing isocyanurate-modified polymeric polyisocyanate, (ニ): will this isocyanurate-modified polymeric polyisocyanate and to contain (a2) number-average molecular weight at least be that the compound with reactive hydrogen of 100～2000 diatomic alcohol compounds carries out the urethane reaction, preparation (A) has the operation of prepolymer of the end band isocyanate group of isocyanuric acid ester group and carbamate groups, (ト): should (A) and (B) carry out the blended operation, (A) being the prepolymer with end band isocyanate group of isocyanuric acid ester group and carbamate groups, (B) is the prepolymer with end band isocyanate group of carbamate groups.

21. the laminating adhesive of claim 20 preparation method of polyisocyanate curing agent, aforesaid organic multiple isocyanate is (a1) aromatic diisocyanate, and the aforesaid compound that contains reactive hydrogen is that (a2) number-average molecular weight is 100～2000 diatomic alcohol compounds.

22. the laminating adhesive of claim 20 is with the preparation method of polyisocyanate curing agent, aforementioned component (B) is by (b1) organic diisocyanate and (b2) the polyol reaction prepolymer that makes, have the end band isocyanate group of carbamate groups.

23. the laminating adhesive of claim 3 preparation method of polyisocyanate curing agent, it is characterized in that comprising that following (ホ) reaches (チ) operation, (ホ): will contain the organic multiple isocyanate of (a1) aromatic diisocyanate at least and contain (a2) number-average molecular weight at least is that the compound with reactive hydrogen of 100～2000 diatomic alcohol compounds carries out urethane reaction and isocyanuric acid esterification reaction simultaneously, preparation (A) has the operation of prepolymer of the end band isocyanate group of isocyanuric acid ester group and carbamate groups, (チ): should (A) and (B) carry out the blended operation, (A) being the prepolymer with end band isocyanate group of isocyanuric acid ester group and carbamate groups, (B) is the prepolymer with end band isocyanate group of carbamate groups.

24. the laminating adhesive of claim 23 preparation method of polyisocyanate curing agent, aforesaid organic multiple isocyanate is (a1) aromatic diisocyanate, and the aforementioned compound that contains reactive hydrogen is that (a2) number-average molecular weight is 100～2000 diatomic alcohol compounds.

25. the laminating adhesive of claim 23 is with the preparation method of polyisocyanate curing agent, aforementioned component (B) is by (b1) organic diisocyanate and (b2) the polyol reaction prepolymer that makes, have the end band isocyanate group of carbamate groups.