CN110062798A - Two-solution curing type adhesive composite, laminated film and its manufacturing method - Google Patents

Abstract

The two-solution curing type adhesive composite that can be used for the bonding of gas barrier film contains: containing carboxyl moieties with carboxyl；With the carbodiimide ingredient containing carbodiimide compound.

Description

Two-solution curing type adhesive composite, laminated film and its manufacturing method

Technical field

The present invention relates to two-solution curing type adhesive composite, laminated film and its manufacturing methods, specifically, are related to two liquid The manufacturing method of curing type adhesive composite, the laminated film for having used the two-solution curing type adhesive composite and laminated film.

Background technique

In the past, laminating composite film made of being bonded various substrates using lamination bonding agent is in food, medical treatment, family It is widely applied in the various industrial fields such as electricity, electronic component.In addition, as lamination bonding agent, for example, comprising by polyalcohol shape At host agent and the two-solution curing type polyurethane adhesive of the curing agent formed by isocyanates be known.

The substrate of laminating composite film can suitably be selected according to its purposes.For example, carrying out vacuum-packed vacuum to core material On the way, as packaging material, the gas barrier film with barrier properties for gases may be selected, in addition, requiring height in the use of heat-barrier material In the case where the barrier properties for gases of degree, the laminating composite film for being laminated multi-disc gas barrier film can be used.

Additionally, it is known that polyurethane adhesive is due to having functional group's (urethane bond) of display strong hydrogen bonding binding ability So showing excellent adhesive property.

However, there are following situations: isocyanide when being bonded multi-disc gas barrier film with two-solution curing type polyurethane adhesive Perester radical (- NCO) and the moisture in the moisture of gas barrier film surface, atmosphere, moisture in bonding agent (fluid,matching) etc. react, Amino (- NH is formed via carbamic acid base (- NHCOOH)₂), and generate carbon dioxide (CO₂).Moreover, if the titanium dioxide Carbon is sealed between gas barrier film, then has bad feelings as the bad order for causing air bubble-shaped in laminating composite film Condition.

Therefore, the laminating composite film of the barrier properties for gases of excellent appearance is studied, is passed through for example, proposing use The compound of amino is protected with ketone group, cured bonding agent is carried out with reacting for the compound with epoxy group and there will be gas Gas barrier film laminated body made of the more substrates bonding of body barrier property is (for example, with reference to patent document 1.).

Existing technical literature

Patent document

Patent document 1: Japanese Unexamined Patent Publication 2006-051751 bulletin

Summary of the invention

Problems to be solved by the invention

However, for by protecting amino with ketone group (end-capping reagent) compound, with the compound with epoxy group Reaction is come for carrying out cured bonding agent, and in solidification, ketone group (end-capping reagent) is from the de- sealing end of amino, free ketone group (sealing end Agent) it is remained in the solidfied material of bonding agent.

Therefore, if the laminating composite film of above-mentioned bonding agent will have been used to use as the packaging material of vacuum heat insulation material, Then there is following such unfavorable condition: end-capping reagent is slowly discharged into vacuum, and vacuum degree is caused to decline, thermal insulation decline.

The purpose of the present invention is to provide not only excellent appearance but also the two-solution curing type with excellent bonding force is bonded Agent composition, the barrier properties for gases obtained using the two-solution curing type adhesive composite excellent laminated film and laminated film Manufacturing method.It is also an objective in order to provide for obtaining for that can press down in the case where vacuum heat insulation material The two-solution curing type adhesive composite of the laminated film of vacuum degree decline processed is obtained using the two-solution curing type adhesive composite Laminated film and laminated film manufacturing method.

Means for solving the problems

[1] of the invention includes two-solution curing type adhesive composite, is two will be bonded between multi-disc gas barrier film Solution curing type adhesive composite, contains: containing carboxyl moieties with carboxyl；With carbon containing two containing carbodiimide compound Imines ingredient.

[2] of the invention include two-solution curing type adhesive composite described in above-mentioned [1], wherein aforementioned to contain carboxyl moieties Acid anhydride adduct containing polyester polyol.

[3] of the invention include two-solution curing type adhesive composite described in above-mentioned [2], wherein relative to aforementioned polyester For 1 mole of hydroxyl of polyalcohol, ratio that anhydride group in aforementioned acid anhydrides is 0.7 mole or more.

[4] of the invention include two-solution curing type adhesive composite described in any one of above-mentioned [1]~[3], wherein phase For it is aforementioned containing 1 mole of carboxyl in carboxyl moieties for, the carbodiimide in aforementioned carbodiimide ingredient is with 1.3 moles Above and 4 moles of ratios below are contained.

[5] of the invention include laminated film, are had: multi-disc gas barrier film；And adhesive layer, it is in above-mentioned [1]~[4] The solidfied material of described in any item two-solution curing type adhesive composites, and be situated between and be between multi-disc These gases barrier film.

[6] of the invention include the manufacturing method of laminated film, have following processes: preparatory process, prepare the resistance of multi-disc gas Diaphragm；And laminating process will be more via two-solution curing type adhesive composite described in any one of above-mentioned [1]~[4] The fitting of piece gas barrier film, obtains laminated body.

[7] of the invention include the manufacturing method of laminated film described in above-mentioned [6], wherein are had after aforementioned laminating process It is standby that heat-cured maintenance process is carried out to aforementioned laminated body.

The effect of invention

Two-solution curing type adhesive composite of the invention contains: containing carboxyl moieties with carboxyl；It is sub- with carbon two is contained The carbodiimide ingredient of amine compounds.

For such two-solution curing type adhesive composite, due to carboxyl and carbodiimide containing carboxyl moieties The carbodiimide of ingredient carries out acylureas reaction, therefore, carbon dioxide is not generated in solidification, in addition, from its structure side From the point of view of face, in solidification (bonding) even if passing through at any time afterwards, the possibility of carbon dioxide generation is caused because of the moisture etc. in atmosphere Property is also very low, therefore, can inhibit to generate bubble between the film of laminated film, can obtain excellent appearance.Especially, just it is used as base For the film of material has the laminated film of barrier properties for gases, if generating gas in adhesive layer, the loss position of gas is restricted, Occasionally result in serious bad order.On the other hand, for two-solution curing type adhesive composite of the invention, substantially There is no the gas passed through at any time generations, therefore, the lamination suitable for gas barrier film.

In addition, the two-solution curing type adhesive composite equally shows that strong hydrogen bonding is bonded with urethane bond due to containing The acyl group urea groups of ability, thus show excellent adhesive property.

In addition, can press down in the case where not using end-capping reagent for such two-solution curing type adhesive composite Gas processed generates.As described above, the free of end-capping reagent will not occur when solidifying if not using end-capping reagent, therefore, solid Free end-capping reagent is not remained in compound.Therefore, in the case where being used for vacuum heat insulation material, the decline of vacuum degree can be inhibited.

Detailed description of the invention

[Fig. 1] Fig. 1 is the skeleton diagram for indicating an embodiment of laminated film of the invention.

Specific embodiment

Two-solution curing type adhesive composite of the invention is two liquid that will be bonded between multi-disc gas barrier film (aftermentioned) Curing type adhesive composite, contain: with carboxyl containing carboxyl moieties (in the application, sometimes referred to as host agent.)；With contain Carbodiimide compound carbodiimide ingredient (in the application, sometimes referred to as curing agent.).

Containing carboxyl moieties for example containing the compound with carboxyl.As the compound with carboxyl, it can enumerate and for example exist Molecular end has the compound of carboxyl.

As the compound in molecular end with carboxyl, specifically, the terminal hydroxyl for example in polyalcohol can be enumerated Addition has the compound of acid anhydrides (hereinafter, the acid anhydride adduct of sometimes referred to as polyalcohol.) etc..

As polyalcohol, such as high molecular weight polyols and low molecular weight polyols can be enumerated.

High molecular weight polyols be the number-average molecular weight with 2 or more hydroxyls be 400 or more, preferably 500 or more and 20000 or less, it is polynary can to enumerate such as polyether polyol, polyester polyol, polyesteramide for preferably 10000 compound below Alcohol, polycarbonate polyol, polyurethane polyol, epoxy polyol, vegetable oil polyol, polyolefin polyhydric alcohol, acrylic acid series Polyalcohol, vinyl monomer modified polyalcohol.

As polyether polyol, such as polyalkylene polyol, polytetramethylene ether diol, polytrimethylene ether can be enumerated Glycol etc..

As polyalkylene polyol, can enumerate for example more with aftermentioned low molecular weight polyols or aromatic/aliphatic Amine be initiator, the alkylene oxides such as ethylene oxide, propylene oxide addition polymer (random including two or more alkylene oxide and/ Or block copolymer.).

As polyether polyol, specifically, such as polyethylene polyols, polypropylene polyalcohol, polyethylene can be enumerated Polypropylene copolymer (random copolymer, block copolymer) etc..

As polytetramethylene ether diol, it is poly- that such as open loop as obtained from the cationic polymerization of tetrahydrofuran can be enumerated Close object, by amorphism polytetramethylene ether diol obtained from the polymerized unit of tetrahydrofuran and aftermentioned diol copolymer etc..

In addition, can also enumerate tetrahydrofuran the coming from as starting material to manufacture based on furfural etc. from the raw material of plant The polytetramethylene ether diol of plant.

As polytrimethylene ether glycol, it can enumerate and for example be manufactured by from the polycondensation of the 1,3-PD of plant Polyalcohol.

As polyester polyol, can enumerate for example makes aftermentioned low molecular weight polyols (preferably two under the conditions of known First alcohol) become excessively for the carboxyl of polyacid with polyacid (preferably binary acid) with the hydroxyl of low molecular weight polyols Mole ratio carry out esterification obtained from condensation polymer.

As polyacid, such as oxalic acid, malonic acid, succinic acid, methylsuccinic acid, glutaric acid, adipic acid, 1,1- can be enumerated The saturated aliphatic dicarboxylic acids, example such as dimethyl -1,3- dicarboxyl propane, 3- methyl -3- ethylglutaric acid, azelaic acid, decanedioic acid Such as maleic acid, fumaric acid, itaconic acid unsaturated aliphatic dicarboxylic acids, such as phthalic acid, M-phthalic acid, terephthaldehyde Aromatic dicarboxylic acids, the alicyclic dicarboxylic acid such as hexahydrophthalic acid, such as two such as acid, toluene dioctyl phthalate, naphthalenedicarboxylic acid Other carboxylic acids such as polyacids, hydrogenated dimer acids, HET acid and the acid anhydrides as derived from these carboxylic acids, such as oxalic anhydride, succinic anhydride, Maleic anhydride, phthalic anhydride, 2- alkyl (C12~C18) succinic anhydride, tetrabydrophthalic anhydride, trimellitic anhydride, Pyromellitic dianhydride, benzophenone tetracarboxylic dianhydride and the carboxylic acid halides as derived from these carboxylic acids etc., such as oxalyl dichloro, oneself two Acyl dichloro, sehacoyl chloride etc. and, for example, sour (two) methyl esters (for example, dimethyl terephthalate (DMT) etc.).

In addition, as polyester polyol, can enumerate for example make under the conditions of known aftermentioned low molecular weight polyols with The vegetable fatty acids of hydroxyl are (for example, the Castor Oil Fatty Acid containing ricinoleic acid, the hydrogenation containing 12- hydroxy stearic acid Castor Oil Fatty Acid etc.) etc. hydroxycarboxylic acids carry out vegetable oil system polyester polyol etc. obtained from condensation reaction.

In addition, can enumerate for example is to draw with aftermentioned low molecular weight polyols (preferably dihydric alcohol) as polyester polyol Hair agent makes the lactone such as 6-caprolactone, gamma-valerolactone carry out polycaprolactone polyol obtained from ring-opening polymerisation, in poly- penta Ester polyol and lactone system polyester polyol obtained from being copolymerized they and aftermentioned dihydric alcohol etc..

As polyester amide polyol, can enumerate for example by the esterification of above-mentioned polyester polyol and with low Molecular weight polyamine (for example, ethylenediamine, propane diamine, 1,6- hexamethylene diamine etc.) is used as polyester amide polyol obtained from raw material etc..

As polycarbonate polyol, can enumerate for example with aftermentioned low molecular weight polyols (preferably dihydric alcohol) for initiation The ring-opening polymerization polymer of the ethylene carbonate of agent, for example by 1,4-butanediol, 1,5-PD, 3- methyl-1,5- pentanediol, 1,6- Amorphism polycarbonate polyol obtained from the dihydric alcohols such as hexylene glycol and ring-opening polymerization polymer are copolymerized etc..

In addition, polyurethane polyol can be greater than 1 by the equivalent proportion (OH/NCO) with hydroxyl relative to isocyanate group Ratio makes the polyether polyol obtained through the above way, polyester polyol and/or polycarbonate polyol and aftermentioned polyisocyanate Cyanate carry out reaction to polyester polyurethane polyol, polyether-polyurethane polyalcohol, polycarbonate polyurethane polyalcohol or The forms such as polyester polyether-polyurethane polyalcohol obtain.

As epoxy polyol, can enumerate for example through aftermentioned low molecular weight polyols and such as epichlorohydrin, Beta-methyl Epoxy polyol obtained from the reaction of the multifunctional halohydrin such as epichlorohydrin.

As vegetable oil polyol, the vegetable oil etc. of the hydroxyl such as castor oil, coconut oil can be enumerated.It can enumerate for example Castor oil polyhydric alcohol or the ester modified castor oil polyhydric alcohol as obtained from the reacting of castor oil polyhydric alcohol and polypropylene polyalcohol Deng.

As polyolefin polyhydric alcohol (poly- hydroxyl alkane), such as polybutadiene polyol, partly-hydrolysed ethylene-second can be enumerated Vinyl acetate copolymer etc..

As acrylic acid series multiple alcohol, can enumerate for example by make hydroxyl (methyl) acrylate, with can with containing hydroxyl Copolymer obtained from the copolymerizable vinyl monomer of (methyl) acrylic ester copolymer of base is copolymerized.

It should be noted that so-called (methyl) propylene-, is defined as propylene-and/or metering system-, so-called (methyl) third Olefin(e) acid ester is defined as acrylate and/or methacrylate.

As (methyl) acrylate of hydroxyl, such as (methyl) acrylic acid 2- hydroxy methacrylate, (methyl) third can be enumerated Olefin(e) acid hydroxy propyl ester, (methyl) hydroxy butyl acrylate, the own ester of (methyl) acrylic acid 6- hydroxyl, (methyl) acrylic acid 2,2- dihydroxy Ylmethyl butyl ester, poly hydroxyalkyl acrylate, poly- fumaric acid hydroxyalkyl acrylate etc..

As copolymerizable vinyl monomer, such as (methyl) methyl acrylate, (methyl) ethyl acrylate, (first can be enumerated Base) propyl acrylate, (methyl) isopropyl acrylate, (methyl) butyl acrylate, (methyl) isobutyl acrylate, (methyl) third The secondary butyl ester of olefin(e) acid, (methyl) tert-butyl acrylate, (methyl) amyl acrylate, (methyl) isoamyl acrylate, (methyl) propylene The own ester of acid, the different nonyl ester of (methyl) acrylic acid, (methyl) 2-EHA, cyclohexyl acrylate, (methyl) acrylic acid are different Borneol base ester etc. (methyl) alkyl acrylate (carbon atom number is 1~12), such as styrene, vinyltoluene, Alpha-Methyl benzene The aromatic vinyl monomers such as ethylene, such as vinyl cyanides such as (methyl) acrylonitrile, such as ethylene glycol two (methyl) acrylate, Butanediol two (methyl) acrylate, hexylene glycol two (methyl) acrylate, oligoethylene glycol two (methyl) acrylate, three hydroxyls Poly- (methyl) propylene of the alkane polyols such as methylpropane two (methyl) acrylate, trimethylolpropane tris (methyl) acrylate Acid esters, vinyl monomer such as 3- (2- isocyanate group -2- propyl)-α-methylstyrene comprising isocyanate group etc..

As copolymerizable vinyl monomer, (methyl) alkyl acrylate that carbon atom number is 2~12 can be preferably enumerated.

That is, can preferably enumerate (methyl) acrylate of hydroxyl as acrylic acid series multiple alcohol, be 2 with carbon atom number The copolymer of~12 (methyl) alkyl acrylate.

Moreover, acrylic acid series multiple alcohol can be by making these hydroxyls in the presence of solvent appropriate and polymerization initiator (methyl) acrylate and copolymerizable vinyl monomer be copolymerized and obtained.

In addition, in acrylic acid series multiple alcohol, such as include polysiloxane polyhydric alcohol, fluorine polyalcohol.

As polysiloxane polyhydric alcohol, it can enumerate and for example cooperate for example in the copolymerization of above-mentioned acrylic acid series multiple alcohol γ-methacryloxypropyl trimethoxy silane etc. includes the polysiloxane compound of vinyl as copolymerizable vinyl Acrylic acid series multiple alcohol obtained from monomer.

As fluorine polyalcohol, it can enumerate and for example cooperate such as tetrafluoro second in the copolymerization of above-mentioned acrylic acid series multiple alcohol Alkene, chlorotrifluoroethylene etc. include the fluorine compounds of vinyl as acrylic acid series multiple obtained from copolymerizable vinyl monomer Alcohol.

Vinyl monomer modified polyalcohol can be obtained by above-mentioned high molecular weight polyols with reacting for vinyl monomer It arrives.As high molecular weight polyols, can preferably enumerate in polyether polyol, polyester polyol and polycarbonate polyol High molecular weight polyols.

In addition, (methyl) alkyl acrylate, vinyl cyanide or inclined two as escribed above can be enumerated as vinyl monomer Acrylonitrile etc..These vinyl monomers may be used singly or in combination of two or more kinds.In addition, can preferably be enumerated (methyl) in these Alkyl acrylate.

Moreover, vinyl monomer modified polyalcohol can be for example, by (such as persulfate, having in radical polymerization initiator Machine peroxide, azo compound etc.) in the presence of etc. react above-mentioned high molecular weight polyols with vinyl monomer And it obtains.

These high molecular weight polyols may be used singly or in combination of two or more kinds.

As high molecular weight polyols, polyester polyol can be preferably enumerated.

The viscosity (25 DEG C) of high molecular weight polyols is, for example, 1000mPas or more, preferably 2000mPas or more, For example, 1000000mPas is hereinafter, preferably 300000mPas or less.

It should be noted that viscosity can be measured according to JIS K 5600-2-3 (2014) using vertebral plate viscosimeter.

Low molecular weight polyols are that the number-average molecular weight with 2 or more hydroxyls is 60 or more, preferably 100 or more and small In 400, preferably smaller than 500 compound, can enumerate for example ethylene glycol, 1,2-PD, 1,3-PD, 1,4-butanediol, 1,3-BDO, 1,2- butanediol, 1,5-PD, 1,6- hexylene glycol, neopentyl glycol, 3- methyl-1,5- pentanediol, 2,2,2- Trimethylpentanediol, 3,3- dihydroxymethyl heptane, alkane (C7~20) glycol, 1,3- or 1,4-CHDM and they Mixture, 1,3- or Isosorbide-5-Nitrae-cyclohexanediol and their mixture, hydrogenated bisphenol A, Isosorbide-5-Nitrae-dihydroxy -2- butylene, 2,6- diformazan Dihydric alcohols, such as glycerol, trihydroxy methyl such as base -1- octene -3,8- glycol, bisphenol-A, diethylene glycol, triethylene glycol, dipropylene glycol The trihydroxylic alcohols such as propane, triisopropanolamine, tetrahydroxylic alcohol, such as xylitol such as tetramethylol methane (pentaerythrite), diglycerol Equal pentabasis alcohols, such as D-sorbite, mannitol, allitol, iditol, dulcitol, altritol, inositol, two Ji Wusi The hexahydroxylic alcohols such as alcohol, the heptabasic alcohol such as persitol, eight yuan of alcohol etc. such as sucrose.

These low molecular weight polyols may be used singly or in combination of two or more kinds.

Polyalcohol may be used singly or in combination of two or more kinds.

As polyalcohol, high molecular weight polyols can be preferably enumerated, can more preferably enumerate polyester polyol.

Acid anhydrides is compound (the also referred to as acid anhydrides at least one anhydride group.), it can enumerate for example more in above-mentioned polyester Acid anhydrides used in the manufacture of first alcohol etc., specifically, such as oxalic anhydride, succinic anhydride, maleic anhydride, O-phthalic can be enumerated Acid anhydrides, 2- alkyl (C12~C18) succinic anhydride, tetrabydrophthalic anhydride, trimellitic anhydride, pyromellitic dianhydride, hexichol Ketone tetracarboxylic acid dianhydride etc..

These acid anhydrides may be used singly or in combination of two or more kinds.

As acid anhydrides, maleic anhydride, phthalic anhydride, trimellitic anhydride can be preferably enumerated, can more preferably enumerate neighbour Phthalate anhydride, maleic anhydride.

As making these acid anhydrides additions such as add acid anhydrides into polyalcohol in the method for the terminal hydroxyl of polyalcohol, into Row heats and makes its reaction.

In the cooperation of acid anhydrides, the hydroxyl of anhydride group and polyalcohol can be equivalent, and being also possible to either side is excess, It is insufficient amount alternatively, it is also possible to be either side.

More specifically, for example, for 1 mole of hydroxyl of polyalcohol, the anhydride group in acid anhydrides be, for example, 0.3 with On, preferably 0.5 mole or more, more preferably 0.7 mole or more, for example, 3 hereinafter, preferably 2 moles hereinafter, more preferably 1.5 moles or less.

When the mixing ratio of acid anhydrides is above range, the stacking for having both excellent appearance and excellent cementability can be obtained Body.

In addition, reaction temperature is, for example, 100 DEG C or more in above-mentioned reaction, preferably 130 DEG C or more, for example, 200 DEG C Hereinafter, preferably 180 DEG C or less.

In addition, the reaction time is, for example, 60 minutes or more, preferably 120 minutes or more, for example, 600 minutes hereinafter, excellent It is selected as 300 minutes or less.

The acid anhydride adduct of polyalcohol can be obtained as a result,.

It should be noted that for 1 mole of hydroxyl of polyalcohol, anhydride group is to rub less than 1 in above-mentioned reaction In the case where your ratio (that is, acid anhydrides is insufficient ratio), a part of hydroxyl of polyalcohol occurs acid and is modified, remaining hydroxyl Sour modification does not occur and remains.

In addition, anhydride group is the ratio greater than 1 mole (that is, acid anhydrides was for 1 mole of hydroxyl of polyalcohol The ratio of amount) in the case where, the acid anhydride adduct of polyalcohol is obtained in the form of the composition containing unreacted anhydride group.

In addition, above-mentioned reaction can carry out under solvent-free conditions, can also cooperate organic molten as needed It is carried out in the presence of agent.

As organic solvent, the ketone such as acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), cyclohexanone, such as can be enumerated The alkyl esters such as the nitriles such as acetonitrile, methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, such as n-hexane, normal heptane, The aliphatic hydrocarbons such as octane, the alicyclic hydro carbons such as hexamethylene, hexahydrotoluene, the virtue such as toluene, dimethylbenzene, ethylo benzene Fragrant race's hydro carbons, such as methylcellosolve acetate, ethyl cellosolve acetate, methyl carbitol acetic acid esters, ethyl carbitol second Acid esters, ethylene glycol monoethyl ether acetate, methyl proxitol acetate (PMA), acetic acid 3- methyl -3- methoxybutyl, 3- second The diol alcohol esters such as oxygroup ethyl propionate, the ethers such as ether, tetrahydrofuran, dioxane, such as chloromethanes, dichloro The halogenated aliphatics such as methane, chloroform, carbon tetrachloride, bromomethane, diiodomethane, dichloroethanes hydro carbons, such as N- crassitude Ketone, dimethylformamide, N, N '-dimethyl acetamide, dimethyl sulfoxide, the non-proton class of hexamethyl phosphoramide isopolarity etc..

These organic solvents may be used singly or in combination of two or more kinds.

In addition, after reaction, as needed, using method known to the way of distillation, extraction etc. by unreacted acid All or part of removing of acid anhydride, organic solvent.In addition, after reaction, above-mentioned organic solvent can also be added, to polyalcohol The concentration of acid anhydride adduct be adjusted.

In addition, the acid anhydride adduct of above-mentioned polyalcohol is not limited to the compound of carboxyl in molecular end, for example, Can by make under the conditions of known in the manufacture of above-mentioned polyester polyol low molecular weight polyols (preferably dihydric alcohol) with Polyacid (preferably binary acid) is with the carboxyl of polyacid as molar excess for the hydroxyl of low molecular weight polyols Ratio carries out esterification and obtains.

These in molecular end there is the compound of carboxyl may be used singly or in combination of two or more kinds.

As the compound in molecular end with carboxyl, the acid anhydride adduct of polyalcohol can be preferably enumerated, more preferably may be used Enumerate the acid anhydride adduct of polyester polyol.

In addition, as the compound with carboxyl, in addition to it is above-mentioned in the compound that molecular end has carboxyl other than, also The compound that there is carboxyl in strand midway can be enumerated.

As the compound in strand midway with carboxyl, the low molecular weight that can enumerate such as carboxyl containing branch is polynary Alcohol, high molecular weight polyols of the carboxyl containing branch etc..

The low molecular weight polyols of the carboxyl containing branch are to have 1 or more carboxyl and in molecular end in strand midway Number-average molecular weight with 2 or more hydroxyls is 60 or more, preferably 100 or more and less than 400, preferably smaller than 500 chemical combination Object can enumerate such as 2,2- dihydroxymethyl acetic acid, 2,2- dihydroxymethyl lactic acid, 2,2- dihydromethyl propionic acid (alias: dihydroxymethyl Propionic acid (DMPA)), 2,2- dimethylolpropionic acid, 2,2- dihydroxymethyl butyric acid, the polyhydroxyalkanes acid such as 2,2- dimethylol pentanoic acid Deng can preferably enumerate 2,2- dihydromethyl propionic acid.

The high molecular weight polyols of the carboxyl containing branch are to have 1 or more carboxyl and in molecular end in strand midway Number-average molecular weight with 2 or more hydroxyls is 400 or more, preferably 500 or more and 20000 or less, preferably 10000 below Compound, can enumerate the polyether polyol of such as carboxyl containing branch, the polyester polyol of the carboxyl containing branch, the carboxyl containing branch it is poly- Esteramides polyalcohol, the polycarbonate polyol of the carboxyl containing branch, the polyurethane polyol of the carboxyl containing branch, the carboxyl containing branch Epoxy polyol, the vegetable oil polyol of the carboxyl containing branch, the polyolefin polyhydric alcohol of the carboxyl containing branch, the carboxyl containing branch propylene The vinyl monomer modified polyalcohol of acid system polyalcohol, the carboxyl containing branch.It is preferred that can enumerate the polyether polyol of the carboxyl containing branch, The polyurethane polyol of the polyester polyol of the carboxyl containing branch, the carboxyl containing branch.

The polyether polyol of the carboxyl containing branch for example can contain branch by using in the manufacture of above-mentioned polyether polyol The low molecular weight polyols of carboxyl are obtained as initiator.

The polyester polyol of the carboxyl containing branch for example can contain branch by using in the manufacture of above-mentioned polyester polyol The low molecular weight polyols of carboxyl are obtained as raw material (low molecular weight polyols).

The polyurethane polyol of the carboxyl containing branch for example can by the manufacture of above-mentioned polyurethane polyol use contain Low molecular weight polyols, the polyether polyol of the carboxyl containing branch, polyester polyol of the carboxyl containing branch of branch carboxyl etc. and obtain It arrives.

These in strand midway there is the compound of carboxyl may be used singly or in combination of two or more kinds.As in molecule Chain midway has the compound of carboxyl, can preferably enumerate the high molecular weight polyols of the carboxyl containing branch.

In addition, above-mentioned method can also be used by the further addition of acid anhydrides in the compound in strand midway with carboxyl The hydroxyl of the molecular end of (there is carboxyl in strand midway and there is the compound of hydroxyl in molecular end).It can obtain as a result, To the compound in molecular end and strand midway with carboxyl.

In addition, having the compound of carboxyl for example can also be by manufacture carboxylic containing branch in molecular end and strand midway Make low molecular weight polyols and the polyacid of the carboxyl containing branch with the carboxyl of polyacid relative to containing branch when the polyester polyol of base The ratio that the hydroxyl of the low molecular weight polyols of chain carboxyl becomes molar excess carries out esterification and obtains.

As described above, can enumerate and for example be obtained in the hydroxyl addition acid anhydrides of molecular end as the compound with carboxyl To, in strand midway not having the compound of carboxyl, (molecular end addition has acid anhydrides-strand midway not contain carboxyl Compound)；Such as by with molecular end become carboxyl mixing ratio make raw material (polyacid and low molecular weight polyols) into Not having the compound of carboxyl obtained from row reaction, in strand midway, (molecular end contains carboxyl-strand midway and is free of There is the compound of carboxyl)；Such as there is carboxyl, at compound (molecule end of the molecular end without carboxyl in strand midway End is without containing carboxyl-compound of the strand midway containing carboxyl)；Such as molecular end hydroxyl addition acid anhydrides and obtain , in strand midway having the compound of carboxyl, (molecular end addition has chemical combination of the acid anhydrides-strand midway containing carboxyl Object)；Such as the mixing ratio by becoming carboxyl with molecular end makes raw material (polyacid, low molecular weight polyols and containing branch The low molecular weight polyols of carboxyl) reacted obtained from, in strand midway having the compound of carboxyl, (molecular end contains Have carboxyl-compound of the strand midway containing carboxyl) etc..

These compounds with carboxyl may be used singly or in combination of two or more kinds.

As the compound with carboxyl, can preferably enumerate at least has the compound of carboxyl in molecular end.That is, it is preferred that Molecular end addition, which can be enumerated, that acid anhydrides-strand midway does not contain the compound of carboxyl, molecular end contains carboxyl-strand Midway does not contain the compound of carboxyl, molecular end addition has acid anhydrides-strand midway compound containing carboxyl, molecular end Containing carboxyl-compound of the strand midway containing carboxyl, can more preferably enumerate molecular end addition has acid anhydrides-strand midway Compound without containing carboxyl.The acid anhydride adduct that polyalcohol can further preferably be enumerated, can particularly preferably enumerate polyester polyols The acid anhydride adduct of alcohol.

Compound with carboxyl number-average molecular weight (by GPC conversion by weight of polystyrene based on molecular weight) Mn is, for example, 2000 or more, and preferably 3000 or more, for example, 20000 hereinafter, preferably 10000 or less.

Solid component concentration containing carboxyl moieties is, for example, 30 mass % or more, preferably 50 mass % or more, for example, 100 mass % hereinafter, preferably 90 mass % hereinafter, more preferably 80 mass % or less.

Acid value (according to JIS K 1557-5 (2007)) containing carboxyl moieties is, for example, 1mgKOH/g or more, preferably 5mgKOH/g or more, more preferably 10mgKOH/g or more, for example, 100mgKOH/g hereinafter, preferably 70mgKOH/g hereinafter, More preferably 50mgKOH/g or less.

In addition, containing carboxyl moieties (solid state component) carboxyl equivalent (56100/ acid value (mgKOH/g)) be, for example, 561 with On, preferably 801 or more, more preferably 1122 or more, for example, 56100 hereinafter, preferably 11220 hereinafter, more preferably 5610 or less.

It can be containing a kind of individually above-mentioned compound with carboxyl, in addition, can also contain of more than two kinds containing carboxyl moieties The above-mentioned compound with carboxyl.In addition, aftermentioned additive can also be contained.

For the total amount containing carboxyl moieties, the content ratio of the compound with carboxyl be, for example, 50 mass % with On, preferably 80 mass % or more, for example, 100 mass % are hereinafter, preferably 99 mass % or less.

The carbodiimide compound contained in carbodiimide ingredient can for example be changed with the carbodiimide of polyisocyanates The form of property object obtains.

The carbodiimide modified object of polyisocyanates is the polyisocyanic acid in 1 molecule at least one carbodiimide The modifier (derivative) of ester.

The carbodiimide modified object of polyisocyanates for example can by the presence of carbodiimidization catalyst to polyisocyanate Cyanate is heated, it is made to carry out carbodiimidization reaction and obtain.

As polyisocyanates, such as aliphatic polyisocyante, aromatic polyisocyanate, aromatic-aliphatic can be enumerated The polyisocynate monomers such as polyisocyanates.

As aliphatic polyisocyante, such as chain (straight-chain or branched: non-ring type) aliphatic polyisocyanate can be enumerated Cyanate, specifically, such as second diisocyanate, the third diisocyanate of 1,3-, the third diisocyanate of 1,2-, fourth two can be enumerated Isocyanates (Isosorbide-5-Nitrae-fourth diisocyanate, 1,2- fourth diisocyanate, 2,3- fourth diisocyanate, 1,3- fourth diisocyanate Ester), 1,5-, penta diisocyanate (PDI), 1, hexamethylene-diisocyanate (HDI), 2,4,4- or 2,2,4- trimethyls -1,6- oneself two The chain fatties race diisocyanates such as isocyanates, 2,6- cyanato methyl capronate, ten dimethylene diisocyanates Ester etc..

In addition, alicyclic polyisocyanates can also be enumerated as aliphatic polyisocyante.

As alicyclic polyisocyanates, such as 1,3- cyclopentene diisocyanate, two isocyanide of Isosorbide-5-Nitrae-hexamethylene can be enumerated Acid esters, 1,3- cyclohexane diisocyanate, 3- isocyanatomethyl -3,5,5- trimethylcyclohexylisocyanate (different Fo Er Ketone diisocyanate；IPDI), 4,4 '-, 2,4 '-or 2, (the hydrogenation of or mixtures thereof 2 '-dicyclohexyl methyl hydride diisocyanates MDI), methyl -2,4- cyclohexane diisocyanate, methyl -2,6- cyclohexane diisocyanate, 1,3- or the bis- (isocyanic acids of Isosorbide-5-Nitrae - Ester group methyl) alicyclic diisocyanates such as or mixtures thereof hexamethylene (hydrogenation XDI), norbornene alkyl diisocyanate (NBDI) Deng.

As aromatic polyisocyanate, between can enumerating for example or or mixtures thereof paraphenylene diisocyanate, 2,4- or 2, Or mixtures thereof 6- toluene di-isocyanate(TDI) (TDI), 4,4 '-, 2,4 '-or 2,2 '-methyl diphenylene diisocyanates or it is mixed Conjunction object (MDI), 4,4 '-toluidine diisocyanates (TODI), 4,4 '-diphenyl ether diisocyanates, 4,4 '-diphenyl two are different Aromatic diisocyanates such as cyanate, 1,5- naphthalene diisocyanate (NDI) etc..

As aromatic-aliphatic polyisocyanates, such as 1,3- or Isosorbide-5-Nitrae-xylylene diisocyanate can be enumerated or it is mixed Or mixtures thereof conjunction object (XDI), 1,3- or Isosorbide-5-Nitrae-tetramethyl xylylene diisocyanate (TMXDI), ω, ω '-diisocyanate Araliphatic diisocyanates such as ester group-Isosorbide-5-Nitrae-diethylbenzene etc..

These polyisocyanates may be used singly or in combination of two or more kinds.

As polyisocyanates, chain fatty race polyisocyanates, aromatic-aliphatic polyisocyanates can be preferably enumerated, more It is preferred that 1,5-, penta diisocyanate (PDI) can be enumerated.

It as carbodiimidization catalyst, is not particularly limited, such as trialkyl phosphates based compound, phosphorus alkene can be enumerated Oxide based compound, phosphorus alkene thioether based compound, phosphine oxide based compound, phosphine based compound etc..

As trialkyl phosphates, the carbon atom number such as trimethyl phosphate, triethyl phosphate, trioctyl phosphate can be enumerated For 3~24 trialkyl phosphates based compound etc..

As phosphorus olefinic oxide based compound, can enumerate such as 3- methyl-1-phenyl-2- phosphorus alkene-1- oxide (MPPO), 1- ethyl -3- methyl -2- phosphorus alkene -1- oxide (EMPO), 1,3- dimethyl -2- phosphorus alkene -1- oxide, 1- phenyl -2- phosphorus alkene - The carbon such as 1- oxide, 1- methyl -2- phosphorus alkene -1- oxide, 1- ethyl -2- phosphorus alkene -1- oxide and their double bond isomer The phosphorus olefinic oxide based compound etc. that atomicity is 4~18.

As phosphorus alkene thioether based compound, can enumerate the carbon atom number such as 1- phenyl -2- phosphorus alkene -1- thioether is 4~18 Phosphorus alkene thioether based compound etc..

As phosphine oxide based compound, can enumerate the carbon atom number such as triphenylphosphine oxide, trimethylphenyl phosphine oxide is 3 ~21 phosphine oxide based compound etc..

As phosphine based compound, the phosphine that the carbon atom number such as bis- (oxa- diphenylphosphino) ethane is 3~30 can be enumerated Based compound etc..

These carbodiimidization catalyst may be used singly or in combination of two or more kinds.

The mixing ratio of carbodiimidization catalyst is not particularly limited, and can be suitably set according to purpose and purposes.

As heating condition, under normal pressure and non-active gas (nitrogen etc.) atmosphere, heating temperature is, for example, 30 DEG C or more, Preferably 60 DEG C or more, for example, 200 DEG C are hereinafter, preferably 180 DEG C or less.In addition, heating time is, for example, 1 hour or more, Preferably 3 hours or more, for example, 50 hours are hereinafter, preferably 40 hours or less.

Decarboxylation condensation occurs for polyisocyanates as a result, and carbodiimide compound can be obtained (that is, the carbon two of polyisocyanates Imine modified object).

In addition, as needed, above-mentioned organic solvent can be cooperated in carbodiimidization reaction, in addition, reaction terminates Afterwards, as needed, using method known to the way of distillation, extraction etc. by unreacted polyisocyanates, organic solvent it is complete Portion or a part remove.In addition, above-mentioned organic solvent can also be added after the completion of reaction, to the solution of carbodiimide compound Concentration be adjusted.

In addition, before carbodiimidization reaction, using known alcohol (polyoxyethylene monomethyl ether, 1- methoxyl group -2- Propyl alcohol etc.) it is modified to polyisocyanates progress alcohol.In alcohol is modified, for example, with the hydroxyl of alcohol relative to the different of polyisocyanates Ratio of the equivalent proportion (OH/NCO) of cyanic acid ester group less than 1 carries out urethane reaction.In addition, as needed, can cooperate Above-mentioned organic solvent and known urethanation catalyst, in addition, after reaction, as needed, using distillation Method known to method, extraction etc. by unreacted polyisocyanates, organic solvent all or part of removing.

In the solution of carbodiimide compound, solid component concentration is, for example, 50 mass % or more, preferably 60 matter Measure % or more, for example, 100 mass % hereinafter, preferably 90 mass % hereinafter, more preferably 80 mass % or less.

In addition, the carbodiimide equivalent of carbodiimide compound (solid state component) is, for example, 150 or more, preferably 200 More than, for example, 500 hereinafter, preferably 400 or less.

It should be noted that carbodiimide equivalent can according to aftermentioned embodiment by¹³C-NMR wave spectrum is found out.

In addition, for carbodiimide compound number-average molecular weight (by GPC conversion by weight of polystyrene based on Molecular weight) for Mn, from the viewpoint of the appearance of obtained laminated body and cementability, for example, 1000 or more, preferably 2000 or more, in addition, for example, 5000 hereinafter, preferably 4000 or less from the viewpoint of lamination strength.

In addition, for carbodiimide compound weight average molecular weight (by GPC conversion by weight of polystyrene based on Molecular weight) for Mw, from the viewpoint of the appearance of obtained laminated body, for example, 1500 or more, preferably 2000 or more, separately Outside, from the viewpoint of lamination strength, for example, 15000 hereinafter, preferably 10000 or less.

In addition, for molecular weight distribution (dispersion degree) Mw/Mn, from the appearance and layer for realizing obtained laminated body simultaneously From the viewpoint of Compressive Strength, for example, 1 or more, preferably 2 or more, for example, 10 hereinafter, preferably 5 or less.

It should be noted that above-mentioned carbodiimide compound can also be obtained in the form of commercially available product, can enumerate for example CARBODILITE V05S (solid component concentration is 90 mass %, and carbodiimide equivalent is 291 (solid state component equivalents 262), Nisshinbo Industries Inc's system), (solid component concentration is 50 mass % to CARBODILITE V07, and carbodiimide equivalent is 404 (solid state component equivalents 202), Nisshinbo Industries Inc's system), CARBODILITE V09GB (solid component concentration be 70 matter % is measured, carbodiimide equivalent is 298 (solid state component equivalents 209), Nisshinbo Industries Inc's system) etc..

Carbodiimide ingredient can be containing a kind of independent above-mentioned carbodiimide compound, in addition, can also contain two or more Above-mentioned carbodiimide compound.In addition, aftermentioned additive can also be contained.

For the total amount of carbodiimide ingredient, the content ratio of carbodiimide compound is, for example, 50 mass % More than, preferably 80 mass % or more, for example, 100 mass % are hereinafter, preferably 99 mass % or less.

In addition, for two-solution curing type adhesive composite, it as needed, can be containing carboxyl moieties (host agent) and carbon containing It is appropriate as needed in either side or this two side in diimine ingredient (curing agent) to cooperate such as phosphoric acid or derivatives thereof, silicon Alkane coupling agent and epoxy resin, catalyst, coating modifying agent, levelling agent, defoaming agent, antioxidant, ultraviolet absorbing agent The additives such as equal stabilizers, plasticizer, surfactant, pigment, filler, organic or inorganic particle, mould inhibitor.Additive Use level can be suitably determined according to its purpose and purposes.

Moreover, for such two-solution curing type adhesive composite when in use, carboxyl moieties will be contained as master Agent, and using carbodiimide ingredient as curing agent, they are cooperated and prepares mixed liquor, as needed with organic solvent pair Mixed liquor is diluted, and is coated on substrate (bonded object).

About the mixing ratio containing carboxyl moieties and carbodiimide ingredient, for example, relative to containing the carboxylic in carboxyl moieties For 1 mole of base (carboxyl containing the compound with carboxyl for including in carboxyl moieties), the carbon two in carbodiimide ingredient Imido grpup (carbodiimide for the carbodiimide compound for including in carbodiimide ingredient) is, for example, 1 mole or more, preferably It is 1.3 moles or more, more preferably 1.5 moles or more, for example, 5 moles hereinafter, preferably 4 moles hereinafter, more preferably 3 rub You are following.

When mixing ratio containing carboxyl moieties and carbodiimide ingredient is above range, obtained laminated body can have both excellent Different appearance and excellent cementability.

Moreover, such two-solution curing type adhesive composite contains: containing carboxyl moieties with carboxyl；With contain carbon two The carbodiimide ingredient of group with imine moiety.For such two-solution curing type adhesive composite, due to containing carboxyl at The carboxyl divided carries out acylureas with the carbodiimide of carbodiimide ingredient and reacts, and therefore, does not generate dioxy in solidification Change carbon, in addition, in solidification (bonding) even if passing through at any time afterwards, leading because of the moisture etc. in atmosphere from the point of view of its configuration aspects A possibility that causing carbon dioxide to generate is also very low, therefore, can inhibit to generate bubble between the film of laminated film, can obtain excellent Appearance.

Especially, for there is the laminated film of barrier properties for gases as the film of substrate, if generating gas in adhesive layer, Then the loss position of gas is restricted, and occasionally results in serious bad order.On the other hand, for two-solution curing type of the invention For adhesive composite, the gas passed through at any time is substantially absent and generates, therefore, the layer suitable for gas barrier film Pressure.

In addition, the two-solution curing type adhesive composite equally shows that strong hydrogen bonding is bonded with urethane bond due to containing The acyl group urea groups of ability, thus show excellent adhesive property.

In addition, can press down in the case where not using end-capping reagent for such two-solution curing type adhesive composite Gas processed generates.As described above, the free of end-capping reagent will not occur when solidifying if not using end-capping reagent, therefore, solid Free end-capping reagent is not remained in compound.Therefore, in the case where being used for vacuum heat insulation material, the decline of vacuum degree can be inhibited.

Hereinafter, laminated film (laminated body) to the barrier properties for gases for using two-solution curing type adhesive composite to obtain and its Manufacturing method is described in detail.

In Fig. 1, the laminated film 1 of barrier properties for gases has multi-disc (2) gas barrier film 2 and Jie is gas barrier film 2 Between adhesive layer 3.

So-called gas barrier film 2 is the film with barrier properties for gases, be defined as oxygen transmission degree (25 DEG C, 80%RH (JIS K 7126-2 (2006)) it is 100mL/m²RMPa or less, preferably 50mL/m for 24 hours²RMPa film below for 24 hours.

It should be noted that the oxygen transmission degree measurement device of Modern Control corporation can also be used to survey in oxygen transmission degree It is fixed.

As gas barrier film 2, specifically, can enumerate such as metal foil (for example, aluminium foil) etc..In addition, can also lift Out such as the plastic foil for having metal film (for example, aluminium film), have metal deposition film (aluminium-vapour deposition film, silica steam plating film, Aoxidize aluminium-vapour deposition film, silica alumina binary evaporation film etc.) plastic foil etc..In addition, example can be enumerated as plastic foil Such as polyethylene terephthalate (PET) film, nylon (NY) film, cellulose acetate (TAC) film, can preferably enumerate PET film, Cellulose acetate (TAC) film.It should be noted that the thickness of the thickness of metal film, metal deposition film and the thickness of plastic foil do not have There is special limitation, can be suitably set according to purpose and purposes.

These gas barrier films 2 may be used singly or in combination of two or more kinds.

As gas barrier film 2, the plastic foil for having metal deposition film can be preferably enumerated.It can more preferably enumerate and have dioxy The plastic foil of SiClx evaporation film, has silica alumina binary evaporation film at the plastic foil for having oxidation aluminium-vapour deposition film Plastic foil.In addition, can preferably enumerate PET film, cellulose acetate (TAC) as such plastic foil for having metal deposition film Film.

As gas barrier film 2, it can further preferably enumerate the PET film for having silica steam plating film, have aluminium oxide The PET film of evaporation film, the PET film for having silica alumina binary evaporation film.

In Fig. 1, as gas barrier film 2, the plastic foil 5 for having metal deposition film 4 is shown.

In addition, though not illustrated in Fig. 1, but gas barrier film 2 for example can be between metal deposition film 4 and plastic foil 5 Has anchor coating, furthermore it is possible to which the surface in metal deposition film 3 is (another for a face for being formed with plastic foil 4 A face) have external coating.

The thickness of gas barrier film 2 is, for example, 5 μm or more, preferably 10 or more, for example, 30 μm hereinafter, preferably 20 μm Below.

Adhesive layer 3 is the solidfied material of above-mentioned two-solution curing type adhesive composite, is laminated in the resistance of multi-disc (2) gas Between diaphragm 2.In other words, when multi-disc (2) gas barrier film 2 being bonded with two-solution curing type adhesive composite, adhesive layer 3 It is formed between gas barrier film 2.

In the manufacture of laminated film 1, for example, can be via adhesive layer 3, in the mutually opposite mode of each metal deposition film 4 Multi-disc (2) gas barrier film 2 is bonded.

In addition, for example, multi-disc (2) gas can also be hindered in each plastic foil 5 mutually opposite mode via adhesive layer 3 Diaphragm 2 is bonded.

In addition, for example, can also be via adhesive layer 3, with the metal vapor deposition layer 4 of a piece of gas barrier film 2 and another gas The mutually opposite mode of the plastic foil 5 of barrier film 2, multi-disc (2) gas barrier film 2 is bonded.

Preferably, as shown in Figure 1, via adhesive layer 3, in the mutually opposite mode of each metal deposition film 4 by multi-disc (2 Piece) fitting of gas barrier film 2.

The thickness of adhesive layer 3 is, for example, 1 μm or more, preferably 2 or more, for example, 10 μm hereinafter, preferably 5 μm or less.

It should be noted that being shown in Fig. 1 by laminated film 1 made of 2 fittings of gas barrier films 2, but gas barrier The not limited to of film 2 can also be used above-mentioned method and be bonded 3 or more gas barrier films 2 in above-mentioned number.

In addition, as shown in phantom in Figure 1, laminated film 1 can have hot sealing layer 6 in one face or two sides.

Hot sealing layer 6 is the layer that heat sealability is assigned to laminated film 1, can be enumerated such as polyethylene film, un-stretched polypropylene film Thermoplastic polyolefin film etc..

The thickness of hot sealing layer 6 is, for example, 10 μm or more, and preferably 20 μm or more, for example, 200 μm are hereinafter, preferably 150 μ M or less.

Specifically, hot sealing layer 6 can be laminated in the surface of gas barrier film 2 (relative to being formed with via heat sealing adhesive layer 7 Another face for one face of adhesive layer 3).

It should be noted that heat sealing adhesive layer 7 for example can be the solidification of above-mentioned two-solution curing type adhesive composite Object, alternatively, it is also possible to the solidfied material for other known bonding agent (polyurethane adhesive etc.).

The thickness of heat sealing adhesive layer 7 be, for example, 1 μm or more, preferably 2 or more, for example, 10 μm hereinafter, preferably 5 μm with Under.

In addition, as needed, anchor coating agent can also be coated on the surface of gas barrier film 2, then polyethylene extrusion etc. is set Hot sealing layer 6 is laminated rouge.In this case, the coating weight of the coating layer of anchor coating agent is, for example, 0.1g/m²More than, preferably 0.2g/m²More than, for example, 2.0g/m²Hereinafter, preferably 1.0g/m²Below.

Moreover, (preparing to manufacture such laminated film 1 for example, preparing multi-disc (such as 2) gas barrier film 2 first Process).

Next, via above-mentioned two-solution curing type adhesive composite, multi-disc gas barrier film 2 is pasted in this method It closes, obtains laminated body (laminating process).

Specifically, in laminating process, for example, following methods can be used: carboxyl moieties will be contained with above-mentioned organic solvent And carbodiimide component diluent and cooperated, then, obtained mixture is coated on each gas using solvent type laminating machine Body obstructs film surface, after so that solvent is volatilized, coated face is bonded, is then conserved under room temperature or heating, keeps its cured Method；Alternatively, the cooperation viscosity containing carboxyl moieties and carbodiimide ingredient at room temperature~100 DEG C be, for example, about 100~ In the case where 10000mPas, preferably from about 100~5000mPas, such as directly cooperation is containing carboxyl moieties and carbon containing two Asia Then obtained mixture is coated on each gas barrier film surface using no-solvent type laminating machine, will be coated with face paste by amine component The method of conjunction；Etc..

It should be noted that for the coating weight of two-solution curing type adhesive composite, for example, in solvent type feelings Under condition, by solvent volatilize after every square metre of weight (solid state component) in terms of, be 2.0~8.0g/m², the no-solvent type the case where Under, it is 1.0~4.0g/m²。

As a result, containing in carboxyl moieties carboxyl, in carbodiimide ingredient carbodiimide carry out acylureasization it is anti- It answers, two-solution curing type adhesive composite is cured.As a result, layer can be obtained in the form of the laminated body of gas barrier film 2 Press mold 1.

In addition, as needed, carrying out heating curing (maintenance process) to obtained laminated body in this method.

Conserve process in curing temperature be, for example, 20 DEG C or more, preferably 40 DEG C or more, for example, 80 DEG C hereinafter, it is preferred that It is 70 DEG C or less.

In addition, curing time is, for example, 24 hours or more, preferably 48 hours or more, for example, 240 hours hereinafter, it is preferred that It is 120 hours or less.

It is able to achieve the raising of the cementability between gas barrier film 2 as a result,.

In addition, as needed, can also be operated in the same way with above-mentioned laminating process, via heat sealing adhesive layer 7, hindered in gas The surface of diaphragm 2 is bonded hot sealing layer 6 (referring to Fig. 1 dotted line).As a result, heat sealability can be assigned to laminated film 1.

Moreover, obtained laminated film 1 is excellent relative to the barrier properties for gases of oxygen and vapor etc., it can be in gas barrier film Field, the packaging film, the food container that are specially the heat-insulated field such as vacuum heat insulation material and food pharmaceuticals etc. (including bottle.), optical film, suitably use in industrial film etc., can especially be closed in the heat-insulated field such as vacuum heat insulation material It uses suitablely.

It should be noted that in the present invention, it can be in the range of not interfering its purpose effect comprising removing above-mentioned host agent And ingredient (the sometimes referred to as other compositions other than curing agent.).The containing ratio of the other compositions is total relative to adhesive composite For amount be preferably 40 mass % hereinafter, more preferably 20 mass % hereinafter, further preferably 10 mass % or less.

[embodiment]

Next, illustrating the present invention based on Production Example, Examples and Comparative Examples, but the present invention is not by following embodiments Limitation.It should be noted that unless otherwise specified, " part " and " % " is on the basis of quality.In addition, in record below Used in the specific numerical value such as mixing ratio (content ratio), physics value, parameter can be replaced in above-mentioned " specific embodiment party Record in formula " it is corresponding to their corresponding mixing ratio (content ratio), physics value, parameters etc. record upper limit value (with " with Under ", the numerical value of " being less than " formal definition) or lower limit value (with " more than ", the numerical value of " being greater than " formal definition).

In addition, various measuring methods are recorded in hereafter.

<acid value>

Suitable sample is weighed, the in the mixed solvent of toluene and methanol=7/3 (weight ratio) is dissolved in, is added dropwise few drops Phenolphthalein indicator is titrated with the alcohol repellency potassium hydroxide solution of 0.1mol/L and is found out.

<carboxyl equivalent (solid state component)>

Using the acid value above found out, found out using following formula.

Carboxyl equivalent=56100/ acid value

<carbodiimide equivalent (solid state component)>

Using aftermentioned poly- carbodiimide composition, following device and under the conditions of measure¹³C-NMR, by aftermentioned official The integrated value and charge that can be rolled into a ball calculate carbodiimide equivalent (solid state component).It should be noted that as chemical shift ppm Benchmark, used CDCL₃Tetramethylsilane (0ppm) in solvent.

Device: ECA-500 type (Japan Electronics system)

Condition: measurement frequency: 125MHz, solvent: CDCL₃, solute concentration: 50 mass %

Measuring temperature: room temperature, scanning times 8500 times

Repetition time: 3.0 seconds, pulse width: 30 ° (3.70 microsecond)

The ownership peak of the carbon of carbodiimide (the N=C=N yl in carbodiimide): 139ppm

The ownership peak of the carbon of carbamate groups (the C=O yl in carbamate groups): 156ppm

It should be noted that carbodiimide equivalent can be calculated based on above-mentioned NMR measurement result using conventional method.

<terminal hydroxyl amount>

Suitable sample is weighed, acetic anhydride/pyridine (30mL/400mL) mixed solution 20mL and 4- dimethylamino is added Pyridine solution (concentration 1g/100mL) 2mL of pyridine carries out 30 minutes stirring and dissolvings in room temperature, in C-terminal addition acetic acid Acid anhydride.Next, being diluted with pyridine 50mL, back titration then is carried out to remaining acid with 1mol/L sodium hydrate aqueous solution, Find out acetyl value (mgKOH/g).The acid value by the result (value) and separately measured, finds out terminal hydroxyl amount (hydroxyl using following formula Value).

Hydroxyl value=acetyl value+acid value

<host agent (containing carboxyl moieties)>

Production Example 1 (preparation of host agent A)

By terephthalic acid (TPA) 184.8g, M-phthalic acid 246.4g, adipic acid 216.6g, ethylene glycol 131.2g, diethyl two Alcohol 168.2g and neopentyl glycol 165.1g are respectively charged into reaction vessel, in 180~220 DEG C of progress esterifications.In acid value As 8mgKOH/g time point below, four butanol titanium (TTB) 0.07g are added, continue to carry out esterification.

Then, the viscosity at 150 DEG C is become 1930mPas and (is measured using vertebral plate viscosimeter；According to JIS K 5600- 2-3 (2014) (hereinafter also the same)) time point, terminal hydroxyl amount is found out using titration, to become its equimultiple equivalent The mode of (1 mole of anhydride group: 1 mole of hydroxyl) adds maleic anhydride, carries out stirring for 90 minutes in 150 DEG C, makes its addition in hydroxyl Base.The compound that there is carboxyl in molecular end is obtained as a result,.

Then, ethyl acetate 374.1g is added, will there is the compound of carboxyl to dissolve in molecular end.In turn, it adds KBM403 (Shin-Etsu Silicone system, silane coupling agent (hereinafter also the same)) 1.75g, KBM603 (Shin-Etsu Silicone system, silane coupling agent (hereinafter also the same)) 0.87g, phosphoric acid 0.44g, obtaining solid state component is 73.2% Host agent A.Acid value is 25.2mgKOH/g, and carboxyl equivalent (solid state component) is 1629.

Production Example 2 (preparation of host agent B)

By terephthalic acid (TPA) 310.5g, M-phthalic acid 414g, adipic acid 363.9g, ethylene glycol 220.4g, diethylene glycol 282.6g and neopentyl glycol 277.3g are respectively charged into reaction vessel, in 180~220 DEG C of progress esterifications.Acid value at For 8mgKOH/g time point below, four butanol titanium (TTB) 0.15g are added, continue to carry out esterification.

Then, the viscosity at 150 DEG C is become 5040mPas and (is measured using vertebral plate viscosimeter；According to JIS K) when Between point, find out terminal hydroxyl amount using titration, by become its equimultiple equivalent (1 mole of anhydride group: 1 mole of hydroxyl) in a manner of add Maleic anhydride, carries out stirring for 90 minutes in 150 DEG C, makes its addition in hydroxyl.The change that there is carboxyl in molecular end is obtained as a result, Close object.

Then, ethyl acetate 628.5g is added, will there is the compound of carboxyl to dissolve in molecular end.In turn, it adds KBM4032.93g, KBM6031.47g, phosphoric acid 0.73g obtain the host agent B that solid state component is 72.0%.Acid value is 16.3mgKOH/g, carboxyl equivalent (solid state component) are 2478.

Production Example 3 (preparation of host agent C)

By terephthalic acid (TPA) 310.5g, M-phthalic acid 414g, adipic acid 363.9g, ethylene glycol 220.4g, diethylene glycol 282.6g and neopentyl glycol 277.3g are respectively charged into reaction vessel, in 180~220 DEG C of progress esterifications.Acid value at For 8mgKOH/g time point below, four butanol titanium (TTB) 0.15g are added, continue to carry out esterification.

Then, the viscosity at 150 DEG C is become 9640mPas and (is measured using vertebral plate viscosimeter；According to JIS K 5600- 2-3 (2014)) time point, find out terminal hydroxyl amount using titration, with become (1 mole of anhydride group: hydroxyl of its equimultiple equivalent 1 mole) mode add maleic anhydride, in 150 DEG C carry out 90 minutes stir, make its addition in hydroxyl.It is obtained as a result, in molecule End has the compound of carboxyl.

Then, ethyl acetate 1100g is added, will there is the compound of carboxyl to dissolve in molecular end.In turn, it adds KBM403 2.93g, KBM603 1.47g, phosphoric acid 0.73g obtain the host agent C that solid state component is 60.6%.Acid value is 11.3mgKOH/g, carboxyl equivalent (solid state component) are 2994.

Production Example 4 (preparation of host agent D)

By terephthalic acid (TPA) 310.5g, M-phthalic acid 414g, adipic acid 363.9g, ethylene glycol 220.4g, diethylene glycol 282.6g and neopentyl glycol 277.3g are respectively charged into reaction vessel, in 180~220 DEG C of progress esterifications.Acid value at For 8mgKOH/g time point below, four butanol titanium (TTB) 0.15g are added, continue to carry out esterification.

Then, the viscosity at 150 DEG C is become 9230mPas and (is measured using vertebral plate viscosimeter；According to JIS K 5600- 2-3 (2014)) time point, find out terminal hydroxyl amount using titration, with become (2 moles of anhydride group: hydroxyl 1 of its 2 times of equivalents Mole) mode add maleic anhydride, in 150 DEG C carry out 120 minutes stir, make its addition in hydroxyl.It is obtained as a result, in molecule End has the compound of carboxyl.

Then, ethyl acetate 1146g is added, will there is the compound of carboxyl to dissolve in molecular end.In turn, it adds KBM403 2.93g, KBM603 1.47g, phosphoric acid 0.73g obtain the host agent D that solid state component is 57.1%.Acid value is 23.4mgKOH/g, carboxyl equivalent (solid state component) are 1369.

Production Example 5 (preparation of host agent E)

By terephthalic acid (TPA) 310.5g, M-phthalic acid 414g, adipic acid 363.9g, ethylene glycol 220.4g, diethylene glycol 282.6g and neopentyl glycol 277.3g are respectively charged into reaction vessel, in 180~220 DEG C of progress esterifications.Acid value at For 8mgKOH/g time point below, four butanol titanium (TTB) 0.15g are added, continue to carry out esterification.

Then, the viscosity at 150 DEG C is become 9360mPas and (is measured using vertebral plate viscosimeter；According to JIS K 5600- 2-3 (2014)) time point, find out terminal hydroxyl amount using titration, with become its 0.5 times of equivalent (0.5 mole of anhydride group: 1 mole of hydroxyl) mode add maleic anhydride, in 150 DEG C carry out 120 minutes stir, make its addition in hydroxyl.It obtains as a result, There is the compound of carboxyl in molecular end.

Then, ethyl acetate 1100g is added, will there is the compound of carboxyl to dissolve in molecular end.In turn, it adds KBM403 2.93g, KBM603 1.47g, phosphoric acid 0.73g obtain the host agent E that solid state component is 60.5%.Acid value is 5.95mgKOH/g, carboxyl equivalent (solid state component) are 5705.

Production Example 6 (preparation of host agent F)

By terephthalic acid (TPA) 310.5g, M-phthalic acid 414g, adipic acid 363.9g, ethylene glycol 220.4g, diethylene glycol 282.6g and neopentyl glycol 277.3g are respectively charged into reaction vessel, in 180~220 DEG C of progress esterifications.Acid value at For 8mgKOH/g time point below, four butanol titanium (TTB) 0.15g are added, continue to carry out esterification.

Then, the viscosity at 150 DEG C is become 9100mPas and (is measured using vertebral plate viscosimeter；According to JIS K 5600- 2-3 (2014)) time point, find out terminal hydroxyl amount using titration, with become (1 mole of anhydride group: hydroxyl of its equimultiple equivalent 1 mole) mode add trimellitic anhydride, in 150 DEG C carry out 120 minutes stir, make its addition in hydroxyl.It obtains as a result, There is the compound of carboxyl in molecular end.

Then, ethyl acetate 1100g is added, will there is the compound of carboxyl to dissolve in molecular end.In turn, it adds KBM403 2.93g, KBM603 1.47g, phosphoric acid 0.73g obtain the host agent F that solid state component is 60.5%.Acid value is 23.8mgKOH/g, carboxyl equivalent (solid state component) are 1428.

Production Example 7 (preparation of host agent G)

By terephthalic acid (TPA) 310.5g, M-phthalic acid 414g, adipic acid 363.9g, ethylene glycol 220.4g, diethylene glycol 282.6g and neopentyl glycol 277.3g are respectively charged into reaction vessel, in 180~220 DEG C of progress esterifications.Acid value at For 8mgKOH/g time point below, four butanol titanium (TTB) 0.15g are added, continue to carry out esterification.

Then, the viscosity at 150 DEG C is become 7400mPas and (is measured using vertebral plate viscosimeter；According to JIS K 5600- 2-3 (2014)) time point, find out terminal hydroxyl amount using titration, with become (1 mole of anhydride group: hydroxyl of its equimultiple equivalent 1 mole) mode add phthalic anhydride, in 150 DEG C carry out 120 minutes stir, make its addition in hydroxyl.It obtains as a result, There is the compound of carboxyl in molecular end.

Then, ethyl acetate 1100g is added, will there is the compound of carboxyl to dissolve in molecular end.In turn, it adds KBM403 2.93g, KBM603 1.47g, phosphoric acid 0.73g obtain the host agent G that solid state component is 64.9%.Acid value is 17.0mgKOH/g, carboxyl equivalent (solid state component) are 2142.

Production Example 8 (preparation of host agent H)

By terephthalic acid (TPA) 274.3g, M-phthalic acid 240g, ethylene glycol 117g, neopentyl glycol 163.4g, 1,6- oneself two Alcohol 216.3g, zinc acetate 0.14g are respectively charged into reaction vessel, in 180~220 DEG C of progress esterifications.Become in acid value 20 time points below added adipic acid 150.8g, continued to carry out esterification.

Then, the viscosity at 150 DEG C is become 5160mPas and (is measured using vertebral plate viscosimeter；According to JIS K 5600- 2-3 (2014)) time point, find out terminal hydroxyl amount using titration, with become (1 mole of anhydride group: hydroxyl of its equimultiple equivalent 1 mole) mode add maleic anhydride, in 150 DEG C carry out 120 minutes stir, make its addition in hydroxyl.It obtains dividing as a result, Sub- end has the compound of carboxyl.

Then, ethyl acetate 667g is added, will there is the compound of carboxyl to dissolve in molecular end.In turn, it adds KBM403 1.65g, KBM603 0.82g, phosphoric acid 0.41g obtain the host agent H that solid state component is 64.7%.Acid value is 30.7mgKOH/g, carboxyl equivalent (solid state component) are 1184.

Production Example 9 (host agent I)

TAKELAC A-620 (polyester polyol, Mitsui Chemicals, Inc.'s system) is used as host agent I.

Production Example 10 (preparation of host agent J)

By terephthalic acid (TPA) 310.5g, M-phthalic acid 414g, adipic acid 363.9g, ethylene glycol 220.4g, diethylene glycol 282.6g and neopentyl glycol 277.3g are respectively charged into reaction vessel, in 180~220 DEG C of progress esterifications.Acid value at For 8mgKOH/g time point below, four butanol titanium (TTB) 0.15g are added, continue to carry out esterification.

Then, the viscosity at 150 DEG C is become 9820mPas and (is measured using vertebral plate viscosimeter；According to JIS K 5600- 2-3 (2014)) time point, find out terminal hydroxyl amount using titration, with become (1 mole of anhydride group: hydroxyl of its equimultiple equivalent 1 mole) mode add maleic anhydride, in 150 DEG C carry out 90 minutes stir, make its addition in hydroxyl.It is obtained as a result, in molecule End has the compound of carboxyl.

Then, ethyl acetate 1100g is added, will there is the compound of carboxyl to dissolve in molecular end, obtain solid state component For 59.3% host agent C.Acid value is 10.4mgKOH/g, and carboxyl equivalent (solid state component) is 3199.

<curing agent (carbodiimide ingredient)>

As curing agent A~C and curing agent E, product below is used.

In addition, manufacturing curing agent D, F and G using the following method.

Curing agent A: Nisshinbo corporation CARBODILITE V05S, solid component concentration is 90 mass %, carbodiimide Base equivalent is 291 (solid state component equivalents 262)

Curing agent B: Nisshinbo corporation CARBODILITE V07, solid component concentration is 50 mass %, carbodiimide Equivalent is 404 (solid state component equivalents 202)

Curing agent C: Nisshinbo corporation CARBODILITE V09GB, solid component concentration is 70 mass %, carbodiimide Base equivalent is 298 (solid state component equivalents 209)

Curing agent E:TAKENATE A-50 (polyurethane resin containing terminal isocyanate group, Mitsui Chemicals, Inc.'s system)

Curing agent D: curing agent D is manufactured using the following method.

At room temperature, 1,5- penta 2 is packed into the four-necked bottle for having blender, thermometer, return pipe and nitrogen ingress pipe 100.0 mass parts of isocyanates, UNIOX M400 (polyoxyethylene monomethyl ether (day oil system) 44.2 mass parts, 1- methoxyl group -2- 13.4 mass parts of propyl alcohol.Nitrogen is imported on one side, is heated to 80 DEG C under normal pressure on one side, stir within 6 hours, and carbamic acid is carried out Esterification.

Next, being loaded as 330.5 mass parts of dimethylbenzene of organic solvent, the 3- first as carbodiimidization catalyst Base -1- phenyl -2- phosphorus alkene -1- oxide (MPPO) 2.0 mass parts stir within 8 hours for (141 DEG C), terminate anti-under reflux It answers.

After reaction, 80 DEG C are cooled to, dimethylbenzene is distilled off under reduced pressure, in the form of poly- carbodiimide composition Obtain curing agent D.Solid component concentration is 98.8%, and carbodiimide equivalent (solid state component) is 299.

Curing agent F: curing agent F is manufactured using the following method.

At room temperature, to be packed into 1,3- into the four-necked bottle for having blender, thermometer, return pipe and nitrogen ingress pipe bis- (different Cyanate ylmethyl) 100.0 mass parts of hexamethylene, 9.54 mass parts of isobutanol.Nitrogen is imported on one side, is heated under normal pressure on one side To 80 DEG C, stir within 6 hours, carries out urethane reaction.

Next, being loaded as 231.0 mass parts of propylene glycol monomethyl ether (PMA) of organic solvent, as carbon The 3- methyl-1 of diimine catalyst-phenyl -2- phosphorus alkene -1- oxide (MPPO) 2.0 mass parts, under reflux (150 DEG C) Stir within 8 hours, reaction was completed.

After reaction, 80 DEG C are cooled to, a part of PMA is distilled off under reduced pressure, with poly- carbodiimide composition Form obtains curing agent F.Solid component concentration is 88.4%, and carbodiimide equivalent (solid state component) is 265.

Curing agent G: curing agent G is manufactured using the following method.

At room temperature, isophorone is packed into the four-necked bottle for having blender, thermometer, return pipe and nitrogen ingress pipe 100.0 mass parts of diisocyanate, 8.34 mass parts of isobutanol.Nitrogen is imported on one side, is heated to 80 DEG C under normal pressure on one side, into It stirs within row 6 hours, carries out urethane reaction.

Next, being loaded as 228.5 mass parts of propylene glycol monomethyl ether (PMA) of organic solvent, as carbon The 3- methyl-1 of diimine catalyst-phenyl -2- phosphorus alkene -1- oxide (MPPO) 2.0 mass parts, under reflux (150 DEG C) Stir within 8 hours, reaction was completed.

After reaction, 80 DEG C are cooled to, a part of PMA is distilled off under reduced pressure, with poly- carbodiimide composition Form obtains curing agent G.Solid component concentration is 74.5%, and carbodiimide equivalent (solid state component) is 310.

Examples 1 to 25 and comparative example 1

With the match ratio R (carbodiimide/carboxyl (molar ratio)) that is recorded in table 1~5 by host agent (containing carboxyl moieties) and Curing agent (carbodiimide ingredient) mixing, and then diluted with solvent (ethyl acetate) to obtain mixed liquor, with coating weight at For 3.3g/m²Obtained mixed liquor is coated on the TECHBARRIER TX as gas barrier film by the mode of (dry film thickness) (Resins Corporation, Mitsubishi system, has a PET film of silica steam plating film, and 12 μm, 5.0mL/m²RMPa for 24 hours), gas is hindered The silica steam plating layer of diaphragm is bonded each other.Then, obtained laminated body conserve within 3 days in 60 DEG C.

<evaluation>

(visual inspection of laminate)

It is evaluated according to the appearance that reference pin below carries out the laminate after maintenance in 3 days for 60 DEG C

Zero: without foaming

△: several foaming

×: foaming

(peel strength of laminated film)

According to JIS K 6854-3 (1999), at 24 DEG C, with the width of 15mm, 300mm/min tensile speed into Row measurement.

(the hot peel strength of laminated film)

According to JIS K 6854-3 (1999), at 120 DEG C, with the width of 15mm, 300mm/min tensile speed into Row measurement.

(the resistance to thermal creep of laminated film)

The strip that test film width is 15mm is cut out, is removed, the counterweight of 100g is placed on the film of side, At 120 DEG C, the offset width of measurement 3 minutes takes value obtained from being scaled every 1 minute offset width.

[table 1]

Table 1

[table 2]

Table 2

[table 3]

Table 3

[table 4]

Table 4

[table 5]

Table 5

It should be noted that foregoing invention is to provide as example embodiment of the invention, but this is only Example, being not construed as limiting property are explained.The variation of the invention that those skilled in the art are illustrated is also included within appended In claims.

Industrial availability

Two-solution curing type adhesive composite, laminated film and its manufacturing method of the invention can vacuum heat insulation material etc. every The packaging films of hot field and food pharmaceuticals etc., food container (including bottle.), optical film, the gases such as industrial film Barrier suitably uses in field.

Description of symbols

1 laminated film

2 gas barrier films

3 adhesive layers

Claims (7)

1. two-solution curing type adhesive composite is the two-solution curing type bonding agent group that will be bonded between multi-disc gas barrier film Close object, which is characterized in that contain:

Contain carboxyl moieties with carboxyl；With

Carbodiimide ingredient containing carbodiimide compound.

2. two-solution curing type adhesive composite as described in claim 1, which is characterized in that it is described containing carboxyl moieties contain it is poly- The acid anhydride adduct of ester polyol.

3. two-solution curing type adhesive composite as claimed in claim 2, which is characterized in that relative to the polyester polyol 1 mole of hydroxyl for, ratio that anhydride group in the acid anhydrides is 0.7 mole or more.

4. two-solution curing type adhesive composite as described in claim 1, which is characterized in that contain carboxyl moieties relative to described In 1 mole of carboxyl for,

In the carbodiimide ingredient carbodiimide is with 1.3 moles or more and 4 moles of ratios below are contained.

5. laminated film, which is characterized in that have:

Multi-disc gas barrier film；With

Adhesive layer is the solidfied material of two-solution curing type adhesive composite described in claim 1, and is situated between and is described in multi-disc Between gas barrier film.

6. the manufacturing method of laminated film, which is characterized in that have following processes:

Preparatory process prepares multi-disc gas barrier film；With

Multi-disc gas barrier film is bonded by laminating process via two-solution curing type adhesive composite described in claim 1, Obtain laminated body.

7. the manufacturing method of laminated film as claimed in claim 6, which is characterized in that have after the laminating process to institute It states laminated body and carries out heat-cured maintenance process.