CN1184139A - Binding agent composition for lamination and method for producing laminated film using the same - Google Patents
Binding agent composition for lamination and method for producing laminated film using the same Download PDFInfo
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- CN1184139A CN1184139A CN96121512A CN96121512A CN1184139A CN 1184139 A CN1184139 A CN 1184139A CN 96121512 A CN96121512 A CN 96121512A CN 96121512 A CN96121512 A CN 96121512A CN 1184139 A CN1184139 A CN 1184139A
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Abstract
The adhesive composite for making laminated film can complete solidification reaction in short period and at normal temperature and has high productivity and excellent use property. It is prepared by using organic compound, which has functional group capable of reacting with isocyanic ester and isocyanic ester radical, organic isocyanic ester compound, catalyst and coupling agent added according to requirement.
Description
The present invention relates to be applicable to the binder composition of film laminating technology and use said composition to make the laminated film method.
Recently; as Packaging Method; operation during from the intensity, commodity protectiveness of packing, packing, the effect of publicity of packing are considered, and because a large amount of, the offering of lower priced articles of plastic material make reasons such as Packing Fee reduction, are caused compound flexibility to be packed and obtained significant development.
As the tackiness agent that in film laminating technology, uses, from bond properties and cold-resistant, excellent heat resistance, base materials such as various plastics, tinsel suitable general enclosed aspect such as wide to be considered, usually, the two liquid type polyurethane class tackiness agent of being made up of host with hydroxyl isoreactivity hydrogen and the solidifying agent with isocyanate group is a main flow.
But present two liquid type polyurethane class adhesive for lamination is very slow at the curing reaction of bonding back tackiness agent, so must there be the curing that is called ageing (aging) to promote operation.Specifically, the film of lamination process must be placed 3-5 days in 35-60 ℃ moist closet, so that its ageing, thereby tackiness agent is solidified.At this moment, the state of cure of tackiness agent changes because of the difference of ageing condition, therefore influences the bond strength of laminated film sometimes, under the inadequate situation of ageing, because the bad meeting of curing of tackiness agent causes delamination (layer is peeled off).Particularly for aliphatic polyurethane class tackiness agent, its curing reaction needs considerable time.Therefore this ageing operation is in the formula laminating technology it is indispensable operation, therefore need be used for the ageing facility investment of moist closet and heat-preserving equipment expense after this etc.
The objective of the invention is to provide a kind of can be at normal temperatures, finish curing reaction in the short period of time, the adhesive for lamination composition that productivity and operation are good, and use the manufacture method of the laminated film of this adhesive for lamination composition.
Present inventors are for solving the problem that exists in the above-mentioned prior art, carried out deep research, found that, by (A) have can and the organic compound of the functional group of isocyanic ester radical reaction and (B) the organic isocyanate compound and (C) binder composition formed of catalyzer and (D) coupler as required when being used for bonding between the film, can finish curing reaction at short notice, thereby finish the present invention.
Promptly, adhesive for lamination composition of the present invention by (A) have can with the organic compound of the functional group of isocyanic ester radical reaction and (B) the organic isocyanate compound and (C) catalyzer form, it is characterized in that above-mentioned (A) has can be the organic compound that is obtained by (a) polymeric polyisocyanate composition and (b) isocyanate group reactive ingredients reaction with the organic compound of the functional group of isocyanic ester radical reaction.
Another kind of adhesive for lamination composition of the present invention by (A) have can with the organic compound of the functional group of isocyanic ester radical reaction and (B) the organic isocyanate compound and (C) catalyzer and (D) coupler form, it is characterized in that above-mentioned (A) has can be the organic compound that is obtained by (a) polymeric polyisocyanate composition and (b) isocyanate group reactive ingredients reaction with the organic compound of the functional group of isocyanic ester radical reaction.
In above-mentioned each adhesive for lamination composition of the present invention, above-mentioned isocyanate group reactive ingredients (b) contains rosin polyvalent alcohol (rosinpolyol) (b1).
In addition, the present invention also provides a kind of manufacture method of laminated film, it is characterized in that, is coated in above-mentioned various adhesive for lamination compositions on the 1st film and makes its drying, then with the 2nd film laminating in the above and ageing at normal temperatures.
At first for can describing with the organic compound (A) of the functional group of isocyanic ester radical reaction as having of the necessary composition among the present invention.
This organic compound (A) be with (a) polymeric polyisocyanate composition and (b) isocyanate group reactive ingredients preferably in the equivalent of isocyanate group/can obtain with the ratio reaction of the equivalent=0.50/l-0.98/l of the functional group of isocyanic ester radical reaction have can with the compound of the functional group of isocyanic ester radical reaction.The number-average molecular weight of this organic compound (A) is 3,000-60, and 000, be preferably 10 especially, 000-40,000.
Have can with the organic compound (A) of the functional group of isocyanic ester radical reaction, be with molten state or loose condition (of surface), or use in polyurethane industrial for example toluene of inert solvent commonly used as required, aromatic hydrocarbon solvents such as dimethylbenzene, ethyl acetate, esters solvents such as butylacetate, methyl ethyl ketone, ketones solvents such as pimelinketone, ethyl cellosolve acetate, propylene glycol methyl ether acetate, ethyl-diol alcohol esters solvents such as 3-ethoxy-c acid esters, ether solvents such as tetrahydrofuran (THF) diox, dimethyl formamide, N,N-DIMETHYLACETAMIDE, N-Methyl pyrrolidone, in the furfural isopolarity solvent more than a kind or 2 kinds, preferably below 100 ℃, in above-mentioned matching requirements scope, make reacting behind each composition uniform mixing.
As reaction unit, can use any device that can finish above-mentioned reaction, for example have the reactor or the kneader of whipping appts, mixing such as one or the multiaxis extrusion reaction machine device that mixes.Be accelerated reaction, also can use in the manufacturing of urethane or polyureas tertiary amine catalysts such as metal catalyst such as dibutyl tin laurate commonly used or triethylamine.
As polymeric polyisocyanate composition (a), except that the polymeric polyisocyanate monomer more than a kind or 2 kinds, also have polyisocyanate compounds such as its polycondensate.
For example 2,4-toluene support vulcabond, 2,6-toluene support vulcabond, dimethylbenzene-1, the 4-vulcabond, dimethylbenzene-1, the 3-vulcabond, 4,4 '-diphenylmethanediisocyanate, 2,4 '-diphenylmethanediisocyanate, 4,4 '-diphenyl ether vulcabond, 2-nitro phenylbenzene-4,4 '-vulcabond, 2,2 '-diphenyl propane-4,4 '-vulcabond, 3,3 '-dimethyl diphenylmethane-4,4 '-vulcabond, 4,4 '-diphenyl propane vulcabond, the metaphenylene vulcabond, to phenylene vulcabond, naphthylidene-1, the 4-vulcabond, naphthylidene-1, the 5-vulcabond, 3,3-dimethoxy phenylbenzene-4, aromatic diisocyanates such as 4 '-vulcabond, or tetramethylene vulcabond, HDI (being designated hereinafter simply as HDI), aliphatic diisocyanates such as Trimethyl glycine vulcabond, or isophorone diisocyanate (being designated hereinafter simply as IPDI), hydrogenation toluene support vulcabond, hydrogenated xylene diisocyanate, hydrogenated diphenyl methane diisocyanate, vulcabond such as alicyclic diisocyanate such as tetramethylxylene diisocyanate, or the biuret body of above-mentioned vulcabond, dipolymer, trimer, the dipolymer trimer, polycondensates such as urethane imido (ゥ レ ト Application ィ ミ Application) modification body, or by 2 officials can be above polyvalent alcohol etc. and above-mentioned vulcabond or the reaction of its polycondensate and the adducts of the polymeric polyisocyanate that obtains.
Isocyanate group reactive ingredients (b) be contain can with the compound of the functional group of isocyanic ester radical reaction, preferably contain can with the compound of isocyanate group reactive activity hydrogen.
Concrete is outside dewatering, and preferably contains the material more than a kind or 2 kinds of selection from polyvalent alcohol, the polyamines that contains amino etc., urea resin, melmac, vibrin, Gum Rosin, acrylic resin, polyvinyl alcohol etc.
As polyvalent alcohol, known polyalcohols in polyurethane industrial such as polyester polyol, polyesteramide polyvalent alcohol, polyether glycol, polyester ether polylol, polycarbonate polyol, rosin polyvalent alcohol (b1) is for example arranged.
As concrete example, can enumerate: by known Succinic Acid, hexanodioic acid, sebacic acid, nonane diacid, terephthalic acid, m-phthalic acid, six hydrogen terephthalic acids, dicarboxylic acid such as six hydrogen m-phthalic acids, the ester that these are sour, acid anhydrides etc. and ethylene glycol (hereinafter to be referred as EG), 1, ammediol, 1, the 2-propylene glycol, 1, the 4-butyleneglycol, 1, the 5-pentanediol, 1, the 6-hexylene glycol, the 3-methyl isophthalic acid, the 5-pentanediol, 2-butyl-2-ethyl-1, ammediol, NPG, 1, the 8-ethohexadiol, 1, the 9-nonanediol, Diethylene Glycol, hexanaphthene-1, the 4-glycol, hexanaphthene-1, the 4-dimethanol, the sour glycol of dimerization (ダ ィ マ one), TriMethylolPropane(TMP), glycerol, glycol or triols such as the oxyethane of hexanetriol or dihydroxyphenyl propane or propylene oxide adduct, perhaps with hexamethylene diamine, N, N, N ', N '-four (2-hydroxypropyl) quadrol, dimethylphenylene diamine, isophorone diamine, Monoethanolamine MEA BASF, diamines such as Virahol triamine, triamine or amino alcohol etc. separately or their mixture carry out dehydration condensation and the polyester polyol that obtains, polyesteramide polyvalent alcohol etc.
Also can enumerate: cyclic esters such as δ-Wu Neizhi (being lactone) the monomeric ring-opening polymerization that 6-caprolactone, δ-Wu Neizhi, the alkyl that is replaced by 6-caprolactone, alkyl replaces and the lactone polyester polyol that obtains.
As polyether glycol, for example can enumerate: polyoxyethylene glycol, poly-propyl ether polyvalent alcohol, poly-butyl ether polyvalent alcohol etc.As polyester ether polylol, can enumerate the polyester ether polylol of making by these polyether glycols and above-mentioned dicarboxylic acid or acid anhydrides etc.
As polycarbonate polyol, for example can enumerate: by hexylene glycol, 3-methyl isophthalic acid, 5-pentanediol, 1,4-cyclohexanedimethanols etc. react and the product of acquisition with diethyl carbonate, diphenyl carbonate etc., as concrete commodity, can enumerate: two ッ Port ラ Application 980 of Japanese Port リ ゥ レ Application industry (strain) system, ニ ッ Port ラ Application 981 etc.
In addition, raw material as above-mentioned polyester polyol, the unit molecule glycol or the triol that can use oneself to mention, just: EG, 1, ammediol, 1, the 2-propylene glycol, 1, the 4-butyleneglycol, 1, the 5-pentanediol, 1,6 hexylene glycol, the 3-methyl isophthalic acid, the 5-pentanediol, NPG, 1, the 8-ethohexadiol, 1, the 9-nonanediol, Diethylene Glycol, hexanaphthene-1, the 4-glycol, hexanaphthene-1, the 4-dimethanol, the dimeracid glycol, TriMethylolPropane(TMP), glycerol, hexanetriol, the oxyethane of trihydroxybutane (Network オ De ロ Le) or dihydroxyphenyl propane or propylene oxide adduct etc. and those compounds that use as above-mentioned polyvalent alcohol.
As the above-mentioned polyamines that contains amino etc., can enumerate: unit molecule diamines, triamines such as hexamethylene diamine, ethylene diamine, isophorone diamine; Aromatic diamine and on the end of polyethers, have amino polyether polyamine etc.
In addition, said urea resin, melmac, Resins, epoxy, vibrin, acrylic resin, polyvinyl alcohol etc., so long as it is known in polyurethane industrial usually, wherein contain the product of the isocyanate-reactive group of 2 above active hydrogens etc., promptly can be with its all or part of use as composition (b).
The molecular weight of said composition (b) is preferably 18～20, and 000, especially preferably water and molecular weight are 400～10,000 material.If molecular weight is excessive, the introducing amount of urethane ester group etc. is reduced, thereby the obdurability of organifying compound (A) and strong cohesive force reduce, therefore not preferred.If molecular weight is too small, then organic compound (A) has the tendency that becomes fragile, and is therefore also not preferred.This molecular weight must carry out appropriate selection according to its purposes, from improving thermotolerance and condensing and can consider, preferably uses low-molecular-weight compound.
In addition, under situation about considering with the adhesive property of base material film, to use aromatic series kind polyester polyvalent alcohol that terephthalic acid, m-phthalic acid etc. make or the polyester polyol that uses hexanodioic acid to make comparatively suitable.
Under the situation of considering adhesive property, more preferably with one one or all use of rosin polyvalent alcohol (b1) as composition (b).
As rosin polyvalent alcohol (b1), can enumerate: have can with the functional group of isocyanic ester radical reaction, rosin ester (opening flat 2-155978 communique) that makes by rosin and polyvalent alcohol or the rosin ester (opening flat 5-155972 communique) that makes by epoxy compounds and rosin with reference to the spy with reference to the spy.And, preferably have the polyethers of rosin skeleton.
Wherein particularly preferably be the rosin ester (opening flat 5-263059 communique) that makes by di-epoxy compounds 1 molecule and hydrogenation, non-homogenizing purified rosin based 2 molecules with reference to the spy, because it imports in the molecule of organic compound (A) easily, the molecular weight of the organic compound that is generated is simultaneously controlled easily.As these rosin polyvalent alcohols (b1), can enumerate particularly by KE-601, the KE-615-3 of waste river chemical industry (strain) system, KE-622, KE-623, KE-624 etc.
In the present invention as the organic isocyanate compound (B) of neccessary composition, above-mentioned compound can be used, コ ロ ネ one ト L, コ ロ ネ one ト 3401, コ ロ ネ one ト HL, コ ロ ネ one ト HX etc. can be enumerated particularly by Japanese Port リ ゥ レ Application industry (strain) system as polymeric polyisocyanate composition (a).
The use level of this organic isocyanate compound (B) is that solids component 100 weight parts with respect to above-mentioned organic compound (A) are preferably the 1-30 weight part by solids component by calculation, are preferably 3～15 weight parts especially.
The following describes in the present invention catalyzer (C) as neccessary composition.
Catalyzer (C) comprises as generally well-known catalyzer such as transesterification catalyst, urethane esterification catalyzer, blocked isocyanate dissociation catalyst, isocyanuric acid esterification catalyzer, can enumerate particularly: tin class catalyzer such as dibutyl tin laurate, stannous octoate; Triethylenediamine, triethylamine, N, N, N ' N '-tetramethyl-trimethylene diamines, N, N, N ', N '-four (2-hydroxypropyl) ethylene diamine, N-methylmorpholine, 1,2 dimethylimidazole, 1,5-diazabicyclo (4,3,0) 5-nonene, 1,8-diazabicyclo (5,4,0) 7-undecylene (being designated hereinafter simply as DBU); The various amine salt series catalysts of the borate of these amines catalysts, DBU phenolate, DBU octylate, DBU carbonate etc.; Magnesium naphthenate, lead naphthenate, CH
3Metal carboxylates such as COOK; The trialkyl phosphine class of triethyl phosphine, tribenzyl phosphine etc.; CH
3Pure salt such as ONa; Zinc class organo-metallic catalyst etc.
In these catalyzer, consider from the aspects such as stability of catalytic effect and interpolation back binder composition, preferably use the various hydrochlorates of DBU and DBU.
The kind and the addition of the catalyzer of curing speed and interpolation have much relations, but by to the suitable selection of catalyzer, and near can be room temperature temperature province preferably obtains practical curing speed in 15～35 ℃.
But, if the addition of catalyzer is with respect to the solids component of organic compound (A), for example be lower than under the situation of 0.01 weight %, be difficult to reach the facilitation effect of curing reaction by interpolation, in addition, if addition surpasses 5.00 weight %, then curing speed is too fast, the coating operation is had any problem, and also has the disadvantage of the tackiness agent hydrolysis after may promoting to solidify in addition, and is therefore bad.
Therefore, can be 0.01-5.00 weight % with the addition of the catalyzer of the solids component of the organic compound (A) of the functional group of isocyanic ester radical reaction with respect to having, preferred especially 0.05-2.00 weight %.
As the coupler that can use in the present invention (D), silane coupling agent, titanate ester coupler, aluminium class coupler etc. are for example arranged.
Can be preferably the 0.05-10.00 weight part with the addition of the coupler of solids component 100 weight parts of the organic compound (A) of the functional group of isocyanic ester radical reaction with respect to having.0.1-5.00 weight part more preferably.Here shown addition is to consider that coupler calculates on the basis of the lining area on the base material film and lining efficient and adhesive property.
As silane coupling agent, suitable has: the vinyl silane compound of γ-methacryloxypropyl trimethoxy silane, vinyltriethoxysilane etc.; The epoxy silane compounds of β-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane, γ-glycidoxypropyltrime,hoxysilane etc.; The amino silane compounds of γ-An Bingjisanyiyangjiguiwan, N-β-aminoethyl-γ-aminopropyl methyl dimethoxysilane etc.; The hydrosulphonyl silane compound of γ-Qiu Jibingjisanjiayangjiguiwan etc. etc.
As the titanate ester coupler; can enumerate: sec.-propyl three isostearoyl base titanic acid ester; sec.-propyl three (dodecyl) benzenesulfonyl titanic acid ester; sec.-propyl three (dioctyl pyrophosphate) titanic acid ester; two (dioctylphosphoric acid ester) titanic acid ester of tetra isopropyl; four octyl groups two (the two tridecane esters of phosphoric acid) titanic acid ester; four (2; 2-two allyloxy methyl isophthalic acid-butyl) two (the two tridecane esters of phosphoric acid) titanic acid ester; two (dioctyl pyrophosphate) ethoxyacetic acid ester titanic acid ester; two (dioctyl pyrophosphate) ethylidene titanic acid ester; sec.-propyl three capryloyl titanic acid ester; sec.-propyl dimethyl propylene enoyl-iso stearate base titanic acid ester; the hard ester acyl group two acryl titanic acid ester of isopropyl; sec.-propyl three (dioctylphosphoric acid ester) titanic acid ester; sec.-propyl three cumenyl phenyl titanium acid esters; sec.-propyl three (N-amide group ethylamino ethyl) titanic acid ester; two cumenyl phenylium ester titanic acid ester; two isostearoyl base ethylidene titanic acid ester etc.; what specifically, be suitable for has: the プ レ Application ァ Network ト KR TTS of aginomoto (strain) system; KR 46B; KR 55; KR 41B; KR 38S; KR 1388; KR 238S; KR 338X; KR 12; KR 44; KR 9SA; KR 34S etc.
As aluminium class coupler, can enumerate acetyl aluminum alkoxide diisopropyl acid esters etc., as commodity, the プ レ Application ァ Network ト AL-M that aginomoto (strain) system is arranged that is suitable for etc.
In above-mentioned coupler, consider that from improving epoxy silane compounds, amino silane compounds, phosphoric acid class titanic acid ester etc. are preferably arranged with the bounding force aspect of the polyethylene terephthalate film of using widely now, thin film lead, nylon film, polyolefin film etc.
Wherein, as the preferred especially epoxy silane compounds of coupler (D), use the various hydrochlorates of DBU and DBU as the special preferably combination of catalyzer (C).
As being used for the film that lamination of the present invention is used, plastic films such as oriented polypropylene, no oriented polypropylene (being designated hereinafter simply as CPP), polyester (being designated hereinafter simply as PET), nylon (being designated hereinafter simply as NY), new LDPE (film grade), high density polyethylene(HDPE), ethylene-vinyl acetate copolymer, polyvinyl alcohol, ethylene-vinyl alcohol copolymer (being designated hereinafter simply as EVOH), polystyrene, polycarbonate, polyvinylidene chloride, polyvinyl chloride are for example arranged, tinsel such as Al, Cu, paper etc., and the film that coated polymer obtains on these materials.
For these films, preferably before carrying out lamination, carry out suitable surface treatments such as Corona discharge Treatment, can improve bounding force.
In addition, because the possibility that the polymeric coating film has problems such as bubbling, bounding force reduction to occur, so must consider kind, coated weight and the surface property etc. of the polymkeric substance that applies in advance.
The following describes the laminating method of film.
Adhesive for lamination composition of the present invention can be used for known laminating methods such as dried lamination, hot melt lamination, hot pressing lamination, will be finished curing reaction by laminated film carries out certain hour (in preferred 24 hours) under normal temperature (preferred 15-35 ℃) ageing then.
Utilize method of the present invention as above, not only can make the film of 2 film lamination, and can make the film of the film lamination more than 3.
Embodiment
Describe embodiments of the invention below in detail, but the present invention is not subjected to the qualification of these embodiment.Do not having under the situation about specifying, part and % in synthesis example, embodiment and the comparative example represent that respectively " weight part " reaches " weight % ".
Have can be with the organic compound of the functional group of isocyanic ester radical reaction synthetic
Synthesis example 1
In the reactor that has stirrer, thermometer, nitrogen-sealed pipe and water cooler, add HDI100 part and, by 1323 parts of the polyester polyols of dimethyl terephthalate (DMT)/sebacic acid=1/1 (mol ratio) and EG/NPG=3/7 (mol ratio) synthetic number-average molecular weight 2000 and, 1423 parts of ethyl acetate, 75 ℃ of reactions down.After 4 hours, utilize the FT-IR to confirm that the absorption peak of isocyanate group disappears after, finish reaction, obtain (having active hydrogen) urethane resin (following identical).With it as PU-A.
Synthesis example 2
In the reactor that has stirrer, thermometer, nitrogen-sealed pipe and water cooler, add HDI100 part and, by m-phthalic acid/nonane diacid=1/1 (mol ratio) and 3-methyl isophthalic acid, 5-pentanediol/1,2-PG=8/2 (mol ratio) synthetic number-average molecular weight be 1293 parts of 2000 polyester polyols (being designated hereinafter simply as polyvalent alcohol A) and, 1393 parts of ethyl acetate, 75 ℃ of reactions down.After 4 hours, utilize FT-IR to confirm that the absorption peak of isocyanate group disappears after, finish reaction, obtain urethane resin.With it as PU-B.
Synthesis example 3
In the reactor that has stirrer, thermometer, nitrogen-sealed pipe and water cooler, add HDI100 part and, 1035 parts of polyvalent alcohol A and, rosin polyvalent alcohol KE-601 (waste river chemical industry (strain) system, hydroxyl value 111.2KOH mg/g, acid number 1.8KOH mg/g, number-average molecular weight 1010) 129 parts and, 1264 parts of ethyl acetate, 75 ℃ of reactions down.After 4 hours, utilize FT-IR to confirm that the absorption peak of isocyanate group disappears after, finish reaction, obtain urethane resin.With it as PU-C.
Synthesis example 4
In the reactor that has stirrer, thermometer, nitrogen-sealed pipe and water cooler, adding IPDI100 part reaches, polyvalent alcohol A720 part reaches, rosin polyvalent alcohol KE-615-3 (waste river chemical industry (strain) system, hydroxyl value 58.5KOH mg/g, acid number 1.5KOH mg/g, number-average molecular weight 2000) 168 parts and, 988 parts of ethyl acetate, 75 ℃ of reactions down.After 4 hours, utilize FT-IR to confirm that the absorption peak of isocyanate group disappears after, finish reaction, obtain urethane resin.With it as PU-D.
Embodiment 1-5 and comparative example 1-4
The modulation of adhesive for lamination composition
With urethane resin, organic isocyanate compound, catalyzer, and the coupler that according to circumstances adds be modulated into the adhesive for lamination composition.As shown in table 1 respectively.
(table 1)
| Embodiment | Comparative example | ||||||||
| ??1 | ??2 | ??3 | ??4 | ??5 | ??1 | ??2 | ??3 | ??4 | |
| Urethane resin (part) PU-A PU-B PU-C PU-D | ? ?100 | ? ? ?100 | ? ? ? ?100 | ? ? ? ? ?100 | ? ? ? ?100 | ? ? ? ?100 | ? ? ? ?100 | ? ? ? ? ?100 | ? ? ? ?100 |
| Organic isocyanate compound (part) コ ロ ネ-ト HX コ ロ ネ-ト HL | ? ?7 | ? ? ?5 | ? ? ?5 | ? ? ?5 | ? ? ?5 | ? ? ?5 | ? ? ?5 | ? ? ?5 | |
| Catalyzer (part) two lauric acid tin octylate DBU phenates | ? ?0.2 | ? ? ?0.05 | ? ? ?0.05 | ? ? ?0.05 | ? ? ?0.05 | ? ? ?0.05 | |||
| Coupler (part) γ-glycidoxypropyltrime,hoxysilane | ? ?0.5 | ? ?0.5 | ? ?0.5 | ? ?0.5 | ? ?0.5 | ? ?0.5 | ? ?0.5 | ||
The manufacturing of laminated film
By condition as follows, the binder composition of embodiment 1-5 and comparative example 1-4 is coated on the 1st plastic film, after the drying, thereon with nip rolls fit the 2nd plastic film or tinsel, after applying above-mentioned binder composition and drying more thereon, thereon with nip rolls the 3rd plastic film of fitting, laminated film is made in ageing again.
The solid composition branch of binder composition: 25% (diluting) with ethyl acetate
The formation of laminated film: 25 μ NY/15 μ EVOH/50 μ CPP
12μPET/7μAl/70μCPP
The coated weight of binder composition: 3.5g/m
2(dry back)
Drying conditions: 80 ℃ * 15 seconds
Ageing condition: 25 ℃ * 24 hours
The evaluation of laminated film is by condition evaluating laminated film as follows.The result is shown in table 2-table 6.Peel adhesion strength: T type stripping test (JIS K 6854)
Draw speed: 300mm/min steams the processing of boiling: make after will being sealed by the laminated film that NY/EVOH/CPP forms
Pouch boiled under 95 ℃ 30 minutes after being full of water.Distillation is handled: make little after will being sealed by the laminated film that PET/Al/CPP forms
Bag, be full of behind the water 120 ℃ down distillation handled 30 minutes.
Table 2
| The binder composition of embodiment 1 | The binder composition of embodiment 2 | |||||||
| The formation of laminated film | ????NY/EVOH/ ??????CPP | ?????PET/Al/CPP | ???????NY/EVOH/CPP | ?????PET/Al/CPP | ||||
| Released part | ??NY/ ??EVO ??H | ?EV ?OH/ ?CPP | ??PET/ ??Al | ??Al/ ??CPP | ??NY/ ??EVOH | ??EVOH/ ??CPP | ??PET/ ??Al | ??Al/ ??CPP |
| After peel adhesion strength (gf/15mm) standard state is boiled and is handled back distillation processing | ? ? ??460 ??450 | ? ? ?660 ?630 | ? ? ??420 ??400 | ? ? ??650 ??590 | ? ? ??460 ??460 | ? ? ??690 ??560 | ? ? ??450 ? ??400 | ? ? ??720 ? ??600 |
| After outward appearance is boiled or is distilled and handles | Well | Well | ||||||
Table 3
| The binder composition of embodiment 3 | The binder composition of embodiment 4 | |||||||
| The formation of laminated film | ????NY/EVOH/ ???????CPP | ?????PET/Al/CPP | ???????NY/EVOH/CPP | ?????PET/Al/CPP | ||||
| Released part | ??NY/ ??EVO ??H | ?EVO ?H/ ?CPP | ?PET/ ?Al | ??Al/ ??CPP | ??NY/ ??EVOH | ??EVOH/ ??CPP | ??PET/ ??Al | ??Al/ ??CPP |
| After peel adhesion strength (gf/15mm) standard state is boiled and is handled back distillation processing | ? ? ??500 ??490 | ? ? ?780 ?600 | ? ? ??520 ? ??470 | ? ? ??800 ? ??680 | ? ? ??480 ??480 | ? ? ??740 ??600 | ? ? ??480 ? ??420 | ? ? ??770 ? ??620 |
| After outward appearance is boiled or is distilled and handles | Well | Well | ||||||
Table 4
| The binder composition of embodiment 5 | ||||
| The formation of laminated film | ????????????NY/EVOH/CPP | ????????PET/Al/CPP | ||
| Released part | ???NY/EVOH | ??EVOH/CPP | ??PET/Al | ??Al/CPP |
| After peel adhesion strength (gf/15mm) standard state is boiled and is handled back distillation processing | ? ? ????480 ????470 | ? ? ????700 ????580 | ? ? ????490 ? ????450 | ? ? ????720 ? ????620 |
| After outward appearance is boiled or is distilled and handles | Well | |||
Table 5
| The binder composition of comparative example 1 | The binder composition of comparative example 2 | |||||||
| The formation of laminated film | ?????NY/EVOH/CPP | ??????PET/Al/CPP | ??????NY/EVOH/CPP | ?????PET/Al/ ???????CPP | ||||
| Released part | ???NY/ ???EVOH | ??EVOH/ ??CPP | ??PET/ ??Al | ??Al/ ??CPP | ??NY/ ??EVOH | ??EVOH/ ??CPP | ??PET ??/Al | ??Al/ ??CPP |
| After peel adhesion strength (gf/15mm) standard state is boiled and is handled back distillation processing | ? ? ???260 ???120 | ? ? ??310 ??120 | ? ? ??250 ? ??110 | ? ? ??280 ? ??120 | ? ? ??300 ??170 | ? ? ??370 ??120 | ? ? ??270 ??120 | ? ? ??350 ??160 |
| After outward appearance is boiled or is distilled and handles | Delamination | Delamination | ||||||
Table 6
| The binder composition of comparative example 3 | The binder composition of comparative example 4 | |||||||
| The formation of laminated film | ??????NY/EVOH/CPP | ?????PET/Al/CPP | ????????NY/EVOH/ ??????????CPP | ??????PET/Al/ ????????CPP | ||||
| Released part | ??NY/ ??EVOH | ??EVOH/ ??CPP | ??PET/ ??Al | ??Al/ ??CPP | ??NY/ ??EVOH | ??EVOH/ ??CPP | ??PET/ ??Al | ??Al/ ??CPP |
| After peel adhesion strength (gf/15mm) standard state is boiled and is handled back distillation processing | ? ? ??240 ??120 | ? ? ??320 ??100 | ? ? ??250 ? ??110 | ? ? ??350 ? ??120 | ? ? ??300 ??120 | ? ? ??320 ??100 | ? ? ??250 ? ??100 | ? ? ??320 ? ??100 |
| After outward appearance is boiled or is distilled and handles | Delamination | Delamination | ||||||
Use laminated films such as plastic film that adhesive for lamination composition of the present invention makes and tinsel, have good adhesive strength at normal temperatures, compare, can make that digestion time shortens, the reduction of ageing temperature with existing known binder composition.In addition, even boiling unusual phenomenoies such as also finding no delamination after processing or distillation are handled, affirmation can keep practical high bond strength.
Therefore, utilize the present invention can increase substantially the productivity and the operation of laminated film, reduce cost and the shortening cycle.
Claims (4)
- One kind by (A) have can with the organic compound of the functional group of isocyanic ester radical reaction and (B) organic isocyanate compound and (C) the adhesive for lamination composition formed of catalyzer, it is characterized in that it can be the organic compound that is obtained by (a) polymeric polyisocyanate composition and (b) isocyanate group reactive ingredients reaction with the organic compound of the functional group of isocyanic ester radical reaction that above-mentioned (A) has.
- One kind by (A) have can with the organic compound of the functional group of isocyanic ester radical reaction and (B) organic isocyanate compound and (C) catalyzer and (D) the adhesive for lamination composition formed of coupler, it is characterized in that it can be the organic compound that is obtained by (a) polymeric polyisocyanate composition and (b) isocyanate group reactive ingredients reaction with the organic compound of the functional group of isocyanic ester radical reaction that above-mentioned (A) has.
- In the claim 1 or 2 record the adhesive for lamination composition, wherein isocyanate group reactive ingredients (b) contains rosin polyvalent alcohol (rosin polyol) (b1).
- 4. the manufacture method of a laminated film is characterized in that, the adhesive for lamination composition of record in the claim 1,2 or 3 is coated on the 1st film and drying after, the 2nd film of fitting thereon, ageing at normal temperatures then.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96121512A CN1184139A (en) | 1996-12-03 | 1996-12-03 | Binding agent composition for lamination and method for producing laminated film using the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96121512A CN1184139A (en) | 1996-12-03 | 1996-12-03 | Binding agent composition for lamination and method for producing laminated film using the same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1184139A true CN1184139A (en) | 1998-06-10 |
Family
ID=5126929
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN96121512A Pending CN1184139A (en) | 1996-12-03 | 1996-12-03 | Binding agent composition for lamination and method for producing laminated film using the same |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1184139A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009094905A1 (en) * | 2008-01-28 | 2009-08-06 | National Starch And Chemical Investment Holding Corporation | Adhesive and its application |
| CN109705340A (en) * | 2018-08-29 | 2019-05-03 | 旭川化学（苏州）有限公司 | A kind of polyamide modified polyester polyol and preparation method thereof, application method |
-
1996
- 1996-12-03 CN CN96121512A patent/CN1184139A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009094905A1 (en) * | 2008-01-28 | 2009-08-06 | National Starch And Chemical Investment Holding Corporation | Adhesive and its application |
| US20110003146A1 (en) * | 2008-01-28 | 2011-01-06 | Henkel Ag & Co. Kgaa | Adhesive and its application |
| CN109705340A (en) * | 2018-08-29 | 2019-05-03 | 旭川化学（苏州）有限公司 | A kind of polyamide modified polyester polyol and preparation method thereof, application method |
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