CN102786905A - Polyester adhesive and thin-film laminated body using the same - Google Patents
Polyester adhesive and thin-film laminated body using the same Download PDFInfo
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- CN102786905A CN102786905A CN2012103069423A CN201210306942A CN102786905A CN 102786905 A CN102786905 A CN 102786905A CN 2012103069423 A CN2012103069423 A CN 2012103069423A CN 201210306942 A CN201210306942 A CN 201210306942A CN 102786905 A CN102786905 A CN 102786905A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
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Abstract
The invention relates to polyester adhesive and a thin-film laminated body. The polyester adhesive comprises a polyester resin component, 50mol%-100mol% of ester bonds in the polymer main chain of the polyester resin are the ester bonds from aromatic carboxylic acids, 0mol%-50mol% of the ester bonds are the ester bonds from aliphatic carboxylic acids or alicyclic carboxylic acids, and the atomic group between the ester bonds in the polymer main chain comprises more than three carbon atoms, the number average molecular weight of the polyester resin is 5000-35000, and the fusion temperature is in the range of 50 DEG C-200 DEG C; the polyester adhesive also comprises an epoxy compound component with more than two functions and selectively comprises an isocyanate component. The polyester adhesive and the thin-film laminated body are provided with good hydrolysis resistance, and longer service lifetime and higher credibility for solar cell back-side protection films, semiconductor integrated circuit part, etc. having higher requirement for wet and heat resistance compared with present products.
Description
Technical field
What the present invention relates to is to possess a polyester binder of superior resistance to hydrolysis and this is used for the layered product of film that bonding coat constitutes, tinsel, metal sheet, mf, ceramic membrane etc.
Background technology
With polyethylene terephthalate, polybutylene terephthalate is that the vibrin of main raw material has superior mechanical characteristics, thermotolerance, electric insulating quality, anti-chemical agent property, security and forming process property etc.Because these advantages, they as fiber, film, molding resin in the whole world by mass production and a large amount of the use, its suitable application area is well-known.Vibrin is entertained the resistance to hydrolysis problem in itself, when being used under the wet heat condition of harshness as back protection film of solar cell etc. in recent years, just resistance to hydrolysis is proposed higher requirement.With regard to film,, generally all use the use that is bonded together of tackiness agent and other materials seldom by independent use.Polyester film is had a polyester binder of good adhesive property, in most cases all be used together with polyester film.Therefore, a polyester binder is required that too higher improvement is being arranged aspect the resistance to hydrolysis.
As everyone knows, acid or alkaline condition can promote the hydrolysis reaction of polyester.End carboxyl that exists in the polyester and the phosphate cpd that adds for the pyrolysis etc. that suppresses in the polymerization process also all are acidic substance.There is motion to claim to guarantee carboxyl-content and the phosphate cpd content (Te Kaiping (patent openly puts down) 8-3428 communique, spy open (patent is open) 2011-6659 communique) below prescribed value in the polyester material.In addition; Through buffer reagents such as interpolation inorganic phosphates; Thereby suppress the free of proton, and then the idea that suppresses hydrolysis also is suggested (spy open (patent is open) 2007-277548 communique, spy are opened (patent is open) 2008-7750 communique, the spy opens (patent is open) 2011-89090 communique).Idea through interpolation and carboxyl reaction and end capped epoxy compounds, carbodiimide compound, oxazoline compound also is suggested (the patent document spy opens (patent disclose clear with) 54-6051 communique, spy and opens (patent disclose clear with) 46-5389 communique, Te Kaiping (patent openly puts down) 8-113699 communique, Te Kaiping (patent openly puts down) 6-287442 communique) very early.The method that reduces the end carboxyl also is considered, and the polyester that utilizes solid state polymerization to obtain high molecular weight polyesters and reduction low-molecular-weight oligomer content also is used as the resistance to hydrolysis polyester and proposes (spy opens (patent is open) 2002-26354 communique, the spy opens (patent is open) 2002-100788 communique).The chemical structure of considering polyester itself is also with water-disintegrable relevant, and the ester group proportion in polyester more also is difficult to take place hydrolysis.Thereby propose by the 2-methyl isophthalic acid; 8-ethohexadiol and/or 1; 9-nonane alcohol (spy opens (patent disclose clear with) 63-182330 communique), 3-methylglutaric acid (Te Kaiping (patent openly puts down) 10-130377 communique), 3, the glycols (spy opens (patent is open) 2007-320218 communique) of 7-dimethyl--heptanediol (Te Kaiping (patent openly puts down) 11-236436 communique), dimer (fatty acid) yl or the generation of reductive dimerization lipid acid and the polyester that obtains.
As stated, all promoted the hydrolysis deterioration technology of improvement polyester in the every field of using vibrin.Just as above-mentioned back protection film of solar cell, can keep in the endurance test of doing more than 20 years for making performance, require in the environment of 85 ℃/relative humidity 85%, to keep more than 2000 hours.Because the hydrolysis deterioration of a polyester binder causes the layered product delamination and then has influence on the problem long-term existence of its weather resistance.Same, also there is above-mentioned common problem at electric insulating parts such as printed circuit board component, electrical condenser and flat cable, engine protection parts, stickup window with fields such as material of construction such as film, outdoor use laminate steels.
Summary of the invention
Technical problem to be solved by this invention is on the basis of considering above-mentioned problem, provides to can be used for above-mentioned industrial circle and a polyester binder that in long-time damp and hot deterioration environment, can be competent at and the film like layered product that uses this tackiness agent.
For solving above technical problem, a kind of technical scheme that the present invention takes is:
A kind of a polyester binder; It comprises the vibrin component; 50mol%～100mol% in the ester bond in the main polymer chain of vibrin is that ester bond, the 0mol%～50mol% in the ester bond from aromatic carboxylic acid is the ester bond from aliphatic carboxylic acid or alicyclic carboxylic acid; And ester bond in the main polymer chain and the atomic group between the ester bond contain 3 above carbon atoms, but the number-average molecular weight of vibrin is that 5000～35000 fusion temperatures are between 50 ℃～200 ℃; A polyester binder also comprises the epoxy compounds component that difunctionality is above and optionally includes the isocyanic ester component; The epoxy compounds component is 0.1/99.9～30/70 with the ratio of the weight of vibrin; The isocyanic ester component is the masked isocyanate compound of the above isocyanic ester of difunctionality and/or said isocyanic ester and blocker reaction generation, and the isocyanic ester component is 0/100～30/70 with the ratio of the weight of vibrin.
According to the present invention, the number-average molecular weight of described vibrin is preferably 8000～25000.The acid number of vibrin is preferably below the 3mgKOH/g resin.
Preferably, said a polyester binder also comprises and is used for the said epoxy compounds catalyst for reaction of catalysis.
Preferably, the dissociation temperature of said masked isocyanate compound is 90 ℃～200 ℃.
The another technical scheme that the present invention takes is: a kind of film like layered product, comprise thin film layer, and this film like layered product also comprises the bonding coat that one deck at least is made up of the above-mentioned a polyester binder of the present invention.
According to further embodiment of the present invention: said thin film layer can be by one or more constitute in polymeric film, tinsel, mf, metal sheet and the ceramic membrane.Described polymeric film comprises polyester film, polycarbonate film, fluorine resin film, vinyl resin film, polyolefin film and alkene and contains the monomeric copolymer resins film of oxygen etc.; Tinsel comprises Copper Foil, aluminium foil etc.; Metal sheet comprises copper coin, aluminium sheet, steel plate etc.; Ceramic membrane comprises silicon oxide, aluminum oxide film etc.
The invention still further relates to above-mentioned film like layered product and be used for the purposes of solar module back protection film.
In addition, the invention still further relates to the purposes that above-mentioned film like layered product is used for SIC material, flat cable material, bus rod row's material and lamination joint steel plate materials.
Because the enforcement of above technical scheme, the present invention compared with prior art has following advantage:
A polyester binder of the present invention and contain the film like layered product of the binder layer that this tackiness agent forms; It is water-disintegrable to possess good resistance, all higher than up to now product aspect work-ing life of damp and hot life requirement higher solar energy cell backside protective membrane, SIC parts, electric insulating part, electric wiring parts, lamination joint steel sheet component, confidence level.
Embodiment
Of the present invention first is characterized as: it is water-disintegrable that the structure of vibrin self is given its excellent anti.That is to say; Used in the present invention is to form that the 50mol～100mol% in all ester bonds is the ester bond from aromatic carboxylic acid in the main polymer chain of polyester; Be present in the polyester that ester bond and the atomic group between the ester bond in the main polymer chain contain 3 above carbon numbers; Its number-average molecular weight is 5000～35000, but is the polyester that between 50～200 ℃, has fusion temperature.
Compare with the aliphatic carboxylic acid composition, the coherency between the molecule of aromatic carboxylic acid composition is higher, is difficult to decomposed by water intrusion.Meanwhile also given its anti-chemical agent property, be difficult to be dissolved in adhesive field solvent commonly used but then, so use range has been restricted.In addition, the aromatic carboxylic acid composition can improve the second-order transition temperature and the fusing point of formed vibrin, gives the resin rigidity.There are conflicting situation in the desired characteristic of tackiness agent and above-mentioned these characteristics of being used for film, thin plate etc.Therefore, gratifying is to form that 50mol～100mol% in all ester bonds is the ester bond from aromatic carboxylic acid in the main polymer chain of vibrin of the present invention.The ester bond and the atomic group between the ester bond that are present in the main polymer chain contain 3 above carbon numbers.This is based on when having found 3 of contained carbon number less thaies of the atomic group that exists between the ester bond, and the fact of hydrolysis takes place polyester based easily.
The number-average molecular weight of the used polyester of the present invention is 5000～35000, and wherein more gratifying number-average molecular weight is 8000～25000 polyester.Under 5000 situation, by the meeting of the binder layer behind polyfunctionality isocyanic ester and multi-functional epoxy compound crosslink hardening, and the clinging power variation; In case surpass 35000, soltion viscosity and melt viscosity strengthen, and are difficult to implement bonding processing, will not recommend.
But polyester of the present invention is the polyester of fusion temperature between 50～200 ℃.Polyester of the present invention is adhered on the base material after certain is fused into liquid state more than the temperature.This just means finds that its adhesive temperature is in 50 ℃～200 ℃ scope.In other words, just can soak and treat adhesive face, satisfy adherent initial stage process, also promptly be illustrated under this temperature and find tackiness through under this temperature, increasing suitable pressure.If this temperature is less than 50 ℃, be difficult to implementation and operation from the processing procedure that begins after the polymerization till the adjustment of tackiness agent, the viscosity that is applied in addition behind film and the paper tinsel also will become problem.Surpass under 200 ℃ of states when bonding, plastics film may deform, and will not recommend.
The acid number of polyester of the present invention is preferably below the 3mgKOH/g resin.Because acid number is too high, in resin preservation process and the stage of blockading before the carboxyl with linking agent can promote hydrolysis.
If the form with acid illustrates the aromatic carboxylic acid that constitutes polyester of the present invention, the acid that can give an example has terephthalic acid, m-phthalic acid, phthalic acid, 4,4 '-biphenyl dicarboxylic acid, 1,5-naphthalic acid, 2, aromatic dicarboxylic acids such as 6-naphthalic acid.If the form with acid illustrates aliphatic dicarboxylic acid, the alicyclic dicarboxylic acid who constitutes polyester of the present invention and adopt; The acid that can give an example has hexanodioic acid, pimelic acid, suberic acid, nonane diacid, sebacic acid, dodecyl dicarboxylicacid, dimeracid and hydrogen additive and 1, and carbon numbers such as 4-cyclohexane diacid are at aliphaticdicarboxylic acid more than 5 etc.In addition, the polyester tackiness also can be used the above carboxylic acids of 3 officials ability such as trimellitic acid, PMA, UVNUL MS-40 tetracarboxylic acid, diphenylsulfone acid in range of indication.
If illustrate the polyvalent alcohol that constitutes polyester of the present invention, that can give an example has 1, ammediol, 1,2-Ucar 35,2-methyl isophthalic acid; Ammediol, 2,1,4-butyleneglycol, 1; 5-pentanediol, 1,6-pinakon, 1,7-heptanediol, 1,8-ethohexadiol, 1; 9-nonanediol, decamethylene-glycol, 1, aliphatic diols such as 12-dodecyl glycol, 1,4 cyclohexane dimethanol; The ethylene oxide adduct of terepthaloyl moietie, triglycol, dihydroxyphenyl propane; Polyether glycol such as polyoxyethylene glycol, polytetramethylene glycol class.In addition, the polyester tackiness also can be used the above alcohols of 3 officials ability such as USP Kosher, tetramethylolmethane in range of indication.
If the form with cyclic lactone is illustrated as oxygen carbonic acid and the cyclic ester monomer thereof that constitutes polyester of the present invention and adopt, the gamma-butyrolactone of can giving an example out, 6-caprolactone etc.
According to the present invention, the polyester compound method and the equipment of polyester routine capable of using prepare.Usually; In transesterification reaction, use the polycondensation catalysts such as catalyst for ester exchange reaction such as zinc acetate, manganous acetate, lime acetate, tetra-n-butyl titanate and germanium oxide, weisspiessglanz, titanium potassium oxalate(T.P.O.), tetra-n-butyl titanate of the 0.005mol%～0.05mol% of total acid composition.In esterification process, use above-mentioned polycondensation catalyst.In addition, in polycondensation, also can add P contained compounds such as SULPHOSUCCINIC ACID ESTER and phosphite as thermo-stabilizer.As the addition of the phosphorus compound of stablizer, its phosphorus element content is preferably 5～200ppm.
A polyester binder according to the present invention is that staple is the tackiness agent of vibrin, and this polyester also can be the mixture and the block type polyester of polyester more than 2 kinds.In addition, also can be in advance through the hydroxyl of isocyanate compound and epoxy compounds and polyester end and the polyester of the modification that carboxyl reaction obtains.
Second characteristic of the present invention is: with above-mentioned polyester as the A component; With isocyanate compound more than the difunctionality and/or masked isocyanate is the B component; As the C component, and A/B (weight ratio) is 100/0～70/30, A/C (weight ratio) 99.9/0.1～70/30 with the epoxy compounds more than the difunctionality.Isocyanate compound that difunctionality is above and/or masked isocyanate B component, the above epoxy compounds C component of difunctionality; Except the linking agent as polyester of the present invention plays a role; All have the new carboxyl that sealing produces because of hydrolysis, and when suppressing its katalysis, have and repair and make between the polyester chain that is cut off bonded function once more.In addition, isocyanate compound and epoxy compounds also can react between isocyanate compound and the epoxy compounds also having certain effect aspect the binding property that improves metal and pottery.For these reasons, compare, global design is become to contain the B component and the C component of superfluous functional group reactions amount more than 2 times with end pet reaction amount.According to the viewpoint of above resistance to hydrolysis with to the requirement of tackiness agent, A/B (weight ratio) is set at 100/0～70/30.That is to say; Not isocyanate compound and/or masked isocyanate; Mainly be when utilizing scorification coating, system film tackiness agent of the present invention; Isocyanate compound (for example also can use encapsulated type) is difficult to the melt-processed condition of independent control polyester and the condition of reacting with isocyanate compound, and less than 70/30 o'clock, the binding property of polyester itself will be destroyed.
Equally, according to the viewpoint of above-mentioned resistance to hydrolysis with to the requirement of tackiness agent, A/C (weight ratio) is set at 99.9/0.1～70/30.In other words, 99.9/0.1 just can't obtain the epoxy group(ing) of q.s and the carboxyl of polyester generation reacts in case this weight ratio surpasses; And weight ratio can be destroyed the binding property of polyester itself again less than under 70/30 the situation.Also can use other compounds (for example, carbodiimide compound 、 oxazoline compound) that can react with hydroxyl and carboxyl simultaneously as isocyanate compound, epoxy compounds.
If illustrate the above isocyanate compound of difunctionality used in the present invention; What can give an example aspect aliphatic isocyanates or the alicyclic isocyanate hexamethylene diisocyanate, isophorone diisocyanate, an xylylene isocyanic ester, 4,4 arranged "-3 functional isocyanate such as affixture class that dicyclohexyl methane diisocyanate and vulcabond thereof derive, biuret class, isocyanuric acid ester class.About aromatic isocyanate; That can give an example has 2; 4-tolylene diisocyanate, 2; 6-tolylene diisocyanate, 4,4 '-'-diphenylmethane diisocyanate, 1,3 functional isocyanate such as the affixture class that 5-naphthalene diisocyanate and vulcabond thereof derive, biuret class, isocyanuric acid ester class.
About a polyester binder of the present invention, can select suitable isocyanic ester according to end-use, have in thermotolerance aspect the purposes of particular requirement tackiness agent, generally adopt isocyanic ester that 3 officials can be above as linking agent.Aspect the purposes that thermotolerance and photostabilization is all had particular requirement, preferably use aliphatic isocyanates that 3 officials can be above as linking agent.
Used masked isocyanate is exactly the resultant that reacts of isocyanic ester and blocker as stated among the present invention; That with regard to blocker, can give an example has formyl amidoxime, hydroxyl acetamidine, ethamine oxime, an acetoxime; Lactams such as phenols, hexanolactam such as oximes such as methyl ethyl ketoxime, methyl-malonate, ethyl malonate, methyl acetoacetate, methyl ethyl diketone isoreactivity diformazan base class and phenol, cresylol; Alcohols such as 2-Ethylhexyl Alcohol, 2, amines such as 3-dimethyl pyrazole.Wherein gratifying is the blocker of oximes, lactams, amine.
The dissociation temperature of masked isocyanate is recommended between 90 ℃～200 ℃, wherein is preferably 90～150 ℃.Be lower than under 90 ℃ the state, might in the solvent seasoning process of tackiness agent, dissociate and binding property is damaged, and when surpassing 200 ℃, have laminated plastics film that rotten worry takes place again.
Among the present invention can and with more than 2 kinds, isocyanate compound and/or masked isocyanate more than the difunctionality.Under the situation that isocyanic ester and masked isocyanate use simultaneously, the amount of used masked isocyanate is 20%～100% of both gross weights, and this is the present invention's one big gratifying embodiment.Can take into account the curing characteristics and the permanent stability of tackiness agent.
If illustrate the above epoxy compounds of difunctionality used among the present invention, specifiable have 1, the glycidyl ether of aliphatic polyols such as 6-pinakon, NSC 6366, polyoxyethylene glycol, sorbyl alcohol, USP Kosher, TriMethylolPropane(TMP); Cyclohexanedimethanol, 2, the glycidyl ether of 2-pair-alicyclic polyols such as (p-hydroxy-cyclohexyl) propane; Terephthalic acid, m-phthalic acid, trimellitic acid, 1, aromatic series such as 6-cyclohexane cyclohexanedimethanodibasic, sebacic acid, hexanodioic acid, alicyclic, aliphatics polyvalent carboxylic acid's glycidyl ester; Resorcinol, two-(p-hydroxy phenyl) methane, 2, the glycidyl ether of 2-pair-(p-hydroxy phenyl) propane, three-polyphenol such as (p-hydroxy phenyl) methane; The epoxies that diolefine such as divinyl, α-Pai Xi, cyclooctadiene derive; N.N-diglycidylaniline, N, the glycidyl derivatives of amines such as N-diglycidylether aniline; Glyceryl ester isocyanuric acid ester, ortho-cresol type epoxy resin, phenol phenol aldehyde type epoxy resin etc.In addition, these epoxy compoundss also can be the epoxy compoundss that produces with phosphoric acid or derivatives thereof reaction back.Above-mentioned epoxy compounds can use separately, perhaps also uses more than 2 kinds.
For the carboxyl of polyester hydrolysis generation of can blockading; And repair cut polyester chain; It is connect again, be engaged in the catalyzer of hydroxyl and carboxyl and NCO and epoxy reaction in the tackiness agent in advance, this is another big gratifying embodiment of the present invention.With regard to the catalysts of NCO; That can give an example has dibutyl-two (2-ethylhexanoate) tin; Tin compounds, 1 such as dibutyl tin dilaurate, dibutylester tin-oxide, dioctyltin oxide; Tertiary amine classes such as 8-diazabicylo [5,4,0] 11 carbon-7-alkene (being commonly called as DBU), triethylamine, tri-n-butylamine.The combined amount of these catalyzer, gratifying scope are the 0.01wt%～2wt% that accounts for isocyanate compound and/or masked isocyanate B component and polyester A component gross weight.With regard to the catalysts of epoxy group(ing), that can give an example has quarternary ammonium salts such as phosphides such as imdazole derivatives such as DMIZ 1,2 dimethylimidazole, 1 benzyl 2 methyl imidazole, triphenylphosphine, triphenyl phosphite, Tetrabutyl amonium bromide.The combined amount of these catalysts, gratifying scope are the 0.01wt%～2wt% that accounts for epoxy compounds C component and polyester A component gross weight.
In a polyester binder of the present invention, can suitably add inhibitors such as photostabilizers such as UV light absorbers such as UVNUL MS-40, benzotriazole, triazine, hindered amine, hindered phenol system, phosphorus system, sulphur system, vitamin E, fire retardant, viscosity adjustment agent, the toughener of filming, organic cpds, mineral compound, MOX etc. as tinting pigment etc.
Be 1 μ m～50 μ m under the thickness of a polyester binder of the present invention, dryness, be generally 2 μ m～15 μ m.Can use the excellent coating machine of silk, coating equipments such as intaglio plate roll-type coating machine, roll-coater, extrusion-type (Die) coating machine, comma scraper formula coating machine, with dissolving gained coating fluid in the solvent perhaps/and water in disperse the gained dispersion liquid to be applied on the base material.In addition, also available melt extrusion mould is implemented extrusion coating.
With regard to employed solvent; That can give an example has aromatic hydrocarbons, N such as ethers, toluene, YLENE such as ester classes such as ketones such as acetone, methylethylketone, pimelinketone, ETHYLE ACETATE, N-BUTYL ACETATE, THF 、 diox; Aprotic polar solvents such as dinethylformamide, DMAC N,N, N-Methyl pyrrolidone.These solvents can use separately, or mix more than 2 kinds and use.
As stated, any one side of laminate substrate perhaps/surface on two sides on after the application, dry tackiness agent of the present invention, can be at 50 ℃～200 ℃, 1kg/cm
2～30kg/cm
2Utilize thermocompressor or warming mill to bond them together under the state.Then, can under 20 ℃～100 ℃ temperature, carry out 1 hour curing reaction to 1 week.
As laminate substrate of the present invention, that can give an example has polyester such as polyethylene terephthalate, polybutylene terephthalate; Gather valeramide, gather decyl amide, polymethylene acid amides etc. is polyamide-based; Polyolefins such as Vilaterm, Vestolen PP 7052; Acrylic acid or the like such as polymethylmethacrylate, polyacrylonitrile; Polyolefins such as Vinyl Acetate Copolymer, polyvinyl butyral acetal; Gather single vinyl fluoride, pvdf, gather (ethylene-tetrafluoroethylene), gather (hexafluoropropylene (HFP)/tetrafluoroethylene (TFE)), gather (trifluorochloroethylene), tetrafluoroethylene-hydroxy butyl vinyl ether multipolymer, trifluorochloroethylene-hydroxy butyl vinyl ether multipolymer, vinylidene-fluorine type resins such as hydroxy butyl vinyl ether multipolymer; Polymethyl siloxane, phenyl silicone, gather silica types such as (methyl-phenyl siloxanes); Also have polyimide, polyethers ketone, polysulfones, polycarbonate-based, polyoxymethylene class in addition, gather homopolymer such as (2,5-dimethyl benzene ether) class grade, multipolymer, polymer blend, polymer alloy.The film that constitutes by cross-linking agent, copper, aluminium, steel, silicon oxide, aluminum oxide, glass etc.The film that constitutes by glass, paper tinsel, plate etc.At the surface laminated binder layer of above-mentioned base material, the also direct constituent material layer of lamination not.Can adopt solution coat, melt coated, vapor deposition, sputter, technologies such as ion plating, chemical vapor deposition (CVD), wet method plating directly form material layer.
About the thickness of these base materials, can illustrationally be generally film, paper tinsel, the coating layer of film, the 1 μ m～500 μ m of 5nm～500nm, the plate of 0.5mm～5mm.
These films, paper tinsel, film can use common Industrial products.In addition, also can film, film, paper tinsel, plate more than 2 kinds be carried out compound, lamination.For example, the laminated film of the laminated film of resin, film and mf and metal oxide film, multiple metal laminate film etc. more than 2 kinds.Can implement chemistry, physics, machinery or electric processing to the surface of film, coating layer, film, paper tinsel, plate etc.For example, the corona treatment of film, plasma treatment, chemical milling; The oxide treatment of tinsel and plate, roughening treatment, electroplating processes, Alloying Treatment etc.
If illustrate the structure of the film like layered product that uses a polyester binder of the present invention and constitute; The layered product that can give an example is following: constitute behind the single sided lamination binder layer of the present invention of tinsels such as the film of polyester etc. and Copper Foil two layer laminate, just become three layer laminate after laminating layer film and the tinsel again on this binder layer, the laminating layer binder layer just becomes four layer laminate again on this layered product, the rest may be inferred can constitute five layers, six layers ... N layer laminate (N is generally 20 positive integers with interior (comprising 20)).
The following specific examples of can giving an example, two layer laminate that constitute by pet film/binder layer, three layer laminate that constitute by pet film/binder layer/release layer, three layer laminate that constitute by pet film/binder layer/electrolytic copper foil, four layer laminate that constitute by polyvinylidene fluoride film/binder layer/pet film/binder layer, five layer laminate that constitute by polyvinylidene fluoride film/binder layer/pet film/binder layer/polyvinylidene fluoride film, by eight layer laminate that polyvinylidene fluoride film/binder layer/silica-alumina composite oxide film lamination pet film/binder layer/pet film/binder layer/polyvinylidene fluoride film constitutes etc.
Below through concrete embodiment the present invention is described further, but the invention is not restricted to following examples.
In following examples and the Comparative Examples, starting material and shortenings thereof that related starting material and allotment tackiness agent are used are following:
The starting material that the production polyester is used are following: TPA: terephthalic acid; IPA: m-phthalic acid; OPA: phthalic acid; AA: hexanodioic acid; SA: sebacic acid; EG: terepthaloyl moietie; The 2-MPD:2-methyl isophthalic acid, ammediol; NPG: NSC 6366; 1,4-BD:1,4-butyleneglycol; 1,5-PD:1,5-pentane diol; 1,6-HD:1,6-hexane diol; 1,4-CHD:1,4-cyclohexanedimethanol.
The starting material that the allotment tackiness agent is used are following: how anti-moral TPA-100: hexamethylene diisocyanate class (isocyanuric acid ester class) 3 functional isocyanate that chemical company of Asahi Chemical Industry produces; EPIKOTE 827: the epoxy resin (dihydroxyphenyl propane class) that japan epoxy resin company produces; CARBODILITE V-05: day is spun the polycarbodiimide resin that company produces clearly.
TP and measuring method that following examples and Comparative Examples adopted are following:
1. polyester is synthetic
In the stainless steel cauldron that stirrer, rectifying tower, cooling tube, nitrogen input tube, TM, water outlet receptor are housed; Add dicarboxylic acid component, 2-methyl isophthalic acids such as terephthalic acid, m-phthalic acid; Ammediol, 1, is the 0.04mol% of all sour compositions as the germanium dioxide add-on of polycondensation catalyst at glycol component such as 6-hexane diol.Logical nitrogen makes the temperature of rectifier remain on below 100 ℃, and esterification is carried out in heating under 160 ℃～240 ℃ temperature simultaneously.In this reaction mixture, add triethyl phosphate (P is 100PPm), stir after 5 minutes, when slowly heating up, reduce pressure, make it reach 265 ℃, 650Pa at 30 minutes as stablizer.After carrying out 30 minutes reaction under this same terms, reduce pressure when slowly heating up once more, carry out polycondensation being decompressed under 265 ℃, state below the 40Pa.Check the melt viscosity of reaction system during this, input nitrogen and finish polycondensation when meeting the requirements of viscosity.
2. the formation of polyester
0.25g resin dissolves in the 5ml deuterochloroform, with the high resolution nuclear magnetic resonance instrument of 400MHz, is measured down at 60 ℃.Confirm its composition according to the spectrum elucidation that records.As the case may be, also can select to adopt alkalescence decomposition-vapor-phase chromatography (GC) simultaneously.
3. the number-average molecular weight of polyester
To adopt gel permeation chromatography (GPC), column temperature be 35 ℃, use THF as elutriant, and flow is to measure under 1ml/ minute the state.With PS as the high molecular molecular weight of conversion canonical representation.
4. but fusion temperature
Clamp the square resin sheet of 1mm with deckglass; It is inserted on the hot-plate of the fusing point test instrument that TM (perhaps temperature indicator), hot-plate, reading lens, Polarizer are housed; Under 2 ℃/minute state, heat up; With tweezers pressing cover slide lightly, confirm resin flow with range estimation, and read temperature.For the crystal type resin, under polarized light, observe the spherocrystal situation, but confirm fusion temperature through the disappearance at bright position.
5. the modulation of tackiness agent
The vibrin of preparation is dissolved in the ETHYLE ACETATE; Add 3 functional isocyanate (chemical company of Asahi Chemical Industry makes how anti-moral TPA-100), bisphenol A type epoxy resin (japan epoxy resin manufactured EPIKOTE 827), carbodiimide compound (day is spun manufactured CARBODILITE V-05 clearly) etc., at room temperature stirring and dissolving.With solid weight than the composition of representing tackiness agent.
6. the formation of layered product
Polyvinylidene fluoride film to 25 μ m is implemented corona treatment, coating and the dry ethyl acetate solution that is dissolved with tackiness agent, and forming thickness is the binder layer of 10 μ m.Then, 1 polyvinylidene fluoride film through 25 μ m of corona treatment that on this, superposes again is at 80 ℃, 10kg/cm
2State under carry out lamination.The last solidification treatment of under 80 ℃ temperature, laminated film being implemented 50 hours.
7. interlayer adhesion
Adopting the sample of 10mm width, is under the state of 10cm/min in room temperature (20 ℃, 65%RH) and tension force speed, carries out 180 degree and peels off, and the result representes with N/cm.
Embodiment 1
The result is as follows:
The composition of polyester: TPA/IPA//2-MPD/1,6-HD=41/59//11/89 (mol ratio);
The number-average molecular weight of polyester: 16000;
Binding property (50 ℃～200 ℃): can;
The composition of tackiness agent: polyester/how anti-moral TPA100/EPIKOTE 827/CARBODILITE V-05=100/10/10/1 (solid weight ratio);
The interlayer adhesion at initial stage: 6.8N/cm;
Interlayer adhesion after handling 1000 hours under the state of 85 ℃/85%RH: 6.5N/cm;
Interlayer adhesion after handling 3000 hours under the state of 85 ℃/85%RH: 5.6N/cm.
Embodiment 2
The result is as follows:
The composition of polyester: IPA/OPA/SA//NPG/1,5-PD/1,6-HD=47/26/27//70/12/18 (mol ratio);
The number-average molecular weight of polyester: 18000;
Binding property (50 ℃～200 ℃): can;
The composition of tackiness agent: polyester/how anti-moral TPA100/EPIKOTE 827=100/10/6 (solid weight ratio);
The interlayer adhesion at initial stage: 7.1N/cm;
Interlayer adhesion after handling 1000 hours under the state of 85 ℃/85%RH: 7.0N/cm;
Interlayer adhesion after handling 3000 hours under the state of 85 ℃/85%RH: 6.4N/cm.
Embodiment 3
The result is as follows:
The composition of polyester: IPA/OPA/SA//NPG/1,4-CHD=40/20/40//80/20 (mol ratio);
The number-average molecular weight of polyester: 16000;
Binding property (50 ℃～200 ℃): can;
The composition of tackiness agent: polyester/how anti-moral TPA100/EPIKOTE 827=100/10/6 (solid weight ratio);
The interlayer adhesion at initial stage: 5.7N/cm;
Interlayer adhesion after handling 1000 hours under the state of 85 ℃/85%RH: 5.4N/cm;
Interlayer adhesion after handling 3000 hours under the state of 85 ℃/85%RH: 4.1N/cm.
Embodiment 4
The result is as follows:
The composition of polyester: IPA/OPA//2-MPD/1,6-HD=71/29//10/90 (mol ratio);
The number-average molecular weight of polyester: 17000;
Binding property (50 ℃～200 ℃): can;
The composition of tackiness agent: polyester/how anti-moral TPA100/EPIKOTE 827=100/10/6 (solid weight ratio);
The interlayer adhesion at initial stage: 7.0N/cm;
Interlayer adhesion after handling 1000 hours under the state of 85 ℃/85%RH: 7.1N/cm;
Interlayer adhesion after handling 3000 hours under the state of 85 ℃/85%RH: 4.9N/cm;
Comparative Examples 1
The result is as follows:
The composition of polyester: TPA/IPA/AA//EG/NPG=30/30/40//60/40 (mol ratio);
The number-average molecular weight of polyester: 19000;
Binding property (50 ℃～200 ℃): can;
The composition of tackiness agent: polyester/how anti-moral TPA100/EPIKOTE 827=100/10/10 (solid weight ratio);
The interlayer adhesion at initial stage: 8.4N/cm;
Interlayer adhesion after handling 1000 hours under the state of 85 ℃/85%RH: 3.9N/cm;
Interlayer adhesion after handling 3000 hours under the state of 85 ℃/85%RH: 1.5N/cm.
Comparative Examples 2
The result is as follows:
The composition of polyester: TPA/IPA//2-MPD/1,6-HD=39/61//10/90 (mol ratio);
The number-average molecular weight of polyester: 16000;
Binding property (50 ℃～200 ℃): can;
The composition of tackiness agent: polyester/how anti-moral TPA100/CARBODILITE V-05=100/10/2 (solid weight ratio);
The interlayer adhesion at initial stage: 6.3N/cm;
Interlayer adhesion after handling 1000 hours under the state of 85 ℃/85%RH: 3.4N/cm;
Interlayer adhesion after handling 3000 hours under the state of 85 ℃/85%RH: 0N/cm.
To sum up; A polyester binder of the present invention and the film like layered product that contains the bonding coat that tackiness agent thus constitutes; Possess the superior resistance to hydrolysis that under 85 ℃/85%RH state, can stand more than 3000 hours, can be used for to resistance to hydrolysis have particular requirement electric insulating parts such as printed circuit board components such as back protection film of solar cell, SIC and mulch film, electrical condenser and flat cable, engine protection parts, paste window with fields such as material of construction such as film, outdoor use laminate steels
More than the present invention has been done detailed description; Its purpose is to let the personage that is familiar with this art can understand content of the present invention and implements; Can not limit protection scope of the present invention with this; All equivalences of doing according to spirit of the present invention change or modify, and all should be encompassed in protection scope of the present invention.
Claims (10)
1. a polyester binder; It comprises the vibrin component; It is characterized in that: the 50mol%～100mol% in the ester bond in the main polymer chain of said vibrin for from the ester bond of aromatic carboxylic acid, 0mol%～50mol% in the ester bond for from the ester bond of aliphatic carboxylic acid or alicyclic carboxylic acid; And ester bond in the main polymer chain and the atomic group between the ester bond contain 3 above carbon atoms, but the number-average molecular weight of described vibrin is that 5000～35000 fusion temperatures are between 50 ℃～200 ℃; Described a polyester binder also comprises the epoxy compounds component that difunctionality is above and optionally includes the isocyanic ester component; Said epoxy compounds component is 0.1/99.9～30/70 with the ratio of the weight of vibrin; Said isocyanic ester component is the masked isocyanate compound of the above isocyanic ester of difunctionality and/or said isocyanic ester and blocker reaction generation, and the isocyanic ester component is 0/100～30/70 with the ratio of the weight of vibrin.
2. a polyester binder according to claim 1 is characterized in that: the number-average molecular weight of described vibrin is 8000～25000.
3. a polyester binder according to claim 1 is characterized in that: the acid number of said vibrin is below the 3mgKOH/g resin.
4. a polyester binder according to claim 1 is characterized in that: said a polyester binder also comprises and is used for the said epoxy compounds catalyst for reaction of catalysis.
5. a polyester binder according to claim 1 is characterized in that: the dissociation temperature of said masked isocyanate compound is 90 ℃～200 ℃.
6. a film like layered product comprises thin film layer, it is characterized in that: this film like layered product also comprises the bonding coat that one deck at least is made up of the described a polyester binder of each claim in the claim 1 to 5.
7. film like layered product according to claim 6 is characterized in that: said thin film layer is by one or more constitute in polymeric film, tinsel, mf, metal sheet and the ceramic membrane.
8. film like layered product according to claim 7 is characterized in that: described polymeric film comprises polyester film, polycarbonate film, fluorine resin film, vinyl resin film, polyolefin film and alkene and contains the monomeric copolymer resins film of oxygen; Described tinsel comprises Copper Foil, aluminium foil; Described metal sheet comprises copper coin, aluminium sheet, steel plate; Described ceramic membrane comprises silicon oxide, aluminum oxide film.
9. the described film like layered product of each claim is used for the purposes of solar module back protection film in the claim 6～8.
10. the described film like layered product of each claim is used for the purposes of SIC material, flat cable material, bus rod row's material and lamination joint steel plate materials in the claim 6～8.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
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| JP2011-179374 | 2011-08-19 | ||
| JP2011179374A JP2013039784A (en) | 2011-08-19 | 2011-08-19 | Polyester type adhesive and sheet-like laminate using the same |
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| CN102786905A true CN102786905A (en) | 2012-11-21 |
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| CN2012103069423A Pending CN102786905A (en) | 2011-08-19 | 2012-08-16 | Polyester adhesive and thin-film laminated body using the same |
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| CN (1) | CN102786905A (en) |
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| CN103897646A (en) * | 2012-12-28 | 2014-07-02 | 上海轻工业研究所有限公司 | Hydrolysis resisting polyester hot melt adhesive and preparation method thereof |
| CN107556957A (en) * | 2017-10-04 | 2018-01-09 | 镇江市星耀智能装备有限公司 | A kind of coated metallic plate |
| CN107722906A (en) * | 2017-09-29 | 2018-02-23 | 镇江市星耀智能装备有限公司 | A kind of bonded adhesives for coated metallic plate |
| WO2018176300A1 (en) * | 2017-03-30 | 2018-10-04 | Dow Global Technologies Llc | A novel mdi-based prepolymer binder for moisture curing binder application |
| CN110114433A (en) * | 2016-12-28 | 2019-08-09 | 三菱化学株式会社 | Polyester adhesive composition, Polyester adhesive, bonding sheet and the optical component with adhesive phase |
| CN110268030A (en) * | 2017-03-28 | 2019-09-20 | 东洋纺株式会社 | Polyester adhesive composition containing carboxylic acid group |
| CN110527470A (en) * | 2019-08-29 | 2019-12-03 | 苏州瀚海新材料有限公司 | A kind of Adhesive composition for FFC |
| CN110791247A (en) * | 2019-11-28 | 2020-02-14 | 沈阳化工研究院有限公司 | Solar cell backboard adhesive resin and preparation method thereof |
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| WO2020045439A1 (en) * | 2018-08-27 | 2020-03-05 | 国立大学法人名古屋工業大学 | Soft crosslinked polyester resin/film exhibiting self-adhesive property, re-formability, and flaw-repairing property, and production method therefor |
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| CN101805578A (en) * | 2010-03-19 | 2010-08-18 | 苏州赛伍应用技术有限公司 | Polyester resin adhesive and use thereof in preparation of back protection film of solar cell |
| US20110152394A1 (en) * | 2009-12-21 | 2011-06-23 | Ah Ram Pyun | Adhesive composition for stealth dicing of semiconductor, adhesive film, and semiconductor device including the adhesive film |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US20110152394A1 (en) * | 2009-12-21 | 2011-06-23 | Ah Ram Pyun | Adhesive composition for stealth dicing of semiconductor, adhesive film, and semiconductor device including the adhesive film |
| CN101805578A (en) * | 2010-03-19 | 2010-08-18 | 苏州赛伍应用技术有限公司 | Polyester resin adhesive and use thereof in preparation of back protection film of solar cell |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103897646A (en) * | 2012-12-28 | 2014-07-02 | 上海轻工业研究所有限公司 | Hydrolysis resisting polyester hot melt adhesive and preparation method thereof |
| CN110114433A (en) * | 2016-12-28 | 2019-08-09 | 三菱化学株式会社 | Polyester adhesive composition, Polyester adhesive, bonding sheet and the optical component with adhesive phase |
| CN110268030A (en) * | 2017-03-28 | 2019-09-20 | 东洋纺株式会社 | Polyester adhesive composition containing carboxylic acid group |
| CN110268030B (en) * | 2017-03-28 | 2021-12-28 | 东洋纺株式会社 | Polyester-based adhesive composition containing carboxylic acid group |
| WO2018176300A1 (en) * | 2017-03-30 | 2018-10-04 | Dow Global Technologies Llc | A novel mdi-based prepolymer binder for moisture curing binder application |
| CN107722906A (en) * | 2017-09-29 | 2018-02-23 | 镇江市星耀智能装备有限公司 | A kind of bonded adhesives for coated metallic plate |
| CN107556957A (en) * | 2017-10-04 | 2018-01-09 | 镇江市星耀智能装备有限公司 | A kind of coated metallic plate |
| CN110527470A (en) * | 2019-08-29 | 2019-12-03 | 苏州瀚海新材料有限公司 | A kind of Adhesive composition for FFC |
| CN110791247A (en) * | 2019-11-28 | 2020-02-14 | 沈阳化工研究院有限公司 | Solar cell backboard adhesive resin and preparation method thereof |
| CN112890279A (en) * | 2021-01-21 | 2021-06-04 | 河南中烟工业有限责任公司 | Cooling film for heating non-combustion cigarette filter tip, cooling filter tip and preparation method |
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Application publication date: 20121121 |