CN103975035B - Battery use packing material polyurethane(s) solid, battery use packing material, battery container and battery - Google Patents

Battery use packing material polyurethane(s) solid, battery use packing material, battery container and battery Download PDF

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Publication number
CN103975035B
CN103975035B CN201380003598.3A CN201380003598A CN103975035B CN 103975035 B CN103975035 B CN 103975035B CN 201380003598 A CN201380003598 A CN 201380003598A CN 103975035 B CN103975035 B CN 103975035B
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CN
China
Prior art keywords
packing material
battery
use packing
polyester polyol
layer
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CN201380003598.3A
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Chinese (zh)
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CN103975035A (en
Inventor
前田谕志
中岛康喜
贝原正人
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Toyo Morton Ltd
Toyochem Co Ltd
Artience Co Ltd
Original Assignee
Toyo Morton Ltd
Toyo Ink SC Holdings Co Ltd
Toyochem Co Ltd
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Publication of CN103975035A publication Critical patent/CN103975035A/en
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/116—Primary casings; Jackets or wrappings characterised by the material
    • H01M50/121—Organic material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B32B15/095—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyurethanes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B1/00—Layered products having a non-planar shape
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/102—Primary casings; Jackets or wrappings characterised by their shape or physical structure
    • H01M50/105—Pouches or flexible bags
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/116—Primary casings; Jackets or wrappings characterised by the material
    • H01M50/117—Inorganic material
    • H01M50/119—Metals
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/116—Primary casings; Jackets or wrappings characterised by the material
    • H01M50/124—Primary casings; Jackets or wrappings characterised by the material having a layered structure
    • H01M50/126—Primary casings; Jackets or wrappings characterised by the material having a layered structure comprising three or more layers
    • H01M50/129—Primary casings; Jackets or wrappings characterised by the material having a layered structure comprising three or more layers with two or more layers of only organic material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/31—Heat sealable
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2553/00—Packaging equipment or accessories not otherwise provided for
    • 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
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Sealing Battery Cases Or Jackets (AREA)
  • Laminated Bodies (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

The invention provides and be a kind ofly formed in the also high and solid of the battery use packing material of formability excellence of Bonding strength after long-term long duration test.Battery use packing material polyurethane(s) solid of the present invention contains host and polymeric polyisocyanate stiffening agent, host comprises polyhydroxy reactant (A) and silane coupling agent (B), the polyester polyol (A2) that above-mentioned polyhydroxy reactant (A) is less than 40 DEG C than the polyester polyol (A1) containing glass transition temperature being more than 40 DEG C with glass transition temperature with specific composition, isocyanato contained in stiffening agent is set to 10 ~ 30 relative to equivalence ratio [NCO]/([OH]+[COOH]) of the total of the hydroxyl and carboxyl that are derived from polyhydroxy reactant (A).

Description

Battery use packing material polyurethane(s) solid, battery use packing material, battery container and battery
Technical field
The present invention relates to a kind of battery use packing material polyurethane(s) solid in order to form battery container or battery package.In addition, the present invention relates to a kind of battery use packing material using above-mentioned battery use packing material polyurethane(s) solid and lamination.And, the present invention relates to a kind of by battery container shaping for above-mentioned battery use packing material and the battery with above-mentioned battery container.
Background technology
Due to the development rapidly of the electronics such as mobil phone, portable computer, and light weight and the demand of the secondary cells such as small-sized lithium ion battery increase.As the exterior body of secondary cell, use metal tank, but with regard to lightweight or productive viewpoint, the wrapping material of lamination plastic film or tinsel etc. become main flow gradually before.As the most easy wrapping material, can enumerate: sequentially lamination outer layer side resin film layer (11), outer layer side adhesion agent layer (12), metal foil layer (13), internal layer side adhesion agent layer (14) and comprise the laminate of internal surface layer (15) of heat sealing layer etc. from outer layer side as shown in Figure 1.As battery container, such as shown in Figure 2 as, have shaping for wrapping material (drawing and forming processing, outstanding forming process etc.) person in the mode that outer layer side resin film layer (11) is formed convex surface, internal surface layer (15) is formed concave surface.By enclosing electrode or electrolytic solution etc. in the concave side of battery container, wrapping material are sealed, and manufacture battery.
As battery use packing material, disclose: outer layer side lamination heat-resistant resin extend rete, do not extend rete at internal layer side lamination thermoplastic resin, between described two films lamination aluminium foil layer battery container wrapping material in, use specific adhesion agent layer to carry out then by not extending at thermoplastic resin between rete and aluminium foil layer, and the cell box wrapping material (patent documentation 1) of formability excellence can be provided.
In addition, as battery use packing material, disclose: at least sequentially battery exterior body of laminated base material layer and aluminium foil layer and hot adherence resin layer, and there is the ring stiffness (loopstiffness) of specified range, thickness is used to be that the aluminium through anneal of more than 80 μm is as aluminium foil layer, and obtain the exterior material of formability excellence, the lithium ion battery that ensure that safety performance (patent documentation 2) can be provided by above-mentioned exterior material.
In addition, as the laminate formation solid in order to pack the non-food products such as shampoo, disclose: be the solid (patent documentation 3) that the organic polyhydric alcohol 5 % by weight ~ 50 % by weight of more than 40 DEG C and glass transition temperature are less than the mixture of the organic polyhydric alcohol (wherein, not having carboxyl in the molecule thereof) 95 % by weight ~ 50 % by weight of 40 DEG C containing comprising glass transition temperature.
Prior art document
Patent documentation
Patent documentation 1: Japanese Patent Laid-Open 2010-92703 publication
Patent documentation 2: Japanese Patent Laid-Open 2008-251342 publication
Patent documentation 3: Japanese Patent Laid-Open 2001-322221 publication
Summary of the invention
The problem of invention for solving
In recent years, along with the purposes such as vehicle-mounted or family's electric power storage expand, and require the high capacity of secondary cell, and the formedness of formability is required to battery use packing material.In addition, secondary cell that is vehicle-mounted or family's electric power storage purposes is arranged at outdoor, and requires long-term durable years, and requires that the Bonding strength of the interlayer of each plastic film of wrapping material or tinsel etc. is also high and outward appearance is also without exception after long-term long duration test.
The present invention forms in view of above-mentioned background, problem be to provide a kind of there is excellent formability, the Bonding strength battery that also high, aesthetic appearance is excellent of interlayer after long-duration experiments, battery container, battery use packing material and battery use packing material polyurethane(s) solid.
Solve the means that problem adopts
The present invention forms in view of above-mentioned problem, relate to a kind of solid, it uses the polyhydroxy reactant (A) comprising the different polyester polyol of glass transition temperature (A1), polyester polyol (A2) with specified proportion, as the hydroxyl moieties in order to form polyurethane(s), and containing the reactive functional group relative to above-mentioned polyhydroxy reactant (A), and quite excessive isocyanate prepolymer composition is as stiffening agent.
Namely, the invention relates to a kind of battery use packing material polyurethane(s) solid, it contains host and polymeric polyisocyanate stiffening agent, and it is characterized in that: above-mentioned host contains polyhydroxy reactant (A) and silane coupling agent (B), it is the polyester polyol (A2) 95 % by weight ~ 50 % by weight that the polyester polyol (A1) 5 % by weight ~ 50 % by weight of more than 40 DEG C and glass transition temperature are less than 40 DEG C that above-mentioned polyhydroxy reactant (A) comprises glass transition temperature, isocyanato contained in above-mentioned polymeric polyisocyanate stiffening agent is 10 ~ 30 relative to equivalence ratio [NCO]/([OH]+[COOH]) of the total of the hydroxyl and carboxyl that are derived from above-mentioned polyhydroxy reactant (A).
Battery use packing material polyurethane(s) solid of the present invention be preferably further containing can with the compound of carboxyl reaction (C).
In addition, the invention relates to a kind of battery use packing material, its sequentially lamination outer layer side resin film layer (11), outer layer side adhesion agent layer (12), metal foil layer (13), internal layer side adhesion agent layer (14) and internal surface layer (15) form, above-mentioned outer layer side adhesion agent layer (12) is formed by above-mentioned battery use packing material polyurethane(s) solid.
And the invention relates to a kind of battery container, it forms by above-mentioned battery use packing material is shaping, and outer layer side resin film layer (11) forms convex surface, and internal surface layer (15) forms concave surface.
And the invention relates to a kind of battery, it uses above-mentioned battery container to form.
The effect of invention
According to the present invention, there is the effect of the excellence that can provide the Bonding strength battery that also high, aesthetic appearance is excellent, battery container, battery use packing material and the battery use packing material polyurethane(s) solid with interlayer after excellent formability, long-duration experiments.In the battery use packing material of sequentially lamination outer layer side resin film layer (11), outer layer side adhesion agent layer (12), metal foil layer (13), internal layer side adhesion agent layer (14), internal surface layer (15), in order to form outer layer side adhesion agent layer, the polyurethane(s) solid of the application of the invention, and can Bonding strength between providing layer excellent, shaping time film do not produce protuberance and the battery use packing material that after endurance test, above-mentioned performance is also excellent without fracture, forming part.By using the battery container of above-mentioned battery use packing material, and battery excellent in reliability can be provided.
Accompanying drawing explanation
[Fig. 1] is the schematic cross sectional view of the form representing battery use packing material of the present invention.
[Fig. 2] is the schematic perspective view of the form representing battery container of the present invention.
Embodiment
Below, example of the present invention is described in detail.In addition, in this specification sheets, the record of " count A ~ arbitrarily arbitrarily and count B " is Index A and the scope being greater than several A, and number B and be less than the scope of several B.
Polyurethane(s) solid of the present invention is for the formation of the battery use packing material in order to obtain battery container.Fig. 1 represents the schematic cross sectional view of a form of battery use packing material of the present invention, and Fig. 2 represents the schematic perspective view of a form of battery container of the present invention.The shape of battery container is not particularly limited, and except as shown in Figure 2 hypocraterimorphous, can illustrate: tubular (cylinder, square tube, cylindroid etc.).Those battery containers the battery use packing material of flat form are carried out forming process and obtain.The inner side of battery container, be namely internal surface layer (15) with the face of electrolyte contacts.As the preferably example of internal surface layer (15), heat sealing layer can be enumerated.By using heat sealing layer, and make the internal surface layer of flange part (15), with internal surface layer (15) subtend of the internal surface layer (15) of other formation battery use packing material or the flange part of other battery container, contact, and heat, internal surface layer (15) can be made by this to fuse each other, and enclose electrolytic solution.
Battery container possesses tinsel (13).In battery container, usually with tinsel (13) for boundary, be called " inner side " by near the side of electrolytic solution, the layer of inner side be called " internal layer ", the side away from electrolytic solution be called " outside ", the layer in outside be called " skin ".Therefore, in the predetermined battery use packing material forming battery container, also with tinsel (13) for boundary, the predetermined side be positioned near electrolytic solution place is called " inner side ", the layer of inner side is called " internal layer ", is called " outside " by being positioned at, is called " skin " by the layer in outside away from the predetermined side at electrolytic solution place.Polyurethane(s) system of the present invention solid is suitable as the purposes of outer layer side resin film layer (11) with metal foil layer (13) lamination (laminating).
Polyurethane(s) system of the present invention solid uses host and stiffening agent.Can be so-called 2 liquid mixed type solids host mixed with stiffening agent in use, also can be the 1 liquid type solid being pre-mixed host and stiffening agent.And, also can be the type mixing multiple host and/or multiple stiffening agent in use.
Polyurethane(s) system of the present invention solid contains polyhydroxy reactant (A) and silane coupling agent (B).It is the polyester polyol (A2) 95 % by weight ~ 50 % by weight that the polyester polyol (A1) 5 % by weight ~ 50 % by weight of more than 40 DEG C and glass transition temperature are less than 40 DEG C that polyhydroxy reactant (A) comprises glass transition temperature.Polyhydroxy reactant (A) can comprise the polyvalent alcohol beyond polyester polyol (A1), polyester polyol (A2) further in the scope meeting object of the present invention, effect.
As the polyester polyol (A1) that glass transition temperature is more than 40 DEG C, and the polyester polyol (A2) that glass transition temperature is less than 40 DEG C, such as make: m-phthalic acid, terephthalic acid, naphthalic acid, Tetra hydro Phthalic anhydride, hexanodioic acid, nonane diacid, sebacic acid, succsinic acid, pentanedioic acid, Tetra Hydro Phthalic Anhydride, hexahydrophthalic anhydride, MALEIC ANHYDRIDE, independent or the mixture of itaconic anhydride and ester cpds etc. thereof (gather above and be called polyacid constituent), with such as ethylene glycol, Diethylene Glycol, triethylene glycol, propylene glycol, dipropylene glycol, 1, 6-hexylene glycol, neopentyl glycol, 1, 4-butyleneglycol, 1, 4-cyclohexanedimethanol, TriMethylolPropane(TMP), glycerine, 1, 9-nonanediol, 3-methyl isophthalic acid, 5-pentanediol, polyether glycol, polycarbonate polyol, polyolefin polyhydric alcohol, acrylic acid series multiple alcohol, polyurethane ester polyol etc. (gather above and be called polyhydroxy reactant) separately or mixture reaction and obtaining.
In addition, as polyester polyol (A1), the preferably example of polyester polyol (A2), polyester urethane polyvalent alcohol can be illustrated, it makes above-mentioned polyacid constituent and above-mentioned polyhydroxy reactant react and obtain polyester polyol, and make the polyester polyol and such as 2 of gained, 4-tolylene diisocyanate, 2, 6-tolylene diisocyanate, Xylene Diisocyanate, diphenylmethanediisocyanate, isophorone diisocyanate, 1, 5-naphthalene diisocyanate, hexamethylene diisocyanate, the polymeric polyisocyanates such as hydrogenated diphenyl methane diisocyanate react and obtain.
In addition, as the preferably example of polyester polyol (A1), polyester polyol (A2), (intramolecule or molecular end) in molecule can be illustrated there is the polyester polyol of carboxyl, it makes above-mentioned polyacid constituent and above-mentioned polyhydroxy reactant react and obtain polyester polyol, and make the polyprotonic acids such as the polyester polyol of gained and such as phthalic acid, trimellitic acid, Pyromellitic Acid and those anhydride reaction and obtain.
In the polyhydroxy reactant (A) contained by host, be that the polyester polyol (A1) of more than 40 DEG C is set to 5 % by weight ~ 50 % by weight, is preferably 10 % by weight ~ 40 % by weight by glass transition temperature, the polyester polyol (A2) glass transition temperature being less than 40 DEG C is set to 95 % by weight ~ 50 % by weight, is preferably 90 % by weight ~ 60 % by weight, the Bonding strength of the interlayer of outer layer side resin film layer (11) and metal foil layer (13) can be improved by this, and obtain the battery use packing material of good forming ability.By the polyester polyol (A2) that the polyester polyol (A1) of more than 40 DEG C is set to more than 5 % by weight, glass transition temperature is less than 40 DEG C is set to less than 95 % by weight, and sufficient formability can be obtained.In addition, by the polyester polyol (A2) that the polyester polyol (A1) of more than 40 DEG C is set to less than 50 % by weight, glass transition temperature is less than 40 DEG C is set to more than 50 % by weight, and the Bonding strength of the interlayer of outer layer side resin film layer (11) and metal foil layer (13) can be obtained fully.
Be the molecular weight that the polyester polyol (A1) of more than 40 DEG C and glass transition temperature are less than the polyester polyol (A2) of 40 DEG C as glass transition temperature, particularly number average molecular weight is preferably 5, and 000 ~ 100,000, be more preferred from 10,000 ~ 50,000.When industrially producing battery use packing material, rectangular state person is coiled into web-like.Further, in order to make the adhesion agent layer coiled in the laminate of web-like harden fully, and in the warehouse being maintained high temperature aging a couple of days.If the number average molecular weight of polyester polyol (A1), polyester polyol (A2) is less than 5,000, the cohesive force being in the adhesion agent layer of sclerosis midway before then aging is low, therefore has to produce to batch in state to occur sliding or worry that the processing such as bad order of protuberance is abnormal.On the other hand, if the number average molecular weight of polyester polyol (A1), polyester polyol (A2) more than 100,000, then has the solvability in diluting solvent to become shortage, viscosity during solid coating uprises, and screening characteristics becomes the worry of shortage.
The mensuration of the glass transition temperature of polyester polyol (A1), polyester polyol (A2) is that the differential scanning calorimeter (DifferentialScanningCalorimeter, DSC) " RDC220 " using Seiko electronics (SeikoInstruments) company to manufacture carries out.The polyester polyol (A1), the polyester polyol (A2) that measure about 10mg are respectively put into aluminum pot, and be arranged at by after cooled with liquid nitrogen extremely-100 DEG C in DSC device, the DSC chart obtained according to heating up with 10 DEG C/min calculates glass transition temperature.When polyester polyol (A1), polyester polyol (A2) are dissolved in solvent, solvent are distilled after drying is carried out in removing and carry out DSC mensuration.
The number average molecular weight of polyester polyol (A1) and polyester polyol (A2) is the value of the polystyrene conversion by gel permeation chromatography (GelPermeationChromatography, GPC).Such as the temperature of tubing string (KF-805L, KF-803L and KF-802 that Showa electrician company manufactures) is set to 40 DEG C, use tetrahydrofuran (THF) (Tetrahydrofuran, THF) as eluat, flow velocity is set to 0.2mL/min, detection is set to RI, sample solution concentration is set to 0.02%, uses polystyrene to carry out as standard test specimen.Number average molecular weight of the present invention records the value measured by aforesaid method.
As the polyhydroxy reactant (A) contained by host, also can and with glass transition temperature be the polyester polyol (A1) of more than 40 DEG C and glass transition temperature be less than 40 DEG C polyester polyol (A2) beyond polyvalent alcohol.Include, for example: the low molecular polylol such as ethylene glycol or TriMethylolPropane(TMP) and polyether glycol, polycarbonate polyol, polyolefin polyhydric alcohol, acrylic acid series multiple alcohol or by those separately or and the polyurethane ester polyol etc. reacting by two or more and organic isocyanate and obtain, can use not causing in dysgenic degree Bonding strength or formability.
Just improve with regard to the viewpoint of the raw-material Bonding strengths of metal system such as tinsel, polyurethane(s) solid of the present invention comprises silane coupling agent (B).As silane coupling agent (B), include, for example: vinyltrimethoxy silane, vinyltriethoxysilane etc. have the trialkoxy silane of vinyl; APTES, N-(2-amino-ethyl) 3-TSL 8330 etc. have amino trialkoxy silane; 3-glycidoxypropyltrimewasxysilane, 2-(3,4-epoxycyclohexyl) ethyl trimethoxy silane, 3-glycidoxypropyl triethoxyl silane etc. have the trialkoxy silane of glycidyl.Those can be used alone respectively, or at random combine two or more and use.Relative to solids component 100 weight part of polyhydroxy reactant (A), the addition of silane coupling agent (B) is preferably 0.1 weight part ~ 5 weight part, is more preferred from 0.5 weight part ~ 3 weight part.When the addition of silane coupling agent (B) is less than 0.1 weight part, lacks the Bonding strength to tinsel caused because adding silane coupling agent and improve effect, even if add more than 5 weight parts, also cannot expect the raising having its above performance again.
In order to the bad order maintaining the Bonding strength after endurance test or more effectively suppress the protuberance because of film to cause, polyurethane(s) solid of the present invention can use further can with the compound of carboxyl reaction (C).Can be contained in host with the compound of carboxyl reaction (C), also can be contained in stiffening agent, also can add when host is mixed with stiffening agent in addition.As can with the compound of carboxyl reaction (C), be preferably in molecule the compound with glycidyl or there is the compound of carbon imide base or there is the compound of oxazoline group.By use can with the compound of carboxyl reaction (C), and the carboxylic acid reaction decomposing with the ester bond in adhesion agent layer in long-duration experiments and produce, thus the cohesive force that the molecular weight because of adhesion agent layer can be suppressed to reduce cause reduces, and suppress the reduction of Bonding strength or the generation of bad order.
As the compound in molecule with glycidyl, can enumerate: bisphenol A type epoxy resin, bisphenol f type epoxy resin, bisphenol-s epoxy resin, brominated bisphenol a type epoxy resin, bisphenol-A epoxy resin, united phenol-type epoxy resin, di-toluene phenol-type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, brominated phenol phenolic resin varnish type epoxy resin, the phenolic resin varnish type epoxy resin of dihydroxyphenyl propane, trihydroxybenzene methylmethane type epoxy resin, four phenolic group ethane type epoxy resin, phenol novolak type epoxy resin containing naphthalene skeleton, the glycidyl ether compounds such as the phenol novolak type epoxy resin containing Dicyclopentadiene (DCPD) skeleton, the epihydric alcohol ester compounds such as terephthalic acid diglycidyl ester, the alicyclic epoxy resins such as the EHPE-3150 that Daicel chemical industry (DAICELCHEMICALINDUSTRIES) company manufactures, the hetero ring type epoxy resin such as triglycidylisocyanurates, N, N, N ', the Racemic glycidol amines such as N '-four glycidyl group m-xylene diamine, or (methyl) glycidyl acrylate and the multipolymer etc. of compound with ethene unsaturated double-bond.Those can be used alone, also can and use two or more.
As the compound in molecule with carbon imide base, can enumerate: N, N '-two-adjacent toluyl carbon imide, N, N '-phenylbenzene carbon imide, N, N '-two-2, 6-3,5-dimethylphenyl carbon imide, N, N '-bis-(2, 6-diisopropyl phenyl) carbon imide, N, N '-dioctyl decyl carbon imide, N-tri-base-N '-cyclohexyl carbon imide, N, N '-two-2, 2-bis--tributyl phenyl carbons imide, N-tri-base-N '-phenyl carbons imide, N, N '-two-p-nitrophenyl carbon imide, N, N '-two-p-aminophenyl carbon imide, N, N '-two-p-hydroxybenzene carbon imide, N, N '-two-cyclohexyl carbon imide, and N, N '-two-to toluyl carbon imide etc.
As the compound in molecule with oxazoline group, can enumerate: 2-oxazoline, 2-methyl-2-oxazoline, 2-phenyl-2-oxazoline, 2,5-dimethyl-2-oxazoline, 2, the monosubstituted oxazolyl quinoline compounds such as 4-phenylbenzene-2-oxazoline, 2,2 '-(1,3-phenylene)-bis-(2-oxazoline), 2,2 '-(1,2-ethylidene)-bis-(2-oxazoline), 2,2 '-(tetramethylene)-bis-(2-oxazoline), 2,2 '-(Isosorbide-5-Nitrae-phenylene)-bis-(2-oxazolines) etc.
As can with the compound of carboxyl reaction (C), be preferably biphenol type epoxy compound, be preferably the bisphenol-type epoxy resin that number average molecular weight is 400 ~ 5,000.If the number average molecular weight of epoxy resin is less than 400, then adhesion agent layer is had to become soft and the tendency of sufficient weather resistance cannot be obtained.If the number average molecular weight of epoxy resin is greater than 5,000, then has and reduce with the consistency of polyester polyol, and produce the worry of bad order.In addition, relative to polyhydroxy reactant (A) 100 weight part, can be preferably containing 1 weight part ~ 100 weight part with the compound of carboxyl reaction (C), be more preferred from containing 5 weight part ~ 50 weight parts.
In addition, as solid purposes, known additive can be allocated in host or stiffening agent.Such as reaction promotor can be used.Include, for example: the metal system catalyst such as dibutyl tin acetate, dibutyl tin dilaurate, dioctyl tin cinnamic acid tin, dibutyl two maleic acid tin; 1,8-diaza-dicyclo (5,4,0) undecylene-7,1,5-diazabicyclo (4,3,0) nonene-5, tertiary amine such as 6-dibutylamino-1,8-diazabicyclo (5,4,0) undecylene-7 grade; As the reactive tertiary amine etc. of trolamine, the one kind or two or more reaction promotor being selected from those cohorts can be used.
In order to improve laminated appearance, also known levelling agent or defoamer can be allocated in host.As levelling agent, include, for example: polyethers upgrading polydimethylsiloxane, polyester upgrading polydimethylsiloxane, aralkyl upgrading gathers methyl alkyl siloxane, polyester upgrading contains hydroxyl polydimethylsiloxane, polyether ester upgrading contain the polydimethylsiloxane of hydroxyl, acrylic copolymer, methacrylic acid based copolymer, polyethers upgrading gather methyl alkyl siloxane, alkyl acrylate copolymer, methacrylate copolymer, Yelkin TTS etc.As defoamer, can enumerate: the multipolymer of silicone resin, silicone solution, alkyl vinyl ether and alkyl acrylate and alkyl methacrylate etc. are known.
Polyurethane(s) solid of the present invention comprises polymeric polyisocyanate as stiffening agent.Polymeric polyisocyanate can be the state of being diluted by polymeric polyisocyanate by organic solvent, also can be undiluted state.As polymeric polyisocyanate, include, for example: trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, 1,2-propylene vulcabond, 1,2-butylene vulcabond, 2,3-butene diisocyanate, 1,3-butene diisocyanate, 2,4,4-trimethyl hexamethylene diisocyanate or 2,2,4-trimethyl hexamethylene diisocyanate, the aliphatic diisocyanates such as 2,6-vulcabond methylhexanoic acid ester, Isosorbide-5-Nitrae-cyclohexyl diisocyanate, 1,3-cyclohexyl diisocyanate, 3-isocyanatomethyl-3,5,5-trimethylcyclohexylisocyanate, 4,4 '-methylene-bis (cyclohexyl isocyanate), methyl 2,4-cyclohexyl diisocyanate, methyl 2,6-cyclohexyl diisocyanate, Isosorbide-5-Nitrae-bis-(isocyanatomethyl) hexanaphthene, the ester ring type vulcabond such as two (isocyanatomethyl) hexanaphthenes of 1,3-, m-benzene diisocyanate, PPDI, 4,4 '-diphenyl diisocyanate, 1,5-naphthalene diisocyanate, 4,4 '-diphenylmethanediisocyanate, 2,4 toluene diisocyanate or 2,6-tolylene diisocyanate or its mixture, 4,4 '-toluidine diisocyanate, dianisidine diisocyanate, 4, the aromatic diisocyanates such as 4 '-diphenyl ether diisocyanate, 1,3-Xylene Diisocyanate or Isosorbide-5-Nitrae-Xylene Diisocyanate or its mixture, ω, ω '-two isocyanatos-Isosorbide-5-Nitrae-diethylbenzene, two (1-isocyanato-1-methylethyl) benzene of 1,3-or Isosorbide-5-Nitrae-bis-(1-isocyanato-1-methylethyl) araliphatic diisocyanate such as benzene or its mixture, triphenyl methane-4,4 ', 4 "-triisocyanate, benzene-1,3,5-triisocyanate, Toluene-2,4-diisocyanate, organic triisocyanates such as 4,6-triisocyanate, 4,4 '-diphenyldimethyhnethane-2,2 ', the polymeric polyisocyanate monomers such as organic tetraisocyanate such as 5,5 '-tetraisocyanate, by the dipolymer of above-mentioned polymeric polyisocyanate monomer derived, trimer, biuret, allophanate, the polymeric polyisocyanate with 2,4,6-oxadiazines triketone ring obtained by carbonic acid gas and above-mentioned polymeric polyisocyanate monomer, such as with ethylene glycol, propylene glycol, butyleneglycol, hexylene glycol, neopentyl glycol, 1,6-hexylene glycol, 3-methyl isophthalic acid, 5-pentanediol, 3,3 '-dihydroxy methylpropane, cyclohexanedimethanol, Diethylene Glycol, triethylene glycol, dipropylene glycol, glycerine, TriMethylolPropane(TMP), tetramethylolmethane, Sorbitol Powder equimolecular quantity is less than the affixture of the low molecular polylol of 200, or is the polyester polyol of 200 ~ 20,000 with molecular weight, polyester ether polylol, polyester amide polyol, polycaprolactone polyol, poly-valerolactonepolyol, acrylic acid series multiple alcohol, polycarbonate polyol, poly-hydroxyl alkane, Viscotrol C, the affixture etc. of polyurethane ester polyol etc.Wherein, with regard to the productivity of wrapping material and the viewpoint of formability, the organic polyisocyanates derived by aromatic diisocyanate is more preferred from.
In polyurethane(s) solid of the present invention, equivalence ratio [NCO]/([OH]+[COOH]) of the total of the hydroxyl that isocyanato contained in polymeric polyisocyanate stiffening agent (2) has relative to polyhydroxy reactant (A) contained in host (1) and carboxyl, be preferably 10 ~ 30, be more preferred from 15 ~ 25.That is, relative to the total 1 mole of hydroxyl and carboxyl, when isocyanato is less than 10 moles, sufficient formability cannot be obtained, if more than 30 moles, then setting time, wholesomeness, economy in unfavorable.
Battery use packing material of the present invention such as manufactures by method usually used.Such as use polyurethane(s) solid lamination outer layer side resin film layer (11) of the present invention and metal foil layer (13), and laminate in the middle of obtaining.Then, internal layer side solid (14) can be used at metal foil layer (13) area layer internal surface layer (15) of middle laminate.Or use internal layer side solid lamination metal foil layer (13) and internal surface layer (15), and laminate in the middle of obtaining.Then, polyurethane(s) solid of the present invention can be used, the metal foil layer (13) of the middle laminate of lamination and outer layer side resin film layer (11).For the former time, polyurethane(s) solid of the present invention is coated on the one side of arbitrary base material of outer layer side resin film layer (11) or metal foil layer (13), after making solvent evaporates, under heating and pressurizing in adhesion agent layer another base material overlapping, then at normal temperature or carry out aging under heating, adhesion agent layer is hardened.Adhesion agent layer amount is preferably 1g/m 2~ 15g/m 2left and right.During for the latter, also equally, polyurethane(s) solid of the present invention coats any surface in metal foil layer (13) face of outer layer side resin film layer (11) or middle laminate.
When polyurethane(s) system solid is coated on base material, in order to coating fluid being adjusted to the viscosity of appropriateness, and in drying step, solvent can be comprised in scope base material not impacted.As solvent, can enumerate: the ketone based compounds such as acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), pimelinketone, the ester based compounds such as methyl acetate, ethyl acetate, butylacetate, ethyl lactate, methoxy ethyl acetate, the ether such as diethyl ether, glycol dimethyl ether based compound, the aromatics such as toluene, dimethylbenzene, the fatty compounds such as pentane, hexane, the halogenated hydrocarbon compounds such as methylene dichloride, chlorobenzene, chloroform, the alcohols such as ethanol, Virahol, propyl carbinol, water etc.Those solvents can be used alone, also can and use two or more.
In the present invention as the device of coating polyurethane(s) system solid, can enumerate: unfilled corner wheel coating machine (commacoater), dry adhered machine, knife over roll coating machine (rollknifecoater), mould are coated with machine, roller coating machine, bar coater, gravure roll coating machine, inverse roll-coater, knife coater (bladecoater), gravure coater, micro-gravure coater etc.
The outer layer side resin film layer (11) forming battery use packing material of the present invention is not particularly limited, and is preferably the stretchable film using and comprise polymeric amide or polyester.In addition, also undertaken painted by the pigment such as carbon black or titanium oxide.In addition, also coating agent or the ink etc. such as anti-slight crack coating agent can be coated with.In addition, also can the film of lamination more than 2 layers in advance.The thickness of rete is not particularly limited, and is preferably 12 μm ~ 100 μm.
The metal foil layer (13) forming battery use packing material of the present invention is not particularly limited, and is preferably aluminium foil layer.The thickness of rete is not particularly limited, and is preferably 20 μm ~ 80 μm.In addition, be preferably the surface treatment carrying out by phosphoric acid salt, chromic salt, fluorochemical, triazine thiol compound, isocyanate compound etc. in metal foil surface, by implementing surface treatment, and the protuberance of the interlayer in metal foil surfaces caused because of the electrolytic solution of battery or the impact of electrolytic solution can be suppressed.
The internal surface layer (15) forming battery use packing material of the present invention is not particularly limited, and is preferably the heat sealing layer of the non-stretchable film comprised containing at least a kind of thermoplastic resin being selected from the cohort be made up of polyethylene, polypropylene, olefin copolymer, those sour modifier and ionomer.The thickness of heat sealing layer is not particularly limited, and is preferably 20 μm ~ 150 μm.
The solid forming internal layer side adhesion agent layer (14) forming battery use packing material of the present invention is not particularly limited, the Bonding strength being preferably metal foil layer (13) and internal surface layer (15) can not reduce because of the electrolytic solution of battery, can use known solid.Such as, make by gravure coater etc. the solid that polyolefin resin and polyfunctional isocyanate combined or the solid that polyvalent alcohol and polyfunctional isocyanate combine is coated on metal foil layer, make solvent seasoning, under heating and pressurizing in adhesion agent layer overlapping internal surface layer (15), then, at normal temperature or carry out aging under heating and make metal foil layer (13) and internal surface layer (15) fit.Or by T mould forcing machine the solids such as sour upgrading polypropylene are melt extruded and form adhesion agent layer to metal foil layer (13), overlapping internal surface layer (15) in above-mentioned adhesion agent layer, and metal foil layer (13) and internal surface layer (15) are fitted.Outer side joint oxidant layer (12) and internal layer side adhesion agent layer (14) both must carry out aging time, can gather carry out aging.
Battery container of the present invention can use above-mentioned battery use packing material, in the mode that outer layer side resin film layer (11) is formed convex surface, internal surface layer (15) is formed concave surface, carries out shaping and obtains.
Then, embodiment is enumerated and comparative example further illustrates the present invention.% in embodiment and comparative example all refers to quality %.
(synthesis example 1) drops into m-phthalic acid 166.0g, terephthalic acid 166.0g, ethylene glycol 85.6g, neopentyl glycol 95.6g, 6 hours esterifications are carried out at 200 DEG C ~ 220 DEG C, after distillating the water of specified quantitative, add tetrabutyl titanate 0.12g, and reduce pressure lentamente, carry out 6 hours transesterification reactions at 1.3hPa ~ 2.6hPa, at 230 DEG C ~ 250 DEG C, and obtain the polyester polyol that number average molecular weight is 20,000, glass transition temperature (Tg) is 60 DEG C.By ethyl acetate, this polyester polyol being adjusted to nonvolatile component is 50%, and obtains the polyester polyol solution (1) that hydroxyl value is 2.71mgKOH/g, acid number is 0.1mgKOH/g.
In addition, number average molecular weight, glass transition temperature utilize GPC and DSC by method as described above and obtain.In addition, acid number, hydroxyl value are obtained as follows.
The mensuration > of < acid number (AV) critically measures sample (polyester polyol solution) about 1g in tool plug Erlenmeyer flask, adds toluene/ethanol (volume ratio: toluene/ethanol=2/1) mixed solution 100mL and dissolves.In wherein adding phenolphthalein reagent as indicator, and kept for 30 seconds.Then, titration is carried out till solution presents incarnadine by 0.1N alcoholic potassium hydroxide solution.Acid number is obtained by following formula (unit: mgKOH/g).
Acid number (mgKOH/g)=(5.611 × a × F)/S
Wherein, S: the collection capacity (g) of sample
The consumption (mL) of a:0.1N alcoholic potassium hydroxide solution
The titre of F:0.1N alcoholic potassium hydroxide solution
The mensuration > of < hydroxyl value (OHV) critically measures sample (polyester polyol solution) about 1g in tool plug Erlenmeyer flask, adds toluene/ethanol (volume ratio: toluene/ethanol=2/1) mixed solution 100mL and dissolves.Then 5mL acetylizing agent (by pyridinium dissolution diacetyl oxide 25g, the capacity of making is the solution of 100mL) is added exactly, stir about 1 hour.In wherein adding phenolphthalein reagent as indicator, continued for 30 seconds.Then, titration is carried out till solution presents incarnadine by 0.1N alcoholic potassium hydroxide solution.Hydroxyl value is obtained by following formula (unit: mgKOH/g).
Hydroxyl value (mgKOH/g)=[(b-a) × F × 28.25}/S]+D
Wherein, S: the collection capacity (g) of sample
The consumption (mL) of a:0.1N alcoholic potassium hydroxide solution
B: the consumption (mL) of the 0.1N alcoholic potassium hydroxide solution of blank assay
The titre of F:0.1N alcoholic potassium hydroxide solution
D: acid number (mgKOH/g)
(synthesis example 2) drops into m-phthalic acid 149.4g, terephthalic acid 149.4g, ethylene glycol 71.3g, neopentyl glycol 119.6g, 6 hours esterifications are carried out at 200 DEG C ~ 220 DEG C, after distillating the water of specified quantitative, add sebacic acid 40.4g, then carry out 6 hours esterifications.After distillating the water of specified quantitative, add tetrabutyl titanate 0.13g, and reduce pressure lentamente, carry out 6 hours transesterification reactions at 1.3hPa ~ 2.6hPa, at 230 DEG C ~ 250 DEG C, and obtain the polyester polyol that number average molecular weight is 19,800, Tg is 45 DEG C.Then by ethyl acetate, this polyester polyol being adjusted to nonvolatile component is 50%, and obtains the polyester polyol solution (2) that hydroxyl value is 2.33mgKOH/g, acid number is 0.5mgKOH/g.
(synthesis example 3) drops into m-phthalic acid 83.2g, terephthalic acid 83.2g, ethylene glycol 142.6g, carries out 8 hours esterifications at 200 DEG C ~ 220 DEG C, after distillating the water of specified quantitative, adds nonane diacid 188g, then carries out 4 hours esterifications.After distillating the water of specified quantitative, add tetrabutyl titanate 0.13g, and reduce pressure lentamente, carry out 3 hours transesterification reactions at 1.3hPa ~ 2.7hPa, at 230 DEG C ~ 250 DEG C, and obtain that number average molecular weight is 22,000, Tg is the polyester polyol of-5 DEG C.By ethyl acetate, this polyester polyol being adjusted to nonvolatile component is 50%, and obtains the polyester polyol solution (3) that hydroxyl value is 2.45mgKOH/g, acid number is 0.1mgKOH/g.
(synthesis example 4) drops into m-phthalic acid 132.8g, ethylene glycol 42.7g, neopentyl glycol 71.8g, 1,6-hexylene glycol 108.6g, carries out 6 hours esterifications, after distillating the water of specified quantitative at 200 DEG C ~ 230 DEG C, add hexanodioic acid 175.2g, then carry out 6 hours esterifications.After distillating the water of specified quantitative, add tetrabutyl titanate 0.13g, and reduce pressure lentamente, carry out 3 hours transesterification reactions at 1.3hPa ~ 2.6hPa, at 230 DEG C ~ 250 DEG C, and obtain polyester polyol.In order to make about 90% of the hydroxyl of this polyester polyol of gained with Pyromellitic Acid anhydride reactant, and relative to the total amount of this polyester polyol, add pyromellitic dianhydride 7.7g, at 180 DEG C, react about 2 hours.Use liquid chromatography to confirm not remaining unreacted pyromellitic dianhydride in reaction system, and obtain the polyester polyol through pyromellitic dianhydride upgrading that number average molecular weight is 18,000, Tg is-20 DEG C.By ethyl acetate, the polyester polyol through pyromellitic dianhydride upgrading being adjusted to nonvolatile component is 50%, and obtains the polyester polyol solution (4) that hydroxyl value is 0.31mgKOH/g, acid number is 2.8mgKOH/g.
(synthesis example 5) drops into m-phthalic acid 132.8g, ethylene glycol 44.6g, neopentyl glycol 74.8g, 1,6-hexylene glycol 113.3g, carries out 6 hours esterifications, after distillating the water of specified quantitative at 200 DEG C ~ 230 DEG C, add hexanodioic acid 175.2g, then carry out 6 hours esterifications.After distillating the water of specified quantitative, add tetrabutyl titanate 0.13g, and reduce pressure lentamente, carry out 3 hours transesterification reactions at 1.3hPa ~ 2.6hPa, at 230 DEG C ~ 250 DEG C, and obtain polyester polyol.With respect to ethyl acetate, this polyester polyol being adjusted to nonvolatile component is the 80% polyester polyol solution 600g obtained, and add tolylene diisocyanate 3.2g, reaction in 8 hours is carried out at 80 DEG C, and obtain the polyester polyurethane polyvalent alcohol that number average molecular weight is 20,000, Tg is-10 DEG C.Then, by ethyl acetate, this polyester polyol being adjusted to nonvolatile component is 50%, and obtains the polyester polyol solution (5) that hydroxyl value is 2.71mgKOH/g, acid number is 0.1mgKOH/g.
[manufacture of host (1)] allocate polyester polyol solution (1) 60g (solids component is 30g), with polyester polyol solution (3) 140g (solids component is 70g) and KBM-403 (silane coupling agent) 1g after, add ethyl acetate 136g, and obtain the host (1) that nonvolatile component is 30%.The hydroxyl value of host (1) and acid number add up to about 1.56mgKOH/g.
[manufacture of host (2) ~ host (11)] is in the mode identical with the situation of host (1), with the ratio (g) shown in table 1 allocate polyester polyol solution (1) ~ polyester polyol solution (5) and following shown in silane coupling agent and can with the compound of carboxyl reaction after, and add ethyl acetate in the mode that nonvolatile component is 30%, and obtain host (2) ~ host (11).
Silane coupling agent
KBM-403:3-glycidoxypropyltrimewasxysilane (silicon profit light (Shin-EtsuSilicones) company of SHIN-ETSU HANTOTAI manufactures)
KBM-903:3-TSL 8330 (manufacture of Japanese You Nika (NipponUnicar) company)
Can with the composition of carboxyl reaction
YD-012: bisphenol A type epoxy resin (manufacture of chemical company of Nippon Steel)
(manufacture of stiffening agent)
Stiffening agent (1): be that the resin solution of 50% is as stiffening agent (1) using the solids component made with the adducts of TriMethylolPropane(TMP) by diluted ethyl acetate tolylene diisocyanate.The NCO% of stiffening agent (1) is 8.6%.
Stiffening agent (2): the solids component made by the trimer by diluted ethyl acetate hexamethylene diisocyanate is that the resin solution of 50% is as stiffening agent (2).The NCO% of stiffening agent (2) is 8.6%.
Stiffening agent (3): using being mixed with stiffening agent (1) 50 weight part, the solids component of stiffening agent (2) 50 weight part is that the resin solution of 50% is as stiffening agent (3).The NCO% of stiffening agent (3) is 8.6%.
After (embodiment 1 ~ embodiment 13, comparative example 1 ~ comparative example 4) allocates host and stiffening agent with the ratio (g) shown in table 2, be the mode of 30% with nonvolatile component, add ethyl acetate, and obtain polyurethane(s) solid.Isocyanato in stiffening agent, relative to equivalence ratio [NCO]/([OH]+[COOH]) of the total of the hydroxyl value contained by host and acid number, is obtained as follows.
[NCO]/([OH]+[COOH])
=[561 × (NCO% of stiffening agent) × (stiffening agent allotment amount (g) relative to host 100g)]/[(hydroxyl value of host and the total (mgKOH/g) of acid number) × 42 × 100]
At thickness be the aluminium foil of 40 μm a face on, using glue spread: the amount of 5g/ square metre is coated with above-mentioned polyurethane(s) solid as skin solid by dry adhered machine, after making solvent evaporates, lamination thickness is the extension polyamide membrane of 30 μm.Then, on another face of the aluminium foil of the laminated film of gained, with glue spread: the amount of 5g/ square metre is coated with following internal layer solid by dry adhered machine, after making solvent evaporates, lamination thickness is the non-extended polypropylene film of 30 μm, then, carry out the sclerosis (aging) of 60 DEG C, 7 days, make outer with and internal layer solid harden and obtain battery use packing material.
* internal layer solid
Be that following host and stiffening agent are allocated in host/stiffening agent=100/10 with mass ratio range, and add toluene in the mode that nonvolatile component is 30% and make internal layer solid, above-mentioned host adds TuftecM1913 in a reservoir (side chain has the styrene ethylene butadiene-vinylbenzene (Styrene-Ethylene-Butadiene-Styrene of carboxyl, SEBS), Asahi Chemical Industry's chemistry (AsahiKaseiChemicals) company manufactures, styrene content is 30 % by weight, carboxyl amount is 0.19mmol/g, containing 11.4 carboxyls in every 1 molecule): 55 parts, and as stick together imparting agent (B) Huang Chuan chemical industrial company manufacture complete hydrogenation C9 Resin A rkonP-140 (softening temperature is 140 DEG C, without acid number): 45 parts, undertaken diluting by the mixed solvent of toluene/methyl ethyl ketone=8/2 and at 50 DEG C heated and stirred 3 hours and obtaining, above-mentioned stiffening agent is the solids component made by the trimer of dilution with toluene hexamethylene diisocyanate is the solution of 50%.
According to following evaluation assessment in the above described manner and the battery use packing material obtained carries out performance evaluation.
< humidity resistance tests the size that battery use packing material is cut into 200mm × 15mm by forward and backward lamination strength >, be 20 DEG C in temperature, under relative humidity is the environment of 65%, use tensile testing machine to be within 300mm/ minute, carry out the stripping test of T mould with peeling rate.Represent with the mean value of each 5 test films and extend stripping strength (N/15mm width) between polyamide membrane and aluminium foil (humidity resistance test before lamination strength).
In addition, battery use packing material is added to 70 DEG C, in the constant temperature and humidity cabinet of 90%RH environment, leaves standstill after 168 hours, battery use packing material self-constant temperature constant humidity groove is taken out, in the mode identical with before test, measure lamination strength (lamination strength after humidity resistance test).According to the mean value of each stripping strength, carry out the evaluation of following 4 grades.
◎: more than 6N/15mm (excellent in practicality)
Zero: more than 4N/15mm and be less than 6N/15mm (practical region)
△: more than 2N/15mm and be less than 4N/15mm (practical lower limit)
×: be less than 2N/15mm
Above result is shown in table 2 in the lump.
Battery use packing material is cut into the size of 80mm × 80mm by < formability evaluation assessment >, and as blank sample (by forming material, starting material).To above-mentioned blank sample, by forming height can the straight mould (straightmold) of free variation carry out outstanding 1 section shaping, evaluate formability by the protuberance of the fracture or each interlayer that do not produce aluminium foil and maximum forming height.In addition, the square that the tapping and plugging machine shape of the mould used is a limit is 30mm, corner R are 2mm, tapping and plugging machine shoulder R is 1mm, mould shoulder R:1mm.According to shaping height, carry out the evaluation of following 4 grades.
◎: more than 6mm (excellent in practicality)
Zero: more than 4mm and be less than 6mm (practical region)
△: more than 2mm and be less than 4mm (practical lower limit)
×: be less than 2mm
Above result is shown in table 2 in the lump.
Battery use packing material is cut into the size of 80mm × 80mm by the weather resistance > of < forming composition, and as blank sample (by forming material, starting material).To above-mentioned blank sample, by forming height can the straight mould of free variation with forming height to be that 3mm carries out outstanding 1 stage shaping.Then, by being added to 70 DEG C, in constant temperature and humidity cabinet under 90%RH environment through shaping battery container, 168 hours are left standstill.Self-constant temperature constant humidity groove takes out battery container, confirms the outward appearance of battery container, evaluates whether produce protuberance.In addition, the square that the tapping and plugging machine shape of the mould used is a limit is 30mm, corner R are 2mm, tapping and plugging machine shoulder R is 1mm, mould shoulder R:1mm.
Zero: without protuberance
×: produce protuberance
Above result is shown in table 2 in the lump.
According to the result of table 2, the hydroxyl of polyhydroxy reactant (A) and the total of carboxyl is derived from relative to comprising in the host of polyhydroxy reactant (A) and silane coupling agent (B) by using, and the equivalence ratio of isocyanato contained in above-mentioned stiffening agent be 10 ~ 30 scope in allocate the battery use packing material polyurethane(s) solid of polymeric polyisocyanate stiffening agent, and before humidity resistance can be provided to test, after lamination strength, the battery use packing material of formability excellence, above-mentioned polyhydroxy reactant (A) is the polyester polyol (A2) 95 % by weight ~ 50 % by weight that the polyester polyol (A1) 5 % by weight ~ 50 % by weight of more than 40 DEG C and glass transition temperature are less than 40 DEG C containing glass transition temperature.Also known in addition, by the forming composition using the battery use packing material of above-mentioned battery use packing material polyurethane(s) solid can form excellent in te pins of durability.
Comparative example 1 humidity resistance test forward and backward lamination strength in and no less than embodiment, but relative to being derived from the hydroxyl of polyhydroxy reactant (A) and the total of carboxyl in host, the equivalence ratio of isocyanato when comprising polymeric polyisocyanate stiffening agent in above-mentioned stiffening agent is too small, therefore insufficient formability, the weather resistance of forming composition is also poor.In addition, in comparative example 3, relative to being derived from the hydroxyl of polyhydroxy reactant (A) and the total of carboxyl in host, even if the equivalence ratio of isocyanato when comprising polymeric polyisocyanate stiffening agent in above-mentioned stiffening agent is appropriate, the ratio of components of polyester polyol (A1), polyester polyol (A2) is also incorrect, the therefore poor durability of forming composition.
Utilizability in industry
Polyurethane(s) solid of the present invention can be widely used as the solid forming battery container or battery package.Particularly be suitable as to form the battery container of secondary cell or the solids of battery package such as lithium ion battery, lithium ion polymer battery, lead storage battery, alkaline cell, oxidation silver zinc storage battery, metal-air battery, polyvalent cation battery, electrical condenser (condenser), electric capacity (capacitor).Polyurethane(s) solid of the present invention is for by identical or different raw-material adherend bonder, such as can preferably for the joint of the raw-material multilayer laminated boards body of plastic cement system starting material and metal system.Certainly, plastic cement system starting material joint each other, metal system starting material joint each other is also suitable for.Use solid of the present invention and the formability of laminate that obtains is excellent, environmental resistance is high, also can suppress under the condition of outdoor exposure through time Bonding strength reduction, that long-term strong cohesiveness excellent strength, face shaping is also excellent.Therefore; also can be used as blister pack (PressThroughPackage, PTP) or steel plate etc. to need the laminate of formability or protection walls material, roof material, solar cell panel material, window material, outdoor floor material, throw light on and protect the solid of the outdoor industrial applications laminates such as the fabrication such as material, automobile component.
This application case advocates the right of priority based on the Japanese patent application case Patent 2012-242154 of application on November 1st, 2012, and the full content disclosed is incorporated herein.
Nomenclature
(11): outer layer side resin film layer
(12): outer layer side adhesion agent layer
(13): metal foil layer
(14): internal layer side adhesion agent layer
(15): internal surface layer

Claims (9)

1. a battery use packing material polyurethane(s) solid, it contains host and polymeric polyisocyanate stiffening agent, and it is characterized in that:
Described host comprise polyhydroxy reactant (A), with silane coupling agent (B), described polyhydroxy reactant (A) is the polyester polyol (A2) 95 % by weight ~ 50 % by weight that the polyester polyol (A1) 5 % by weight ~ 50 % by weight of more than 40 DEG C and glass transition temperature are less than 40 DEG C containing glass transition temperature, the number average molecular weight of described polyester polyol (A1) and described polyester polyol (A2) is 5,000 ~ 100,000
Isocyanato contained in described polymeric polyisocyanate stiffening agent is 10 ~ 30 relative to equivalence ratio [NCO]/([OH]+[COOH]) of the total of the hydroxyl and carboxyl that are derived from described polyhydroxy reactant (A).
2. battery use packing material polyurethane(s) solid according to claim 1, wherein further containing can with the compound of carboxyl reaction (C).
3. battery use packing material polyurethane(s) solid according to claim 2, it is characterized in that described can with the compound of carboxyl reaction (C) for have glycidyl compound, there is the compound of carbon imide base and there is at least one compound of compound of oxazoline group.
4. battery use packing material polyurethane(s) solid according to claim 3, the compound described in it is characterized in that with glycidyl is biphenol type epoxy compound.
5. battery use packing material polyurethane(s) solid according to claim 1 and 2, is characterized in that described polymeric polyisocyanate stiffening agent contains fragrant family polymeric polyisocyanate.
6. a battery use packing material, it is that sequentially lamination outer layer side resin film layer (11), outer layer side adhesion agent layer (12), metal foil layer (13), internal layer side adhesion agent layer (14) and heat sealing layer (15) form, and it is characterized in that:
Described outer layer side adhesion agent layer (12) is formed by the battery use packing material polyurethane(s) solid such as according to any one of claim 1-5.
7. battery use packing material according to claim 6, it is characterized in that outer layer side resin film layer (11) is for polyamide membrane or polyester film, heat sealing layer (15) is polyolefine mesentery.
8. a battery container, it forms by battery use packing material is as claimed in claims 6 or 7 shaping, and outer layer side resin film layer (11) forms convex surface, and heat sealing layer (15) forms concave surface.
9. a battery, it uses battery container as claimed in claim 8 to form.
CN201380003598.3A 2012-11-01 2013-10-31 Battery use packing material polyurethane(s) solid, battery use packing material, battery container and battery Active CN103975035B (en)

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JP2012242154A JP5267718B1 (en) 2012-11-01 2012-11-01 Polyurethane adhesive for battery packaging material, battery packaging material, battery container and battery
JP2012-242154 2012-11-01
PCT/JP2013/006460 WO2014068986A1 (en) 2012-11-01 2013-10-31 Polyurethane adhesive for packaging materials for batteries, packaging material for batteries, battery container, and battery

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