CN110281612A - Battery exterior laminated body, battery exterior body and battery - Google Patents

Battery exterior laminated body, battery exterior body and battery Download PDF

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Publication number
CN110281612A
CN110281612A CN201910621170.4A CN201910621170A CN110281612A CN 110281612 A CN110281612 A CN 110281612A CN 201910621170 A CN201910621170 A CN 201910621170A CN 110281612 A CN110281612 A CN 110281612A
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CN
China
Prior art keywords
layer
laminated body
battery exterior
battery
acid
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Granted
Application number
CN201910621170.4A
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Chinese (zh)
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CN110281612B (en
Inventor
饭塚宏和
佐藤友纪
武井邦浩
金田康宏
宫胁晃
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Fujimori Kogyo Co Ltd
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Fujimori Kogyo Co Ltd
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Priority claimed from JP2016116658A external-priority patent/JP6768364B2/en
Application filed by Fujimori Kogyo Co Ltd filed Critical Fujimori Kogyo Co Ltd
Publication of CN110281612A publication Critical patent/CN110281612A/en
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Classifications

    • 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
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/18—Layered products comprising a layer of metal comprising iron or steel
    • 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
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • 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
    • B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
    • 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
    • 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
    • B32B2255/00—Coating on the layer surface
    • B32B2255/06—Coating on the layer surface on metal layer
    • 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
    • B32B2255/00—Coating on the layer surface
    • B32B2255/10—Coating on the layer surface on synthetic resin layer or on natural or synthetic rubber layer
    • 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
    • B32B2255/00—Coating on the layer surface
    • B32B2255/20—Inorganic coating
    • 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
    • B32B2255/00—Coating on the layer surface
    • B32B2255/26—Polymeric coating
    • 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
    • B32B2457/00—Electrical equipment
    • B32B2457/10—Batteries
    • 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

Landscapes

  • Laminated Bodies (AREA)
  • Sealing Battery Cases Or Jackets (AREA)

Abstract

The present invention provides a kind of new battery exterior laminated body that can be realized filming, with excellent characteristic, and can be manufactured with high finished product rate and high productivity.The battery exterior laminated body is at least successively with battery exterior laminated body made of first base material layer, first bonding agents layer, the first corrosion-resistant coating, stainless steel foil and the second substrate layer, it is characterized in that, the first base material layer is the layer that is made of polyolefin, and the first bonding agents layer is the layer that is made of the bonding agent of the compound (B) containing 100 mass parts acid-modified polyolefin resins (A) and 1~20 mass parts with multiple epoxy groups.

Description

Battery exterior laminated body, battery exterior body and battery
The application be in August, 2016 applying date 3, Chinese Patent Application No. is 201610629152.7 and denomination of invention For the divisional application of the Chinese patent application of " battery exterior laminated body, battery exterior body and battery ", and the application wants It asks and enjoys that application No. is the priority of the Japanese publication of 2015-184343 and 2016-116658.
Technical field
The present invention relates to a kind of good battery exterior laminated body of exterior body as secondary cell, capacitor etc., with And use the resulting battery exterior body of the laminated body and battery.
Background technique
While the effective use of the natural energy resources such as environmental consciousness raising, sunlight and wind-force, as storing electricity The battery of energy, the capacitors such as the secondary cells such as lithium ion battery or double layer capacitor are gazed at.
For the purpose of miniaturization and lightweight, as the exterior body for being used in these batteries, it can be used and be laminated with metal foil And the battery exterior laminated body of resin layer.By draw molding etc. make such battery exterior with laminated body be shaped to have it is recessed The plate-like in portion, in this, as exterior body vessel.
In addition, with the exterior body vessel likewise, making battery exterior that body formed acquisition exterior body cover be laminated. After storing battery body in the recess portion of this exterior body vessel, it is overlapped in a manner of covering the battery body being contained outer Body cover is filled, by the edge part between bonding vessel and exterior body cover, acquisition is accommodated with battery sheet in exterior body The battery of body.
Such as in patent document 1, it discloses one kind and is sequentially laminated with substrate layer, aluminium foil, by polypropylene or polyethylene layer The battery exterior laminated body of the innermost layer constituted.
Existing technical literature
Patent document
Patent document 1: special open 2012-33393 bulletin
Summary of the invention
The technical problem to be solved in the present invention
In the application field extension of the batteries such as secondary cell, the exploitation of battery small-sized and with large capacity is advanced. Likewise, battery exterior is also maintaining mechanical strength, water resistance, chemical resistance (electrolyte resistance) etc. excellent with laminated body While characteristic, the filming of laminated body itself is sought.In general, mechanical strength, the water resistance, resistance toization of battery exterior laminated body Learn drug (electrolyte resistance) and light-proofness mainly according to the inorganic layers such as metal foil of the battery exterior in laminated body come Ensured.As metal foil, the aluminium foil of excellent in workability is widely used (referring to patent document 1).
But due to aluminium foil compared with other metal foils excellent in workability, laminated body can be manufactured with high finished product rate, separately On the one hand, the bad mechanical strengths such as puncture strength compared with other metal foils.Therefore, mechanical strength in order to obtain, cannot make aluminium foil Thickness certain hereinafter, in the status using aluminium foil, battery exterior is difficult to filming with laminated body.
The present invention is completed in view of above-mentioned status, purpose be provide it is a kind of can filming and the excellent electricity of various characteristics Pond exterior laminated body.
Solve the technological means of technical problem
The present inventor is inquired into repeatedly in order to achieve the above objectives, as a result uses following composition: logical It crosses and replaces aluminium foil using stainless steel foil, it can be with filming while guaranteeing the mechanical strengths such as puncture strength.But know, if Using stainless steel foil manufacture battery exterior laminated body, then be considered as by previous aluminium foil not it has been found that poor attachment There are technical problems in caused planar defect, electrolyte resistance.Then the present inventor has made intensive studies, success Ground new discovery bonding that the stainless steel foil and substrate layer that are surface-treated using anticorrosive can be made suitably to be bonded Agent, so as to complete the present invention.
I.e. present invention employs compositions below:
The first aspect of the present invention is battery exterior laminated body, is that at least successively there is first base material layer, first to glue Connect battery exterior laminated body made of oxidant layer, the first corrosion-resistant coating, stainless steel foil and the second substrate layer, which is characterized in that The first base material layer is the layer being made of polyolefin, and the first bonding agents layer is by modified poly- containing 100 mass parts acid The layer that there is the bonding agent of the compound (B) of multiple epoxy groups to be constituted for olefin resin (A) and 1~20 mass parts.
The compound with multiple epoxy groups is preferably novolac epoxy resin (phenol novolak type epoxy resin)。
The epoxide equivalent of the novolac epoxy resin is preferably 100~300.
The novolac epoxy resin preferably has structure of bisphenol A.
First corrosion-resistant coating preferably comprises metal halide compound.
The metal halide compound is preferably the chloride or fluoride of iron, chromium, manganese or zirconium.
First corrosion-resistant coating preferably comprises resin, metal fluoride compound and phosphorylation with polyvinyl alcohol skeleton Close object.
The thickness of the stainless steel foil is preferably 10~30 μm.
The first base material layer is preferably homopolypropylene or block polypropylene.
The second aspect of the present invention is a kind of battery exterior body, for the battery exterior stacking with the first aspect The battery exterior body of body, which is characterized in that there is the inner space of storage battery, the first base material layer of battery exterior laminated body Side is the inner space side.
The third aspect of the present invention is a kind of battery, which is characterized in that the battery exterior body with the second aspect.
Invention effect
According to the present invention it is possible to provide a kind of to come with excellent characteristic and with high finished product rate and high productivity The battery exterior laminated body of manufacture.In addition, battery exterior laminated body of the invention can be with filming.
Detailed description of the invention
Fig. 1 is to show the schematic sectional view of the first embodiment of battery exterior laminated body of the invention.
Fig. 2 is to show the solid of an example of the secondary cell manufactured using battery exterior of the invention with laminated body Figure.
Fig. 3 is to show the perspective view for the process for manufacturing secondary cell with laminated body using battery exterior of the invention.
Fig. 4 is to show the perspective view for the process for manufacturing secondary cell with laminated body using battery exterior of the invention.
Specific embodiment
Hereinafter, according to suitable embodiment, the present invention will be described.But present embodiment is the purport to invention The more specific description of progress does not limit the present invention without specifying.
[battery exterior laminated body]
The battery exterior laminated body (below sometimes referred to simply as " laminated body ") of the first aspect of the present invention be at least according to It is secondary that there is battery made of first base material layer, first bonding agents layer, the first corrosion-resistant coating, stainless steel foil and the second substrate layer Exterior laminated body, the first base material layer are the layer being made of polyolefin, and the first bonding agents layer is by containing 100 matter There is the bonding agent of the compound (B) of multiple epoxy groups to be constituted for amount part acid-modified polyolefin resin (A) and 1~20 mass parts Layer.
Fig. 1 is to show the section of the schematic structure of battery exterior laminated body 10 of an embodiment of the invention Figure.
The laminated body 10 of present embodiment successively has first base material layer 11, first bonding agents layer 12, the first corrosion-resistant coating 13, stainless steel foil 14, the second corrosion-resistant coating 16, second bonding agents layer 17, the second substrate layer 15 form.
That is, the laminated body 10 of present embodiment is made of 7 layers of structure, which has the two of stainless steel foil 14 The first corrosion-resistant coating 13 and the second corrosion-resistant coating 16 are formed by face, on the first corrosion-resistant coating 13 via first bonding agents Layer 12 and be laminated first base material layer 11, on the second corrosion-resistant coating 16 via second bonding agents layer 17 and be laminated the second substrate Layer 15.
Each layer is described in detail below.
First base material layer 11 is the layer that is made of polyolefin.The layer being made of polyolefin can enumerate polyethylene, poly- third The random copolymer of alkene, poly-1-butylene, polyisobutene, polyethylene, propylene and ethylene or alpha-olefin, propylene and ethylene or α-alkene The block copolymer etc. of hydrocarbon.
Wherein, from the cementability improved with first bonding agents layer 12, preferably homopolypropylene (Noblen；With Down sometimes referred to as " homopolymerization PP "), the nothing of the block copolymer (hereinafter sometimes referred to " block PP ") of propylene-ethylene, propylene-ethylene Advise polypropylene-based resins such as copolymer (hereinafter sometimes referred to " random PP ").Wherein, more preferable homopolymerization PP or block PP, block PP It is particularly preferred due to mechanical strength.
First base material layer 11 can be single layer structure, or multilayered structure.
As long as the fusing point for the layer that polyolefin used in first base material layer 11 is constituted has battery exterior laminated body 10 There is required heat resistance, is then not particularly limited.
For example, can make first base material layer 11 with a thickness of 1~30 μm.
First bonding agents layer 12 is more by having containing 100 mass parts acid-modified polyolefin resins (A) and 1~20 mass parts The layer that the bonding agent of the compound (B) of a epoxy group is constituted.
Above-mentioned battery exterior needs mechanical strength, water resistance, chemical resistance (electrolyte resistance) etc. each with laminated body Kind characteristic.These characteristics are undertaken by battery exterior with the metal foil in laminated body mostly, outside the angle of cell durability, battery The metal foil of dress body plays very important effect.Moreover, in battery in use, in order not to keep the metal foil bad due to rust etc. Change, often will use the metal foil for having been carried out antirust treatment.
For previous used aluminium foil, the structure of the anti-corrosion treatment agent (corrosion-resistant coating) with good anticorrosion ability At being well-known.
On the other hand, the present invention in, in order to balance filming and mechanical strength (puncture strength etc.) and use stainless steel foil. It is well known that in a metal, stainless steel is not easy to get rusty, but for can under the extreme situation of electrolyte contacts etc. used in The stainless steel foil of battery exterior laminated body, carries out antirust treatment preferably samely.Thus it is possible to give stainless steel foil The anti-rust agent for treatment of good rust-proof effect and previous aluminium foil can be different composition with anti-rust agent for treatment.
But the first corrosion-resistant coating being made of the stainless steel foil anti-rust agent for treatment is arranged in stainless steel foil table Face as a result, in previous bonding agent, the first corrosion-resistant coating surface and first base material layer surface cannot be bonded well, sent out The now generation of the planar defect as caused by poor attachment.
Here, the present inventor conducts further research, as making (the first anticorrosion of stainless steel foil antirust coat Layer) with first base material layer can be bonded well bonding agent, it was found that contain 100 mass parts acid-modified polyolefin resins (A) There is the bonding agent of the compound (B) of multiple epoxy groups with 1~20 mass parts.
Then, by using first base material layer, the first bonding agents layer being made of this bonding agent, the first corrosion-resistant coating And stainless steel foil, following effect may be implemented: (1) mechanical strength (puncture strength etc.) being improved by stainless steel foil and realize film Change；(2) rust-proof effect of stainless steel foil is improved by the first corrosion-resistant coating, and thus improves durability；(3) pass through the first bonding Oxidant layer improves mechanical strength (peel strength etc.), reduces the hair of planar defect caused by the poor attachment when manufacturing laminated body It is raw, and improve yield rate.
Bonding agent
The bonding agent for forming first bonding agents layer 12 in the present invention contains 100 mass parts acid-modified polyolefin resins (A) There is the compound (B) of multiple epoxy groups with 1~20 mass parts.
Hereinafter, sometimes referred to as acid-modified polyolefin resin (A) is " (A) ingredient ", the compound (B) with multiple epoxy groups is " (B) ingredient ".
(acid-modified polyolefin resin (A))
In the present invention, acid-modified polyolefin resin (A) is polyene using unsaturated carboxylic acid or derivatives thereof and modified Hydrocarbon resins, the acid functional group with carboxyl or acid anhydride etc. in polyolefin resin.
(A) modification of the ingredient by the polyolefin resin using unsaturated carboxylic acid or derivatives thereof, list containing acid functional group Copolymerization of body and olefines etc. and obtain.Wherein, as (A) ingredient, the modified gained of acid preferably is carried out to polyolefin resin Substance.
As sour method of modifying, it can enumerate and cause in the free radical polymerizations such as organic peroxide or aliphatic azo compound In the presence of agent, melt kneading (melt-kneading) polyolefin resin and the graft modification containing acid functional monomers.
The polyolefin resin can enumerate polyethylene, polypropylene, poly-1-butylene, polyisobutene, propylene and ethylene or α- Random copolymer, propylene and the ethylene of alkene or the block copolymer of alpha-olefin.Wherein, preferred homo-polypropylene (Noblen； Hereinafter sometimes referred to " homopolymerization PP "), the block copolymer (hereinafter sometimes referred to " block PP ") of propylene-ethylene, propylene-ethylene The polypropylene-based resins such as random copolymer (hereinafter sometimes referred to " random PP "), particularly preferred random PP.
As the olefines in the case of copolymerization, ethylene, propylene, 1- butylene, isobutene, 1- hexene, α-alkene can be enumerated The olefin monomers such as hydrocarbon.
It is that there is olefinic double bond, carboxyl or the compound of acid anhydride in same intramolecular containing acid functional monomers, can arranges Enumerate the acid anhydrides of various unsaturated monocarboxylics, dicarboxylic acids or dicarboxylic acids.
As (carboxyl group-containing monomer) containing acid functional monomers with carboxyl, acrylic acid, methacrylic acid, Malaysia can be enumerated Acid, nadic acid, fumaric acid, itaconic acid, citraconic acid, crotonic acid, iso-crotonic acid, tetrahydro phthalandione, interior bicyclic [2.2.1] -5- heptan The alpha, beta-unsaturated carboxylic acids monomers such as alkene -2,3- dicarboxylic acids (5- norbornene -2,3- dicarboxylic acids (endic acid)).
As (monomer containing acid anhydride) containing acid functional monomers with acid anhydride, maleic anhydride, Na Di can be enumerated The unsaturated dicarboxylics anhydride monomers such as gram acid anhydrides, itaconic anhydride, citraconic anhydride, carbic anhydride.
These are can be used alone in (A) ingredient containing acid functional monomers, can also and with two or more.
Wherein, as acid functional monomers are contained, due to high with the reactivity of aftermentioned (B) ingredient, preferably with anhydride group Containing acid functional monomers, more preferable monomer containing acid anhydride, particularly preferred maleic anhydride.
It is unreacted in order to prevent in a part of unreacted situation containing acid functional monomers used in being modified in acid Reduction containing bonding force caused by acid functional monomers will preferably remove the unreacted substance containing acid functional monomers in advance and make For (A) ingredient come using.
In (A) ingredient, polyolefin resin or total amount 100 mass of the ingredient relative to (A) ingredient from olefines Part, it is more than preferably 50 mass parts.
(A) fusing point of ingredient is not particularly limited.
For example, bonding agent used in the present invention does not contain organic solvent, carried out by (A) ingredient and aftermentioned (B) ingredient In the case that melt kneading forms bonding agent, the fusing point of (A) ingredient is preferably 100 DEG C~180 DEG C.It is made of this bonding agent Adhesive layer can suitably be used as heat lamination adhesive layer.
By using (A) ingredient of the fusing point with above range, even if using conventional method and general device In the case where, can also with than the fusing point of (A) ingredient also than sufficiently high temperature melt kneading (A) ingredient and aftermentioned (B) ingredient. In addition, in the case where reacting (A) ingredient with aftermentioned (B) ingredient, the preferred fusing point ratio of (B) ingredient (A) ingredient is low, and by using (A) ingredient of the fusing point with above range, the selection freedom degree of (B) ingredient can be improved.
In addition, the preferably fusing point of (A) ingredient is higher than the fusing point of aftermentioned (B) ingredient as described above, more preferable (A) ingredient melts High 10 DEG C of fusing point or more of point than (B) ingredient, further preferably high 20 DEG C or more, particularly preferably high 30 DEG C or more.Due to (A) at Fusing point ratio (B) ingredient divided is also sufficiently high, and when carrying out melt kneading, (B) ingredient is first dissolved, and is impregnated into and keeps resin shape state (A) ingredient in, (A) ingredient is equably reacted with (B) ingredient, as a result available good durability.
On the other hand, in the case where first bonding agents layer 12 is as dry type stacking adhesive layer, the fusing point of (A) ingredient Preferably 50~100 DEG C.By being arranged by being made of containing fusing point the bonding agent of the polyolefin of 50~100 DEG C of relatively low melting point Layer, can with the relatively low temperature for the degree not deformed on stainless steel foil, i.e., with 100 DEG C nearby or its temperature below, warp There is the stainless steel foil and first base material layer of the first corrosion-resistant coating by first bonding agents layer bonding.
Wherein, preferably maleic anhydride modified poly- from the angle of cementability and the fusing point of appropriateness as (A) ingredient Propylene.
(compound (B) with multiple epoxy resin)
(B) ingredient is the compound with multiple epoxy groups.(B) it is also producing high-molecular that ingredient, which can be low molecular compound, Close object.From the good angle of miscibility with (A) ingredient, (B) ingredient is preferably high-molecular compound (resin).Another party Face, from the angle of the favorable solubility to solvent, (B) ingredient is preferably low molecular compound.
(B) structure of ingredient is not particularly limited as long as having multiple epoxy groups, for example, can enumerate by bisphenols and table chlorine Phenoxy resin, novolac epoxy resin, the bisphenol-type epoxy resin etc. of alcohol synthesis.Wherein, due to the epoxy content of per molecule Height can especially form fine and close cross-linked structure, it is preferable to use novolac epoxy resin with (A) ingredient.
Novolac epoxy resin in the present invention is that will carry out acid by phenol and formaldehyde and be condensed resulting line style phenolic aldehyde Epoxy resin imports the compound of epoxy group as basic structure in a part of this structure.In novolac epoxy resin The epoxy group import volume of per molecule is not particularly limited, but by making the epoxy groups such as epichlorohydrin raw material and novolac epoxy resin Reaction imports a large amount of epoxy groups on a large amount of existing phenolic hydroxyl groups in novolac epoxy resin, therefore usually multifunctional ring Oxygen resin.
Wherein, as novolac epoxy resin, preferably there is the line style phenolic structure as basic framework, and have simultaneously There is the bisphenol A novolak epoxy resin of structure of bisphenol A.In addition, the structure of bisphenol A in novolac epoxy resin can be for by double The derivative obtained structure of phenol A, it is possible to use the hydroxyl at the groups displacement bisphenol-A such as group containing epoxy group both ends.
As an example of bisphenol A novolak epoxy resin, the resin of the following general formula (1) expression can be enumerated.
[chemical formula 1]
In formula (1), R1~R6For hydrogen atom independent or methyl, the integer that n is 0~10, RXFor with epoxy group Group.
In formula (1), R1~R6For hydrogen atom independent or methyl.In the case where the integer that n is 2 or more, R3、R4Respectively From can it is identical can also be different.
In the resin that formula (1) indicates, at least one of following (i)~(iii) is preferably satisfied.
(i)R1And R2The two is methyl；
(ii)R3And R4The two is methyl；
(iii)R5And R6The two is methyl.
For example, by meeting above-mentioned (i), in formula (1), R1And R2In conjunction with carbon atom and the carbon atom combined Two hydroxyphenyls constitute the structure as derived from bisphenol-A.
In formula (1), RXFor the group with epoxy group.As the group with epoxy group, epoxy group, epoxy group can be enumerated With the combination of alkylidene etc., wherein preferred glycidyl.
The epoxide equivalent of bisphenol A novolak epoxy resin preferably 100~300, more preferable 200~300.Epoxide equivalent It (g/eq) is the molecular weight of the epoxy resin of 1 epoxy group, the smaller epoxy group meaned in resin of this numerical value is more.By making With the lesser epoxy resin of epoxide equivalent, even if the additive amount in novolac epoxy resin is line style in less amount of situation The cementability of novolac epoxy resin and adherend is good, and novolac epoxy resin and the acid-modified polyolefin resin are abundant Ground is crosslinked.
As this bisphenol A novolak epoxy resin, can be used society, Mitsubishi Chemical jER154, jER157S70, jER-157S65；EPICLON N-730A, EPICLON N-740, EPICLON N-770, the EPICLON N-775 of DIC society Commercially available products such as (being above trade name).
It is thought that by using above-mentioned epoxy resin, the acid functional group of (A) ingredient and the epoxy group both sides of (B) ingredient Due to playing a role as the cementability functional group for adherend (the especially functional groups such as hydroxyl for having of adherend), because And excellent cementability can be played for first base material layer 11 and the first corrosion-resistant coating 13.
In addition, it is also believed that a part reaction of a part of the acid functional group of (A) ingredient and the epoxy group of (B) ingredient, energy Enough cross-linked structures for forming (A) ingredient and (B) ingredient, according to this cross-linked structure, the intensity of resin is reinforced, obtain it is excellent Also good durability has been obtained while cementability.
In the bonding agent being used in the present invention, contain 1~20 matter of (B) ingredient preferably with respect to 100 mass parts of (A) ingredient Measure part, further preferably contain 5~10 mass parts of (B) ingredient relative to 100 mass parts of (A) ingredient, most preferably relative to (A) at 100 mass parts are divided to contain 5~7 mass parts of (B) ingredient.
Bonding agent used in the present invention can be according to the required appropriate additive containing with miscibility, additional tree Rouge, plasticizer, stabilizer, colorant etc..
In addition, bonding agent of the invention can also further contain or not contain organic solvent.
Become the bonding agent of liquid and containing organic solvent, the bonding for being for example suitable for dry type stacking can be become Agent.By the coating on the layer as lower layer and dry this liquid bonding agent, adhesive layer can be formed.
On the other hand, in the case where being free of organic solvent, pass through melt kneading acid-modified polyolefin resin and asphalt mixtures modified by epoxy resin Rouge, and extrusion molding etc. is carried out after this, the adhesive layer for being suitable for heat lamination etc. can be formed.
In the case where containing organic solvent, as the organic solvent used, as long as can suitably to dissolve above-mentioned tree The substance of rouge is then not particularly limited, and toluene etc. can be used for example.The usage amount of organic solvent is not particularly limited, and solid component is excellent Select 3~30 mass %, more preferable 5~25 mass %, further preferred 10~20 mass %.
Can make first bonding agents layer 12 with a thickness of such as 0.5~10 μm.It, can be with height by making thickness in this range Bonding force is bonded first base material layer 11 and stainless steel foil 14, can prevent splitting.
In present aspect, the first corrosion-resistant coating 13 is for preventing the corrosion caused by rust etc. of stainless steel foil 14 Layer.
First corrosion-resistant coating 13 preferably comprises metal halide compound, can be by aftermentioned metal halide compound directly not Plating is carried out on the surface of rust steel foil 14.By the way that such first corrosion-resistant coating 13 is arranged, it is good stainless steel foil can be given Good rust-proof effect.
Wherein, the first corrosion-resistant coating 13 further preferably water-soluble resin preferably contains water-soluble tree by coating Rouge, metal halide compound, chelating agent water soluble paint after, it is dry to be simultaneously solidified to form.
Water soluble paint
(water-soluble resin)
As water-soluble resin, it is preferable to use more than one among polyvinyl alcohol resin and polyvinylether resinoid.
Polyvinyl alcohol resin is at least one as selected in polyvinyl alcohol resin and modified polyvinylalcohol resin Water-soluble resin.
Polyvinyl alcohol resin can for example, by make vinyl ester monomer polymer or its copolymer saponification come into Row manufacture.
As the polymer or its copolymer of vinyl ester monomer, vinyl formate, vinyl acetate, butyric acid can be enumerated The homopolymers of vinyl esters monomer such as the aromatic vinyls ester such as the fatty acid vinyl esters such as vinyl acetate or benzoic acid vinyl acetate or Copolymer and the copolymer for the other monomers that can be copolymerized with it etc..
As the other monomers that can be copolymerized, it can be mentioned, for example olefines such as ethylene, propylene, alkyl vinyl ether etc. contains ether The monomer, (ketone containing carbonyl such as Diacetone Acrylamide, diacetone (methyl) acrylate, acetoacetic acid allyl ester, acetoacetic ester Base) monomer, the unsaturated carboxylic acids class such as acrylic acid, methacrylic acid, maleic anhydride, the ethylene halides such as vinyl chloride or vinylidene chloride Class and unsaturated sulfonic acid class etc..
The saponification degree of polyvinyl alcohol resin generally preferable 90~100 moles of %, more preferable 95 moles of % or more.
As polyvinyl alcohol resin, can enumerate alkyl oxide modified polyvinyl alcohol resin, carboxy-modified polyvinyl alcohol resin, Acetoacetyl modified polyvinyl alcohol resin, acetamide modified polyvinyl alcohol resin, acrylonitrile modified polyvinyl alcohol resin, carboxyl Modified polyvinylalcohol resin, silicone modified polyvinyl alcohol resin, ethylene modified polyvinyl alcohol resin etc..Wherein, optimizing alkyl ether Modified polyvinylalcohol resin, carboxy-modified polyvinyl alcohol resin, carboxy-modified polyvinyl alcohol resin, acetoacetyl modified poly- second Enol resin.
As the commercially available product that can generally start with of polyvinyl alcohol resin, it can be mentioned, for example Japanese VAM&POVAL (strains) The CROSSMER H serial (trade name) etc. of J-POVAL DF-20 (trade name), the Japan CARBIDE of system industrial (strain) system.It is poly- One kind or two or more mixture can be used in vinyl alcohol resin.
As polyvinylether resinoid, ethyl vinyl ether, n-propyl vinethene, isopropyl-ethylene ether, normal-butyl can be enumerated Vinethene, isobutylvinyl ether, 2- ethylhexyl vinyl ether, cyclohexyl vinyl ether, norborny vinethene, allyl vinyl The homopolymers of aliphatic ethylenes ether such as ether, norbornene vinethene, 2- hydroxyethyl vinyl ether, diethylene glycol monovinyl ether or The copolymer etc. of copolymer and the other monomers that can be copolymerized with it.As other lists that can be copolymerized with vinyl ethers monomer Body can be enumerated and the same substance of other monomers that can be copolymerized with above-mentioned vinyl ester monomer.
Especially 2- hydroxyethyl vinyl ether, diethylene glycol monovinyl ether, 2- hydroxypropyl vinethene and other various two The mono vinyl ether of first alcohol or polyalcohol etc., in monomer containing with hydroxyl aliphatic ethylene ether glymes tree Rouge, due to having water-soluble and cross-linking reaction can be carried out for hydroxyl, it is possible to properly use in the present invention.
These polyvinylether resinoids since vinyl ether monomers can be used in manufacture (polymerization) process of resin, with via The polyvinyl alcohol resin of vinyl esters quasi polymer manufacture is different, can require no saponification process to manufacture.In addition, can also To use the copolymer containing vinyl ester monomer or vinyl ethers monomer or it made to be saponified obtained vinyl alcohol- Vinyl ether copolymers.Also mixing for the polyvinyl alcohol resin and polyvinylether resinoid other than polyvinylether resinoid can be used Close object.
As water-soluble resin, can be used only it is any among polyvinyl alcohol resin and polyvinylether resinoid, Can also two kinds be used in combination.
(metal halide compound)
Metal halide compound preferably has water solubility due to needing to be mixed with aforementioned water-soluble resin.
As metal halide compound, it can be mentioned, for example hafnium halide, iron halide, zirconium halide, halogenated titanium, halogenation hafnium, hydrogen halogen Sour titanium (チ タ Application Ha ロ ゲ Application water element acid) and their salt etc..As halogen atom, chlorine, bromine, fluorine can be enumerated, preferably chlorine or Fluorine.In addition, particularly preferred fluorine.
Wherein, as metal halide compound, the preferably chloride or fluoride of iron, chromium, manganese or zirconium.
Metal halide compound has the function of improving the chemical resistances such as electrolyte resistance.It is passivated stainless steel foil 14 Surface, the corrosion resistance for electrolyte can be improved.Metal halide compound also makes the water-soluble resin crosslinking Effect.
(chelating agent)
Water soluble paint contains chelating agent.The chelating agent is that coordination combination is carried out on metal ion, can form metal The material of ionic complex.
Chelating agent carries out metallic compound (chromium oxide etc.) and the water-soluble resin from metal halide compound In conjunction in order to improve the compressive strength of the first corrosion-resistant coating 13, even if the thickness of the first corrosion-resistant coating 13 is for example more than 0.2 μm And in 1.0 μm of situations below, it is cracked or lifted off that 13 embrittlement of the first corrosion-resistant coating will not occur.Accordingly it is also possible to improve not The adhesive strength become rusty between steel foil 14 and first bonding agents layer 12, and, it is viscous between stainless steel foil 14 and the layer of its upper layer side Connect intensity.
In addition, chelating agent with water-soluble resin or metal halide compound by being chemically reacted, having makes water solubility The effect of the resistance to aquation of resin.
As chelating agent, can be used for example for example amino carboxylic acid quasi-chelate compound, phosphonic acid type chelants, hydroxycarboxylic acid, (poly-) phosphoric acid quasi-chelate compound.
As amino carboxylic acid quasi-chelate compound, it can be mentioned, for example nitrilotriacetic acid (NTA), hydroxyethyliminodiacetic acid (HIDA), ethylenediamine tetra-acetic acid (EDTA), hydroxyethylethylene diamine tri-acetic acid (HEDTA), diethylene-triamine pentaacetic acid (DTPA), Triethylenetetraaminehexaacetic acid (TTHA), trans cvclohexvl ethylenediamine tetraacetic acid (EDTA) (CyDTA), 1,2 diaminopropane tetraacetic acid (1,2- PDTA), 1,3- trimethylen-edinitrilo-tetraacetic acid (1,3-PDTA), 1,4- butanediamine tetraacethyl (1,4-BDTA), 1,3- diamino -2- hydroxyl Propane tetraacethyl (DPTA-OH), ethylene glycol diethyl ether ethylenediamine tetraacetic acid (EDTA) (GEDTA), ethylenediamine o-hydroxy phenylacetic acid (EDHPA), SS- ethylenediamine disuccinic acid (SS-EDDS), ethylenediamine disuccinic acid (EDDS), Beta-alanine oxalic acid (ADA), the sweet ammonia of methyl Sour oxalic acid (MGDA), L-Aspartic acid-N, N- oxalic acid (ASDA), Pidolidone-N, N- oxalic acid (GLDA), N, N '-are bis- (2- hydroxy phenyl) ethylenediamine-N, N '-oxalic acid (HBEDDA).
As phosphonic acid type chelants, as long as having by phosphonic acids (HP (=O) (OH)2) derived from-P (=O) (OH)2Structure Compound, then be not particularly limited, it can be mentioned, for example N, N, N- trimethylene phosphonics (NTMP), 1- hydroxy ethylene -1,1- bis- Phosphonic acids (HEDP), ethylenediamine-N, N, N ', N '-tetramethylene phosphonic acid (EDTMP), diethylenetriamine pentamethylenophosphonic acid (DTPMP), 2- phosphonobutane -1,2,4- tricarboxylic acids (PBTC), nitrilo- three (methylene phosphonic acid) (NTMP).
As hydroxycarboxylic acid quasi-chelate compound, there are glycolic, citric acid, malic acid, gluconic acid, glucoheptonic acid etc..
As (poly-) phosphoric acid quasi-chelate compound, there are phosphoric acid, metaphosphoric acid, tripolyphosphate, four polyphosphoric acids, pyrophosphoric acid, orthophosphoric acid, six Metaphosphoric acid and their salt etc..
As the commercially available product for the chelating agent that can generally start with, it can be mentioned, for example the aminocarboxylics such as CHELEST PD-4H (PDTA) Acids chelating agent；CHELEST PH-540(EDTMP),CHELEST PH-210(HEDP),CHELEST PH-320(NTMP), The phosphonic acid type chelants such as CHELEST PH-430 (PBTC) (are the chelating agent of CHELEST (strain) system, are identified as commodity above Name).
Wherein, as chelating agent, the preferably chelating agent (phosphorus of the phosphoric acid class such as phosphonic acid type chelants, (poly-) phosphoric acid quasi-chelate compound Acid compound), more preferable phosphonic acid type chelants.
In all solids ingredient of water soluble paint, water-soluble resin preferably 3~30 mass %, more preferable 5~20 matter Measure %, further preferred 10~15 mass %.In addition, in all solids ingredient of water soluble paint, metal halide compound It is preferred that 20~60 mass %, more preferable 30~55 mass %, further preferred 40~50 mass %.In the whole of water soluble paint In solid component, chelating agent preferably 20~60 mass %, more preferable 30~50 mass %, further preferred 35~45 mass %.
Water-soluble resin, metal halide compound, chelating agent can be dissolved in the solvent containing water by water soluble paint It is manufactured.As solvent, preferably water.
After considering coating of the first corrosion-resistant coating 13 etc., the solid component in water soluble paint can be suitably determined Concentration generally can be set to 0.1~10 mass %.
Preferably 0.05 μm or more of the thickness of first corrosion-resistant coating 13, more preferably greater than 0.1 μm.By by the first corrosion-resistant coating 13 thickness is set as 0.05 μm or more, while giving sufficient corrosion resistance to battery exterior laminated body 10, can also mention High stainless steel foil 14 and the adhesive strength of first bonding agents layer 12 and the adhesive strength of stainless steel foil 14 and first base material layer 11.
In addition, preferably 1.0 μm of the thickness of the first corrosion-resistant coating 13 hereinafter, more preferable 0.5 μm or less.By by the first anti-corrosion The thickness of erosion layer 13 is set as 1.0 μm hereinafter, while improving the adhesive strength of stainless steel foil 14 and first bonding agents layer 12, can To inhibit material cost.
Stainless steel foil 14 is the metal foil of stainless steel, for example, stainless by austenitic type, ferrite type, martensite etc. Steel is constituted.There are SUS304,316,301 etc. as austenitic type, has SUS430 etc. as ferrite type, have as martensite SUS410 etc..
Stainless steel foil 14, due to high mechanical strengths such as puncture strength, tensile strengths, makes compared with other metal foils such as aluminium foil It can also give battery exterior laminated body 10 sufficient mechanical strength in the case where 40 μm of thinnesses below.As a result, can With by 10 integral thinned of stainless steel foil 14 and laminated body.
Further, since high mechanical strength can reduce the production of aperture (pin hole) when forming recess portion by drawing molding It is raw, as a result, the leakage (such as battery fluid leakage) of content closed in laminated body can be reduced.Further, since stainless The excellent corrosion resistance compared with other metal foils of steel foil 14, so the deterioration caused by corroding can be prevented well.
The thickness of stainless steel foil 14 is preferably 100 μm hereinafter, it is preferred that 5~40 μm, and more preferable 5~30 μm, particularly preferred 10 ~20 μm.By being set as above-mentioned lower limit value or more, gives battery exterior laminated body 10 sufficient mechanical strength, be used in two When the batteries such as primary cell, the durability of battery can be improved.In addition, by make stainless steel foil 14 with a thickness of above-mentioned upper limit value with Under, it is sufficiently thin that battery exterior laminated body 10 can be made, and can give and adequately draw processability.
Second corrosion-resistant coating 16 has structure identical with the first corrosion-resistant coating 13.
Second bonding agents layer 17 can be structure same as first bonding agents layer 12, can also be for by common carbamate The layer that the bonding agents such as class bonding agent, epoxy adhesive are constituted.The thickness of second bonding agents layer 17 can for example be set as 0.5~10 μm.By the way that thickness is set as this range, the second substrate layer 15 and stainless steel foil 14 can be bonded with high bonding force, layer can be prevented Between remove.
Second substrate layer 15 is not particularly limited as long as having sufficient mechanical strength, can be used for example, poly- to benzene two The polyester trees such as formic acid glycol ester (PET), polyethylene naphthalate (PEN), polybutylene terephthalate (PBT) (PBT) Rouge；The polyamides such as nylon (Ny)；The olefin resins such as oriented polypropylene (OPP)；By polyether-ether-ketone (PEEK), polyphenylene sulfide (PPS) synthetic resin film constituted such as.Wherein, preferred PET film.
The thickness of second substrate layer 15 can for example be set as 1~50 μm, preferably 1~30 μm, and further preferred 3~11 μm.
Second substrate layer 15 can be that single layer structure is also multilayered structure.As the second substrate layer 15 with multi-layer structure Example, can enumerate on twin-screw oriented polyamide resin film (ONy) be laminated with polyethylene terephthalate (PET) tree The duplicature of adipose membrane.In addition, the second substrate layer 15 can also be the multilayered structure of 3 layers of stacking or more of film.
In addition, in the embodiment shown in fig. 1, the second substrate layer 15 is outermost layer.Therefore, the second substrate layer is by containing Resin can have desired color and design along with coloring agents such as pigment.
Second substrate layer 15 is preferably the single layer or multilayer film of 200 DEG C or more of heat-resistant resin film by having used fusing point It is constituted.As this heat-resistant resin film, such as have PET film, pen film, PBT film, nylon membrane, PEEK film, PPS film etc., it is special Not preferred advantageous PET film in terms of cost.By using this heat-resistant resin film, battery exterior laminated body can be improved 10 heat resistance improves the durability for having used the battery of battery exterior laminated body 10.
Battery exterior shown in Fig. 1 in laminated body 10, formed on the two sides of stainless steel foil 14 first corrosion-resistant coating 13 with And second corrosion-resistant coating 16 can be with electricity by as inner face side in the battery exterior body for having used battery exterior to use laminated body 10 Solving the contacts such as liquid is 11 side of first base material layer.Therefore, first base material layer 11 of the corrosion-resistant coating at least formed on stainless steel foil 14 Side.I.e., it is possible to become the structure from battery exterior the second corrosion-resistant coating 16 of omission of laminated body 10 of Fig. 1.
For battery exterior shown in Fig. 1 in laminated body 10, the second substrate layer 15 is used as outermost layer, but can be in the second substrate layer 15 more exterior side forms coating layer.
Coating layer (the first coating layer) is by from carbamate resins, acrylic resin, polyvinylidene chloride, inclined two chloroethene Alkene-chloroethylene copolymer resin, maleic anhydride modified polypropylene resin, polyester resin, epoxy resin, phenol resin, phenoxy resin, fluorine Resin, cellulose ester resin, cellulose ether resins, polyamide, polyphenylene oxide resin (PPE), polyphenylene sulfide (PPS), At least one resin selected in the resin group that polyarylether resin (PAE), polyether-ether-ketone resin (PEEK) are constituted is formed.It applies Layer of cloth is preferably constituted with the material of excellent heat resistance.These resins can be used alone, and also can be used together two or more.
Coating layer is preferably coated and dried the resin is dissolved in ordinary organic solvents prepared solvent type to apply The film hardening layer expected and formed.
Battery can be prevented while improving the insulating properties of battery exterior laminated body 10 by the formation of coating layer The surface damage of exterior laminated body 10.In addition, even if battery exterior with laminated body 10 contact electrolyte in the case where, can also To prevent the variation (discoloration etc.) of appearance.
In addition, can be carried out to coating layer by adding colorant and pigment into the solvent based coating for forming coating layer Coloring.In addition it is also possible to which additional coloring and printing, make coating layer show text, figure, portrait, style etc., design sense is improved.
The thickness of coating layer can for example be set as 0.1~20 μm, preferably 2~10 μm.
With in laminated body 10, the second substrate layer 15 and second bonding agents layer 17 are directly bonded battery exterior shown in Fig. 1, but Printing layer for improving design sense can also be set in the inner face side of the second substrate layer 15.
Printing layer can become similarly to be constituted with above-mentioned coating layer.
Battery exterior is preferably 10~500 μm with the thickness of laminated body 10, and more preferable 20~200 μm, further preferred 30 ~100 μm.
As the battery for having used battery exterior laminated body 10, lithium ion battery as secondary cell etc. two can be enumerated Capacitors such as primary cell or double layer capacitor etc. use the object of organic bath in the electrolytic solution.As organic bath, lead to It is often the substance using carbonates such as propene carbonate (PC), ethylene carbonate (DEC), ethylene carbonates as medium, but simultaneously It is not particularly limited as these substances.
Battery exterior laminated body of the invention, such as can be manufactured by method with the following process: stainless The process of the first corrosion-resistant coating is formed on the single side of steel foil；First bonding agents layer is formed on being formed by the first corrosion-resistant coating Process；And configured by first base material layer with being formed by a manner of first bonding agents layer connects, and to the laminated body into The process of row stacking.
It is described in detail below.
Firstly, forming the first corrosion-resistant coating 13 on the single side of stainless steel foil 14.
Specifically, being thermally dried after above-mentioned water soluble paint is coated on the surface of stainless steel foil 14.This When, the first corrosion-resistant coating 13 can be only only formed by being only coated with water soluble paint on the single side of stainless steel foil 14, it can also be with The second corrosion-resistant coating 16 is formed simultaneously and being coated with water soluble paint on the two sides of stainless steel foil 14.In addition, in setting the In the case where two corrosion-resistant coatings 16, the second corrosion-resistant coating 16 shape preferably in the stage before forming first bonding agents layer 12 and waiting At being more preferably formed simultaneously with the first corrosion-resistant coating 13.
In addition, in the case where forming the first corrosion-resistant coating 13 and the second corrosion-resistant coating 16 at the same time, preferably by stainless steel Foil 14 is immersed in water soluble paint, is adhered to after water soluble paint on the two sides of stainless steel foil 14, is thermally dried.
Then, first bonding agents layer 12 is formed on the first corrosion-resistant coating 13.
It is made of specifically, being formed on the face equipped with the first corrosion-resistant coating 13 of stainless steel foil 14 above-mentioned bonding agent Layer, answer needed for heated, dried.
In the case where bonding agent is the heat lamination bonding agent without containing organic solvent, pass through melt kneading (A) ingredient After reacting two ingredients with (B) ingredient, by being coated on the first corrosion-resistant coating 13 and being dried, formed First bonding agents layer 12.
Single screw extrusion machine, multiscrew extrusion machine, Banbury mixer, plastics processing mill can be used in melt kneading (plastomill), device well known to heating roller kneader etc..The decomposition of epoxy group when in order to inhibit melt kneading, moisture etc. can Preferably lead in the case where generation volatile ingredient in addition to going to device, and in the reaction in advance with the volatile ingredient of epoxy reaction Degassing etc. is crossed to be discharged to outside device at any time.The acid-modified polyolefin resin has the case where anhydride group as acid functional group Under, due to the reactivity height with epoxy group, can be reacted in more stable conditions, it is advantageous to.When with regard to melt kneading Heating temperature melt two ingredients sufficiently, and without thermal decomposition this point for, preferably from 240~300 DEG C of range Inside selected.In addition, kneading temperature can be by making thermocouple and the molten state that just squeezes out from melt kneading device The methods of adhesive resin composition contact is measured.
In addition, in the case where bonding agent is the dry type stacking bonding agent containing organic solvent, by (A) ingredient and (B) After ingredient dissolution in organic solvent, by the way that this solution coating is on the first corrosion-resistant coating 13 and dry, formation first is viscous Connect oxidant layer 12.In addition, being formed for first bonding agents layer 12 can be with the lamination process of aftermentioned first base material layer 11 together as one Serial process is carried out using well known dry type stacking machine etc..
Later, it is configured by first base material layer 11 with being formed by a manner of first bonding agents layer 12 connects, stacking should Laminated body.The dry type stacking of preferably 70~150 DEG C of stacking.Pressure when dry type is laminated is preferably 0.1~0.5MPa.
Specifically, the film for constituting first base material layer 11 is prepared in advance, after which is configured on first bonding agents layer Carry out dry type stacking.As long as the temperature of dry type stacking is to be bonded first base material layer 11 and first well via first bonding agents layer The temperature of corrosion-resistant coating 13 and stainless steel foil 14, then be not particularly limited, it may be considered that constitutes the bonding agent of first bonding agents layer 12 Material or fusing point determine.Temperature when dry type is laminated is generally 70~150 DEG C, preferably 80~120 DEG C.
The battery exterior laminated body of present aspect, due to for first base material layer 11 and the first corrosion-resistant coating 13 and stainless steel foil 14 structures being bonded via first bonding agents layer 12 make to become possible using the stacking of above-mentioned dry type when bonding.Then, by adopting The heat lamination for substituting the heating that must exceed 200 DEG C when stacking is laminated with dry type, temperature when stacking can be greatly reduced.
In general, it is low to thermal conductivity, be difficult to the stainless steel foil expanded apply high temperature in the case where, in the width of stainless steel foil (curling) is easily deformed on direction.In the case where carrying out heat lamination using this stainless steel foil, sometimes in face not Heat can fully be propagated, the part not contacted with hot pressing roller can be generated in width direction, without contacting with roller, existed sometimes Bending and fold occurs due to deforming itself when hot pressing.In addition, to stainless steel foil being heated to not deforming In the case where the high temperature of degree, due to the increase of the heat of the reduction or needs of process velocity, productivity can be reduced.
Then, it in the case where in the manufacture of the battery exterior laminated body of present aspect using dry type stacking, is able to suppress The generation of bending and fold, manufactures suitable battery exterior laminated body.
In addition, the process for forming the process of first bonding agents layer 12 and configuring the progress of first base material layer 11 (dry type) stacking can It is carried out using (dry type) stacked laminator well known to being used as series of processes.
Second corrosion-resistant coating 16, second bonding agents layer 17, the second substrate layer 15 forming method be not particularly limited, for example, Second bonding agents layer 17 is formed on the second substrate layer 15 in advance as the laminated body being made of bilayer.Later, by with The mode that two adhesive layers 17 connect with the second corrosion-resistant coating 16 to the bilayer stack and has first base material layer 11, first The laminated body progress dry type stacking of adhesive layer 12, the first corrosion-resistant coating 13, stainless steel foil 14 and the second corrosion-resistant coating 16, can To manufacture the battery exterior laminated body 10 constituted by 7 layers.
More than, battery exterior is illustrated an embodiment of the invention with laminated body 10 according to Fig. 1, this The technical scope of invention is not limited to above embodiment, within the scope of not departing from purport of the invention, can be added each Kind modification.
For example, the second corrosion-resistant coating 16 can be not provided with and become 6 layers of structure.
In addition, can also the side of first base material layer 11 not connected with first bonding agents layer 12 and the second substrate layer 15 not Other layers are arranged in the side to connect with second bonding agents layer 17, to become 7 layers and 8 layers or more of structure.
[battery exterior body]
The battery exterior body of the second aspect of the present invention is outside the battery of the battery exterior laminated body with first aspect Body is filled, for the inner space with storage battery, the side of the first base material layer of battery exterior laminated body is the inner space The battery exterior body of side.Specifically in a manner of first base material level internally space by the battery of first aspect Exterior is shaped to desired shape with laminated body, by object obtained from end part seal etc. needed for answering.
Shape, size of battery exterior body etc. are not particularly limited, and can suitably be determined according to the type of used battery.
Battery exterior body can be made of a component, it is possible to use Fig. 2 combine as be described hereinafter two or more component (such as Vessel and cover) and formed.
[battery]
The battery of the third aspect of the present invention has the battery exterior body of second aspect.
As battery, the secondary cells such as the lithium ion battery as secondary cell or double layer capacitor etc. can be enumerated as The battery for having used organic bath in the electrolytic solution of capacitor etc..
As an example, the perspective view of secondary cell 40 is as shown in Figure 2.Secondary cell 40 is in battery exterior container 20 In include lithium ion battery 27.
Battery exterior container 20 is made of overlapping the battery exterior laminated body 10 of the first aspect of the present invention Vessel 30 and the cover 33 that is made of battery exterior laminated body 10, and seal peripheral part 29 and formed.Symbol 28 To be connected to the anode of lithium ion battery 27 and the contact conductor of cathode.
Battery shown in Fig. 2 can be manufactured in the following manner.
Firstly, making battery exterior laminated body 10 become the plate-like with recess portion 31, by being drawn into as shown in Fig. 3 (a) Type etc. is formed, and obtains vessel 30 with this.The depth of recess portion 31 can be set to such as 2mm or more.
Lithium ion battery (lithium ion battery 27 in Fig. 2) is stored in the recess portion 31 of vessel 30.
Then, as shown in Fig. 3 (b), the cover 33 being made of battery exterior laminated body 10 is overlapped into vessel On 30, by sealing portion flange (flange) 32 of vessel 30 and the peripheral part 34 of cover 33, secondary electricity shown in Fig. 2 is obtained Pond 40.In battery i.e. shown in Fig. 3, by covering cover 33 in the upper surface of vessel 30, formed by recess portion 31 and cover 33 Accommodate the inner space of battery.
In addition, the battery in the present invention can also manufacture in the following manner.
Firstly, by drawing molding etc., being pressed from the first base material layer side of battery exterior laminated body 50 as shown in Fig. 4 (a) Be pressed in a part of longitudinal direction one end in the battery exterior laminated body 50 of rectangle and form, obtain having recess portion 51 at Type body 55.The depth of recess portion 51 can be set to such as 2mm or more.
Then, diagram is omitted, and the lithium ion battery (lithium ion battery in Fig. 2 is stored in the recess portion 51 of formed body 55 27)。
Then, in a part of the another side of the not formed recess portion 51 of formed body 55, it is formed in the short of formed body 55 The broken line L extended on edge direction carries out bending in the side of first base material layer.At this point, in formed body 55, relative to broken line L The region of 51 side of recess portion be " first area 551 ", with the region relative to broken line L and recess portion 51 opposite side for " the secondth area Domain 552 ".
Then, by around the recess portion 51 in first area 551 52 first base material layer and second area 552 with week The first base material layer (peripheral part 54) for enclosing 52 overlappings is overlapped.Second area is overlapped on the recess portion 51 of first area 551 with this 552。
Then, as shown in Fig. 4 (b), pass through first of first base material layer and second area 552 around heat-sealing recess portion 51 Substrate layer obtains the secondary cell 60 with the battery exterior body being made of a component.I.e. in the battery shown in Fig. 4 (b), By covering second area 552 in the upper surface of recess portion 51, the inside for forming receiving battery by recess portion 51 and second area 552 is empty Between.
Embodiment
Hereinafter, by embodiment, the present invention will be described in more detail, but the present invention is not limited by these examples.
[embodiment 1~15, the Comparative Examples 1 to 5]
(Examples 1 to 5)
Firstly, preparing the stainless steel foil with a thickness of 20 μm.Water soluble paint (coating is coated on the two sides of this stainless steel foil Measure 12g/m2), it is thermally dried in 200 DEG C of baking oven, the first corrosion-resistant coating of thickness shown in shape table 1, second prevent respectively Corrosion layer.
Water soluble paint is by the non-crystalline polymer of skeleton containing polyvinyl alcohol with hydroxyl of 0.2 mass %, 0.8 matter Measure the FeCl of %2·4H2O, 0.7 mass % nitrilo- three (methylene phosphonic acid) (trade name: CHELEST PH-320, CHELEST (strain) system)) be dissolved in water made of aqueous solution.
Later, it is coated with first bonding agents on being formed by the first corrosion-resistant coating, forms the first bonding agents with a thickness of 3 μm Layer.By at room temperature, in toluene 10 minutes 100 mass parts maleic anhydride modified polypropylenes (15 DEG C of fusing point) of melt kneading and 7 mass parts novolac epoxy resins (Mitsubishi Chemical's (strain) system, trade name: jER157S70, viscosity=80, epoxide equivalent= 210) first bonding agents are obtained.
By the first bonding agents layer in the laminated body containing this stainless steel foil and by the polypropylene resin film with a thickness of 6 μm The first base material layer constituted is laminated with 120 DEG C by dry type.
In addition, by being set by stretching polyethylene terephthalates (PET) with a thickness of 6~8 μm, with black Coating is by carbamates bonding agent (host agent: TM-K55 (trade name, Japan on the second substrate layer that adipose membrane is constituted MORTON society system), curing agent: CAT-10L (trade name, MORTON society, Japan system)) second bonding agents layer (3 μ of thickness that is constituted M) it forms.
Keep the second bonding agents layer opposite with the second corrosion-resistant coating in above-mentioned gained laminated body, passes through 80 DEG C of dry type layer It is folded to be laminated, obtain battery exterior laminated body.
The surface defect of observation gained battery exterior laminated body by visual observation, is evaluated with following evaluation condition.Knot Fruit is shown in Table 1 as " planar defect ".
A: every 1m21 in-plane defects is not observed inside.
B: every 1m2Inside observe 1~5 in-plane defects.
C: every 1m2Inside observe 6~10 in-plane defects.
D: every 1m2Inside observe 11 or more in-plane defects.
Prepare 3g electrolyte and (LiPF is added to 1mol/ liter6, ethylene carbonate: diethyl carbonate: dimethyl carbonate The solution of=1:1:1vol%), be packed into using battery exterior laminated body make three face hermetic bags (inside dimension 30mm × 50mm, heat seal width 7mm) in.By this three face, hermetic bag is rested in 85 DEG C of thermostat 2000 hours.
After 2000 hours, three face hermetic bags are opened, are observed by visual observation than metal foil layer also in the inner part whether there is or not removing, It is evaluated with following evaluation criterion.As a result it is shown in Table 1 as " electrolyte resistance ".
A: removing is not confirmed
B: a little removing but within the allowable range is confirmed
C: removing is confirmed
D: it is completely exfoliated
In addition, the test film after above-mentioned electrolyte dipping was immersed in pure water after 10 hours, take out, leads to from pure water It crosses and visually observes its state.It is shown in Table 1 using the result that following evaluation criterion is evaluated as " after water retting ".
A: removing is not confirmed
B: a little removing but within the allowable range is confirmed
C: removing is confirmed
D: it is completely exfoliated
Battery exterior laminated body is cut out with 200mm × 100mm size, test film is obtained with this.This test film is placed in In the cold-forming equipment of 100mm × 50mm size, processing is embossed under conditions of drawing depth and being 6mm.By visual observation or Optical microscopy forms the generation of fracture and pin hole (pin hole) in extension section to observe.10 same tests are carried out, It is shown in Table 1 using the result that evaluation criterion below is evaluated as " mouldability ".
A: molding extension section is not broken, does not also generate pin hole.
B: it is in 10 samples that molding extension section, which has occurred a little fracture in allowed band or produces the sample of pin hole, 1~3 sample.
C: molding extension section has occurred a small amount of fracture or produces the sample of pin hole as 1~5 sample in 10 samples Product.
D: molding extension section has occurred large-scale fracture or produces the sample of pin hole as 6 samples in 10 samples It is more than product.
(embodiment 6~10)
Except formed first bonding agents layer first bonding agents in used bonding agent shown in table 1 in addition to, with implementation The identical mode of example 3 manufactures battery exterior laminated body, has carried out evaluation same as Example 1.As a result it is shown in Table 1.
(embodiment 11)
In addition to the stacking of 120 DEG C of dry type of first bonding agents layer and first base material layer is changed to 200 DEG C of heat lamination, Battery exterior laminated body is manufactured in mode same as Example 3, has carried out evaluation same as Example 1.As a result it is shown in In table 1.
(embodiment 12)
In addition to first base material layer is changed to random PP film from block PP film, manufactured in mode same as Example 3 Battery exterior laminated body, has carried out evaluation same as Example 1.As a result it is shown in Table 1.
(embodiment 13~14)
In addition to the stainless steel foil that the stainless steel foil with a thickness of 20 μm is changed to thickness shown in table 1, with 3 phase of embodiment Same mode manufactures battery exterior laminated body, has carried out evaluation same as Example 1.As a result it is shown in Table 1.
(embodiment 15)
Except by the first and second corrosion-resistant coating carry out charomic fluoride plating, obtain with a thickness of 250 μm first with And second except corrosion-resistant coating, manufactures battery exterior laminated body in the same manner as example 1, has carried out and embodiment 1 Identical evaluation.As a result it is shown in Table 1.
(comparative example 1)
Except using the aluminium foil substitution stainless steel foil with a thickness of 20 μm and to use and changed with maleic anhydride as metal foil Except property polypropylene (80 DEG C of fusing point), the bonding agent without novolac epoxy resin are as first bonding agents, with implementation The identical mode of example 11 manufactures battery exterior laminated body, has carried out evaluation same as Example 1.As a result it is shown in Table 1.
(comparative example 2)
Except using the aluminium foil with a thickness of 20 μm to substitute stainless steel foil as metal foil, the CrF of 0.8 mass % is used3·3H2O Instead of the FeCl of 0.8 mass % of the first and second corrosion-resistant coating2·4H2Except O, manufactured in mode same as Example 3 Battery exterior laminated body, has carried out evaluation same as Example 1.As a result it is shown in Table 1.
(comparative example 3)
Only there is maleic anhydride modified polypropylene (80 DEG C of fusing point), the bonding without novolac epoxy resin except using Except agent is as first bonding agents, battery exterior laminated body is manufactured in mode same as Example 3, has been carried out and embodiment 1 identical evaluation.As a result it is shown in Table 1.
(comparative example 4)
In addition to not set first corrosion-resistant coating and the second corrosion-resistant coating, manufacture is electric in the same manner as example 1 Pond exterior laminated body, has carried out evaluation same as Example 1.As a result it is shown in Table 1.
(comparative example 5)
Except formed first bonding agents layer first bonding agents in used bonding agent shown in table 1 in addition to, with implementation The identical mode of example 3 manufactures battery exterior laminated body, has carried out evaluation same as Example 1.As a result it is shown in Table 1.
[table 1]
In table 1, each ellipsis is respectively provided with meaning below.
(bPP): block polypropylene
(rPP): random polypropylene
(Ad-NV1): containing 100 mass parts maleic anhydride modified polypropylenes (80 DEG C of fusing point) and 5 mass parts line style phenol The toluene that the solid content of formaldehyde epoxy resin (society, Mitsubishi Chemical system, trade name: jER154, epoxide equivalent=178) is 15% Solution bonding agent
(Ad-NV2): containing 100 mass parts maleic anhydride modified polypropylenes (80 DEG C of fusing point) and 2 mass parts line style phenol The toluene solution bonding agent that the solid content of formaldehyde epoxy resin jER154 is 15%
(Ad-NV3): containing 100 mass parts maleic anhydride modified polypropylenes (80 DEG C of fusing point) and 7 mass parts line style phenol The toluene solution bonding agent that the solid content of formaldehyde epoxy resin jER154 is 15%
(Ad-NV4): containing 100 mass parts maleic anhydride modified polypropylenes (80 DEG C of fusing point) and 10 mass parts line style phenol The toluene solution bonding agent that the solid content of formaldehyde epoxy resin jER154 is 15%
(Ad-NV5): containing 100 mass parts maleic anhydride modified polypropylenes (80 DEG C of fusing point) and 15 mass parts line style phenol The toluene solution bonding agent that the solid content of formaldehyde epoxy resin jER154 is 15%
(Ad-NV6): containing 100 mass parts maleic anhydride modified polypropylenes (140 DEG C of fusing point) and 5 mass parts line style phenol The bonding agent of formaldehyde epoxy resin jER154
(Ad-BPNV): having containing 100 mass parts maleic anhydride modified polypropylenes (80 DEG C of fusing point) and 5 mass parts double Novolac epoxy resin (the Mitsubishi Chemical's system, trade name: jER157S70, viscosity=80 of phenol A structure；Epoxide equivalent=210) Solid content be 15% toluene solution bonding agent
(Ad-PN): containing 100 mass parts maleic anhydride modified polypropylenes (80 DEG C of fusing point) and 5 mass parts phenoxy resins 15% toluene solution of solid content of (society, Mitsubishi Chemical system, trade name: Epikote 1001, epoxide equivalent=450) is viscous Connect agent
(Ad-PP): containing the bonding agent of 100 mass parts maleic anhydride modified polypropylenes (140 DEG C of fusing point)
(SUS): stainless steel foil
(AL): aluminium foil
From result shown in table 1 it is known that the battery exterior of embodiment 1~15 is with laminated body can inhibit the hair of planar defect It is raw, removing can also be reduced when contact electrolyte or water, and there is good mouldability, the battery exterior with the Comparative Examples 1 to 5 Being compared with laminated body has excellent characteristic (processability mouldability, mechanical strength, chemically-resistant medical fluid water resistance).
[embodiment 16~24]
In above-described embodiment 3, metal halide shown in the table 2 using 0.8 mass % replace the first corrosion-resistant coating and The FeCl of 0.8 mass % in second corrosion-resistant coating2·4H2O is carried out the research of example 16~24.Evaluation method, evaluation Standard is identical as embodiment 1 etc..As a result it is shown in Table 2.
[table 2]
Metal halide Planar defect Electrolyte resistance After water retting Mouldability
Embodiment 16 FeF3 B A B A
Embodiment 17 MnF3 B A B A
Embodiment 18 MnCl2 B B B A
Embodiment 19 CrF3 B A B A
Embodiment 20 CrCl3 B B B A
Embodiment 21 ZrCl3 B B B A
Embodiment 22 TiCl4 B B B A
Embodiment 23 CaCl2 B C C A
Embodiment 24 AlCl4 B C C A
From result shown in table 2 it has been confirmed that even with various compounds as metal halide compound the case where Under, the also effect of available the application.

Claims (6)

1. a kind of battery exterior laminated body is at least successively to have first base material layer, first bonding agents layer, the first anticorrosion Battery exterior laminated body made of layer, stainless steel foil and the second substrate layer, which is characterized in that
The first base material layer is the layer that is made of polyolefin,
The first bonding agents layer is multiple by having containing 100 mass parts acid-modified polyolefin resins (A) and 1~10 mass parts The layer that the bonding agent of the compound (B) of epoxy group is constituted, the compound (B) with multiple epoxy groups are line style phenolic aldehyde ring Oxygen resin.
2. battery exterior laminated body according to claim 1, wherein the novolac epoxy resin has bisphenol-A Structure.
3. battery exterior laminated body according to claim 1, wherein the stainless steel foil with a thickness of 10~30 μm.
4. battery exterior laminated body according to claim 1, wherein the first base material layer is homopolypropylene or embedding Section polypropylene.
5. a kind of battery exterior body, for battery exterior laminated body according to any one of claims 1 to 4 Battery exterior body, which is characterized in that
Inner space with storage battery, the first base material layer side of battery exterior laminated body are the inner space side.
6. a kind of battery, which is characterized in that it is with battery exterior body according to claim 5.
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