CN103222084A - Process for producing sealing film, and sealing film - Google Patents
Process for producing sealing film, and sealing film Download PDFInfo
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- CN103222084A CN103222084A CN2011800540697A CN201180054069A CN103222084A CN 103222084 A CN103222084 A CN 103222084A CN 2011800540697 A CN2011800540697 A CN 2011800540697A CN 201180054069 A CN201180054069 A CN 201180054069A CN 103222084 A CN103222084 A CN 103222084A
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- resin
- diaphragm seal
- layer
- electrode
- bag
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/78—Cases; Housings; Encapsulations; Mountings
- H01G11/80—Gaskets; Sealings
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- 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 of a single cell or a single battery
- H01M50/183—Sealing members
- H01M50/186—Sealing members characterised by the disposition of the sealing members
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- 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
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- 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
- B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
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- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/74—Terminals, e.g. extensions of current collectors
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- 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 of a single cell or a single battery
- H01M50/183—Sealing members
- H01M50/19—Sealing members characterised by the material
- H01M50/193—Organic material
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- 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 of a single cell or a single battery
- H01M50/183—Sealing members
- H01M50/19—Sealing members characterised by the material
- H01M50/197—Sealing members characterised by the material having a layered structure
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- 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
- B32B2323/00—Polyalkenes
- B32B2323/04—Polyethylene
- B32B2323/043—HDPE, i.e. high density polyethylene
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- 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
- B32B2457/16—Capacitors
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- 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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- 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
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/60—Other road transportation technologies with climate change mitigation effect
- Y02T10/70—Energy storage systems for electromobility, e.g. batteries
Abstract
A process for producing a sealing film (1) to be interposed between each electrode (11), as a power-generating element, that has been introduced into a bag (20) and the edge of the bag (20), the process comprising: a melt kneading step in which both an acid-modified polyolefin resin A to which a carboxylic acid has been grafted and a resin B having functional groups capable of reacting with the carboxy groups of the resin A are melted and kneaded together to thereby chemically bond the carboxy groups of the resin A to the functional groups of the resin B and convert the resins into a resin C; a heat-resistant-layer formation step in which the resin C is formed into a layer to form a heat-resistant layer (3); an adhesive-layer formation step in which a carboxylic-acid-modified polyolefin resin D is formed into a layer to form an electrode adhesion layer (2) which adheres to electrodes; and a laminating step in which the heat-resistant layer (3) and the electrode adhesion layer (2) are directly laminated to each other when the resin C and/or the resin D is in a molten state.
Description
Technical field
The present invention relates to the manufacture method and the diaphragm seal of the diaphragm seal that the electrode of generating elements such as a kind of secondary cell that bag is taken in or capacitor seals.
The application is that the Japanese application for a patent for invention that November 11, application number in 2010 are 2010-252940 requires priority according to the applying date, and with its content quotation in the application.
Background technology
In recent years, for example as the power supply of electronic equipments such as notebook computer or mobile phone or the battery of hybrid vehicle, fuel cell car or battery car etc., just progressively adopt secondary cell that the bag that is made of film takes in or capacitor etc.
In the past, these secondary cells or capacitor were that flat generating element is sealed in by in the bag that the polyolefin sealant is laminated to flat bag that the laminated film that forms on the metal forming such as aluminium foil constitutes or drawing and forming and constitute.On the film base material of bag, an end of the feasible electrode that is used to discharge and recharge projects to the outside and seals.In when sealing, by the electrode (electrode protuberance) of the film base material clamping band shape of bag and seal.
The electrode of these secondary cells etc. (below, be sometimes referred to as " battery pack ") is thicker than the sealant of bag, therefore when sealing, be difficult to make resin seamlessly be surrounded on electrode thickness direction around, and around the thickness direction of electrode, produce the gap.If produce the gap around electrode, then under long-term use, high temperature or many conditions such as harsh and unforgiving environments such as wet, the bag that has sealing deterioration or a sealing descends with the bond strength of electrode, causes the possibility of electrolyte self sealss portion leakage.
At these problems, the method for using the table back side utilize the diaphragm seal holding electrode in recent years and sealing with the film base material of bag.But, if improve the degree of adhesion of bag and electrode, and strict when setting sealing heating or the condition of pressurization, then exist the metal forming of bag and the resin attenuation between the electrode or diaphragm seal to be out of shape and cause the possibility of short circuit.
In addition, when the clamping diaphragm seal seals between the film base material of bag and electrode, for example patent documentation 2 put down in writing like that, make diaphragm seal expose several millimeters and seal from the openend of bag.Expose diaphragm seal in this way, can prevent short circuit reliably.But,, because seal bar contact or, make the situation of diaphragm seal fusing or distortion so have the contact of seal bar of Yin Gaowen or radiant heat near this exposed division in when heat-sealing.Thus, electrode becomes easily and to contact with the metal forming of the film base material of bag.
In order to address these problems, for example put down in writing the heat-sealing portion that utilizes lining material to cover terminal material in the patent documentation 1, thereby prevent the formation of short circuit, described lining material has and utilizes the thermal bonding film to clamp the laminar construction that is formed by the refractory layer of weaving cotton cloth, adhesive-bonded fabric or ultra-high molecular weight polyethylene constitute.
Put down in writing in the patent documentation 2 and will press the zygosity film that forms layer by layer through the polyolefin layer and the acid modified polyolefin of electron beam crosslinking again.
The prior art document
Patent documentation
Patent documentation 1: Japanese kokai publication sho 62-61268 communique
Patent documentation 2: TOHKEMY 2001-297748 communique
Summary of the invention
Technical problem
Because the lining material that patent documentation 1 is put down in writing is that utilization is weaved cotton cloth or adhesive-bonded fabric is guaranteed thermal endurance, so need to select be difficult to weaving cotton cloth or adhesive-bonded fabric of fusion.But this moment, these were weaved cotton cloth or adhesive-bonded fabric and thermal bonding film so be difficult to high degree of adhesion lamination owing to weave cotton cloth or not fusion of adhesive-bonded fabric.Therefore, there is formation pin hole easily, the possibility that sealing can't improve.In some cases, sealing can descend on the contrary.And, because it is ultra-high molecular weight polyethylene is difficult to acquisition, unfavorable in the cost aspect.And, ultra-high molecular weight polyethylene can't with the thermal bonding film lamination that constitutes by polypropylene-based resin.Therefore, can't in the sealant of bag, adopt polypropylene-based resin, and be difficult to improve the thermal endurance of bag.
The excellent heat resistance of the zygosity film that patent documentation 2 is put down in writing.But the manufacture method of this film is to make the polyolefin film electron beam crosslinking in advance and the acid modified polyolefin layer is extruded lamination, or carries out electron beam crosslinking by coextrusion behind lamination polyolefin layer and the acid modified polyolefin layer.Therefore, no matter adopt any method all to need the step of electron beam crosslinking.Record following situation in the paragraph 0013 of patent documentation 2: decompose because common polypropylene shines by electron beam, so need to use specific resin.And, behind lamination polyolefin layer and acid modified polyolefin layer, carry out the situation of electron beam crosslinking by coextrusion, acid modified polyolefin also takes place crosslinked and flexibility is descended, therefore become be difficult to make resin seamlessly be surrounded on electrode thickness direction around.
That makes in view of described background the invention provides a kind of village's material that uses easy acquisition, easily make resin seamlessly be surrounded on electrode thickness direction around, and can be by simple steps and reach the diaphragm seal that passes through this manufacture method manufacturing with the manufacture method of the thermal endurance of higher bond strength contact laminating refractory layer and electrode engagement layer and the diaphragm seal of sealing excellence.
Technical scheme
Inventor of the present invention obtains following opinion at the research of the diaphragm seal of thermal endurance and sealing excellence: glycerol polymerization have carboxylic acid acid-modified polyolefin resin carboxyl easily and reactions such as hydroxyl, amido, epoxy radicals, and can easily obtain modification.The present invention is based on this opinion and makes.
That is, according to a first aspect of the invention, can provide the manufacture method of following diaphragm seal.
(1) a kind of manufacture method of diaphragm seal is the manufacture method that is sandwiched in the diaphragm seal between the edge of the electrode of the generating element that bag takes in and bag, and it has following steps:
The melting mixing step, acid-modified polyolefin resin A by glycerol polymerization there being carboxylic acid makes the carboxyl of Resin A and the functional group of resin B carry out chemical bonding and be modified as resin C with have can the two carries out melting mixing with the functional group's of the carboxyl reaction of Resin A resin B;
Refractory layer system film step is shaped to resin C stratiform and forms refractory layer;
Knitting layer system film step is shaped to carboxyl acid modified vistanex D stratiform and forms the electrode engagement layer that is engaged in electrode;
Lamination step, described refractory layer of contact laminating and described electrode engagement layer when any one in resin C and resin D or both are in molten condition.
(2) as the manufacture method of (1) described diaphragm seal, wherein said melting mixing step is carried out in extruder.
(3) as the manufacture method of (1) or (2) described diaphragm seal, wherein said melting mixing step and described refractory layer system film step are carried out continuously.
(4) as the manufacture method of each described diaphragm seal in (1) to (3), wherein said lamination step is any one in described refractory layer system film step and described knitting layer system film step or both and carry out continuously.
(5) as the manufacture method of each described diaphragm seal in (1) to (4), wherein said lamination step is carried out in the coextrusion die head.
(6) as the manufacture method of each described diaphragm seal in (1) to (5), wherein said melting mixing step be with Resin A be 99～90%, resin B is that 1～10% percentage by weight is allocated and carried out.
(7), wherein will have the identical or resin of fusing point that is lower than it of fusing point with Resin A as resin D as the manufacture method of each described diaphragm seal in (1) to (6).
And, according to a second aspect of the invention, can provide following diaphragm seal.
(8) a kind of diaphragm seal, the sealing film is sandwiched between the edge of the electrode of the generating element that bag takes in and bag, and has the laminar construction that the refractory layer contact laminating that will be made of resin C forms on the electrode engagement layer that is made of carboxyl acid modified vistanex D, this resin C be acid-modified polyolefin resin A by glycerol polymerization there being carboxylic acid with have can the two carries out melting mixing with the functional group's of the carboxyl reaction of Resin A resin B, make the carboxyl of Resin A and functional group's chemical bonding of resin B carry out the resin that modification forms.
(9) as (8) described diaphragm seal, wherein resin B be selected from have hydroxyl, one or more resins in the resin of amido or epoxy radicals.
(10) as (8) or (9) described diaphragm seal, wherein Resin A is the acid-modified polyolefin resin that the maleic anhydride glycerol polymerization is formed in polypropylene.
(11) as each described diaphragm seal in (8) to (10), wherein said laminar construction is that the coextrusion by resin C and resin D forms.
(12), wherein be pressed with sealant with the innermost layer thermal welding of bag on described refractory layer upper strata as each described diaphragm seal in (8) to (11).
Beneficial effect
The manufacture method of diaphragm seal of the present invention is to make the carboxyl of Resin A and the functional group of resin B carry out chemical bonding and be modified as resin C, does not therefore need crosslinked operations such as electron beam crosslinking.Therefore, can give thermal endurance to refractory layer by simple technology.
Because only with Resin A and the two melting mixing of resin B, so can in the employed common extruder of filming technology, be modified as resin C.
In the present invention, when any one in resin C and resin D or both are in molten condition, contact laminating refractory layer and electrode engagement layer.Laminating method is that the combination extruder after forming a layer, is extruded another layer of lamination with system film die head.Another laminating method is with refractory layer and the coextrusion of electrode engagement layer.By these methods, in the present invention, can be by simple technology with higher bond strength contact laminating refractory layer and electrode engagement layer.By the resulting diaphragm seal of these methods, be difficult for taking place the contact of seal bar of Yin Gaowen or radiant heat and the diaphragm seal fusing that causes or the phenomenon of distortion in when heat-sealing.Thus, be difficult for causing the short circuit of the metal forming of electrode and bag.
Especially the coextrusion of refractory layer and electrode engagement layer can be by more simple technology with higher bond strength contact laminating refractory layer and electrode engagement layer.
The refractory layer of diaphragm seal of the present invention has the carboxyl of the Resin A of making and functional group's chemical bonding of resin B carries out the less resin C of melt fluidity that modification forms.Thus, when heat-sealing, be difficult for taking place the phenomenon of refractory layer attenuation or diaphragm seal thermal deformation.Therefore, be difficult for causing the short circuit of the metal forming of electrode and bag.
If resin B be selected from have hydroxyl, one or more resins in the resin of amido or epoxy radicals, the easy chemical bonding of the functional group of the carboxyl of Resin A and resin B then, and successfully be modified as resin C.Because by Resin A and resin B melting mixing are modified as resin C, so the functional group of the carboxyl of Resin A and resin B chemical bonding equably easily.
If Resin A is the acid-modified polyolefin resin that the maleic anhydride glycerol polymerization is formed on polypropylene, then the easy chemical bonding of the functional group of the carboxyl of Resin A and resin B becomes and more successfully is modified as resin C.
Form if the laminar construction of diaphragm seal is the coextrusion by resin C and resin D, then the bond strength of laminar construction is higher, and diaphragm seal can thermal deformation when sealing, and is difficult for causing the short circuit of the metal forming of electrode and bag.
If will be laminated on the refractory layer with the sealant of the innermost layer thermal welding of bag, then can improve the thermal welding intensity of the innermost layer and the diaphragm seal of bag.And, if with the sealant contact laminating on refractory layer, then can prevent peeling off of the joint interface that causes by electrolyte.
Description of drawings
Fig. 1 is the profile of an example of expression diaphragm seal of the present invention.
Fig. 2 uses diaphragm seal shown in Figure 1 for expression and engages the profile of the state of the laminated film of bag and electrode.
Fig. 3 A is engaged in diaphragm seal shown in Figure 1 for expression the stereogram of the electrode of the band diaphragm seal that forms on the electrode.
Fig. 3 B is engaged in diaphragm seal shown in Figure 1 for expression the profile of the electrode of the band diaphragm seal that forms on the electrode.
Symbol description:
1: diaphragm seal
2: the electrode engagement layer
3: refractory layer
4: sealant
10: the electrode of band diaphragm seal
11: electrode
20: the laminated film of bag
21: the metal forming of laminated film
22: the sealant of laminated film
23: the film base material of laminated film
Embodiment
Below, the present invention is described in detail based on execution mode.
Fig. 1 is the profile of the summary formation of expression diaphragm seal 1 of the present invention.
Fig. 2 will diaphragm seal shown in Figure 11 inserts between the laminated film 20 of bag and the electrode 11 the also state of welding for expression, and along the profile of the length direction of electrode 11.
Fig. 3 A will scheme the stereogram that the diaphragm seal 1 shown in the l is engaged in the electrode 10 of the band diaphragm seal that forms on the electrode 11 for expression.Fig. 3 B for the expression this band diaphragm seal electrode 10, the profile on the direction vertical with the length direction of electrode 11.
Diaphragm seal l of the present invention is sandwiched between the edge of the electrode of the generating element that bag takes in and bag.The basic layer of this film constitutes as shown in Figures 1 and 2, had lamination electrode engagement layer 2 and refractory layer 3 comprise 2 layers laminar construction at least.The diaphragm seal 1 of the manner example further sealant 4 of sealant 22 thermal weldings of the innermost layer of contact laminating and bag on the refractory layer 3 that basic layer constitutes.
The thickness of diaphragm seal 1 of the present invention is preferably 50 μ m～300 μ m.If the thickness of diaphragm seal 1 less than this scope, then has the situation of insulating properties reduction.Moreover the thickness of diaphragm seal 1 also can be greater than this scope.But, can't expect the further raising of insulating properties, becoming on the contrary is difficult to seal.
The allotment ratio of the resin of this moment is preferably the Resin A with respect to 99～90 weight %, and resin B is 1～10 weight %.If the allotment ratio of resin B is lower than this scope, the modified effect that resin C then can take place is less, makes diaphragm seal 1 lack stable on heating situation.If the allotment ratio of resin B is higher than this scope, then refractory layer 3 becomes fragile easily.Therefore, when battery pack is installed, the situation of slight crack can take place to produce on refractory layer 3 because of the bending of electrode 11.
Acid-modified polyolefin resin A be the polyolefin that is polymerized more than a kind or 2 kinds by will making alkylidene monomer, for example ethene, propylene etc. as matrix resin, glycerol polymerization unsaturated carboxylic acid or derivatives thereof and obtaining.
As polyolefin, for example use polypropylene or poly homopolymers and copolymer.As copolymer, the random copolymer (random PP) of the ethene of use propylene and 1～5 weight % or random or block copolymer, propylene or the ethene of the propylene of block copolymer (block PP), ethene and 1～10 weight % and the carbon number of 1～10 weight % are the copolymer of the alpha-olefin more than 4 and their mixture etc.
For the sealant 22 with the laminated film 20 of bag is made as polyethylene-based resin, and when using polyethylene-based resin as the matrix resin of Resin A in the refractory layer 3 of diaphragm seal 1, being preferably and using fusing point is straight chain shape low density polyethylene (LDPE) or high density polyethylene (HDPE) about 130～140 ℃.
The matrix resin of acid-modified polyolefin resin A is preferably and uses melt flow rate (MFR) is that the homo-polypropylene of 0.5～30g/10min, especially 5～15g/10min and propylene-ethylene random copolymer or MFR are polyethylene and the ethylene-alpha-olefin copolymer of 0.3～30g/10min.
The MFR that forms the resin C of refractory layer 3 is preferably the scope of 0.5g/10min～3g/10min.If less than this scope, then there is the situation that is difficult to moulding in MFR.If MFR is greater than this scope, when then existing in thermal welding, refractory layer 3 can be out of shape or attenuation, and the situation that causes insulating properties to descend.
For refractory layer 3, require when being heat fused in diaphragm seal 1 of the present invention on the electrode 11, to be difficult to fusion or softening.Therefore, it is high more good more to form its fusing point of resin C.Particularly, for the diaphragm seal that is made of polypropylene-based resin, being preferably by the measured fusing point of JIS K6921-2 DSC method is 130～170 ℃ resin.
In order to obtain this resin C, preferable use with the random copolymer of homopolymers, ethene and the propylene of polypropylene (PP) or block copolymer or their polymer alloy as the acid-modified polyolefin resin of matrix resin as Resin A.PP is that resin becomes fragile under low temperature environment usually easily.Because even if the block copolymer fusing point of ethene and propylene is also excellent than high flexibility, and does not become fragile under low temperature environment (cold resistance) yet, so preferable.
As the unsaturated carboxylic acid of glycerol polymerization on the matrix resin of acid-modified polyolefin resin A, for example can enumerate: derivatives such as acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, their acid anhydrides, the ester that reaches them, acid amides, acid imide, slaine.In these unsaturated carboxylic acids, be preferably maleic acid, the best is a maleic anhydride.In order to promote the reaction of polyolefin and these unsaturated carboxylic acids, for example be preferably radical polymerization initiators such as organic peroxides such as using benzoyl peroxide, lauroyl peroxide or azodiisobutyronitrile again.
As the amount of the unsaturated carboxylic acid of glycerol polymerization, the total weight with respect to monomer is 0.5～5 weight % usually.
Method at glycerol polymerization unsaturated carboxylic acid on the polyolefin for example has following method: the method that makes the reaction of polyolefin and unsaturated carboxylic acid under molten condition; Under solution state, make the method for polyolefin and unsaturated carboxylic acid reaction; Under slurry form, make the method for polyolefin and unsaturated carboxylic acid reaction; Under gas phase state, make the method for polyolefin and unsaturated carboxylic acid reaction etc.In these methods, the method for reacting under molten condition is owing to processing ease, so preferable.Particularly, utilize fully polymerization initiators such as the polyolefin shown in the mixing above, unsaturated carboxylic acid, organic peroxide such as cylinder, Henschel mixer.After this, melting mixing and carry out graft reaction.
There is no particular restriction for the method for melting mixing, for example can use extruser, Banbury, mixing roller etc. to carry out.In these methods, extruser is owing to easy and simple to handle, so preferably use extruser.Extruser can be single shaft, twin shaft or its above multiaxis spiral.The temperature of melting mixing is preferably below the decomposition temperature of the above and employed organic peroxide of employed polyolefinic fusing point.Concrete temperature and time is generally 0.3～30 minute under 160～280 ℃, is preferably 1～10 minute under 170～250 ℃.
Will be in acid-modified polyolefin resin A melting mixing resin B and modified resins C is shaped to stratiform, give stable on heating refractory layer 3 thereby form to diaphragm seal.The method that forms refractory layer 3 can be enumerated: the press polish method that resin C is rolled between a plurality of rollers; The extrusion molding that utilizes T pattern head or ring-like die head that the resin C of fusion is extruded.In these methods, extrusion molding is directly extruded the resin C that melting mixing forms owing to can utilize the employed extruder of modification procedure, so preferable.
In the last stage of the modification procedure that is modified as resin C, be preferably increase with carrying out melting mixing in polyolefin and the unsaturated carboxylic acid class input extruder, to be modified as the step of acid-modified polyolefin resin A.After this, be preferably and then resin B is dropped in this extruder, Resin A is modified as resin C.
Moreover therefore the acid-modified polyolefin resin that unsaturated carboxylic acid graft is polymerized also can use commercially available product on sale on the market.
Comprise with the PP based polymer of unsaturated carboxylic acid graft polymerization and to utilize in metal hydroxides, alkoxide, the lower aliphatic hydrochlorate etc. and ionomer that carboxyl forms.
As resin B had can with the functional group of the carboxyl reaction of Resin A, can enumerate hydroxyl, amido, carboxyl, formoxyl, epoxy radicals etc.As the resin B with these functional groups, there is no particular restriction, is preferably the resins for universal use of easy acquisition.As this resins for universal use, can enumerate: polyamide (PA)s such as ethylene-vinyl alcohol copolymer (EVOH), polyvinyl alcohol (PVA), nylon 6 or nylon 66, ethylene-methyl methacrylate glycidyl ester copolymer epoxy-containing yl resins such as (E-GMA, ethylene-glycidyl methacrylate) etc.Therefore, as can with the preferable functional group of the carboxyl reaction of Resin A, can enumerate hydroxyl, amido, epoxy radicals.
Using under the situation of EVOH as resin B, with regard to regard to the viewpoint of the intermiscibility of Resin A or processability, MFR is preferably 1～30g/10min(230 ℃).It is 3～16g/10min that MFR is more preferred from 1～20g/10min, You Jia.As the ethylene contents among the EVOH, ethene is preferably 20～60 moles of %, is more preferred from 25～50 moles of %.
Using under the situation of polyamide as resin B, thereby reduce the polyamide of terminal amine base unit weight compared with the terminal amido of blockading in order to realize stabilisation, being preferably and using the terminal amine base unit weight polyamide identical with the terminal carboxyl group amount or terminal carboxyl group is more than 2 with respect to the mol ratio of terminal amido and the terminal amine base unit weight is 8.0 * l0
-5The polyamide that mole/g is above.This polyamide can improve the shear rate dependence of the melting viscosity of resin C.The fusing point of polyamide is higher relatively in resins for universal use, and therefore the patience at thermal deformation of the resin C that is obtained improves.
Using under the situation of epoxy-containing yl resin as resin B,, be preferably the resin that the vinyl monomer combined polymerization is formed with regard to regard to the viewpoint of the intermiscibility of Resin A or processability.The carboxyl of Resin A is the epoxy ring-opening of epoxy-containing yl resin, and will be by the hydroxy esterification that open loop generated.This esterification is carried out repeatedly.Its result, the molecular configuration of resin C becomes as crosslinked configuration, and the patience at thermal deformation is improved.
Resin D be make alkylidene monomer, for example ethene, propylene etc. more than a kind or 2 kinds with the resin that combined polymerization forms more than a kind or 2 kinds of unsaturated carboxylic acid or derivatives thereof.As copolymer, can enumerate block copolymer, graft copolymer or random copolymer.Using under the situation of graft copolymer, can be with polyolefin identical and identical unsaturated carboxylic acid graft polymerization and make carboxyl acid modified vistanex D with Resin A with Resin A.
As long as electrode engagement layer 2 is guaranteed the thermal welding with electrode 11, then be preferably thinner.Usually, the thickness of electrode engagement layer 2 is 20 μ m～60 μ m.If the situation that the thickness of electrode engagement layer 2 less than this scope, then exists the bond strength of electrode engagement layer 2 and electrode 11 to reduce.If greater than this scope, then existing diaphragm seal 1 to become, the thickness of electrode engagement layer 2 lacks stable on heating situation.
The fusing point that forms the resin D of electrode engagement layer 2 is preferably the fusing point that is lower than the resin C that forms refractory layer 3.For the diaphragm seal 1 that is made of polypropylene-based resin, the fusing point of resin D is preferably 130 ℃～150 ℃.If the fusing point of resin D is lower than this scope, then exists diaphragm seal l to become and lack stable on heating situation.If the fusing point of resin D is higher than this scope, it is poor then to be difficult to increase with the fusing point of the resin C that forms refractory layer 3.If the fusing point difference of resin D and resin C is more than 10 ℃, then the temperature treatment during thermal welding becomes easily, so preferable.
The fusing point of resin D is preferably the fusing point that is equal to or less than Resin A.If Resin A is modified as resin C, then the molecular linkage of resin B and increases the molecular weight of resin C on the molecule of Resin A, is higher than Resin A thereby the fusing point of resin C is become.Thus, become the fusing point difference of resin D and resin C is reached more than 10 ℃.If resin D is adopted identical resin with Resin A, then the management of resin becomes easy.
The method that forms electrode engagement layer 2 can be enumerated the extrusion molding that uses extruder that the resin D of fusion is extruded from T pattern head or ring-like die head.Use under the situation of graft copolymer as resin D, can when utilizing extruder to extrude, make polyolefin and the glycerol polymerization of unsaturated carboxylic acid class according to the mode identical with Resin A.
In order to make the diaphragm seal that comprises polyethylene-based resin, when in electrode engagement layer 2, adopting sour modified poly ethylene, be preferably fusing point and be the maleic anhydride graft copolymerization polyethylene about 90～120 ℃.The acid modified poly ethylene comprises the ionomer that the carboxyl neutralization is formed.
The MFR that forms the acid-modified polyolefin resin D of electrode engagement layer 2 is preferably the scope of 3g/10min～30g/10min.MFR is more preferred from the scope of 5g/10min～l0g/10min.If MFR is less than these scopes, then when thermal welding, acid modified polyolefin be difficult to fully to be surrounded on electrode 11 around.If MFR is greater than these scopes, then electrode engagement layer 2 attenuation, and make the bond strength deficiency.
Among the present invention, MFR is according to JIS K7210, all measures under 230 ℃ at polypropylene-based resin, all measures under 190 ℃ at polyethylene-based resin.
Moreover therefore carboxyl acid modified vistanex also can use commercially available product on sale on the market.
As the method for contact laminating, can enumerate: the electrode engagement layer 2 of institute's moulding and refractory layer 3 is overlapping and carry out the heat lamination of heat welded; After in shaped electrode knitting layer 2 and the refractory layer 3 any one, extrude another person from T pattern head on one side with molten condition in advance, carries out the extruding layer platen press of lamination on one side; When the two is in molten condition at electrode engagement layer 2 and refractory layer 3, from coextrusion die head extrude on one side, carry out the co-extrusion laminating method of lamination on one side.In these methods,, and in the coextrusion die head, carry out contact laminating while the co-extrusion laminating method is by melting mixing is modified as the extruder of resin C, extrusion resin C and another extruder of extrusion resin D is connected on the coextrusion die head with carrying out.Thus, modification, the formation of refractory layer 3, the formation of electrode engagement layer 2, electrode engagement layer 2 to resin C are carried out, so preferable with being laminated in the step of refractory layer 3.
In the manner example, on the face opposite that sealant 4 is laminated to refractory layer 3 with electrode engagement layer 2.Sealant 4 is the layers with sealant 22 welding by heating and pressurizing of the laminated film 20 of bag.
As laminating method, based on identical with the lamination of electrode engagement layer 2 and refractory layer 3 former thereby adopt identical method.In these methods, owing to therefore electrode engagement layer 2, refractory layer 3 and sealant 4 disposable laminations can be preferably and utilize the co-extrusion laminating method to carry out lamination.
As long as sealant 4 is guaranteed and the welding of the sealant 22 of bag, then is preferably thinner.Usually, the thickness of sealant 4 is 20 μ m～40 μ m.If the thickness of sealant 4 is less than these scopes, then sealant 4 may reduce with the heat seal strength of the sealant 22 of bag.If the thickness of sealant 4 is greater than this scope, the diaphragm seal l shortage thermal endurance that may become then.
With regard to easily with regard to sealant 22 weldings of the laminated film 20 of bag, the resin of formation sealant 4 (below, be called resin E) is preferably the resin of the same race or identical with the resin that constitutes sealant 22.Usually, with regard to the excellent heat resistance aspect, diaphragm seal 1 is that resin constitutes by PP.
Is resin when constituting at diaphragm seal 1 by PP, and resin E can enumerate: the random copolymer of the homopolymers of PP, ethene and propylene or block copolymer or their mixture or their polymer alloy etc.Wherein, with regard to the excellent aspect of flexibility, be preferably the random copolymer of ethene and propylene.
By PP be resin when constituting diaphragm seal, the fusing point that forms the resin E of sealant 4 is preferably 130 ℃～170 ℃.If the fusing point of resin E is lower than this scope, then exists diaphragm seal 1 to become and lack stable on heating situation.Be higher than this scope if form the fusing point of the resin E of sealant 4, it is poor then to be difficult to increase with the fusing point of the resin C that forms refractory layer 3.If the difference of the fusing point of the fusing point of resin E and resin C reaches more than 10 ℃, then the temperature treatment when the laminated film 20 of bag carries out welding becomes easily, so preferable.
Adopt in sealant 4 under the situation of polyethylene-based resin for diaphragm seal 1 is made polyethylene-based resin, being preferably and using fusing point is low density polyethylene (LDPE) or straight chain shape low density polyethylene (LDPE) about 100～120 ℃.
By PP be resin when constituting diaphragm seal, the MFR that forms the resin E of sealant 4 is preferably the scope of 3g/10min～30g/10min, is more preferred from the scope of 5g/10min～l0g/10min.Lamination is extruded in utilization or co-extrusion laminating carries out lamination if the MFR of resin E less than these scopes, then is difficult to.If the MFR of resin E then is difficult to utilize the ring-like die head of coextrusion to carry out moulding greater than these scopes.
Moreover sealant 4 is the layer that is provided with arbitrarily, under the situation of the welding of the sealant 22 that can guarantee refractory layer 3 and bag, also sealant 4 can be set.
The diaphragm seal 1 of the manner example for the location of realizing diaphragm seal 1 when the welding with make resin seamlessly be surrounded on electrode thickness direction around, and as shown in Figure 3A, be preferably the electrode engagement layer 2 that uses diaphragm seal 1 in advance and diaphragm seal 1 of the present invention is heat fused in the one side at least of electrode 11, be preferably the two sides.Thus, can use the sealant 4 or the refractory layer 3 of diaphragm seal 1, easily and reliably the sealant 22 to bag carries out welding.At this moment, if diaphragm seal l is painted, when then the electrode protuberance that diaphragm seal is arranged in innermost layer and welding to bag carries out thermal welding, can in the welding assembly line of automation, use photoreceptor and electrode protuberance and diaphragm seal 1 are correctly located.
In the thermal welding of diaphragm seal 1 and electrode 11, can use heat sealing machine or moment sealing machine etc., utilize the seal bar heating and carry out crimping.Again, when diaphragm seal l is heated,, then suppress caused the flowing of fusion by the Outboard Sections of sealant 4 or refractory layer 3 if use electromagnetic induction heating or energising to heat and direct heating electrode 11, promote the softening or fusion of the inside part or the electrode engagement layer 2 of refractory layer 3, so preferable.
But the shape illustration band shape of electrode 11 or pole etc.There is no particular restriction for the size of electrode 11, if for example banded, then thickness is 50 μ m～500 μ m, and width is 5mm～l00mm, and length is about 40mm～l00mm.Banded electrode 11 also can become circle with its crest line (angle edge portion).And, though its surface also can be the state through the machined surface of calendering processing, be preferably by surface treatments such as sandblast or etchings and improve roughness.By improving roughness, the bond strength of diaphragm seal 1 can improve.Also can implement bottom layer treatment such as chemical conversion processing again.
As the material of electrode 11, for example can use metals such as aluminium, copper, nickel, iron, gold, platinum or various alloys.Wherein, from excellent electric conductivity and the aspect favourable, be preferably and use aluminium or copper cost.But there are following situation in aluminium or copper: the patience for the hydrogen fluoride that may produce in the electrolyte in battery pack (hydrofluoric acid) is insufficient.If PP is that resin contacts with copper, then there is the possibility that promotes the resin deterioration again.Therefore, be preferably with conductivity higher and to the nickel plating of the patience excellence of hydrofluoric acid on the underlying metal of aluminium or copper.
Welding has the laminated film 20 of the bag of diaphragm seal 1 of the present invention for example can enumerate laminating seal layer 22 on the one side of metal forming 21 as shown in Figure 2 and the laminated film that forms at another side upper laminate film base material 23 etc.But in the laminated film 20 also lamination other the layer.
The laminated film 20 of bag is shaped to the bag of drawn moulding or puts down bag etc.As metal forming 21, can enumerate aluminium foil, stainless steel foil, Copper Foil, iron foil etc.Metal forming 21 also can be implemented bottom layer treatment such as chemical conversion processing.
Form bag laminated film 20 sealant 22 Choice of Resin can with the resin of sealant 4 weldings of diaphragm seal 1.As this resin, for example the sealant 4 at diaphragm seal 1 is under the situation of resin for PP, can use the homopolymers of PP or the copolymer of PP and ethene etc.Under the situation of using polyethylene-based resin, can use low density polyethylene (LDPE) or straight chain shape low density polyethylene (LDPE) etc.There is no particular restriction for the resin of formation film base material 23, is preferably the bigger polyamide of working strength, polyethylene terephthalate (PET) or PP etc.If these resins are extended and the formation film, then can obtain higher physical strength.But these films are a plurality of layers of lamination also.
More than, though the present invention will be described based on preferred implementation, the present invention is not limited to above-mentioned execution mode, can carry out various changes.
For example, diaphragm seal 1 also can further contain other layers such as resin bed in order to improve zygosity, physical strength or the insulating properties etc. between each resin bed.At this moment, other layer is preferably and is difficult to fusion and the higher layer of flexibility when thermal welding.And, also the lamination strength of each interlayer can be controlled to be proper range, and diaphragm seal 1 be given the function of the safety valve of preparing at the situation of temperature in the bag or pressure anomaly rising.
Embodiment
Use resin shown below and make the embodiment and the comparative example of the diaphragm seal 1 shown in the table 1.
Resin A: the maleic anhydride glycerol polymerization is formed on random PP maleic anhydride modified PP(MFR2.4g/10min(230 ℃), fusing point is 143 ℃)
Resin B
Resin B-1: EVOH(MFR15g/10min(230 ℃ of ethene ratio 48mol%), fusing point is 160 ℃)
Resin B-2: EVOH(MFR3.6g/10min(230 ℃ of ethene ratio 32mol%), fusing point is 183 ℃)
Resin B-3: 220 ℃ of nylon 6(relative viscosity 3.37, fusing points)
Resin B-4: 220 ℃ of nylon 6(relative viscosity 4.08, fusing points)
Resin B-5: 105 ℃ of the E-GMA copolymer of glycidyl methacrylate containing ratio 6wt% (MFR 3g/10min(190 ℃), fusing points)
Resin D
Resin D-1: the maleic anhydride glycerol polymerization is formed on random PP maleic anhydride modified PP(MFR7.5g/10min(230 ℃), fusing point is 135 ℃)
Resin D-2: the maleic anhydride glycerol polymerization is formed on random PP maleic anhydride modified PP(MFR7.0g/10min(230 ℃), fusing point is 140 ℃)
Resin E: block PP(MFR2.3g(230 ℃)/163 ℃ of 10min, fusing point)
＜embodiment 1～15 〉
With Resin A with resin B with the allotment shown in the table 1 than in the hopper that is added into extruder, one side makes it to be modified as resin C with the extrusion temperature shown in the table 1 and simultaneously extrudes, and in coextrusion T pattern head, carry out lamination with the resin D that extrudes from another extruder, and the embodiment 1～15 of cast molding diaphragm seal 1.
Constitute among the embodiment that a hurdle is written as 3 layers at the layer of table l, when the coextrusion cast molding, and then carry out co-extrusion laminating from another extruder extrusion resin E.And, in colouring agent one hurdle of table 1 is written as 3 parts embodiment, when allotment Resin A and resin B, add the pigment masterbatch of the PP matrix of 3 weight portions.
The extrusion temperature of resin D and resin E all is made as 240 ℃.
The laminated film of the three-layer structure that the laminated film of the double-layer structural that will be made of the refractory layer 3 of the thickness shown in refractory layer one hurdle of the electrode engagement layer 2 of 40 μ m and table 1 with above-mentioned mode moulding and sealant 4 laminations of 20 μ m form.This laminated film is cut into the width of 25mm, and make the embodiment 1～15 of diaphragm seal 1.
＜comparative example 1 〉
At 240 ℃ of down respectively extrusion resin D-1 and resin E, and in coextrusion T pattern head, carry out lamination, the laminated film of the double-layer structural that is constituted by the sealant 4 of the electrode engagement layer 2 of 20 μ m and 80 μ m with moulding by casting.This laminated film cut into the width of 25mm and make the diaphragm seal l of comparative example 1.
[table 1]
At this, " part " in the table 1 all refers to " weight portion ".
The mensuration of＜electrode engagement intensity 〉
Used thickness is that 50 μ m, width are that 50mm, length are that the foursquare aluminium foil of 50mm is as electrode 11.The length that the embodiment 1～15 and the comparative example 1 of diaphragm seal 1 cut into 60mm respectively.Electrode engagement layer 2 with diaphragm seal 1 is inboard being overlapped on the electrode 11.Use heat sealing machine, under 200 ℃, 0.2MPa, the condition in 3 seconds, heat at one end residual not weld portion, and the thermal welding other end from the aluminium foil side.
Use Instron type cupping machine that the electrode engagement layer 2 of each diaphragm seal 1 is measured with the peel strength of electrode 11.When measuring peel strength, be not fixed on two chucks of cupping machine being fused to the end of the diaphragm seal 1 on the electrode 11 and the end of electrode 11, and stretch, and 180 degree peel strengths are measured with the speed of 300mm/min.The electrode engagement layer 2 of each diaphragm seal 1 seals with the sealing intensity of electrode 11 with 27.5～32.8N/25mm.
The mensuration of＜laminated film heat seal strength 〉
By dry lamination will be that the twin shaft of 12 μ m extends the PET film, is that the ethene of 40 μ m and the random copolymer film of propylene carry out lamination as the aluminium foil of the thickness 40 μ m of metal forming 21 and as the thickness of sealant 22 as the thickness of film base material 23.The laminated film of gained is cut into the square that the length of side is 100mm, and produce the laminated film 20 of two bags.
The length that the embodiment 1～15 and the comparative example 1 of diaphragm seal 1 cut into 60mm respectively.Make two bags laminated film 20 sealant 22 toward each other, and between it, sandwich diaphragm seal l.When sandwiching diaphragm seal 1, make diaphragm seal 1 expose 5mm from the end of laminated film 20.
Heat both sides from the laminated film 20 of two bags under the condition identical with the mensuration of electrode engagement intensity, and the end that diaphragm seal 1 exposes side is carried out welding.The other end is as weld portion not and residual.When frit seal film 1, the root of the exposed portions serve of self sealss film 1 contacts with seal bar with the width of 2mm approximately.
In the mode identical with the mensuration of electrode engagement intensity, the end of the not weld portion of diaphragm seal 1 and the end of laminated film 20 are fixed on two chucks of cupping machine, under the condition identical, the sealant 4 or the refractory layer 3 of each diaphragm seal 1 are measured with the heat seal strength of laminated film 20 with the mensuration of electrode engagement intensity.Each diaphragm seal 1 seals with the sealing intensity of laminated film 20 with 124.2～143.3N/25mm.
And the part of exposing from laminated film 20 of the diaphragm seal 1 among arbitrary embodiment does not have the sign of thermal deformation or fusion.On the other hand, in comparative example, the part root that exposes from laminated film 20 has slightly and dwindles.
The MFR of＜mixing product 〉
The melting mixing product (resin C-3) of the resin B-3 of the Resin A of the melting mixing product (resin C-l) of the resin B-1 of the Resin A of 95 weight portions and 5 weight portions, 95 weight portions and 5 weight portions are extruded separately respectively, and measured MFR under 230 ℃.The MFR of original Resin A is 2.4.The MFR of resin C-l is 1.9, compares MFR with Resin A and descends.Moreover the MFR of resin C-3 is 2.5, compares MFR with Resin A and rises.Infer that thus the reason of the thermal endurance of diaphragm seal l raising in the present invention not only is to make the molecule quantitative change big because of the functional group's of the carboxyl of Resin A and resin B chemical bonding, also is subjected to partial cross-linked influence.
Utilizability on the industry
The present invention can be widely used in sealing the manufacture method and the diaphragm seal of diaphragm seal of the electrode of generating elements such as secondary cell that bag takes in or capacitor.
Claims (12)
1. the manufacture method of a diaphragm seal is the manufacture method that is sandwiched in the diaphragm seal between the edge of the electrode of the generating element that bag takes in and bag, and it has following steps:
The melting mixing step, acid-modified polyolefin resin A by glycerol polymerization there being carboxylic acid makes the carboxyl of Resin A and the functional group of resin B carry out chemical bonding and be modified as resin C with have can the two carries out melting mixing with the functional group's of the carboxyl reaction of Resin A resin B;
Refractory layer system film step is shaped to resin C stratiform and forms refractory layer;
Knitting layer system film step is shaped to carboxyl acid modified vistanex D stratiform and forms the electrode engagement layer that is engaged in electrode;
Lamination step, described refractory layer of contact laminating and described electrode engagement layer when any one in resin C and resin D or both are in molten condition.
2. the manufacture method of diaphragm seal as claimed in claim 1, wherein said melting mixing step is carried out in extruder.
3. the manufacture method of diaphragm seal as claimed in claim 1 or 2, wherein said melting mixing step and described refractory layer system film step are carried out continuously.
4. as the manufacture method of each described diaphragm seal in the claim 1 to 3, wherein said lamination step is any one in described refractory layer system film step and described knitting layer system film step or both and carry out continuously.
5. as the manufacture method of each described diaphragm seal in the claim 1 to 4, wherein said lamination step is carried out in the coextrusion die head.
6. as the manufacture method of each described diaphragm seal in the claim 1 to 5, wherein said melting mixing step be with Resin A be 99～90%, resin B is that 1～10% percentage by weight is allocated and carried out.
7. as the manufacture method of each described diaphragm seal in the claim 1 to 6, wherein will have the identical or resin of fusing point that is lower than it of fusing point with Resin A as resin D.
8. diaphragm seal, the sealing film is sandwiched between the edge of the electrode of the generating element that bag takes in and bag, and has the laminar construction that the refractory layer contact laminating that will be made of resin C forms on the electrode engagement layer that is made of carboxyl acid modified vistanex D, this resin C be acid-modified polyolefin resin A by glycerol polymerization there being carboxylic acid with have can the two carries out melting mixing with the functional group's of the carboxyl reaction of Resin A resin B, make the carboxyl of Resin A and functional group's chemical bonding of resin B carry out the resin that modification forms.
9. diaphragm seal as claimed in claim 8, wherein resin B be selected from have hydroxyl, one or more resins in the resin of amido or epoxy radicals.
10. diaphragm seal as claimed in claim 8 or 9, wherein Resin A is the acid-modified polyolefin resin that the maleic anhydride glycerol polymerization is formed in polypropylene.
11. as each described diaphragm seal in the claim 8 to 10, wherein said laminar construction is that the coextrusion by resin C and resin D forms.
12., wherein be pressed with sealant with the innermost layer thermal welding of bag on described refractory layer upper strata as each described diaphragm seal in the claim 8 to 11.
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| JP2010252940 | 2010-11-11 | ||
| JP2010-252940 | 2010-11-11 | ||
| PCT/JP2011/075560 WO2012063764A1 (en) | 2010-11-11 | 2011-11-07 | Process for producing sealing film, and sealing film |
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| CN103222084A true CN103222084A (en) | 2013-07-24 |
| CN103222084B CN103222084B (en) | 2015-07-08 |
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| JP (1) | JP5659241B2 (en) |
| KR (1) | KR101494811B1 (en) |
| CN (1) | CN103222084B (en) |
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| CN110494523A (en) * | 2017-04-05 | 2019-11-22 | 大日本印刷株式会社 | Cementability protective film, battery and its manufacturing method |
| CN110494523B (en) * | 2017-04-05 | 2022-06-17 | 大日本印刷株式会社 | Adhesive protective film, battery and method for manufacturing same |
| CN111656556A (en) * | 2018-11-23 | 2020-09-11 | 株式会社大北制作所 | Housing member with terminal and method for manufacturing the same |
| CN111656556B (en) * | 2018-11-23 | 2021-10-22 | 株式会社大北制作所 | Housing member with terminal and method for manufacturing the same |
| CN114096628A (en) * | 2019-07-10 | 2022-02-25 | 大日本印刷株式会社 | Adhesive film for metal terminal, metal terminal with adhesive film for metal terminal, electric storage device using adhesive film for metal terminal, and method for manufacturing electric storage device |
Also Published As
| Publication number | Publication date |
|---|---|
| TW201240817A (en) | 2012-10-16 |
| JPWO2012063764A1 (en) | 2014-05-12 |
| WO2012063764A1 (en) | 2012-05-18 |
| KR101494811B1 (en) | 2015-02-23 |
| JP5659241B2 (en) | 2015-01-28 |
| TW201522056A (en) | 2015-06-16 |
| TWI480160B (en) | 2015-04-11 |
| KR20140003420A (en) | 2014-01-09 |
| TWI601640B (en) | 2017-10-11 |
| CN103222084B (en) | 2015-07-08 |
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