CN103222084B - Process for producing sealing film, and sealing film - Google Patents

Process for producing sealing film, and sealing film Download PDF

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Publication number
CN103222084B
CN103222084B CN201180054069.7A CN201180054069A CN103222084B CN 103222084 B CN103222084 B CN 103222084B CN 201180054069 A CN201180054069 A CN 201180054069A CN 103222084 B CN103222084 B CN 103222084B
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China
Prior art keywords
resin
diaphragm seal
layer
electrode
bag
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CN201180054069.7A
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CN103222084A (en
Inventor
鹿岛甲介
山本史郎
小林新一
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Fujimori Kogyo Co Ltd
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Fujimori Kogyo Co Ltd
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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
    • H01M50/183—Sealing members
    • H01M50/186—Sealing members characterised by the disposition of the sealing members
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
    • 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
    • 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
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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, LIGHT-SENSITIVE OR TEMPERATURE-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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/183—Sealing members
    • H01M50/19—Sealing members characterised by the material
    • H01M50/193—Organic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/183—Sealing members
    • H01M50/19—Sealing members characterised by the material
    • H01M50/197—Sealing members characterised by the material having a layered structure
    • 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
    • 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
    • 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
    • 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

Landscapes

  • Engineering & Computer Science (AREA)
  • Power Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Sealing Battery Cases Or Jackets (AREA)
  • Laminated Bodies (AREA)
  • Electric Double-Layer Capacitors Or The Like (AREA)

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

The manufacture method of diaphragm seal and diaphragm seal
Technical field
The present invention relates to a kind of manufacture method to the diaphragm seal that the electrode of the generating element such as secondary cell or capacitor that bag is received seals and diaphragm seal.
The application according to the applying date be on November 11st, 2010, application number is the Japanese invention patent application hereby claims priority of 2010-252940, and by its content quotation in the application.
Background technology
In recent years, such as, as the power supply of the electronic equipment such as notebook computer or mobile phone or the battery etc. of hybrid vehicle, fuel cell car or battery car, the secondary cell just progressively adopting the bag be made up of film to receive or capacitor etc.
In the past, these secondary cells or capacitor form in the bag flat generating element being sealed in flat bag or the drawing and forming be made up of the laminated film be laminated in the metal formings such as aluminium foil by polyolefin sealant.On the film base material of bag, one end of the electrode for carrying out discharge and recharge is made to project to outside and seal.When sealing, being clamped banded electrode (electrode projection) by the film base material of bag and being sealed.
The electrode of these secondary cells etc. (following, be sometimes referred to as " battery pack ") is thicker than the sealant of bag, therefore when sealing, is difficult to make resin seamlessly be surrounded on around the thickness direction of electrode, and around the thickness direction of electrode generation gap.If generation gap around electrode, then, under Long-Time Service, high temperature or the conditions such as harsh and unforgiving environments such as many wet, there is sealing deterioration or the bag of sealing and the bond strength of electrode declines, and causes the possibility that electrolyte self sealss portion leaks.
For these problems, use in recent years and utilize the table back side of diaphragm seal holding electrode and carry out with the film base material of bag the method that seals.But, if improve the degree of adhesion of bag and electrode, and the condition of heating when strictly setting sealing or pressurization, then to there is the thinning or diaphragm seal of resin between the metal forming of bag and electrode and be out of shape and cause the possibility of short circuit.
In addition, when grip seal film seals between the film base material and electrode of bag, such as, described in patent documentation 2, diaphragm seal is made to expose several millimeters from the openend of bag and seal.Expose diaphragm seal in this way, reliably can prevent short circuit.But, when sealing, due to seal bar contact or close to this exposed division, so there is the contact of the seal bar of Yin Gaowen or radiant heat and make diaphragm seal melt or the situation of distortion.Thus, electrode becomes and easily contacts with the metal forming of the film base material of bag.
In order to address these problems, such as, describe the heat-sealing portion utilizing lining material to cover terminal material in patent documentation 1, thus prevent the formation of short circuit, described lining material have utilize that thermal bonding film is clamped by weaving cotton cloth, the laminar construction of refractory layer that adhesive-bonded fabric or ultra-high molecular weight polyethylene are formed.
Again, the zygosity film of being pressed layer by layer by polyolefin layer and the acid modified polyolefin through electron beam crosslinking is described in patent documentation 2.
Prior art document
Patent documentation
Patent documentation 1: Japanese Laid-Open Patent Publication 62-61268 publication
Patent documentation 2: Japanese Unexamined Patent Publication 2001-297748 publication
Summary of the invention
Technical problem
Lining material described in patent documentation 1 be utilize weave cotton cloth or adhesive-bonded fabric to guarantee thermal endurance, so need select be difficult to weaving cotton cloth or adhesive-bonded fabric of melting.But now owing to weaving cotton cloth or adhesive-bonded fabric not melting, so be difficult to high degree of adhesion lamination, these are weaved cotton cloth or adhesive-bonded fabric and thermal bonding film.Therefore, existence easily forms pin hole, the possibility that sealing cannot improve.In some cases, sealing can decline on the contrary.And, because ultra-high molecular weight polyethylene is difficult to obtain, unfavorable in cost aspect.And ultra-high molecular weight polyethylene cannot with the thermal bonding rete pressure be made up of polypropylene-based resin.Therefore, polypropylene-based resin cannot be adopted in the sealant of bag, and be difficult to the thermal endurance improving bag.
The excellent heat resistance of the zygosity film described in patent documentation 2.But the manufacture method of this film makes polyolefin film electron beam crosslinking in advance and acid modified polyolefin layer extruded lamination, or carry out electron beam crosslinking by coextrusion after lamination polyolefin layer and acid modified polyolefin layer.Therefore, any method no matter is adopted all to need the step of electron beam crosslinking.Following situation is recorded: because common polypropylene is decomposed by electron beam irradiation, so need to use specific resin in the paragraph 0013 of patent documentation 2.And, the situation of electron beam crosslinking is carried out after lamination polyolefin layer and acid modified polyolefin layer by coextrusion, acid modified polyolefin also occurs crosslinked and flexibility is declined, and therefore becomes and is difficult to resin is seamlessly surrounded on around the thickness direction of electrode.
A kind of village easily obtained that uses that the invention provides made in view of described background expects, resin is easily made seamlessly to be surrounded on around the thickness direction of electrode, and by simple step with the manufacture method of higher bond strength contact laminating refractory layer and the thermal endurance of electrode engagement layer and the diaphragm seal of sealing excellence and by the diaphragm seal manufactured by this manufacture method.
Technical scheme
Inventor of the present invention obtains following opinion in the research of the diaphragm seal for thermal endurance and sealing excellence: the carboxyl that glycerol polymerization has an acid-modified polyolefin resin of carboxylic acid easily and the reaction such as hydroxyl, amido, epoxy radicals, and easily can obtain modification.The present invention makes based on this opinion.
That is, according to a first aspect of the invention, the manufacture method of following diaphragm seal can be provided.
(1) manufacture method for diaphragm seal, be the manufacture method of the diaphragm seal be sandwiched between the electrode of the generating element that bag is received and the edge of bag, it has following steps:
Melting mixing step, by glycerol polymerization being had the acid-modified polyolefin resin A of carboxylic acid and having and can carry out melting mixing with both resin B of the functional group of the carboxyl reaction of Resin A, the functional group of the carboxyl of Resin A and resin B is made to carry out chemical bonding and be modified as resin C;
Refractory layer masking step, is shaped to stratiform by resin C and forms refractory layer;
Knitting layer masking step, is shaped to stratiform by carboxyl acid modified vistanex D and forms the electrode engagement layer being engaged in electrode;
Lamination step, refractory layer and described electrode engagement layer described in contact laminating when any one or both in resin C and resin D are in molten condition.
(2) manufacture method of the diaphragm seal as described in (1), wherein said melting mixing step is carried out in extruder.
(3) manufacture method of the diaphragm seal as described in (1) or (2), wherein said melting mixing step and described refractory layer masking step are carried out continuously.
(4) manufacture method of the diaphragm seal according to any one of (1) to (3), any one or both of wherein said lamination step continuously in described refractory layer masking step and described knitting layer masking step and carry out.
(5) manufacture method of the diaphragm seal according to any one of (1) to (4), wherein said lamination step is carried out in coextrusion die head.
(6) manufacture method of the diaphragm seal according to any one of (1) to (5), wherein said melting mixing step be with Resin A be 99 ~ 90%, resin B be 1 ~ 10% percentage by weight carry out allocating and carry out.
(7) manufacture method of the diaphragm seal according to any one of (1) to (6), is wherein used as resin D by having identical with the fusing point of Resin A or lower than its fusing point resin.
And, according to a second aspect of the invention, following diaphragm seal can be provided.
(8) a kind of diaphragm seal, between the electrode that sealing film is sandwiched in the generating element that bag is received and the edge of bag, and have the laminar construction of the refractory layer contact laminating be made up of resin C on the electrode engagement layer be made up of carboxyl acid modified vistanex D, this resin C is by glycerol polymerization being had the acid-modified polyolefin resin A of carboxylic acid and having and can carry out melting mixing with both resin B of the functional group of the carboxyl reaction of Resin A, makes the carboxyl of Resin A and functional group's chemical bonding of resin B carry out the resin of modification.
(9) diaphragm seal as described in (8), wherein resin B be selected from there is hydroxyl, amido or epoxy radicals resin in one or more resins.
(10) diaphragm seal as described in (8) or (9), wherein Resin A makes maleic anhydride glycerol polymerization in the acid-modified polyolefin resin of polypropylene.
(11) diaphragm seal according to any one of (8) to (10), wherein said laminar construction is formed by the coextrusion of resin C and resin D.
(12) diaphragm seal according to any one of (8) to (11), is wherein pressed with the sealant with the innermost layer thermal welding of bag on described refractory layer upper strata.
Beneficial effect
The manufacture method of diaphragm seal of the present invention makes the functional group of the carboxyl of Resin A and resin B carry out chemical bonding and be modified as resin C, therefore do not need the cross-linking process step such as electron beam crosslinking.Therefore, thermal endurance is given by simple technique to refractory layer.
Due to only by both Resin A and resin B melting mixing, so resin C can be modified as in the common extruder that filming technology uses.
In the present invention, in resin C and resin D any one or both are in molten condition time, contact laminating refractory layer and electrode engagement layer.Laminating method is combination extruder and masking die head and after forming a layer, extrude another layer of lamination.Another laminating method is by refractory layer and the coextrusion of electrode engagement layer.By these methods, in the present invention, by simple technique with higher bond strength contact laminating refractory layer and electrode engagement layer.By the diaphragm seal that these methods obtain, not easily there is the contact of the seal bar of Yin Gaowen or radiant heat when sealing and the phenomenon of the diaphragm seal fusing that causes or distortion.Thus, the short circuit of the metal forming of electrode and bag is not easily caused.
Especially the coextrusion of refractory layer and electrode engagement layer by more simple technique with higher bond strength contact laminating refractory layer and electrode engagement layer.
The refractory layer of diaphragm seal of the present invention has makes functional group's chemical bonding of the carboxyl of Resin A and resin B carry out the less resin C of the melt fluidity of modification.Thus, when sealing, not easily there is the phenomenon of the thinning or diaphragm seal thermal deformation of refractory layer.Therefore, the short circuit of the metal forming of electrode and bag is not easily caused.
If resin B be selected from there is hydroxyl, amido or epoxy radicals resin in one or more resins, then the carboxyl of Resin A and the easy chemical bonding of the functional group of resin B, and be successfully modified as resin C.Due to by Resin A and resin B melting mixing are modified as resin C, so the easy chemical bonding equably of the functional group of the carboxyl of Resin A and resin B.
If Resin A is make the acid-modified polyolefin resin of maleic anhydride glycerol polymerization on polypropylene, then the carboxyl of Resin A and the easy chemical bonding of the functional group of resin B, become and be more successfully modified as resin C.
If the laminar construction of diaphragm seal is formed by the coextrusion of resin C and resin D, then the bond strength of laminar construction is higher, and when sealing, diaphragm seal can not thermal deformation, not easily causes the short circuit of the metal forming of electrode and bag.
If be laminated on refractory layer by the sealant of the innermost layer thermal welding with bag, then can improve the innermost layer of bag and the thermal welding intensity of diaphragm seal.And, if by sealant contact laminating on refractory layer, then can prevent the stripping of the joint interface caused by electrolyte.
Accompanying drawing explanation
Fig. 1 is the profile of the example representing diaphragm seal of the present invention.
Fig. 2 is for representing that the diaphragm seal shown in use Fig. 1 engages the profile of the laminated film of bag and the state of electrode.
Fig. 3 A is for representing the stereogram of the electrode diaphragm seal shown in Fig. 1 being engaged in the band diaphragm seal on electrode.
Fig. 3 B is for representing the profile of the electrode diaphragm seal shown in Fig. 1 being engaged in the band diaphragm seal on electrode.
Symbol description:
1: diaphragm seal
2: 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, based on execution mode, the present invention is described in detail.
Fig. 1 is the profile of the schematic configuration representing diaphragm seal 1 of the present invention.
Diaphragm seal 1 shown in Fig. 1 to insert between the laminated film 20 of bag and electrode 11 and the state of welding for representing by Fig. 2, and the profile of length direction along electrode 11.
Fig. 3 A is for representing the stereogram of the electrode 10 diaphragm seal 1 shown in Fig. 1 being engaged in the band diaphragm seal on electrode 11.Fig. 3 B is that represent the electrode 10 of this band diaphragm seal, on the direction vertical with the length direction of electrode 11 profile.
Between the electrode that diaphragm seal l of the present invention is sandwiched into the generating element that bag is received and the edge of bag.The basic layer of this film is formed as shown in Figures 1 and 2, has the laminar construction at least comprising 2 layers of lamination electrode engagement layer 2 and refractory layer 3.The sealant 4 of sealant 22 thermal welding of the innermost layer of contact laminating and bag further on the refractory layer 3 that the diaphragm seal 1 of the manner example is formed at basic layer.
The thickness of diaphragm seal 1 of the present invention is preferably 50 μm ~ 300 μm.If the thickness of diaphragm seal 1 is less than this scope, then there is the situation that insulating properties reduces.Moreover the thickness of diaphragm seal 1 also can be greater than this scope.But, the further raising of insulating properties cannot be expected, become on the contrary and be difficult to seal.
Refractory layer 3 is made up of resin C, this resin C is by glycerol polymerization being had the acid-modified polyolefin resin A of carboxylic acid and having and can carry out melting mixing with both resin B of the functional group of the carboxyl reaction of Resin A, makes the carboxyl of Resin A and the functional group of resin B carry out the resin of chemical bonding and modification.
The allotment ratio of resin is now preferably relative to 99 ~ Resin A of 90 % by weight, and resin B is 1 ~ 10 % by weight.If the allotment ratio of resin B is lower than this scope, then the modified effect that resin C can occur is less, makes diaphragm seal 1 lack the situation of thermal endurance.If the allotment ratio of resin B is higher than this scope, then refractory layer 3 easily becomes fragile.Therefore, when being provided with battery pack, the situation producing slight crack because of the bending of electrode 11 on refractory layer 3 can be there is.
Refractory layer 3 guarantees the metal forming 21 of the laminated film 20 of bag and the insulating properties of electrode 11.The thermal deformation of refractory layer 3 diaphragm seal 1 when preventing thermal welding and under the prerequisite of insulating properties can be guaranteed, ideally thin as far as possible.The thickness of refractory layer 3 is preferably 30 μm ~ 150 μm.If the thickness of refractory layer 3 does not reach 30 μm, then can there is thermal deformation or thinning when thermal welding in diaphragm seal 1 sometimes, and become shortage insulating properties.Moreover the thickness of refractory layer 3 also can more than 150 μm.But, the further raising of insulating properties cannot be expected.Form the resin of refractory layer 3 compared with Resin A, the degree be chemically bound in Resin A according to resin B be producing high-molecular, relatively firmly and melt fluidity is lower.Therefore, if the thickness of refractory layer 3 is more than essential value, then, when being sandwiched between two panels diaphragm seal 1,1 by electrode 11, the gap that the step difference caused by the thickness of electrode 11 produces is difficult to fill up when thermal welding.Thus, between diaphragm seal 1,1, pin hole is produced sometimes.
Acid-modified polyolefin resin A is by will the one kind or two or more polyolefin be polymerized of alkylidene monomer, such as ethene, propylene etc. be made as matrix resin, glycerol polymerization unsaturated carboxylic acid or derivatives thereof and obtaining.
As polyolefin, such as use polypropylene or poly homopolymers and copolymer.As copolymer, use the random copolymer (random PP) of ethene of propylene and 1 ~ 5 % by weight or block copolymer (block PP), the random or block copolymer of propylene of ethene and 1 ~ 10 % by weight, propylene or ethene and 1 ~ 10 % by weight carbon number be copolymer and their mixture etc. of the alpha-olefin of more than 4.
In order to the sealant 22 of the laminated film 20 by bag is set to polyethylene-based resin, and when using the matrix resin of polyethylene-based resin as Resin A in the refractory layer 3 of diaphragm seal 1, be preferably and use fusing point to be straight-chain low density polyethylene (LDPE) or the high density polyethylene (HDPE) of about 130 ~ 140 DEG C.
The matrix resin of acid-modified polyolefin resin A is preferably the polyethylene and the ethylene-alpha-olefin copolymer that use melt flow rate (MFR) to be the homo-polypropylene of 0.5 ~ 30g/10min, especially 5 ~ 15g/10min and Propylene-ethylene random copolymer or MFR to be 0.3 ~ 30g/10min.
The MFR forming the resin C of refractory layer 3 is preferably the scope of 0.5g/10min ~ 3g/10min.If MFR is less than this scope, then exists and be difficult to shaping situation.If MFR is greater than this scope, then exist when thermal welding, refractory layer 3 can be out of shape or thinning, and the situation causing insulating properties to decline.
For refractory layer 3, require to be difficult to melting or softening when being heat fused on electrode 11 by diaphragm seal 1 of the present invention.Therefore, the fusing point forming its resin C is more high better.Specifically, for the diaphragm seal be made up of polypropylene-based resin, being preferably by the fusing point measured by JIS K6921-2 DSC method is the resin of 130 ~ 170 DEG C.
In order to obtain this resin C, better use is using the random copolymer of the homopolymers of polypropylene (PP), ethene and propylene or block copolymer or their polymer alloy as the acid-modified polyolefin resin of matrix resin as Resin A.PP system resin easily becomes fragile usually at low ambient temperatures.Even if due to the block copolymer fusing point of ethene and propylene, comparatively high flexibility is also excellent, and also do not become fragile at low ambient temperatures (cold resistance), so better.
As the unsaturated carboxylic acid of glycerol polymerization on the matrix resin of acid-modified polyolefin resin A, include, for example: acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, their derivative such as acid anhydrides and their ester, acid amides, acid imide, slaine.In these unsaturated carboxylic acids, be preferably maleic acid, the best is maleic anhydride.Again, in order to promote the reaction of polyolefin and these unsaturated carboxylic acids, such as, be preferably and use the radical polymerization initiator such as the organic peroxide such as benzoyl peroxide, lauroyl peroxide or azodiisobutyronitrile.
As the amount of the unsaturated carboxylic acid of glycerol polymerization, be 0.5 ~ 5 % by weight relative to the total weight of monomer usually.
On polyolefin, the method for glycerol polymerization unsaturated carboxylic acid such as has following method: make the method that polyolefin and unsaturated carboxylic acid react in the molten state; The method that polyolefin and unsaturated carboxylic acid react is made under solution state; Make the method that polyolefin and unsaturated carboxylic acid react in the slurry state; The method etc. that polyolefin and unsaturated carboxylic acid react is made under gas phase state.In these methods, the method for reacting in the molten state due to processing ease, so better.Specifically, the fully polymerization initiators such as polyolefin, unsaturated carboxylic acid, organic peroxide shown in mixing above such as cylinder, Henschel mixer is utilized.After this, melting mixing and carry out graft reaction.
There is no particular restriction for the method for melting mixing, such as, extruser, Banbury, mixing roller etc. can be used to carry out.In these methods, extruser due 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 more than used polyolefinic fusing point and below the decomposition temperature of the organic peroxide used.Concrete temperature and time is generally 0.3 ~ 30 minute at 160 ~ 280 DEG C, is preferably 1 ~ 10 minute at 170 ~ 250 DEG C.
By melting mixing resin B in acid-modified polyolefin resin A, the resin C of modification is shaped to stratiform, thus forms the refractory layer 3 diaphragm seal being given to thermal endurance.The method forming refractory layer 3 can be enumerated: resin C is carried out between multiple roller the press polish method of rolling; Utilize the extrusion molding that the resin C of melting extrudes by T-shaped die head or ring-like die head.In these methods, the resin C of melting mixing directly extrudes, so better due to the extruder that can utilize modification procedure and use by extrusion molding.
In the last stage of modification procedure being modified as resin C, be preferably to increase polyolefin and unsaturated carboxylic acid class to drop in extruder and carry out melting mixing, to be modified as the step of acid-modified polyolefin resin A.After this, be preferably and then resin B dropped in this extruder, Resin A is modified as resin C.
Moreover the acid-modified polyolefin resin be polymerized by unsaturated carboxylic acid graft, on sale on the market, therefore also can use commercially available product.
The PP based polymer be polymerized with unsaturated carboxylic acid graft comprises and utilizes in metal hydroxides, alkoxide, lower aliphatic hydrochlorate etc. and the ionomer of carboxyl.
As resin B have can with the functional group of the carboxyl reaction of Resin A, hydroxyl, amido, carboxyl, formoxyl, epoxy radicals etc. can be enumerated.As the resin B with these functional groups, there is no particular restriction, is preferably the resins for universal use easily obtained.As this resins for universal use, can enumerate: the epoxy-containing yl resins etc. such as the polyamide (PA)s such as ethylene-vinyl alcohol copolymer (EVOH), polyvinyl alcohol (PVA), nylon 6 or nylon66 fiber, ethylene-methyl methacrylate glycidyl ester copolymer (E-GMA, ethylene-glycidyl methacrylate).Therefore, as can with the better functional group of the carboxyl reaction of Resin A, hydroxyl, amido, epoxy radicals can be enumerated.
Use EVOH as resin B when, with regard to the intermiscibility of Resin A or the viewpoint of processability with regard to, MFR is preferably 1 ~ 30g/10min(230 DEG C).It is 3 ~ 16g/10min that MFR is more preferred from 1 ~ 20g/10min, You Jia.As the ethylene contents in EVOH, ethene is preferably 20 ~ 60 % by mole, is more preferred from 25 ~ 50 % by mole.
When using polyamide as resin B, to blockade terminal amido thus reduce the polyamide of terminal amine base unit weight compared with in order to realize stabilisation, being preferably and using polyamide that terminal amine base unit weight is identical with terminal carboxyl group amount or terminal carboxyl group is more than 2 relative to the mol ratio of terminal amido and terminal amine base unit weight is 8.0 × l0 -5mole/polyamide of more than g.This polyamide can improve the shear rate dependence of the melting viscosity of resin C.The fusing point of polyamide is relatively high in resins for universal use, and the patience for thermal deformation of therefore obtained resin C improves.
Use epoxy-containing yl resin as resin B when, with regard to the intermiscibility of Resin A or the viewpoint of processability with regard to, be preferably by fluoride monomers close resin.The carboxyl of Resin A is by the epoxy ring-opening of epoxy-containing yl resin, and the hydroxy esterification will generated by open loop.This esterification is carried out repeatedly.Its result, the molecular configuration of resin C becomes as crosslinked configuration, and the patience for thermal deformation is improved.
Electrode engagement layer 2 diaphragm seal 1 is heated on electrode 11 layer that thermal welding is carried out in pressurization.Electrode engagement layer 2 is made up of the carboxyl acid modified vistanex D of the zygosity excellence with metal.
Resin D is the resin making the one kind or two or more of alkylidene monomer, such as ethene, propylene etc. and the one kind or two or more combined polymerization of unsaturated carboxylic acid or derivatives thereof.As copolymer, block copolymer, graft copolymer or random copolymer can be enumerated.When using graft copolymer, the polyolefin identical with Resin A and the unsaturated carboxylic acid graft identical with Resin A can be polymerized and make carboxyl acid modified vistanex D.
As long as electrode engagement layer 2 guarantees the thermal welding with electrode 11, be then preferably thinner.Usually, the thickness of electrode engagement layer 2 is 20 μm ~ 60 μm.If the thickness of electrode engagement layer 2 is less than this scope, then there is the situation that electrode engagement layer 2 reduces with the bond strength of electrode 11.If the thickness of electrode engagement layer 2 is greater than this scope, then there is diaphragm seal 1 and become the situation lacking thermal endurance.
The fusing point forming the resin D of electrode engagement layer 2 is preferably the fusing point of the resin C lower than formation refractory layer 3.For the diaphragm seal 1 be made up of polypropylene-based resin, the fusing point of resin D is preferably 130 DEG C ~ 150 DEG C.If the fusing point of resin D is lower than this scope, then there is diaphragm seal l and become the situation lacking thermal endurance.If the fusing point of resin D is higher than this scope, then the fusing point being difficult to increase with the resin C forming refractory layer 3 is poor.If the fusing point difference of resin D and resin C is more than 10 DEG C, then temperature treatment during thermal welding becomes easy, so better.
The fusing point of resin D is preferably the fusing point being equal to or less than Resin A.If Resin A to be modified as resin C, then the molecular linkage of resin B is on the molecule of Resin A, and the molecular weight of resin C is increased, thus the fusing point of resin C is become higher than Resin A.Thus, become and easily make the fusing point difference of resin D and resin C reach more than 10 DEG C.If resin D is adopted identical resin with Resin A, then the management of resin becomes easy.
The method forming electrode engagement layer 2 can enumerate the extrusion molding using extruder to be extruded from T-shaped die head or ring-like die head by the resin D of melting.When using graft copolymer as resin D, according to the mode identical with Resin A, polyolefin and the glycerol polymerization of unsaturated carboxylic acid class can be made when utilizing extruder to extrude.
In order to make the diaphragm seal comprising polyethylene-based resin, when adopting sour modified poly ethylene in electrode engagement layer 2, be preferably the maleic anhydride graft copolymerization polyethylene that fusing point is about 90 ~ 120 DEG C.Acid modified poly ethylene comprises the ionomer neutralized by carboxyl.
The MFR forming 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 is difficult to fully be surrounded on electrode 11 around.If MFR is greater than these scopes, then electrode engagement layer 2 is thinning, and makes bond strength not enough.
In the present invention, MFR is according to JIS K7210, all measures at 230 DEG C, all measure at 190 DEG C for polyethylene-based resin for polypropylene-based resin.
Moreover carboxyl acid modified vistanex, on sale on the market, therefore also can use commercially available product.
Electrode engagement layer 2 and refractory layer 3 contact laminating, instead of carry out lamination at interlayer via cement layers or tackifier layer.Thus, can prevent by intrusion from electrolyte to laminate interface caused by stripping and the decline of flexibility of diaphragm seal l.In diaphragm seal 1, not only electrode engagement layer 2, refractory layer 3 to around electrode 11 around also very important.Only otherwise affect flexibility or the interaction with electrolyte, cement also can be used to carry out dry lamination.And, when carrying out extruding lamination, also can tackifier be used.
As the method for contact laminating, can enumerate: by overlapping with refractory layer 3 for shaping electrode engagement layer 2 and carry out the heat lamination of heat welded; In advance after shaped electrode knitting layer 2 and any one in refractory layer 3, from T-shaped die head, another one is extruded with molten condition, while carry out the extruding layer platen press of lamination; When electrode engagement layer 2 is in molten condition with both refractory layers 3, extrude from coextrusion die head, while carry out the co-extrusion laminating method of lamination.In these methods, co-extrusion laminating method is that another extruder of extruder and extrusion resin D by being modified as resin C extrusion resin C by carrying out melting mixing is connected on coextrusion die head, and carries out contact laminating in coextrusion die head.Thus, can make to carry out in one step, so better to the formation of the modification of resin C, refractory layer 3, the formation of electrode engagement layer 2, electrode engagement layer 2 with the lamination of refractory layer 3.
In the manner example, sealant 4 is laminated on the face contrary with electrode engagement layer 2 of refractory layer 3.Sealant 4 pressurizes and the layer of welding by heating with the sealant 22 of the laminated film 20 of bag.
As laminating method, adopt identical method based on the reason identical with the lamination of refractory layer 3 with electrode engagement layer 2.In these methods, owing to by electrode engagement layer 2, refractory layer 3 and the disposable lamination of sealant 4, therefore can be preferably and utilizing co-extrusion laminating method to carry out lamination.
As long as sealant 4 is guaranteed with the welding of the sealant 22 of bag, to be then preferably thinner.Usually, the thickness of sealant 4 is 20 μm ~ 40 μm.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, then diaphragm seal l may become shortage thermal endurance.
With regard to easily with sealant 22 welding of the laminated film 20 of bag with regard to, the resin (hereinafter referred to as resin E) of formation sealant 4 is preferably the resin of the same race or identical with the resin forming sealant 22.Usually, with regard to excellent heat resistance aspect, diaphragm seal 1 is made up of PP system resin.
When diaphragm seal 1 is made up of PP system resin, 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, the random copolymer of ethene and propylene is preferably.
When forming diaphragm seal by PP system resin, the fusing point forming the resin E of sealant 4 is preferably 130 DEG C ~ 170 DEG C.If the fusing point of resin E is lower than this scope, then there is diaphragm seal 1 and become the situation lacking thermal endurance.If the fusing point forming the resin E of sealant 4 is higher than this scope, then the fusing point being difficult to increase with the resin C forming refractory layer 3 is poor.If the difference of the fusing point of the fusing point of resin E and resin C reaches more than 10 DEG C, then temperature treatment when carrying out welding to the laminated film 20 of bag becomes easy, so better.
When adopting polyethylene-based resin in sealant 4 in order to diaphragm seal 1 is made polyethylene-based resin, be preferably low density polyethylene (LDPE) or straight-chain low density polyethylene (LDPE) that use fusing point is about 100 ~ 120 DEG C.
When forming diaphragm seal by PP system resin, the MFR forming 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.If the MFR of resin E is less than these scopes, is then difficult to utilization and extrudes lamination or co-extrusion laminating carries out lamination.If the MFR of resin E is greater than these scopes, be then difficult to utilize the ring-like die head of coextrusion to carry out shaping.
Moreover sealant 4 is the layer arranged arbitrarily, when the welding of sealant 22 can guaranteeing refractory layer 3 and bag, also sealant 4 can not be set.
Diaphragm seal 1 of the present invention is fused between the sealant 22 of bag and electrode 11.During frit seal film 1, as shown in Figure 2, the diaphragm seal 1 of preset width is made to expose from the end of laminated film 20 and carry out welding.Now, in order to make the location of diaphragm seal 1 become easy, being preferably and carrying out painted at least one in two panels diaphragm seal 1 in advance.Painted method can use at least one layer of layer forming diaphragm seal 1 printed, dye, the method such as the stirring infiltration of the colouring agent such as dyestuff or pigment.In these methods, because the stirring of colouring agent is infiltrated comparatively easy, so better.Painted layer also can be used for confirming that whether the welding with the sealant 22 of bag is good.Therefore, painted layer is preferably the refractory layer 3 when welding without distortion or melting.
The diaphragm seal 1 of the manner example is in order to realize the location of diaphragm seal 1 and make resin seamlessly be surrounded on around the thickness direction of electrode when welding, and as shown in Figure 3A, be preferably in advance use diaphragm seal 1 electrode engagement layer 2 and diaphragm seal 1 of the present invention is heat fused in electrode 11 at least one side, be preferably two sides.Thus, sealant 4 or the refractory layer 3 of diaphragm seal 1 can be used, easily and reliably carry out welding to the sealant 22 of bag.Now, if by painted for diaphragm seal l, then, when having the electrode projection of diaphragm seal to carry out thermal welding to the innermost layer of bag and welding, can in the welding assembly line of automation, use photoreceptor and electrode projection and diaphragm seal 1 correctly be located.
In diaphragm seal 1 thermal welding with electrode 11, can use heat sealing machine or moment sealing machine etc., utilize seal bar heat and crimp.Again, when heating diaphragm seal l, if use electromagnetic induction heating or electrified regulation and direct heating electrode 11, then suppress the flowing caused by the melting of the Outboard Sections of sealant 4 or refractory layer 3, the inboard portion of promotion refractory layer 3 or softening or melting, so better of electrode engagement layer 2.
The shape of electrode 11 can illustrate band shape or pole etc.There is no particular restriction for the size of electrode 11, if such as banded, then thickness is 50 μm ~ 500 μm, and width is 5mm ~ l00mm, and length is about 40mm ~ l00mm.Its crest line (edge, angle) also can be become circle by banded electrode 11.And, although its surface also can be the state of the machined surface through calendering processing, be preferably and improve roughness by the surface treatment such as sandblasting or etching.By improving roughness, the bond strength of diaphragm seal 1 can improve.Again, also the bottom layer treatment such as chemical conversion treatment can be implemented.
As the material of electrode 11, such as, can use the metals such as aluminium, copper, nickel, iron, gold, platinum or various alloys.Wherein, the aspect from excellent electric conductivity and for cost advantages, is preferably and uses aluminium or copper.But there is 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.Again, if PP system resin contacts with copper, then there is the possibility promoting resin deterioration.Therefore, be preferably conductivity is 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 to include, for example laminating seal layer 22 in the one side of metal forming 21 as shown in Figure 2 and at the laminated film etc. of another side upper laminate film base material 23.Also can other layer of lamination in laminated film 20.
The laminated film 20 of bag is shaped to the shaping bag of drawn or flat bag etc.As metal forming 21, aluminium foil, stainless steel foil, Copper Foil, iron foil etc. can be enumerated.Metal forming 21 also can implement the bottom layer treatment such as chemical conversion treatment.
Formed bag laminated film 20 sealant 22 Choice of Resin can with the resin of sealant 4 welding of diaphragm seal 1.As this resin, such as, when the sealant 4 of diaphragm seal 1 is PP system resin, the homopolymers of PP or the copolymer etc. of PP and ethene can be used.When using polyethylene-based resin, low density polyethylene (LDPE) or straight-chain low density polyethylene (LDPE) etc. can be used.There is no particular restriction for the resin of formation film base material 23, is preferably the larger polyamide of working strength, polyethylene terephthalate (PET) or PP etc.If extended by these resins and form film, then can obtain higher physical strength.These films also can the multiple layer of lamination.
Above, although the present invention will be described based on preferably execution mode, the present invention is not limited to above-mentioned execution mode, can carry out various change.
Such as, diaphragm seal 1, also can further containing other layers such as resin beds in order to improve zygosity, physical strength or the insulating properties etc. between each resin bed.Now, other layer is preferably and is difficult to melting when thermal welding and the higher layer of flexibility.And, also the lamination strength of each interlayer can be controlled as proper range, and diaphragm seal 1 be given to the function of the safety valve of the situation preparation of rising for the temperature in bag or pressure anomaly.
Embodiment
Use resin shown below and the embodiment of the diaphragm seal 1 shown in making table 1 and comparative example.
Resin A: by the maleic anhydride modified PP(MFR2.4g/10min(230 DEG C of maleic anhydride glycerol polymerization on random PP), fusing point 143 DEG C)
Resin B
Resin B-1: the EVOH(MFR15g/10min(230 DEG C of ethene ratio 48mol%), fusing point 160 DEG C)
Resin B-2: the EVOH(MFR3.6g/10min(230 DEG C of ethene ratio 32mol%), fusing point 183 DEG C)
Resin B-3: nylon 6(relative viscosity 3.37, fusing point 220 DEG C)
Resin B-4: nylon 6(relative viscosity 4.08, fusing point 220 DEG C)
Resin B-5: the E-GMA copolymer (MFR3g/10min(190 DEG C) of glycidyl methacrylate containing ratio 6wt%, fusing point 105 DEG C)
Resin D
Resin D-1: by the maleic anhydride modified PP(MFR7.5g/10min(230 DEG C of maleic anhydride glycerol polymerization on random PP), fusing point 135 DEG C)
Resin D-2: by the maleic anhydride modified PP(MFR7.0g/10min(230 DEG C of maleic anhydride glycerol polymerization on random PP), fusing point 140 DEG C)
/ 10min, fusing point 163 DEG C) resin E: block PP(MFR2.3g(230 DEG C)
< embodiment 1 ~ 15>
By Resin A with resin B with the allotment shown in table 1 than being added in the hopper of extruder, one side makes it to be modified as resin C one side with the extrusion temperature shown in table 1 and extrudes, and lamination is carried out with the resin D extruded from another extruder in the T-shaped die head of coextrusion, and the embodiment 1 ~ 15 of cast molding diaphragm seal 1.
Forming a hurdle at the layer of table l is written as in the embodiment of 3 layers, when coextrusion cast molding, and then carries out co-extrusion laminating from another extruder extrusion resin E.And, being written as in the embodiment of 3 parts on colouring agent one hurdle of table 1, adding the pigment masterbatch of the PP matrix of 3 weight portions when allocating Resin A and resin B.
The extrusion temperature of resin D and resin E is all set to 240 DEG C.
With the laminated film of the three-layer structure of the shaping laminated film of double-layer structural that the refractory layer 3 of the thickness shown in refractory layer one hurdle by the electrode engagement layer 2 of 40 μm and table 1 is formed of above-mentioned mode and sealant 4 lamination of 20 μm.This laminated film is cut into the width of 25mm, and make the embodiment 1 ~ 15 of diaphragm seal 1.
< comparative example 1>
Difference extrusion resin D-1 and resin E at 240 DEG C, and in the T-shaped die head of coextrusion, carry out lamination, the laminated film of the double-layer structural be made up of the electrode engagement layer 2 of 20 μm and the sealant 4 of 80 μm with moulding by casting.This laminated film is cut into the width of 25mm and the diaphragm seal l of comparison example 1.
[table 1]
At this, " part " in table 1 all refers to " weight portion ".
The mensuration > of < electrode engagement intensity
The foursquare aluminium foil that use thickness is 50 μm, width is 50mm, length is 50mm is as electrode 11.Respectively the embodiment 1 ~ 15 of diaphragm seal 1 and comparative example 1 are cut into the length of 60mm.Be overlapped on electrode 11 for inner side with the electrode engagement layer 2 of diaphragm seal 1.Use heat sealing machine, 200 DEG C, 0.2MPa, to heat from aluminium foil side under the condition in 3 seconds, at one end residual non-weld portion, and the thermal welding other end.
Instron type cupping machine is used to measure the electrode engagement layer 2 of each diaphragm seal 1 and the peel strength of electrode 11.When measuring peel strength, by the end of diaphragm seal 1 that is not fused on electrode 11 and the end winding support of electrode 11 on two chucks of cupping machine, and stretching with the speed of 300mm/min, and 180 degree of peel strengths are measured.Electrode engagement layer 2 and the electrode 11 of each diaphragm seal 1 seal with the sealing intensity of 27.5 ~ 32.8N/25mm.
The mensuration > of < laminated film heat seal strength
By dry lamination, the twin shaft as the thickness of film base material 23 being 12 μm is extended PET film, as the aluminium foil of the thickness 40 μm of metal forming 21 and be that the ethene of 40 μm and the random copolymer film of propylene carry out lamination as the thickness of sealant 22.The laminated film of gained is cut into the square that the length of side is 100mm, and produces the laminated film 20 of two bags.
Respectively the embodiment 1 ~ 15 of diaphragm seal 1 and comparative example 1 are cut into the length of 60mm.Make the sealant 22 of the laminated film 20 of two bags toward each other, and sandwich diaphragm seal l in-between.When sandwiching diaphragm seal 1, diaphragm seal 1 is made to expose 5mm from the end of laminated film 20.
Heat from the both sides of the laminated film 20 of two bags under the condition identical with the mensuration of electrode engagement intensity, and welding is carried out in the one end of diaphragm seal 1 being exposed side.The other end remains as non-weld portion.When frit seal film 1, the root of the exposed portion of self sealss film 1 about contacts with seal bar with the width of 2mm.
In the mode identical with the mensuration of electrode engagement intensity, by the end of the non-weld portion of diaphragm seal 1 and the end winding support of laminated film 20 on two chucks of cupping machine, under the condition identical with the mensuration of electrode engagement intensity, the sealant 4 of each diaphragm seal 1 or the heat seal strength of refractory layer 3 and laminated film 20 are measured.Each diaphragm seal 1 seals with the sealing intensity of 124.2 ~ 143.3N/25mm with laminated film 20.
And the part exposed from laminated film 20 of the diaphragm seal 1 in any embodiment does not have the sign of thermal deformation or melting.On the other hand, in a comparative example, the part root exposed from laminated film 20 slightly reduces.
The MFR> of the mixing product of <
The melting mixing product (resin C-3) 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, the Resin A of 95 weight portions and the resin B-3 of 5 weight portions are individually extruded, and measures the MFR at 230 DEG C.The MFR of original Resin A is 2.4.The MFR of resin C-l is 1.9, and MFR declines compared with Resin A.Moreover the MFR of resin C-3 is 2.5, MFR rises compared with Resin A.Infer thus, the reason that the thermal endurance of diaphragm seal l improves in the present invention is not only chemical bonding because of the carboxyl of Resin A and the functional group of resin B and makes molecule quantitative change greatly, is also subject to partial cross-linked impact.
Utilizability in industry
The present invention can be widely used in manufacture method and the diaphragm seal of the diaphragm seal of the electrode sealing the generating elements such as the secondary cell received of bag or capacitor.

Claims (12)

1. a manufacture method for diaphragm seal, be the manufacture method of the diaphragm seal be sandwiched between the electrode of the generating element that bag is received and the edge of bag, it has following steps:
Melting mixing step, by glycerol polymerization being had the acid-modified polyolefin resin A of carboxylic acid and having and can carry out melting mixing with both resin B of the functional group of the carboxyl reaction of Resin A, the functional group of the carboxyl of Resin A and resin B is made to carry out chemical bonding and be modified as resin C;
Refractory layer masking step, is shaped to stratiform by resin C and forms refractory layer;
Knitting layer masking step, is shaped to stratiform by carboxyl acid modified vistanex D and forms the electrode engagement layer being engaged in electrode;
Lamination step, refractory layer and described electrode engagement layer described in contact laminating when any one or both in resin C and resin D 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 masking step are carried out continuously.
4. the manufacture method of diaphragm seal as claimed in claim 1 or 2, any one or both of wherein said lamination step continuously in described refractory layer masking step and described knitting layer masking step and carry out.
5. the manufacture method of diaphragm seal as claimed in claim 1 or 2, wherein said lamination step is carried out in coextrusion die head.
6. the manufacture method of diaphragm seal as claimed in claim 1 or 2, wherein said melting mixing step be with Resin A be 99 ~ 90%, resin B be 1 ~ 10% percentage by weight carry out allocating and carry out.
7. the manufacture method of diaphragm seal as claimed in claim 1 or 2, is wherein used as resin D by having identical with the fusing point of Resin A or lower than its fusing point resin.
8. a diaphragm seal, between the electrode that sealing film is sandwiched in the generating element that bag is received and the edge of bag, and by the laminar construction of the refractory layer contact laminating be made up of resin C on the electrode engagement layer be made up of carboxyl acid modified vistanex D when any one or both that have in resin C and resin D are in molten condition, this resin C is by glycerol polymerization being had the acid-modified polyolefin resin A of carboxylic acid and having and can carry out melting mixing with both resin B of the functional group of the carboxyl reaction of Resin A, the carboxyl of Resin A and functional group's chemical bonding of resin B is made to carry out the resin of modification.
9. diaphragm seal as claimed in claim 8, wherein resin B be selected from there is hydroxyl, amido or epoxy radicals resin in one or more resins.
10. diaphragm seal as claimed in claim 8 or 9, wherein Resin A makes maleic anhydride glycerol polymerization in the acid-modified polyolefin resin of polypropylene.
11. diaphragm seals as claimed in claim 8 or 9, wherein said laminar construction is formed by the coextrusion of resin C and resin D.
12. diaphragm seals as claimed in claim 8 or 9, are wherein pressed with the sealant with the innermost layer thermal welding of bag on described refractory layer upper strata.
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