CN217073665U - Laminate and outer package for battery - Google Patents
Laminate and outer package for battery Download PDFInfo
- Publication number
- CN217073665U CN217073665U CN202120889408.4U CN202120889408U CN217073665U CN 217073665 U CN217073665 U CN 217073665U CN 202120889408 U CN202120889408 U CN 202120889408U CN 217073665 U CN217073665 U CN 217073665U
- Authority
- CN
- China
- Prior art keywords
- layer
- heat
- colored
- laminate
- resin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 238000004040 coloring Methods 0.000 claims abstract description 56
- 239000011888 foil Substances 0.000 claims abstract description 55
- 229910052751 metal Inorganic materials 0.000 claims abstract description 54
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- 239000010410 layer Substances 0.000 claims description 342
- 239000012790 adhesive layer Substances 0.000 claims description 35
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- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
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- 239000000020 Nitrocellulose Substances 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
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- DSKYSDCYIODJPC-UHFFFAOYSA-N 2-butyl-2-ethylpropane-1,3-diol Chemical compound CCCCC(CC)(CO)CO DSKYSDCYIODJPC-UHFFFAOYSA-N 0.000 description 1
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- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
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- HGAZMNJKRQFZKS-UHFFFAOYSA-N chloroethene;ethenyl acetate Chemical compound ClC=C.CC(=O)OC=C HGAZMNJKRQFZKS-UHFFFAOYSA-N 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
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- BFGKITSFLPAWGI-UHFFFAOYSA-N chromium(3+) Chemical class [Cr+3] BFGKITSFLPAWGI-UHFFFAOYSA-N 0.000 description 1
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- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
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- 239000011229 interlayer Substances 0.000 description 1
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- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 description 1
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- 239000002344 surface layer Substances 0.000 description 1
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- 239000011787 zinc oxide Substances 0.000 description 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc oxide Inorganic materials [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 1
- RNWHGQJWIACOKP-UHFFFAOYSA-N zinc;oxygen(2-) Chemical compound [O-2].[Zn+2] RNWHGQJWIACOKP-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Laminated Bodies (AREA)
- Sealing Battery Cases Or Jackets (AREA)
Abstract
The utility model relates to a laminate and outer packing body for battery. Provided is a laminate which does not peel off a heat-resistant resin layer even when used in a slightly severe environment such as molding, sealing, and high-temperature and high-humidity environments. The laminate (1) comprises: a heat-resistant resin layer (13) as an outer layer; a heat-fusible resin layer (15) as an inner layer; a metal foil layer (10) disposed between the two layers; and a colored layer (12) disposed between the metal foil layer (10) and the heat-resistant resin layer (13), wherein the colored layer (12) is formed of a coloring composition containing a resin binder and a coloring agent, and is a multilayer formed by stacking at least 2 layers having different coloring agent contents, and the content of the coloring agent in the layer (12a) in contact with the heat-resistant resin layer (13) is lower than that in the other layer (12 b).
Description
Technical Field
The present invention relates to a laminate suitable for use as a case of a secondary battery (lithium ion secondary battery) for a notebook personal computer, a mobile phone, a vehicle, or a stationary type, and further suitable for use as a packaging material for food or a packaging material for pharmaceuticals.
Background
In order to make the appearance and color of devices such as electric devices to be mounted uniform, batteries such as lithium ion secondary batteries are increasingly required to be colored. For example, in order to provide a heavy feeling and a high-grade feeling, the device is often made black, and in this case, the battery is also made black more and more.
Such a battery is obtained by packaging a battery main body with a packaging material (molded case), and the packaging material is usually a laminate in which base resin layers are laminated on both surfaces of a metal foil. In addition, in the coloring of the battery, there are methods of coloring a base resin layer used for a packaging material of the battery, providing a colored print layer under the base resin layer, coloring an adhesive layer between the base resin layer and the metal foil, and coloring the adhesive layer between these layers when the base resin layer is composed of a plurality of layers.
Conventionally, as a battery packaging material having a colored layer, the following configuration has been known: a laminate having a structure in which a base material layer, an adhesive layer, a metal foil layer, and a heat-adhesive resin layer are laminated in this order, wherein one of the base material layer, the adhesive layer, and the metal foil layer contains a pearlescent pigment or a fluorescent pigment as an identification mark (see patent document 1); the adhesive sheet has a structure in which a base material layer, an adhesive layer, a metal foil layer, and a heat-adhesive resin layer are sequentially laminated, and a pigment as a distinguishing mark is added to any one of the base material layer, the adhesive layer, and the metal foil layer (see patent document 2).
Further, an exterior material for a battery is known, which includes a blackbody material layer made of a carbon material or the like between a metal foil layer and an outer layer film in order to improve heat dissipation of the battery (see patent document 3).
Documents of the prior art
Patent document
Patent document 1: international publication No. 2011/016506 pamphlet
Patent document 2: japanese patent laid-open publication No. 2011-054563
Patent document 3: japanese patent laid-open publication No. 2011-096552
SUMMERY OF THE UTILITY MODEL
Problem to be solved by utility model
In general, when a film or a sheet is colored black, a printed layer is generally formed using a printing ink containing an inorganic pigment such as carbon black.
However, in order to color the battery black, when a black printing layer containing carbon black as a pigment is provided on the inner surface of the outer resin layer constituting the battery packaging material, there are the following problems.
That is, when the black packaging material is molded into a container (case) shape by deep drawing or bulging, there is a problem that the outer resin layer is peeled off from the black printing layer of the packaging material. Such peeling of the outer resin layer also occurs when the battery packed with the black casing is used in a somewhat severe environment such as high temperature and humidity in sealing the black casing after the electrodes and the electrolyte are sealed. The above problems occur not only in a black packaging material using carbon black, but also in a colored packaging material similarly colored in various colors using other inorganic pigments.
Means for solving the problems
The present invention has been made in view of the above-mentioned technical background, and an object of the present invention is to provide a laminate material in which a heat-resistant resin layer is not peeled off even when the laminate material is molded or sealed, or when the laminate material is used under a slightly severe environment such as high temperature and humidity.
That is, the present invention has the configurations described in [1] to [8 ].
[1] A laminate comprising: a heat-resistant resin layer as an outer layer; a heat-fusible resin layer as an inner layer; a metal foil layer disposed between the two layers; and a colored layer disposed between the metal foil layer and the heat-resistant resin layer, wherein the laminate is characterized in that,
the colored layer is formed of a coloring composition containing a resin binder and a colorant, the colored layer is a multilayer formed by stacking at least 2 layers having different colorant contents, and the content of the colorant in a layer in contact with the heat-resistant resin layer is lower than that in another layer.
[2] The laminate according to item 1 above, wherein a content of the colorant in a solid content of the coloring composition in the coloring composition constituting a layer of the colored layer in contact with the heat-resistant resin layer is 5% by mass or less.
[3] The laminate according to item 1 above, wherein a content of the colorant in a solid content of the coloring composition in the coloring composition constituting a layer other than a layer in contact with the heat-resistant resin layer is 5 to 60% by mass.
[4] The laminate according to the above item 1, wherein the coloring composition of each of the colored layers contains a common resin binder.
[5] The laminated material according to the aforementioned item 1, wherein an adhesive layer is disposed between the colored layer and the metal foil layer, and the adhesive layer contains a resin component of the same kind as a resin binder of the colored composition constituting the colored layer.
[6] The laminate according to any one of the preceding items 1 to 5, wherein, in the colored composition,
the resin binder is a two-component curing type polyester polyurethane resin binder formed by polyester resin as a main agent and a polyfunctional isocyanate compound as a curing agent,
the polyester resin as the main agent has Mn of 8000 to 25000 as a number average molecular weight, Mw of 15000 to 50000 as a mass average molecular weight, and Mw/Mn as a ratio thereof of 1.3 to 2.5,
50 mol% or more of the polyfunctional isocyanate compound as the curing agent is an aromatic polyfunctional isocyanate compound.
[7] The laminate according to item 1 above, wherein a protective layer containing a resin component and a filler component is laminated on the outside of the heat-resistant resin layer.
[8] A battery exterior body, wherein a battery element chamber for housing a battery element is formed by heat-sealing the joined edge portions of the laminate material described in any one of the preceding items 1 to 7 so that the heat-fusible resin layers face inward.
Effect of the utility model
According to the laminate described in the above [1], the colorant content of the layer in contact with the corrosion-resistant resin layer among the plurality of colored layers is set to be lower than that of the other layers, whereby the adhesiveness to the heat-resistant resin layer can be improved. Therefore, the heat-resistant resin layer is less likely to peel off even when the laminate is used in a somewhat severe environment such as a high temperature and high humidity environment. Further, by not having a non-colored layer between the heat-resistant resin layer and another layer having a high colorant content, it is possible to avoid haziness or blurring of the color development of the colored layer and obtain a stable color development state.
According to the laminate of [2], the coloring composition constituting a layer in contact with the corrosion-resistant resin layer among the plurality of colored layers has a content of the colorant in the solid content of the coloring composition of 5% by mass or less, and therefore, high adhesion to the heat-resistant resin layer can be obtained.
According to the laminate of [3], since the content of the colorant in the solid content of the coloring composition in the coloring composition constituting a layer other than the layer in contact with the corrosion-resistant resin layer among the plurality of colored layers is 5 to 60% by mass, the effect of shielding the metal foil layer can be sufficiently obtained, and a heavy feeling and a high-grade feeling can be sufficiently imparted while avoiding visual recognition of metallic luster, and color unevenness is not generated. In addition, the layer can be prevented from becoming hard and brittle, and the adhesion can be sufficiently ensured.
According to the laminate of [4], since the coloring composition of each layer of the coloring layer contains a common resin binder, the interlayer adhesiveness is improved and the layer having a high colorant content is less likely to peel off.
According to the laminate of [5], since the adhesive layer containing the same resin component as the resin binder of the coloring composition constituting the colored layer is disposed between the colored layer and the metal foil layer, the metal foil layer and the colored layer are less likely to be peeled off.
According to the laminate of item [6] above, particularly high adhesion can be obtained by using a predetermined resin binder for the coloring composition of each layer constituting the coloring layer.
According to the laminate described in the above [7], since the matte coating layer can provide a good sliding property to the surface, sliding between the heat-resistant resin layer and the colored layer is less likely to occur at the time of molding or the like, and the heat-resistant resin layer is less likely to be peeled from the colored layer.
According to the exterior package for a battery described in the above [8], since the heat-resistant resin layer of the laminate is not easily peeled off, the heat-resistant resin layer is not locally cracked and peeled off even when the battery is used under a slightly severe environment such as high temperature and high humidity.
Drawings
Fig. 1 is a cross-sectional view of one embodiment of the laminate of the present invention.
Fig. 2 is a perspective view of the test material.
Description of the reference numerals
1 … laminate
10 … Metal foil layer
11 … adhesive layer No. 1
12 … colored layer
12b … layer 2
13 … Heat-resistant resin layer
14 … adhesive layer 2
15 … Heat-fusible resin layer
Detailed Description
Fig. 1 shows an embodiment of a laminate 1 according to the invention. This laminate is used as a material for an exterior body (case) for a lithium ion secondary battery.
The laminate 1 has a 1 st adhesive layer 11, a colored layer 12, and a heat-resistant resin layer 13 laminated in this order from the metal foil layer 10 side on one surface of a metal foil layer 10, and a 2 nd adhesive 14 and a heat-sealable resin layer 15 laminated in this order from the metal foil layer 10 side on the other surface of the metal foil layer 10, and is integrated. When the laminate 1 is used as a battery exterior, the heat-resistant resin layer 13 serves as an outer layer, and the heat-fusible resin layer 15 serves as an inner layer.
The colored layer 12 is a layer disposed between the metal foil layer 10 and the heat-resistant resin layer 13, and in the above embodiment, is a layer that provides color (including achromatic color) to the outer surface side of the laminated material 1 while supporting the bonding of the 1 st adhesive layer 11 and the heat-resistant resin layer 13.
[ coloring layer ]
The colored layer 12 has a 2-layer structure in which a 1 st layer 12a disposed in contact with the heat-resistant resin layer 13 and a 2 nd layer 12b on the metal foil layer 10 side are laminated. Each layer is composed of a coloring composition containing a resin binder and a colorant. The content (a) of the colorant in the 1 st colored composition constituting the 1 st layer 12a is set to be lower than the content (B) of the colorant in the 2 nd colored composition constituting the 2 nd layer 12B. As described above, by setting the colorant content (a) in the 1 st layer 12a to be low, it is possible to improve the adhesion to the heat-resistant resin layer 13 and to cause the 1 st layer 12a to function as a primer, and by configuring so that no uncolored layer is present between the heat-resistant resin layer 13 and the 2 nd layer 12b, it is possible to avoid haziness or blurring of color development of the colored layer 12 and obtain a stable color development state.
The colored layer 12 preferably has a thickness (cured film) of 0.1 to 3 μm for the 1 st layer 12a and 2 to 5 μm for the 2 nd layer 12 b.
(coloring composition)
As described above, the 1 st layer 12a and the 2 nd layer 12b are each composed of a coloring composition containing a resin binder and a colorant.
From the viewpoint of improving the adhesion to the heat-resistant resin layer 13, the content (a) of the color pigment in the solid content of the 1 st color composition in the 1 st color composition constituting the 1 st layer 12a of the color layer 12 is preferably 5 mass% or less. Addition of a large amount of the colorant causes a decrease in adhesion, but if the amount is 5% by mass or less, sufficient adhesion can be ensured, and peeling of the heat-resistant resin layer 13 from the colored layer 12 can be sufficiently prevented during molding and sealing, and during use in a slightly severe environment such as high temperature and high humidity. From the viewpoint of obtaining a stable color development state of the colored layer 12, the content (a) is preferably 0.005 mass% or more. The particularly preferable content (a) by mass of the colorant in the 1 st layer 12a is 0.01 to 1% by mass.
In addition, the preferable amount of the colorant attached per unit area of the 1 st layer 12a is 0.5g/m in the 1 st layer 12a 2 ～2g/m 2 The 2 nd layer 12b is 2g/m 2 ～5g/m 2 。
On the other hand, the content (B) of the coloring pigment in the solid content of the 2 nd coloring composition constituting the 2 nd layer 12B of the coloring layer 12 is preferably set to 5 to 60 mass% as long as the content (a) of the 1 st layer 12a is higher. By setting the content (B) of the colorant to 5 mass% or more, the effect of shielding the metal foil layer 10 can be sufficiently obtained, a thick and high-grade feeling can be sufficiently given while avoiding the metallic luster from being visually recognized, and local color unevenness does not occur in the molded portion even at the time of molding. Further, by setting the content to 60 mass% or less, the 2 nd layer 12b can be prevented from becoming hard or brittle, and the adhesion can be sufficiently ensured. A particularly preferable content ratio (B) of the colorant in the 2 nd layer 12B is 15% by mass to 50% by mass.
The resin binder of the coloring composition constituting the 1 st layer 12a and the 2 nd layer 12b is preferably common. The common resin binder is the same or the same kind of resin binder, and by using such a resin binder, the adhesion between the 1 st layer 12a and the 2 nd layer 12b is improved, and the 2 nd layer 12b having a high colorant content is more resistant to peeling.
In addition, in the production process of the above laminate 1, for example, the colored layer 12 having a 2-layer structure can be formed by applying the 1 st colored composition to one surface of the heat-resistant resin layer 13 to form a cured film of the 1 st layer 12a, and then applying the 2 nd colored composition to form a cured film of the 2 nd layer 12 b.
The colorant may be a pigment or a dye, and a pigment is preferable in terms of excellent color developability and weather resistance. Examples of the pigment include carbon black, calcium carbonate, zinc oxide, and aluminum powder. The average particle diameter of the pigment is preferably in the range of 0.1 to 5 μm, and particularly preferably in the range of 0.5 to 2.5. mu.m.
Examples of the resin component constituting the resin binder include polyurethane resins, acrylic resins, polyamide resins, nitrocellulose (nitrocellulose), vinyl chloride-vinyl acetate resins, and the like. Among these resins, polyurethane resins are particularly preferable, and polyester polyurethane resins are more preferable.
The resin binder is a two-component curable polyester urethane resin binder comprising a polyester resin as a main component and a polyfunctional isocyanate compound as a curing agent, wherein the polyester resin as the main component has a number average molecular weight (Mn) of 8000 to 25000 and a mass average molecular weight (Mw) of 15000 to 50000, the ratio (Mw/Mn) of these is 1.3 to 2.5, and preferably 50 mol% or more of the polyfunctional isocyanate compound as the curing agent is an aromatic polyfunctional isocyanate compound.
The main agent and the curing agent in the two-component curable polyester urethane resin adhesive are described in detail below.
The polyester resin as the main agent is a copolymer of dicarboxylic acid and diol as raw materials, and preferred materials and compositions are as follows.
As the dicarboxylic acid, both aliphatic dicarboxylic acids and aromatic dicarboxylic acids are preferably used. In addition, the parity of the number of methylene groups in the methylene chain of the aliphatic dicarboxylic acid is a factor that affects the crystallinity of the resin, and since carboxylic acids having even-numbered methylene groups produce hard resins having high crystallinity, aliphatic dicarboxylic acids having even-numbered methylene groups are preferably used. Examples of the aliphatic dicarboxylic acid having an even number of methylene groups include succinic acid (having 2 methylene groups), adipic acid (having 4 methylene groups), suberic acid (having 6 methylene groups), sebacic acid (having 8 methylene groups), and the like. Examples of the aromatic dicarboxylic acid include isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid, and phthalic anhydride.
Further, by setting the content of the aromatic dicarboxylic acid in the range of 40 to 80 mol% relative to the total amount of the aliphatic dicarboxylic acid and the aromatic dicarboxylic acid, in other words, by setting the content of the aliphatic dicarboxylic acid in the range of 20 to 60 mol%, a resin having high adhesive strength and good moldability can be produced, and a laminate which can be molded into a case having a high side wall with good moldability and can sufficiently prevent the heat-resistant resin layer 13 from peeling off from the colored layer 12 can be obtained. If the content of the aromatic dicarboxylic acid is less than 40 mol%, the film properties are reduced, and the aggregation and peeling are likely to occur, and the heat-resistant resin layer 13 is likely to peel from the colored layer 12, which is not preferable. On the other hand, if the content of the aromatic dicarboxylic acid exceeds 80 mol%, the resin tends to be hardened and the adhesion performance tends to be lowered, which is not preferable. Among them, the content of the aromatic dicarboxylic acid is particularly preferably in the range of 50 to 70 mol% based on the total amount of the aliphatic dicarboxylic acid and the aromatic dicarboxylic acid.
Examples of the diol include, but are not particularly limited to, ethylene glycol, propylene glycol, 1, 3-butanediol, 1, 4-butanediol, diethylene glycol, dipropylene glycol, neopentyl glycol, 1, 5-pentanediol, 1, 6-hexanediol, octanediol, 1, 4-cyclohexanediol, and 2-butyl-2-ethyl-1, 3-propanediol.
The molecular weight of the polyester resin (main agent) is defined by a number average molecular weight (Mn) within a range of 8000 to 25000, a weight average molecular weight (Mw) within a range of 15000 to 50000, and a ratio (Mw/Mn) of the number average molecular weight (Mn) to the weight average molecular weight (Mw/Mn) within a range of 1.3 to 2.5. The number average molecular weight (Mn) is 8000 or more and the weight average molecular weight (Mw) is 15000 or more, whereby appropriate strength and heat resistance of the coating film can be obtained, and the number average molecular weight (Mn) is 25000 or less and the weight average molecular weight (Mw) is 50000 or less, whereby excessive hardness can be avoided and appropriate elongation of the coating film can be obtained. Further, by setting the ratio (Mw/Mn) of the two to 1.3 to 2.5, an appropriate molecular weight distribution can be obtained, and a balance between the applicability (wide distribution) and the performance (narrow distribution) of the adhesive can be maintained. The polyester resin has a particularly preferable number average molecular weight (Mn) of 10000 to 23000, a particularly preferable weight average molecular weight (Mw) of 20000 to 40000, and a particularly preferable (Mw/Mn) of 1.5 to 2.3.
The molecular weight of the polyester resin (main agent) can be adjusted by chain extension using a polyfunctional isocyanate. That is, when the polyester components in the main agent are linked by NCO, a polymer having hydroxyl groups at the ends is produced, and the molecular weight of the polyester resin (main agent) can be adjusted by adjusting the equivalent ratio of the isocyanate groups to the hydroxyl groups of the polyester. In the present invention, it is preferable to use a material connected so that the equivalent ratio (OH/NCO) is 1.01 to 10. In addition, another method for adjusting the molecular weight includes adjusting the reaction conditions (the blending molar ratio of the dicarboxylic acid to the diol) of the copolymerization reaction of the dicarboxylic acid and the diol.
As the additive of the main agent (additive of the coloring ink composition), an epoxy resin or an acrylic resin may be added.
When any one or more of the limited configurations listed as preferable configurations is used as the polyester resin (main agent), there is an advantage that a more sufficient adhesion force can be secured as the colored layer. From the viewpoint of obtaining such effects, the preferable configuration of the polyester resin (main agent) is technically important.
As the polyfunctional isocyanate compound of the curing agent, various polyfunctional isocyanate compounds of aromatic type, aliphatic type and alicyclic type can be used. Specific examples thereof include 1 or 2 or more kinds of polyfunctional isocyanates selected from the group consisting of diisocyanates such as aliphatic Hexamethylene Diisocyanate (HDI), isophorone diisocyanate (IPDI), aromatic Toluene Diisocyanate (TDI), and diphenylmethane diisocyanate (MDI), and modified products thereof. Examples of the modification method include adducts with water, polyfunctional active hydrogen compounds such as glycerin and trimethylolpropane, and also polyfunctional isocyanate-modified products obtained by polymerization reactions such as isocyanuric acid esterification, carbodiimidization and polymerization.
The polyfunctional isocyanate compound as the curing agent is composed of an aromatic polyfunctional isocyanate compound in an amount of 50 mol% or more (50 mol% or more and 100 mol% or less). That is, 50 mol% or more of the polyfunctional aromatic isocyanate compound is contained with respect to 100 mol% of the total amount of the polyfunctional isocyanate compounds. Since the adhesive strength after curing can be increased by making 50 mol% or more of the aromatic polyfunctional isocyanate compound, the heat-resistant resin layer 13 can be sufficiently prevented from peeling off from the colored layer 12 at the time of molding, at the time of sealing, and at the time of use in a slightly severe environment such as high temperature and high humidity even when deeper molding is performed. Among these, as the polyfunctional isocyanate compound (as the curing agent), it is preferable that 70 mol% or more of the polyfunctional isocyanate compound is composed of an aromatic polyfunctional isocyanate compound, and it is more preferable that 80 mol% or more of the polyfunctional isocyanate compound is composed of an aromatic polyfunctional isocyanate compound.
When any one or more of the limited structures listed as preferable structures is used as the above-mentioned polyfunctional isocyanate compound (curing agent), there is an advantage that a more sufficient adhesive force can be secured as the colored layer. The preferable structure of the above-mentioned polyfunctional isocyanate compound (curing agent) is technically important in view of obtaining such effects.
In the two-pack curable polyester urethane resin adhesive, the main curing agent is preferably blended in a proportion of 2 to 25 moles of isocyanate functional group (NCO) per 1 mole of polyol hydroxyl group (OH). If the molar ratio (NCO)/(OH) is less than 2 and the isocyanate functional group (NCO) is reduced, a sufficient curing reaction may not proceed, and appropriate coating film strength and heat resistance may not be obtained. On the other hand, if the (NCO)/(OH) exceeds 25 and the isocyanate functional group (NCO) becomes large, the reaction with the functional group other than the polyol proceeds excessively, and the coating film becomes too hard, and there is a possibility that an appropriate elongation cannot be obtained. Particularly preferred molar ratios of polyol hydroxyl groups to isocyanate functional groups (NCO)/(OH) are from 5 to 20.
The adhesive containing the two-component curable polyester urethane resin can be prepared as a low viscosity fluid by polycondensing dicarboxylic acid and diol, which are raw materials of the polyester resin, and if necessary, chain-extending the polyester resin using polyfunctional isocyanate, mixing various additives such as a solvent, a urethane-forming reaction catalyst, a coupling agent for improving adhesion, an epoxy resin, a defoaming agent, a leveling agent, an ultraviolet absorber, and an antioxidant to prepare a fluid polyester resin solution, and adding a polyfunctional isocyanate compound as a curing agent or further adding a solvent thereto.
The solid components in the coloring composition using the two-component curable polyester urethane resin binder are a polyester resin and a colorant as a main component of the two-component curable polyester urethane resin binder. Therefore, the content of the colorant is set to the content ratio of the colorant to the total amount of the polyester resin and the colorant.
[ materials of layers other than the colored layer ]
(Heat-resistant resin layer)
The heat-resistant resin layer 13 is an outer layer (base material layer) when used as a case, and the heat-resistant resin constituting the heat-resistant resin layer 13 is a heat-resistant resin that does not melt at a heat-sealing temperature when heat-sealed. As the heat-resistant resin, a heat-resistant resin having a melting point higher than that of the heat-fusible resin constituting the heat-fusible resin layer 15 by 10 ℃ or more is preferably used, and a heat-resistant resin having a melting point higher than that of the heat-fusible resin by 20 ℃ or more is particularly preferably used. For example, polyamide films, polyester films, and the like can be mentioned, and stretched films using these films are preferred. Among them, as the heat-resistant resin layer 13, a biaxially stretched polyamide film, a biaxially stretched polybutylene terephthalate (PBT) film, a biaxially stretched polyethylene terephthalate (PET) film, or a biaxially stretched polyethylene naphthalate (PEN) film is particularly preferably used in view of moldability and strength. The polyamide film is not particularly limited, and examples thereof include a nylon 6 film, a nylon 6, 6 film, and a nylon MXD film. The heat-resistant resin layer 2 may be formed of a single layer, or may be formed of a plurality of layers formed of, for example, a PET film/polyamide film.
The thickness of the heat-resistant resin layer 13 is preferably 9 to 50 μm. When a polyester film is used, the thickness is preferably 9 to 50 μm, and when a polyamide film is used, the thickness is preferably 10 to 50 μm. By setting the preferable lower limit value or more, sufficient strength can be secured as a packaging material, and by setting the preferable upper limit value or less, stress at the time of bulging or drawing can be reduced, and formability can be improved.
In addition, the heat-resistant resin layer 13 is preferably a transparent resin in order to allow the colored layer 12 to be seen through.
(Heat-fusible resin layer)
The heat-sealable resin layer (inner layer) 15 has excellent chemical resistance to highly corrosive electrolyte solutions used in lithium ion secondary batteries and the like, and plays a role in imparting heat sealability to the laminate.
The heat-fusible resin layer 15 is not particularly limited, and is preferably a thermoplastic resin non-stretch film layer. The non-stretched thermoplastic resin film layer is not particularly limited, and is preferably composed of the following non-stretched film from the viewpoint of chemical resistance and heat sealability: the non-stretched film is formed of at least 1 thermoplastic resin selected from the group consisting of polyethylene, polypropylene, olefin copolymers, acid-modified products thereof, and ionomers.
The thickness of the heat-fusible resin layer 15 is preferably set to 20 μm to 80 μm. The occurrence of pores can be sufficiently prevented by setting the particle diameter to 20 μm or more, and the amount of resin used can be reduced by setting the particle diameter to 80 μm or less, thereby reducing the cost. Among them, the thickness of the heat-fusible resin layer 15 is particularly preferably set to 30 μm to 50 μm. The heat-fusible resin layer 15 may be a single layer or a plurality of layers. Examples of the heat-fusible resin layer 15 having a multilayer structure include a three-layer film in which random polypropylene films are laminated on both surfaces of a block polypropylene film.
(Metal foil layer)
The metal foil layer 10 plays a role of imparting gas barrier properties to the laminate 1 against the intrusion of oxygen and moisture. The metal foil layer 10 is not particularly limited, and examples thereof include an aluminum foil, a copper foil, and a stainless steel foil, and an aluminum foil is generally used. The thickness of the metal foil layer 10 is preferably 20 to 100 μm. By setting the thickness to 20 μm or more, it is possible to prevent the occurrence of voids during rolling for producing a metal foil, and by setting the thickness to 100 μm or less, it is possible to reduce stress during bulging or drawing, and to improve formability.
Preferably, the metal foil layer 10 is subjected to chemical conversion treatment at least on the inner surface (the surface on the 2 nd adhesive layer 14 side). By performing such chemical conversion treatment, corrosion of the surface of the metal foil due to the contents (electrolyte of a battery, food, pharmaceutical, etc.) can be sufficiently prevented. For example, the metal foil is subjected to a chemical conversion treatment by performing the following treatment. That is, for example, the chemical conversion treatment is performed by applying any one of the following substances to the surface of the degreased metal foil and then drying the metal foil:
1) aqueous solution containing a mixture of at least 1 compound selected from the group consisting of phosphoric acid, chromic acid, metal salts of fluoride and non-metal salts of fluoride
2) An aqueous solution containing a mixture of at least 1 resin selected from the group consisting of phosphoric acid, acrylic resins, chitosan derivative resins and phenolic resins, and at least 1 compound selected from the group consisting of chromic acid and chromium (III) salts
3) An aqueous solution comprising a mixture of at least 1 resin selected from the group consisting of phosphoric acid, acrylic resins, chitosan derivative resins, and phenolic resins, at least 1 compound selected from the group consisting of chromic acid and chromium (III) salts, and at least 1 compound selected from the group consisting of metal salts of fluorides and non-metal salts of fluorides.
(No. 1 adhesive layer)
The 1 st adhesive layer 11 is a layer for bonding the metal foil layer 10 and the heat-resistant resin layer 13, and is a layer for bonding the metal foil layer 10 and the heat-resistant resin layer 13 on which the colored layer 12 is laminated in the production process of the laminate 1. The 1 st adhesive layer 11 is not particularly limited, and examples thereof include an adhesive layer formed of a two-pack curable adhesive. Examples of the two-component curable adhesive include a two-component curable adhesive composed of a 1 st liquid containing 1 or 2 or more kinds of polyols selected from the group consisting of polyurethane polyols, polyester polyols, polyether polyols, and polyester polyurethane polyols, and a 2 nd liquid (curing agent) containing isocyanate. Among them, a two-component curable adhesive comprising a 1 st liquid containing 1 or 2 or more kinds of polyols selected from the group consisting of polyester polyols and polyester polyurethane polyols and a 2 nd liquid (curing agent) containing isocyanate is preferably used. The 1 st adhesive layer 11 is formed by applying an adhesive such as the two-pack curable adhesive to the upper surface of the metal foil layer 10 and/or the lower surface of the heat-resistant resin layer 13 (for example, the lower surface of the colored layer 12) by a method such as gravure coating.
The method of bonding the metal foil layer 10 and the heat-resistant resin layer 13 (heat-resistant resin layer on which the colored layer 12 is laminated) is not particularly limited, and a so-called dry lamination method can be recommended. Specifically, the prepared 1 st adhesive is applied to the upper surface of the metal foil layer 10 or the lower surface of the heat-resistant resin layer 13 (the lower surface of the colored layer 12 in the above embodiment), or both surfaces thereof, the solvent is evaporated to form a dry film, and then the metal foil layer 10 and the heat-resistant resin layer 13 are bonded to each other. Thereafter, the adhesive is cured under the curing conditions of the 1 st adhesive. Thereby, the metal foil layer 10 and the heat-resistant resin layer 13 on which the colored layer 12 is laminated are bonded via the 1 st adhesive layer 11. The coating method of the 1 st adhesive may be exemplified by a gravure coating method, a reverse roll coating method, a lip roll coating method, and the like.
(No. 2 adhesive layer)
The 2 nd adhesive layer 14 is not particularly limited, and examples thereof include adhesive layers formed of a polyurethane adhesive, an acrylic adhesive, an epoxy adhesive, a polyolefin adhesive, an elastomer adhesive, a fluorine adhesive, an acid-modified polypropylene adhesive, and the like. Among them, an acrylic adhesive and a polyolefin adhesive are preferably used, and in this case, the electrolyte solution resistance and the water vapor barrier property of the laminate 1 can be improved.
The method of bonding the metal foil layer 10 and the thermoplastic resin layer 15 is not particularly limited, and a dry lamination method of bonding the metal foil layer 10 and the heat-resistant resin layer 15 after applying and drying a 2 nd adhesive can be exemplified as in the case of bonding the metal foil layer 10 and the heat-resistant resin layer 13.
[ other modes of the laminate ]
The laminate 1 of the present invention is not particularly limited to the laminate structure shown in fig. 1, and may be further laminated to form a packaging material to improve the function. For example, a laminate material in which a matte coat layer is formed on the outer surface (the surface opposite to the colored layer 12) of the heat-resistant resin layer 13 can be exemplified.
The matte coat layer is a surface layer provided to impart good slidability to the surface of the laminate 1 and to improve moldability. By providing this optical coating layer, slippage between the heat-resistant resin layer and the colored layer is less likely to occur during molding or the like, and the heat-resistant resin layer is less likely to peel off from the colored layer.
The matte coat layer is a layer formed by dispersing a resin composition containing inorganic fine particles in a heat-resistant resin component. Among them, the matte coating layer is preferably formed of a resin composition in which 0.1 to 1 mass% of inorganic fine particles having an average particle diameter of 0.1 to 10 μm are contained in a two-pack curable heat-resistant resin. Examples of the heat-resistant resin include acrylic resins, epoxy resins, polyester resins, polyurethane resins, polyolefin resins, fluorine resins, phenoxy resins, and the like, and a fluorine resin based on tetrafluoroethylene or vinyl fluoride ether is preferably used because of its excellent heat resistance and chemical resistance. The inorganic fine particles are not particularly limited, and examples thereof include silica, alumina, calcium oxide, calcium carbonate, calcium sulfate, calcium silicate, and the like, and among them, silica is preferably used.
The matte coat layer can be formed by applying a matte coat composition containing the inorganic fine particles and the heat-resistant resin to the surface of the heat-resistant resin layer 13 and curing the composition.
The thickness of the matte coat layer (thickness after curing) is preferably 0.5 to 5 μm. The effect of improving the sliding property can be sufficiently obtained by setting the value to be equal to or higher than the preferable lower limit value, and the cost can be suppressed by setting the value to be equal to or lower than the preferable upper limit value. Among them, the thickness of the matte coat layer (thickness after curing) is particularly preferably 1 μm to 3 μm.
The gloss value of the surface of the matte coat is preferably set to 1% to 15% as measured by a 60 ° reflection angle in accordance with JIS Z8741. The gloss value is measured at a reflection angle of 60 ℃ by a gloss meter "micro-TRI-gloss-s" manufactured by BYK.
The timing (order of execution) of the step of forming the matte coat layer is not particularly limited, and is preferably performed in succession to the step of bonding the heat-resistant resin layer 13 having the colored layer 12 laminated thereon to the metal foil layer 10.
In addition, although the configuration in which the 1 st adhesive layer 11 and the 2 nd adhesive layer 14 are provided is adopted in the above embodiment, both of the layers 11 and 14 are not necessarily required, and a configuration in which neither of them is provided may be adopted. By providing the above adhesive layers 11 and 14, the adhesion to the metal foil layer 10 can be improved. In particular, it is preferable that the 1 st adhesive layer 11 use an adhesive containing the same resin component as the resin adhesive of the 2 nd layer 12b of the colored layer 12, so that the 2 nd layer 12b can be made less likely to peel off.
Further, an easy-adhesion layer containing no colorant may be present between the heat-resistant resin layer 13 and the colored layer 12.
The laminate 1 of the present invention is not limited to the material manufactured by the above-described manufacturing method including the method of bonding each layer, and the like, and the material manufactured by another manufacturing method is also included in the present invention.
The utility model discloses a laminated material is through cutting into needs size or carrying out the shaping as required (deep-drawing shaping, bulging shaping etc.) to can make shaping casings such as extranal packing body for the battery. The outer package for a battery is formed with a battery element chamber for housing a battery element by aligning the laminates so that the heat-fusible resin layers face inward, and heat-sealing the edges. The laminate material of the present invention is not easily peeled off from the heat-resistant resin layer, and therefore, even when a battery using the laminate material as a battery exterior body is used in a slightly severe environment such as a high-temperature and high-humidity environment, the heat-resistant resin layer is not locally cracked and peeled off.
The laminate of the present invention is preferably used as a packaging material for lithium ion secondary battery cases, but is not particularly limited to such use.
Examples
Next, specific embodiments of the present invention will be described. The present invention is not particularly limited to the embodiment.
[ preparation of laminate ]
In examples 1 to 11 and comparative example 2 below, a laminate 1 having a laminated structure shown in fig. 1 was prepared. These examples have a 2-layer structure of the colored layer 12. In addition, as comparative example 1, a laminate (not shown) having a single colored layer was prepared. These laminates differ only in the structure and composition of the colored layers, and other materials are common. The common materials are as follows.
(common Material)
The metal foil layer 10 was an aluminum foil formed of JIS H4160A 8079-O having a thickness of 35 μm, both sides of which were coated with a chemical conversion treatment solution formed of polyacrylic acid, a trivalent chromium compound, water, and an alcohol, and dried at 150 ℃ to form a metal foilAnd (4) chemical conversion coating. The amount of chromium deposited on the chemical conversion coating was 50mg/m per surface 2 。
The heat-resistant resin layer 13 as the outer layer was a biaxially stretched nylon film having a thickness of 15 μm, and the heat-fusible resin layer 15 as the inner layer was a non-stretched polypropylene film having a thickness of 30 μm. A two-pack curable polyester urethane resin adhesive is used for the 1 st adhesive layer 11, and a polyacrylic adhesive is used for the 2 nd adhesive layer 14.
As the colorant, carbon black having an average particle diameter of 0.2 μm was used.
(examples 1 to 3, 8 to 11, comparative example 2)
The 1 st coloring composition constituting the 1 st layer 12a and the 2 nd coloring composition constituting the 2 nd layer 12a of the coloring layer 12 are compositions in which a colorant is dispersed in a two-part curable polyester urethane resin binder. In each example, the resin binders of the 1 st coloring composition and the 2 nd coloring composition are common, and only the content of the colorant is different.
First, a polyester resin (polyester polyol) as a main agent of a resin binder is prepared. A dicarboxylic acid mixture comprising 30 parts by mole of adipic acid as an aliphatic dicarboxylic acid and 70 parts by mole of isophthalic acid as an aromatic dicarboxylic acid was subjected to a polycondensation reaction at 210 ℃ for 20 hours while stirring, while melting 30 parts by mole of neopentyl glycol, 30 parts by mole of ethylene glycol, and 40 parts by mole of 1, 6-hexanediol at 80 ℃, to obtain a polyester polyol (polyester resin) as a main agent. The polyester polyol had a number average molecular weight (Mn) of 12000, a weight average molecular weight (Mw) of 20500, and a ratio (Mw/Mn) of the two was 1.71. Further, 60 parts by mass of ethyl acetate was added to 40 parts by mass of the polyester polyol obtained above to obtain a flowable polyester polyol resin solution. In the polyester polyol resin solution, the hydroxyl value of the polyester polyol was 2.2mgKOH/g (solution value).
Next, 100 parts by mass of the polyester polyol resin solution (40 parts by mass of polyester polyol) and 64.4 parts by mass of ethyl acetate were mixed, and then a colorant in an amount corresponding to the content of the colorant shown in table 1 was dispersed using a pigment dispersing machine, thereby obtaining a main agent composition for layer 1 and a main agent composition for layer 2.
To 100 parts by mass of the above-mentioned main composition for layer 1, 7.1 parts by mass of an adduct of Tolylene Diisocyanate (TDI) and trimethylolpropane (NCO%: 13.0%, solid content: 75% by mass; aromatic polyfunctional isocyanate compound) was added as a curing agent, and 34.1 parts by mass of ethyl acetate was further added and stirred to prepare a 1 st colored composition. Similarly, the 2 nd colored composition is obtained by mixing and stirring the above-mentioned base composition for layer 2 and the above-mentioned curing agent. In the first coloring composition and the second coloring composition, the molar ratio (NCO/OH) of the isocyanate functional group (NCO) to the hydroxyl group (OH) of the polyester polyol is 10.
Next, the 1 st colored composition is applied to one surface of the heat-resistant resin layer 13 and dried, thereby forming the 1 st layer 12a of the colored layer 12. Next, the 2 nd coloring composition is applied on the 1 st layer 12a and dried, thereby forming the 2 nd layer 12b of the coloring layer 12. Thereby, the colored layer 12 having a 2-layer structure is formed on one surface of the heat-resistant resin layer 13. The film thickness and the amount of colorant deposited after drying of the 1 st layer 12a and the 2 nd layer are shown in table 1.
Next, an adhesive is applied to one surface of the metal foil layer 10 having the chemical conversion coatings formed on both surfaces thereof and dried to form a 1 st adhesive layer 11, the colored layer 12 side of the heat-resistant resin layer 13 is bonded to the surface of the 1 st adhesive layer 11, an adhesive is applied to the other surface of the metal foil layer 10 and dried to form a 2 nd adhesive layer 14, and a heat-fusible resin layer 15 is bonded to the surface of the 2 nd adhesive layer 14. The laminate was left to stand at 40 ℃ for 5 days to obtain a laminate 1 having a structure shown in fig. 1.
(example 4)
The same material and the same method as in example 1 were used to prepare a laminate 1, except that acrylic urethane was used as the resin binder of the 1 st layer 12a of the colored layer 12 to prepare a 1 st colored composition.
The number average molecular weight (Mn) and the weight average molecular weight (Mw) of the acrylic urethane, the ratio (Mw/Mn) of the two, the content of the colorant in the 1 st colored composition, the thickness of the coating film after drying of the 1 st layer 12a and the 2 nd layer 12b, and the amount of the colorant deposited are shown in table 1.
(example 5)
The same materials and the same method as in example 1 were used to prepare a laminate 1, except that the 1 st colored composition was prepared using polyurethane as the resin binder of the 1 st layer 12a of the colored layer 12.
The number average molecular weight (Mn) and weight average molecular weight (Mw) of the polyurethane, the ratio (Mw/Mn) of the two, the content of the colorant in the 1 st colored composition, the thickness of the coating film after drying of the 1 st layer 12a and the 2 nd layer 12b, and the amount of the colorant deposited are shown in table 1.
(example 6)
By using the same starting materials as in example 1 above, and changing the blending molar ratio of the total amount of diol components to the total amount of dicarboxylic acids and the reaction conditions in example 1, a polyester polyol having a number average molecular weight (Mn) of 8900, a weight average molecular weight (Mw) of 13000, and a ratio of the two (Mw/Mn) of 1.46 was prepared.
Next, the 1 st coloring composition and the 2 nd coloring composition were prepared in the same manner as in example 1, and the coloring layer 12 having a 2-layer structure was formed on one surface of the heat-resistant resin layer 13, to obtain a laminate having a structure shown in fig. 1 together with other materials. In the first coloring composition and the second coloring composition, the molar ratio (NCO/OH) of the isocyanate functional group (NCO) to the hydroxyl group (OH) of the polyester polyol is 10. The content of the colorant in the 1 st and 2 nd coloring compositions, the thickness of the coating after drying of the 1 st and 2 nd layers 12a and 12b, and the amount of the colorant deposited are shown in table 1.
(example 7)
By using the same starting materials as in example 1 above, and changing the blending molar ratio of the total amount of diol components to the total amount of dicarboxylic acids and the reaction conditions in example 1, a polyester polyol having a number average molecular weight (Mn) of 2100, a weight average molecular weight (Mw) of 43000 and a ratio of the two (Mw/Mn) of 2.05 was prepared.
Next, the 1 st coloring composition and the 2 nd coloring composition were prepared in the same manner as in example 1, and the coloring layer 12 having a 2-layer structure was formed on one surface of the heat-resistant resin layer 13, to obtain a laminate having a structure shown in fig. 1 together with other materials. In the first coloring composition and the second coloring composition, the molar ratio (NCO/OH) of the isocyanate functional group (NCO) to the hydroxyl group (OH) of the polyester polyol is 10. The content of the colorant in the 1 st and 2 nd coloring compositions, the thickness of the coating after drying of the 1 st and 2 nd layers 12a and 12b, and the amount of the colorant deposited are shown in table 1.
Comparative example 1
A laminate was prepared using the same method as in example 1, except that the colored layer was formed as a single layer of the same composition and thickness as the 2 nd layer 12b of example 1.
[ TABLE 1]
Each laminate obtained in the above manner was evaluated based on the following evaluation method. The results are shown in Table 2.
(coloring)
The L value of the surface of the heat-resistant resin layer of the laminate was measured by using a spectrophotometer (CM 2500C manufactured by KONICA MINOLTA). The measured L value of less than 50 was judged to be good (good coloring), and 50 or more was judged to be x (poor coloring).
(with or without peeling)
Using a punch, a die, or the like, deep drawing forming was performed to form convex portions 31 having a length of 33mm × a width of 54mm × a depth of 4.0mm so that the inner heat-fusible resin layer 15 was in contact with the punch with respect to each laminate, and a test material 30 having a shape of a flat flange around the convex portions 31 was prepared (see fig. 2).
The top surfaces 32 of the projections 31 of the test material 30 were crushed, and the crushed test material 30 was subjected to a high-temperature high-humidity test and a warm water immersion test to examine the presence or absence of peeling of the heat-resistant resin layer 13.
In the high temperature and high humidity test, the crushed test material 30 was held in an atmosphere of 70 ℃ and 90% humidity for 2 weeks. Then, the material having no peeling of the heat-resistant resin layer was judged to be good, and the peeled material was judged to be poor.
In the warm water immersion test, the crushed test material 30 was immersed in warm water at 45 ℃ and kept for 2 weeks. Then, the material having no peeling of the heat-resistant resin layer was judged to be good, the material having very little peeling was judged to be good, and the peeled material was judged to be poor.
[ TABLE 2]
As is clear from tables 1 and 2, it was confirmed that a stable color development state was obtained and peeling of the heat-resistant resin layer was suppressed by setting the colored layer to have a 2-layer structure and setting the colorant content of the 1 st layer in contact with the heat-resistant resin layer to be lower than that of the 2 nd layer.
Industrial applicability
The laminate of the present invention is preferably used as a case of a battery such as a lithium ion polymer secondary battery for a notebook personal computer, a mobile phone, a vehicle, or a stationary type, and is also preferably used as a packaging material for food or a packaging material for pharmaceuticals, but is not particularly limited to these applications. Among them, the battery is particularly preferable.
Claims (5)
1. A laminate comprising: a heat-resistant resin layer as an outer layer; a heat-fusible resin layer as an inner layer; a metal foil layer disposed between the two layers; and a colored layer disposed between the metal foil layer and the heat-resistant resin layer, the laminated material being characterized in that,
the colored layer is formed from a coloring composition containing a resin binder and a colorant, the colored layer is a multilayer formed by laminating 2 or more layers having different colorant contents, and the content of the colorant in a layer in contact with the heat-resistant resin layer is lower than that in the other layer.
2. The laminate according to claim 1, wherein the coloring composition of each of the colored layers contains a common resin binder.
3. The laminate according to claim 1, wherein an adhesive layer is disposed between the colored layer and the metal foil layer, and the adhesive layer contains the same resin component as a resin binder of the colored composition constituting the colored layer.
4. The laminate according to claim 1, wherein a protective layer containing a resin component and a filler component is laminated on the outer side of the heat-resistant resin layer.
5. An exterior package for a battery, characterized in that a battery element chamber for housing a battery element is formed by heat-sealing the joined edge portions of the laminate material according to any one of claims 1 to 4 so that the heat-fusible resin layers face inward.
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| CN114551885B (en) * | 2022-02-21 | 2024-06-11 | 上海紫江新材料科技股份有限公司 | Black adhesive for lithium battery aluminum plastic film and use method thereof |
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| JPH11157207A (en) * | 1997-09-24 | 1999-06-15 | Canon Inc | Recording medium, method for forming image using recording medium, and manufacture of recording medium |
| JP2000103177A (en) | 1998-09-28 | 2000-04-11 | Oji Paper Co Ltd | Ink image receiving sheet for molten thermal transfer |
| JP3478198B2 (en) | 1998-10-29 | 2003-12-15 | 日本製紙株式会社 | Thermal recording medium |
| JP4422378B2 (en) | 1999-09-07 | 2010-02-24 | 東洋鋼鈑株式会社 | Polyester resin coated steel sheet for can formation |
| JP2007261192A (en) | 2006-03-29 | 2007-10-11 | Kobe Steel Ltd | Light-reflective coated metal sheet |
| TWI511885B (en) | 2009-04-20 | 2015-12-11 | Toyo Aluminium Kk | Laminated article, packed article, sheet for packing, packing material, label and vessel |
| JP5351350B1 (en) | 2013-04-04 | 2013-11-27 | 株式会社タケトモ | PTP packaging body packaging sheet and PTP packaging body using the same |
| JP5708860B1 (en) | 2013-09-26 | 2015-04-30 | 大日本印刷株式会社 | Battery packaging materials |
| JP2015131482A (en) | 2013-12-09 | 2015-07-23 | 株式会社Ｕａｃｊ製箔 | Aluminum-resin laminated material and packaging material including the same |
| JP6330428B2 (en) | 2014-03-31 | 2018-05-30 | 王子ホールディングス株式会社 | Thermal magnetic recording parking ticket |
| JP6275014B2 (en) | 2014-10-24 | 2018-02-07 | 昭和電工パッケージング株式会社 | Molding packaging material and molding case |
| JP7203483B2 (en) | 2016-12-28 | 2023-01-13 | 昭和電工パッケージング株式会社 | Exterior material for power storage device, exterior case for power storage device, and power storage device |
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