LAMINATE AND METHOD FOR USING LAMINATE

Abstract

The present invention provides a laminate that has excellent flame-shielding performance and heat-shielding performance and can reduce the transmission of flame and heat generated by ignition inside a battery to the outside, especially when used as a cover for an in-vehicle battery. Provided is a laminate including: a fiber layer including a resin and a fiber; and a thermal insulation layer formed on at least one surface of the fiber layer.

Claims

1. A laminate comprising: a fiber layer including a resin and a fiber; and a thermal insulation layer formed on at least one surface of the fiber layer.

2. The laminate according to claim 1, having a thermal conductivity after heating at 800° C. for one minute of 0.01 to 0.15 W/mK.

3. The laminate according to claim 1, wherein a rate of change of thermal conductivity after heating at 800° C. for one minute, represented by the following formula (1), is 1 to 10:
(Rate of change of thermal conductivity)=[(Thermal conductivity before heating)−(Thermal conductivity after heating)]/(Thermal conductivity after heating)  (1).

4. The laminate according to claim 1, wherein a rate of volume expansion, represented by the following formula (3), after heating at 800° C. for one minute is 2 times or greater:
(Rate of volume expansion)=[(Maximum thickness after heating)−(Thickness before heating)]/(Thickness before heating)  (3).

5. The laminate according to claim 1, further comprising, on a surface of the thermal insulation layer opposite to the surface facing the fiber layer, a fiber layer including a resin and a fiber.

6. The laminate according to claim 1, wherein the resin constituting the fiber layer has an oxygen index of 20 or greater.

7. The laminate according to claim 1, wherein the resin constituting the fiber layer is a chlorinated polyvinyl chloride resin having an average degree of polymerization of 400 to 3,000 and a chlorine content of 57 to 72% by mass.

8. The laminate according to claim 1, wherein the fiber constituting the fiber layer is at least one selected from the group consisting of a glass fiber and a carbon fiber.

9. The laminate according to claim 1, wherein an amount of the fiber in the fiber layer is 10 to 80% by mass.

10. The laminate according to claim 1, which is a cover for a lithium-ion battery.

11. A method for using the laminate according to claim 1 as a cover for a lithium-ion battery.

Description

BRIEF DESCRIPTION OF DRAWINGS

[0129] FIG. 1 is a perspective view of a mold for molding a battery cover.

[0130] FIG. 2 is a cross-sectional view illustrating molding of a battery cover.

[0131] FIG. 3 is a perspective view of a drawn sample used for measuring bending strength after drawing.

[0132] FIG. 4 is a perspective view of a bending test sample cut out of the drawn sample.

DESCRIPTION OF EMBODIMENTS

[0133] The present invention is hereinafter described in more detail with reference to examples. The present invention should not be limited to these examples.

[0134] The following materials were used in the examples and the comparative examples.

EXAMPLE 1

Preparation of Fiber Layers (A) and (C)

[0135] One hundred parts by mass of a chlorinated polyvinyl chloride resin (CPVC, produced by Tokuyama Sekisui Co., Ltd., average degree of polymerization 1,000, chlorine content 72.0% by mass) and 10 parts by mass of a thermal stabilizer (produced by Nitto Kasei Co., Ltd., organotin thermal stabilizer “TVS #1380”) were mixed with 400 parts by mass of tetrahydrofuran (THF, produced by FUJIFILM Wako Pure Chemical Corporation) to prepare a resin solution.

[0136] The chlorine content of the resin was measured by a method in conformity with JIS K 7229. The average degree of polymerization of the resin was measured by a method in conformity with JIS K 6720-2:1999.

[0137] Subsequently, a sheet-form glass fiber (“MC450A” produced by Nitto Boseki Co., Ltd., average fiber size 7 pm, average fiber length 50 nm, specific gravity 2.6, weight per unit area 450 g/m.sup.2) was impregnated with the resin solution by a hand lay-up method. The process was repeated seven times to stack seven glass fiber layers. Then, the THF was evaporated by drying with a drier, whereby fiber layers (A) and (C) were obtained. The thickness of the obtained fiber layers (A) and (C) was 1.7 mm. The (fiber mass/resin mass) was 1.13. The average fiber size of the glass fiber was calculated from the average of the fiber sizes at randomly selected 10 points in an image captured with a scanning electron microscope (SEM). The average fiber length was calculated from the average of the fiber lengths of randomly selected 20 samples each measured with a caliper. The specific gravity was calculated with an electronic densimeter (produced by Alfa Mirage, “ED120T”). The weight per unit area of the glass fiber was determined by cutting the sheet-form glass fiber to a size of 10 cm×10 cm, measuring the weight of the cut sheet-form glass fiber, and calculating the weight (g) per m.sup.2.

Preparation of Thermal Insulation Layer (B)

[0138] One hundred parts by mass of a chlorinated polyvinyl chloride resin (produced by CPVC, Tokuyama Sekisui Co., Ltd., average degree of polymerization 500, chlorine content 67.3% by mass), 10 parts by mass of a thermal stabilizer (produced by Nitto Kasei Co., Ltd., organotin thermal stabilizer “TVS #1380”), 2 parts by mass of a lubricant (“WAX-OP” produced by Clariant), and 1 part by mass of an inorganic filler (carbon black, “BLACKPEARLS L” produced by Cabot Corporation) were mixed and roll-kneaded to prepare a thermal insulation layer (B) having a thickness of 0.3 mm.

Preparation of Laminate

[0139] The fiber layer (A), the thermal insulation layer (B), and the fiber layer (C) were stacked (fiber layer (A)-thermal insulation layer (B)-fiber layer (C)) and pressed with a press machine, whereby a laminate was obtained.

EXAMPLE 2

[0140] A laminate was obtained as in Example 1 except that in (Preparation of fiber layers (A) and (C)), the (fiber mass/resin mass) was 1.13, and that in (Preparation of thermal insulation layer (B)), 10 parts by mass of titanium oxide (“TIPAQUE CR-90” produced by Ishihara Sangyo Kaisha, Ltd.) was used instead of 1 part by mass of carbon black.

EXAMPLE 3

[0141] In (Preparation of fiber layers (A) and (C)), a glass fiber-reinforced thermoplastic prepreg containing a polyamide resin (“Tepexdynalite 102-FG290(x)/45%” produced by LANXESS) was used to prepare fiber layers (A) and (C) having a thickness of 1.7 mm. The (fiber mass/resin mass) was 1.12.

[0142] A laminate was obtained as in Example 2 except that the obtained fiber layers (A) and (C) were used.

EXAMPLE 4

[0143] In (Preparation of fiber layers (A) and (C)), a glass fiber-reinforced thermoplastic prepreg containing a polycarbonate resin (“Tepexdynalite 102fr-FG290(x)/45%” produced by LANXESS) was used to prepare fiber layers (A) and (C) having a thickness of 1.7 mm. The (fiber mass/resin mass) was 1.13.

[0144] A laminate was obtained as in Example 2 except that the obtained fiber layers (A) and (C) were used.

EXAMPLE 5

[0145] A laminate was obtained as in Example 2 except that in (Preparation of fiber layers (A) and (C)), a polyvinyl chloride resin (PVC, produced by Tokuyama Sekisui Co., Ltd., average degree of polymerization 1,000, chlorine content 56.7% by mass) was used as the resin, and that the (fiber mass/resin mass) was 1.54.

EXAMPLE 6

[0146] A laminate was obtained as in Example 2 except that in (Preparation of fiber layers (A) and (C)), a chlorinated polyvinyl chloride resin (CPVC, produced by Tokuyama Sekisui Co., Ltd., average degree of polymerization 500, chlorine content 67.3% by mass) was used as the resin, and that the (fiber mass/resin mass) was 1.54.

EXAMPLE 7

[0147] A laminate was obtained as in Example 6 except that in (Preparation of fiber layers (A) and (C)), a sheet-form carbon fiber (“T-700” produced by Toray Industries Inc., average fiber size 10 μm, specific gravity 2.1, weight per unit area 220 g/m.sup.2) as the fiber, and that the (fiber mass/resin mass) was 1.09.

EXAMPLE 8

[0148] A laminate was obtained as in Example 6 except that in (Preparation of thermal insulation layer (B)), a polyvinyl chloride resin (PVC, produced by Tokuyama Sekisui Co., Ltd., average degree of polymerization 500, chlorine content 56.7% by mass) was used as the resin.

EXAMPLE 9

[0149] A laminate was obtained as in Example 6 except that in (Preparation of thermal insulation layer (B)), a polycarbonate resin (produced by Mitsubishi Gas Chemical Company, Inc., PCZ-500) was used as the resin, and that the thermal insulation layer (B) was produced without the addition of the thermal stabilizer and the lubricant.

EXAMPLE 10

[0150] A laminate was obtained as in Example 9 except that in (Preparation of thermal insulation layer (B)), a polyamide resin (produced by Unitika Ltd., A1030BRT) was used as the resin, and that the thermal insulation layer (B) was produced without the addition of the thermal stabilizer and the lubricant.

EXAMPLE 11

[0151] A laminate was obtained as in Example 6 except that in (Preparation of thermal insulation layer (B)), expandable graphite (“EXP-50S300” produced by Fujikokuen Co., Ltd.) was used instead of titanium oxide.

EXAMPLE 12

[0152] A laminate was obtained as in Example 6 except that in (Preparation of fiber layers (A) and (C)), a sheet-form glass fiber (“MC 380A” produced by Nitto Boseki Co., Ltd., average fiber size 7 μm, average fiber length 50 nm, specific gravity 2.6, weight per unit area 380 g/m.sup.2) was used as the fiber, and that the (fiber mass/resin mass) was 1.35.

EXAMPLE 13

[0153] A laminate was obtained as in Example 6 except that in (Preparation of fiber layers (A) and (C)), a sheet-form glass fiber (“MC 600A” produced by Nitto Boseki Co., Ltd., average fiber size 7 μm, average fiber length 50 nm, specific gravity 2.6, weight per unit area 600 g/m.sup.2) was used as the fiber, and that the (fiber mass/resin mass) was 2.10.

EXAMPLE 14

[0154] A laminate was obtained as in Example 3 except that in (Preparation of thermal insulation layer (B)), a polyamide resin (produced by Unitika Ltd., A1030BRT) was used as the resin, and that the thermal insulation layer (B) was produced without the addition of the thermal stabilizer and the lubricant.

EXAMPLE 15

[0155] A laminate was obtained as in Example 4 except that in (Preparation of thermal insulation layer (B)), a polycarbonate resin (produced by Mitsubishi Gas Chemical Company, Inc., PCZ-500) was used as the resin, and that the thermal insulation layer (B) was produced without the addition of the thermal stabilizer and the lubricant.

Comparative Example 1

[0156] One hundred parts by mass of a chlorinated polyvinyl chloride resin (CPVC, produced by Tokuyama Sekisui Co., Ltd., average degree of polymerization 1,000, chlorine content 72.0% by mass), 10 parts by mass of a thermal stabilizer (produced by Nitto Kasei Co., Ltd., “TVS #1380”), and 2 parts by mass of a lubricant (“WAX-OP” produced by Clariant) were mixed and roll-kneaded to prepare resin layers each having a thickness of 0.3 mm.

[0157] The obtained resin layers were stacked and press-molded, whereby a laminate having a thickness of 2.0 mm was obtained.

Comparative Example 2

[0158] One hundred parts by mass of a chlorinated polyvinyl chloride resin (CPVC, produced by Tokuyama Sekisui Co., Ltd., average degree of polymerization 1,000, chlorine content 72.0% by mass) and 10 parts by mass of a thermal stabilizer (produced by Nitto Kasei Co., Ltd., organotin thermal stabilizer “TVS #1380”) were mixed with 400 parts by mass of tetrahydrofuran (THF, produced by FUJIFILM Wako Pure Chemical Corporation) to prepare a resin solution.

[0159] Subsequently, a sheet-form glass fiber (“MC450A-104SS” produced by Nitto Boseki Co., Ltd., average fiber size 7 μm, weight per unit area 450 g/m.sup.2) was impregnated with the resin solution by a hand lay-up method. The process was repeated to stack glass fiber layers. Then the THF was evaporated by drying with a drier, whereby a laminate having a thickness of 2.0 mm was obtained. The (fiber mass/resin mass) was 0.98.

Comparative Example 3

[0160] A glass fiber-reinforced thermoplastic prepreg containing a polyamide resin (“Tepexdynalite 102-FG290(x)/45%” produced by LANXESS) was used to prepare a fiber layer having a thickness of 2.5 mm. The (fiber mass/resin mass) was 1.12.

Comparative Example 4

[0161] A glass fiber-reinforced thermoplastic prepreg containing a polycarbonate resin (“Tepexdynalite 102fr-FG290(x)/45%” produced by LANXESS) was used to prepare a fiber layer having a thickness of 2.0 mm. The (fiber mass/resin mass) was 1.13.

Evaluation

[0162] The resins, laminates, and resin layers used in the examples and the comparative examples were evaluated as follows. Tables 1 to 4 show the results.

(1) Oxygen Index, Weight Average Molecular Weight, and Glass Transition Temperature (Tg) of Resin

[0163] The oxygen index of the resins was measured by a method in conformity with JIS K 7201-2:2007. The weight average molecular weight of the resins was measured by a method in conformity with ASTM D 2503. The glass transition temperature (Tg) of the resins was measured by a method in conformity with the JIS K 7121.

[0164] The weight average molecular weight of the chlorinated polyvinyl chloride resins, polyvinyl chlorides, and polycarbonate resins was specifically measured by the following method.

[0165] First, a resin sample was dissolved in THF and filtrated through a filter having a pore size of 0.2 μm. Measurement was then performed using a GPC unit (pump unit: PU-4180, detector unit: RI-4030, column oven: CO-4065) produced by JASCO Corporation at a flow rate of 0.7 ml/min and an oven temperature of 40° C., whereby the sample was eluted and separated. The molecular weight was determined based on a calibration curve produced using standard polystyrene. The columns used were SHODEX columns LF-804 (two columns connected).

[0166] The weight average molecular weight of the polyamide resins was measured by the following method.

[0167] Specifically, first, a laminate sample was weighed. A predetermined amount of eluent was added, and the sample was allowed to stand at room temperature overnight for dissolution. Subsequently, the obtained solution was shaken gently and then filtered through a 0.45 μm PTFE cartridge filter to separate the polyamide resin as the filtrate.

[0168] Measurement was then performed under the following conditions.

<GPC Device>

[0169] HLC-8420GPC (produced by Tosoh Corporation)

<Column>

[0170] TSKgel SuperAWM-H (6.0 mm I.D.×15 cm)×2 (produced by Tosoh Corporation)

<Detector>

[0171] Differential refractometer (RI detector), polarity=(+)

<Eluent>

[0172] HFIP (1,1,1,3,3,3-hexafluoro-2-propanol) (produced by FUJIFILM Wako Pure Chemical Corporation)+10 mM-CF3COONa (produced by FUJIFILM Wako Pure Chemical Corporation, 1st grade)

<Measurement Conditions>

[0173] Flow rate: 0.3 ml/min [0174] Column temperature: 40° C. [0175] Sample concentration: 1 mg/ml (polyamide-based concentration) [0176] Sample injection volume: 20 μL [0177] Calibration curve: cubic approximation curve produced using standard PMMA (produced by Agilent Technologies, Inc.)

(2) Thermal Conductivity and Rate of Volume Expansion

[0178] The laminates obtained in Examples 1 to 15 and Comparative Examples 1 and 2 and the fiber layers obtained in Comparative Examples 3 and 4 were each cut into a measurement sample having a size of 100 mm×100 mm. The thermal conductivity of the measurement sample was measured in conformity with JIS R 2616.

[0179] Further, the obtained measurement sample was fixed to a fixture such that the thickness direction corresponded to the vertical direction. The sample was heated from below with the distance between the sample and a burner being 20 mm. The heating was continued at 800° C. for one minute, and then the thermal conductivity was measured in the same manner as above. The rate of change of thermal conductivity and the rate of decrease in thermal conductivity were calculated by the following formulas (1) and (2).

(Rate of change of thermal conductivity)=[(Thermal conductivity before heating)−(Thermal conductivity after heating)]/(Thermal conductivity after heating)  (1)

(Rate of decrease in thermal conductivity)=[(Thermal conductivity before heating)−(Thermal conductivity after heating)]/(Thermal conductivity before heating)×100  (2)

[0180] The thickness of the measurement sample after heating at 800° C. for one minute was measured, and the rate of volume expansion was measured by the following formula (3).

(Rate of volume expansion)=[(Maximum thickness after heating)−(Thickness before heating)]/(Thickness before heating)  (3)

[0181] For the laminate obtained in Comparative Example 1, the thermal conductivity after heating, the rate of change of thermal conductivity, the rate of decrease in thermal conductivity, and the rate of volume expansion were unable to be measured because the resin was burned off before 800° C. was reached.

(3) Flame Escape and Back Surface Temperature

[0182] The laminates obtained in Examples 1 to 15 and Comparative Example 1 and 2 and the fiber layers obtained in Comparative Examples 3 and 4 were each cut into a measurement sample having a size of 150 mm×150 mm. The obtained measurement sample was fixed to a fixture such that the thickness direction corresponded to the vertical direction. The sample was heated for five minutes from below with the distance between the sample and a burner being 20 mm. The state during heating was observed and evaluated in accordance with the following criteria. [0183] ○ (Good): No flame escape above the measurement sample was observed. [0184] x (Poor): A flame escape above the measurement sample was observed.

[0185] The temperature of the back surface opposite to the heated surface was monitored with a thermography, and the time required for the back surface temperature to reach 300° C. was measured.

(4) Appearance of Battery Cover

Preparation of Cover for Lithium-Ion Battery

[0186] The laminates obtained in Examples 1 to 15 were each press-molded as shown in FIG. 2 (temperature 200° C., preheating for four minutes, compression for four minutes, cooling for four minutes) using molds shown in FIG. 1 to prepare a molded article simulating a cover for a lithium-ion battery. The obtained molded articles had good appearance free of cracks or fractures.

(5) Bending Strength After Drawing

[0187] The laminates obtained in Examples 1 to 15 and Comparative Examples 1 and 2 and the fiber layers obtained in Comparative Example 3 and 4 were each heated with an infrared heater to a surface temperature of 210° C. (230° C. for a resin including a polycarbonate resin, 240° C. for a resin including a polyamide resin).

[0188] The laminate after heating was placed in a press mold at a mold temperature of 170° C. The laminate was pressed at a clamping force of 30 t and held for 10 seconds. The mold was then cooled to 50° C. over 20 minutes, whereby a drawn sample as shown in FIG. 3 was obtained.

[0189] From a flat portion (portion indicated by dashed lines in FIG. 3) of the drawn sample, a bending test sample (65 mm×10 mm) was cut out as shown in FIG. 4 using a composite material cutter AC-300CF (produced by Maruto Testing Machine Company). The bending strength was measured using “TENSILON” produced by Orientec Corporation in conformity with JIS K7171.

TABLE-US-00001 TABLE 1 Example 1 2 3 4 5 Fiber Resin Type CPVC CPVC Polyamide Polycarbonate PVC layer Average degree of 1000 1000 — — 1000 polymerization Chlorine content 72.0 72.0 — — 56.7 (parts by mass) Oxygen index 65 65 24 25 48 Mw 142000 142000 30000 25000 130000 Tg (° C.) 115 115 50 152 88 Amount 44.7 44.7 40.2 39.5 37.8 (% by weight) Fiber Type Glass Glass Glass Glass Glass fiber fiber fiber fiber fiber Average fiber size 7 7 7 7 7 (μm) Average fiber length 50 50 50 50 50 (mm) Specific gravity 2.6 2.6 2.6 2.6 2.6 Weight per unit area 450 450 450 450 450 (g/m.sup.2) Amount 50.3 50.3 45.1 44.8 58.4 (% by mass) Fiber mass/resin mass 1.13 1.13 1.12 1.13 1.54 Thickness (mm) 1.7 1.7 1.7 1.7 1.7 Thermal Resin Type CPVC CPVC CPVC CPVC CPVC insulation Average degree of 500 500 500 500 500 layer polymerization Chlorine content 67.3 67.3 67.3 67.3 67.3 (% by mass) % by weight 88.5 82.0 82.0 82.0 82.0 Inorganic Type Carbon Titanium Titanium Titanium Titanium filler black oxide oxide oxide oxide % by weight 0.9 8.2 8.2 8.2 8.2 Thickness (mm) 0.3 0.3 0.3 0.3 0.3 Example 6 7 8 9 10 Fiber Resin Type CPVC CPVC CPVC CPVC CPVC layer Average degree of 500 500 500 500 500 polymerization Chlorine content 67.3 67.3 67.3 67.3 67.3 (parts by mass) Oxygen index 60 60 60 60 60 Mw 70000 70000 70000 70000 70000 Tg (° C.) 107 107 107 107 107 Amount 37.8 45.9 37.8 37.8 37.8 (% by weight) Fiber Type Glass Carbon Glass Glass Glass fiber fiber fiber fiber fiber Average fiber size 7 10 7 7 7 (μm) Average fiber length 50 Continuous 50 50 50 (mm) fiber Specific gravity 2.6 2.1 2.6 2.6 2.6 Weight per unit area 450 220 450 450 450 (g/m.sup.2) Amount 58.4 50.1 58.4 58.4 58.4 (% by mass) Fiber mass/resin mass 1.54 1.09 1.54 1.54 1.54 Thickness (mm) 1.7 1.7 1.7 1.7 1.7 Thermal Resin Type CPVC CPVC PVC Polycar- Polyamide bonate insulation Average degree of 500 500 500 — — layer polymerization Chlorine content 67.3 67.3 56.7 — — (% by mass) % by weight 82.0 82.0 82.0 90.9 90.9 Inorganic Type Titanium Titanium Titanium Titanium Titanium filler oxide oxide oxide oxide oxide % by weight 8.2 8.2 8.2 9.1 9.1 Thickness (mm) 0.3 0.3 0.3 0.3 0.3

TABLE-US-00002 TABLE 2 Example 11 12 13 14 15 Fiber Resin Type CPVC CPVC CPVC Polyamide Polycarbonate layer Average degree of 500 500 500 — — polymerization Chlorine content 67.3 67.3 67.3 — — (parts by mass) Oxygen index 60 60 60 24 25 Mw 70000 70000 70000 30000 25000 Tg (° C.) 107 107 107 50 152 Amount 37.8 40.7 30.8 40.2 39.5 (% by weight) Fiber Type Glass Glass Glass Glass Glass fiber fiber fiber fiber fiber Average fiber size 7 7 7 7 7 (μm) Average fiber length 50 50 50 50 50 (mm) Specific gravity 2.6 2.6 2.6 2.6 2.6 Weight per unit area 450 380 600 450 450 (g/m.sup.2) Amount 58.4 54.9 64.8 45.1 44.8 (% by mass) Fiber mass/resin mass 1.54 1.35 2.10 1.12 1.13 Thickness (mm) 1.7 1.7 1.7 1.7 1.7 Thermal Resin Type PVC CPVC CPVC Polyamide Polycarbonate insulation Average degree of 500 500 500 — — layer polymerization Chlorine content 67.3 67.3 67.3 — — (% by mass) % by weight 82.0 82.0 82.0 90.9 90.9 Inorganic Type Expandable Titanium Titanium Titanium Titanium filler graphite oxide oxide oxide oxide % by weight 8.2 8.2 8.2 9.1 9.1 Thickness (mm) 0.3 0.3 0.3 0.3 0.3 Comparative Example 1 2 3 4 Fiber Resin Type — CPVC Polyamide Polycarbonate layer Average degree of — 1000 — — polymerization Chlorine content — 72.0 — — (parts by mass) Oxygen index — 65 24 25 Mw — 142000 30000 25000 Tg (° C.) — 115 50 152 Amount — 35.2 40.2 39.5 (% by weight) Fiber Type — Glass Glass Glass fiber fiber fiber Average fiber size — 7 7 7 (μm) Average fiber length — 50 50 50 (mm) Specific gravity — 2.6 2.6 2.6 Weight per unit area — 450 450 450 (g/m.sup.2) Amount — 60.9 45.1 44.8 (% by mass) Fiber mass/resin mass — 0.98 1.12 1.13 Thickness (mm) — 2 2.5 2 Thermal Resin Type CPVC — — — insulation Average degree of 1000 — — — layer polymerization Chlorine content 72 — — — (% by mass) % by weight 89.3 — — — Inorganic Type — — — — filler % by weight — — — — Thickness (mm) 2 — — —

TABLE-US-00003 TABLE 3 Example 1 2 3 4 5 6 7 8 9 10 Evaluation Thermal Before heating 0.263 0.239 0.295 0.244 0.225 0.245 0.238 0.246 0.255 0.261 conductivity After heating 0.110 0.105 0.112 0.095 0.100 0.098 0.105 0.093 0.116 0.118 (W/mK) Rate of change 1.4 1.3 1.6 1.6 1.3 1.5 1.3 1.6 1.2 1.2 Rate of decrease (%) 58 56 62 61 56 60 56 62 55 55 Rate of volume expansion 5.4 6.8 7.1 5.9 3.9 4.8 3.5 6.1 2.1 2.2 Flame escape ∘ ∘ ∘ ∘ ∘ ∘ ∘ ∘ ∘ ∘ Time at which back surface 154 138 140 126 104 121 95 99 78 69 temperature reached 300° C. (sec) Bending strength after drawing 21 21 21 21 18 20 5 17 20 19

TABLE-US-00004 TABLE 4 Example Comparative Example 11 12 13 14 15 1 2 3 4 Evaluation Thermal Before heating 0.229 0.216 0.215 0.266 0.257 0.17 0.246 0.272 0.259 conductivity After heating 0.018 0.085 0.085 0.129 0.120 Resin 0.121 0.184 0.162 (W/mK) burned off Rate of change 11.7 1.5 1.5 1.1 1.1 — 1.0 0.5 0.6 Rate of decrease (%) 92 61 60 52 53 — 51 32 37 Rate of volume expansion 9.8 4.9 5.5 1.9 2.0 — 1.9 1.7 1.8 Flame escape ∘ ∘ ∘ ∘ ∘ x ∘ ∘ ∘ Time at which back surface temperature 340 85 130 55 62 22 48 53 35 reached 300° C. (sec) Bending strength after drawing 13 22 18 19 17 0.28 19 20 20

INDUSTRIAL APPLICABILITY

[0190] The present invention can provide a laminate that has excellent flame-shielding performance and heat-shielding performance and can reduce the transmission of flame and heat generated by ignition inside a battery to the outside, especially when used as a cover for an in-vehicle battery.

REFERENCE SIGNS LIST

[0191] 1 mold [0192] 2 laminate