Resin Composition

Abstract

A resin composition capable of improving or minimizing a load applied to injection equipment, such as a nozzle, when injected by the equipment is provided. The resin composition includes a thermally conductive filler capable of exhibiting a desired thermal conductivity.

Claims

1. A resin composition, comprising: a resin component; and a filler component, wherein the filler component comprises a first filler having an average particle diameter in a range of 60 μm to 200 μm, a second filler having an average particle diameter in a range of 10 μm to 30 μm and a third filler having an average particle diameter of 5 μm or less, wherein the resin composition has a thermal conductivity of 3.0 W/mK or more after being cured; wherein the following general formulas 1 and 2 are satisfied:
2≤W.sub.A/W.sub.B≤5  [General Formula 1]
0.5≤W.sub.B/W.sub.C≤3  [General Formula 2] wherein, W.sub.A is a weight ratio of the first filler in the filler component, W.sub.B is a weight ratio of the second filler in the filler component, and W.sub.C is a weight ratio of the third filler in the filler component.

2. The resin composition according to claim 1, wherein the resin composition has a load value of greater than 10 kgf and less than 30 kgf.

3. The resin composition according to claim 1, wherein the resin composition comprises the filler component in a ratio of 91 weight % or less.

4. The resin composition according to claim 1, wherein the filler component comprises 50 to 80 weight % of the first filler.

5. The resin composition according to claim 1, wherein the filler component comprises 30 weight % or more of a spherical filler.

6. The resin composition according to claim 1, wherein the filler component comprises 90 weight % or less of an α-phase filler.

7. The resin composition according to claim 1, wherein the filler component comprises fumed silica, clay, calcium carbonate, aluminum oxide (Al.sub.2O.sub.3), aluminum nitride (AlN), boron nitride (BN), silicon nitride (Si.sub.3N.sub.4), silicon carbide (SiC), beryllium oxide (BeO), zinc oxide (ZnO), aluminum hydroxide (Al(OH).sub.3), boehmite, magnesium oxide (MgO), magnesium hydroxide (Mg(OH).sub.2) or a carbon filler.

8. The resin composition according to claim 1, wherein the resin component comprises a main resin or a curing agent.

9. The resin composition according to claim 8, wherein the main resin is a polyol resin, and the curing agent is an isocyanate.

10. The resin composition according to claim 9, wherein the polyol of the polyol resin is an ester polyol.

11. The resin composition according to claim 9, wherein polyol of the polyol resin is an amorphous ester polyol, or an ester polyol having a melting point of less than 15° C.

12. The resin composition according to claim 9, wherein the isocyanate is a non-aromatic polyisocyanate.

13. A battery module, comprising: a module case having a top plate, a bottom plate and sidewalls, and having an internal space formed by the top plate, the bottom plate and the sidewalls; a plurality of battery cells existing in the internal space of the module case; and a resin layer formed by curing the resin composition according to claim 1 and in contact with at least one of the plurality of battery cells and the bottom plate or sidewalls.

14. A battery pack comprising two or more battery modules of claim 13 that are electrically connected to each other.

15. An automobile comprising the battery module of claim 13.

16. An automobile comprising the battery pack of claim 14.

Description

DESCRIPTION OF DRAWINGS

[0164] FIG. 1 is a diagram for exemplarily explaining a process of injecting a resin composition.

[0165] FIG. 2 shows an exemplary mixing machine, which can be applied in the present application.

[0166] FIG. 3 shows an exemplary module case, which can be applied in the present application.

[0167] FIG. 4 schematically shows a form in which battery cells are housed in a module case.

[0168] FIG. 5 shows an exemplary solid matter generating device, which can be applied in the present application.

EXPLANATION OF REFERENCE NUMERALS

[0169] 1: mixing machine [0170] 2, 2a, 2b: cartridge [0171] 3, 3a, 3b: pressurizing means [0172] 4, 4a, 4b: first discharge part [0173] 5: mixer [0174] 6, 6a, 6b: receiving part [0175] 7: second discharge part [0176] 10: module case [0177] 10a: bottom plate [0178] 10b: sidewall [0179] 10c: top plate [0180] 20, 40: battery cell [0181] 30: injection equipment [0182] 20: inlet [0183] 60: solid matter generating device [0184] 61: syringe [0185] 62: discharge part of syringe [0186] 63: filter [0187] 64: pressurizing means

MODE FOR INVENTION

[0188] Hereinafter, the present application will be described in detail through Examples, but the scope of the present application is not limited by Examples below.

[0189] 1. Thermal Conductivity

[0190] The thermal conductivity of the resin layer (layer of the cured product of the resin composition) was measured by a hot-disk method according to ISO 22007-2 standard. Specifically, the resin compositions, which were mixtures of main compositions and curing agent compositions prepared in Examples and Comparative Examples, were each placed in a mold having a thickness of about 7 mm or so, and the thermal conductivity was measured in the through plane direction using the Hot Disk equipment. As stipulated in the above standard (ISO 22007-2), the Hot Disk equipment is an equipment that can check the thermal conductivity by measuring the temperature change (electrical resistance change) while the sensor with the nickel wire double spiral structure is heated, and the thermal conductivity was measured according to this standard.

[0191] 2. Evaluation of Load Values

[0192] The load value (kgf) of the resin composition was measured using the equipment (1) in which two cartridges (2, 2a, 2b) and one static mixer (5) were connected as shown in FIG. 2.

[0193] In the equipment (1) of FIG. 2, as the cartridge (2, 2a, 2b), a cartridge (Sulzer, AB050-01-10-01) including a material injection part of a circle with a diameter of 18 mm and a material discharge part (4, 4a, 4b) of a circle with a diameter of 3 mm, and having a height of 100 mm and an internal volume of 25 ml was used. As the static mixer (5), a stepped type static mixer (Sulzer, MBH-06-16T) including a discharge part (7) of a circle with a diameter of 2 mm and having an element number of 16 was used.

[0194] In addition, as the pressurizing means (3, 3a, 3b) (means for pushing the composition loaded in the cartridge) of the equipment of FIG. 2, a TA (Texture analyzer) was used.

[0195] By loading a main composition into any one of two cartridges (2a, 2b), loading a curing agent composition into the other cartridge, and then applying the constant force to the pressurizing means (3, 3a, 3b), the main and curing agent compositions were mixed in the static mixer (5) via the first discharge part (4a, 4b), and then the load value was measured while being discharged to the second discharge part (7).

[0196] Specifically, the main and curing agent compositions loaded into the two cartridges (2a, 2b), respectively, were pressurized with a TA (Texture analyzer) (3a, 3b) at a constant speed of 1 mm/s, and injected into the static mixer (5), and from the time when the main and curing agent compositions injected into the mixer (5) were mixed in the mixer (5) and first discharged from the discharge part (7), the force applied to the pressurizing means was measured and simultaneously, the force of the maximum value at the point where the force become the maximum value was designated as the load value (Li). That is, when the force applied to the TA is measured in the above manner, usually, the force continuously increases and then decreases, or it shows the tendency that the increased force no longer increases, where the load value is the maximum force before the decrease or the maximum force at the point that it no longer increases.

[0197] 3. Hardness Measurement of Solid Matter

[0198] The hardness of the solid matter of the resin composition was measured for the solid matter produced using a solid matter generating device (60) configured by combining a syringe and a filter as in FIG. 5.

[0199] In the solid matter generating device configured as in FIG. 5, as the syringe (61), a syringe including a resin injection part of a circle with a diameter of about 25 mm and a discharge part (62) of a circle with a diameter of about 8 mm, and having a height of about 80 mm and an internal volume of about 25 ml was used. In addition, as the filter (63), Whatman's PTEF filter (pore size: 0.45 μm, diameter: 13 mm) was used.

[0200] In the configuration as in FIG. 5, a TA (Texture analyzer) was applied as the pressurizing means (64). When the main resin compositions or the curing agent compositions prepared in Examples and Comparative Examples were each filled in the syringe (61), and a pressure of 5 bar was applied to the pressurizing means (64) for 16 hours, a solid matter of the resin composition was generated inside the discharge part (62) combined with the filter (63), and for the same, hardness was measured.

[0201] The solid matter generated inside the discharge part was collected to have a cylindrical shape with a diameter of about 2 mm and a height of about 2 mm, and for the same, hardness was measured. Specifically, when the collected solid matter was pressurized at a constant speed of 0.3 mm/s for the hardness of the solid matter, the force applied to the pressurizing means started to be measured from the time that the solid matter was pressurized, and the force (gf) applied to the pressurizing means at the time of elapsing about 0.5 seconds from the time of pressurization was obtained as the hardness of the solid matter. The TA (Texture analyzer) was used as the pressurizing means.

[0202] 4. Measurement of Average Particle Diameter

[0203] The average particle diameter of the filler mentioned in this specification is the D50 particle diameter of the filler, which is a particle diameter measured by Marvern's MASTERSIZER3000 equipment in accordance with ISO-13320 standard. Upon the measurement, ethanol was used as a solvent. The incident laser is scattered by the fillers dispersed in the solvent, and the values of the intensity and directionality of the scattered laser vary depending on the size of the filler, which are analyzed using the Mie theory, whereby the D50 particle diameter can be obtained. Through the above analysis, the distribution can be obtained through conversion to the diameter of a sphere having the same volume as the dispersed fillers, and the particle diameter can be evaluated by obtaining the D50 value, which is the median value of the distribution.

[0204] 5. Sphericity Evaluation of Filler

[0205] The sphericity of a filler, which is a three-dimensional particle, is defined as the ratio (S′/S) of the surface area (S) of the particle and the surface area (S′) of a sphere having the same volume as that of the particle, and for real particles, it is usually an average value of circularity.

[0206] The circularity is the ratio of the boundary (P) of the image obtained from the two-dimensional image of the particle and the boundary of a circle having the same image and the same area (A), which is theoretically obtained by the following equation, and a value from 0 to 1, where for an ideal circle, the circularity is 1.

Circularity=4 πA/P.sup.2  <Circularity Equation>

[0207] In this specification, the sphericity is an average value of circularity measured by Marvern's particle shape analysis equipment (FPIA-3000).

Example 1

[0208] A resin composition was prepared in a two-component type using the following materials.

[0209] The main resin was a caprolactone polyol represented by the following formula 2, wherein the number of repeating units (m in Formula 2) is at a level of about 1 to 3 or so, R.sub.1 and R.sub.2 are each alkylene having 4 carbon atoms, and as the polyol-derived unit (Y in Formula 3), a polyol containing a 1,4-butanediol unit was used.

##STR00002##

[0210] As a curing agent, polyisocyanate (HDI, hexamethylene diisocyanate) was used.

[0211] A filler component was prepared by mixing a first alumina filler (spherical, sphericity 0.95 or more) having an average particle diameter of about 70 μm, a second alumina filler (spherical, sphericity 0.95 or more) having an average particle diameter of about 20 μm and a third alumina filler (non-spherical, sphericity less than 0.9) having an average particle diameter of about 2 μm. The weight ratio at the time of mixing was 3:1:1 (first alumina filler: second alumina filler: third alumina filler) or so.

[0212] Therefore, the value of General Formula 1 above in the filler component is about 3, and the value of General Formula 2 above is about 1. In addition, when the total weight of the filler component is set to 100 weight %, the filler component comprises about 55 weight % of the alpha phase. The alpha phase was obtained by performing the XRD analysis on the filler component.

[0213] The main composition was prepared by uniformly mixing the main resin and the filler component with a planetary mixer. In addition, the curing agent composition was prepared by uniformly mixing the curing agent and the filler component with a planetary mixer.

[0214] Upon the preparation of the main and curing agent compositions, the main resin and the curing agent were used in an equivalent ratio of 1:1. The filler component in an amount such that about 87.6 parts by weight of the filler component was present in 100 parts by weight of the resin composition in which the main and curing agent compositions were mixed, was divided into two equal weights and blended into each of the main and curing agent compositions.

Example 2

[0215] As the filler component, a mixture of a first alumina filler (spherical, sphericity 0.95 or more) having an average particle diameter of about 70 μm, a second alumina filler (spherical, sphericity 0.95 or more) having an average particle diameter of about 20 μm and a third alumina filler (non-spherical, sphericity less than 0.9) having an average particle diameter of about 2 μm, wherein the weight ratio (first alumina filler: second alumina filler: third alumina filler) between the fillers was about 30:15:10, was used.

[0216] The value of General Formula 1 above for the filler component is about 2, and the value of General Formula 2 above is about 1.5. In addition, when the total weight of the filler component is set to 100 weight %, the filler component comprises about 55 weight % of the alpha phase. The alpha phase was obtained by performing the XRD analysis on the filler component.

[0217] The main and curing agent compositions were prepared in the same manner as in Example 1 using the filler component, except that the filler component in an amount such that about 88.7 parts by weight of the filler component was present in 100 parts by weight of the resin composition in which the main and curing agent compositions were mixed, was divided into two equal weights and blended into each of the main and curing agent compositions.

Example 3

[0218] As the filler component, a mixture of a first alumina filler (spherical, sphericity 0.95 or more) having an average particle diameter of about 70 μm, a second alumina filler (spherical, sphericity 0.95 or more) having an average particle diameter of about 20 μm and a third alumina filler (non-spherical, sphericity less than 0.9) having an average particle diameter of about 2 μm, wherein the weight ratio (first alumina filler: second alumina filler: third alumina filler) between the fillers was about 25:5:10, was used.

[0219] The value of General Formula 1 above for the filler component is about 5, and the value of General Formula 2 above is about 0.5. In addition, when the total weight of the filler component is set to 100 weight %, the filler component comprises about 55 weight % of the alpha phase. The alpha phase was obtained by performing the XRD analysis on the filler component.

[0220] The main and curing agent compositions were prepared in the same manner as in Example 1 using the filler component, except that the filler component in an amount such that about 88.7 parts by weight of the filler component was present in 100 parts by weight of the resin composition in which the main and curing agent compositions were mixed, was divided into two equal weights and blended into each of the main and curing agent compositions.

Example 4

[0221] As the filler component, a mixture of a first alumina filler (spherical, sphericity 0.95 or more) having an average particle diameter of about 65 μm, a second alumina filler (spherical, sphericity 0.95 or more) having an average particle diameter of about 20 μm and a third alumina filler (non-spherical, sphericity less than 0.9) having an average particle diameter of about 2 μm, wherein the weight ratio (first alumina filler: second alumina filler: third alumina filler) between the fillers was about 3:1:1, was used.

[0222] The value of General Formula 1 above for the filler component is about 3, and the value of General Formula 2 above is about 1. In addition, when the total weight of the filler component is set to 100 weight %, the filler component comprises about 55 weight % of the alpha phase. The alpha phase was obtained by performing the XRD analysis on the filler component.

[0223] The main and curing agent compositions were prepared in the same manner as in Example 1 using the filler component, except that the filler component in an amount such that about 88.7 parts by weight of the filler component was present in 100 parts by weight of the resin composition in which the main and curing agent compositions were mixed, was divided into two equal weights and blended into each of the main and curing agent compositions.

Example 5

[0224] As the filler component, a mixture of a first alumina filler (spherical, sphericity 0.95 or more) having an average particle diameter of about 120 μm, a second alumina filler (spherical, sphericity 0.95 or more) having an average particle diameter of about 20 μm and a third alumina filler (non-spherical, sphericity less than 0.9) having an average particle diameter of about 2 μm, wherein the weight ratio (first alumina filler: second alumina filler: third alumina filler) between the fillers was about 3:1:1, was used.

[0225] The value of General Formula 1 above for the filler component is about 3, and the value of General Formula 2 above is about 1. In addition, when the total weight of the filler component is set to 100 weight %, the filler component comprises about 55 weight % of the alpha phase. The alpha phase was obtained by performing the XRD analysis on the filler component.

[0226] The main and curing agent compositions were prepared in the same manner as in Example 1 using the filler component, except that the filler component in an amount such that about 88.7 parts by weight of the filler component was present in 100 parts by weight of the resin composition in which the main and curing agent compositions were mixed, was divided into two equal weights and blended into each of the main and curing agent compositions.

Comparative Example 1

[0227] As the filler component, a mixture of a first alumina filler having an average particle diameter of about 70 μm, a second alumina filler having an average particle diameter of about 20 μm and a third alumina filler having an average particle diameter of about 2 μm, wherein the weight ratio (first alumina filler: second alumina filler: third alumina filler) between the fillers was about 13:10:10, was used.

[0228] The value of General Formula 1 above for the filler component is about 1.3, and the value of General Formula 2 above is about 1.

[0229] The main and curing agent compositions were prepared in the same manner as in Example 1 using the filler component, except that the filler component in an amount such that about 88.7 parts by weight of the filler component was present in 100 parts by weight of the resin composition in which the main and curing agent compositions were mixed, was divided into two equal weights and blended into each of the main and curing agent compositions.

Comparative Example 2

[0230] As the filler component, a mixture of a first alumina filler having an average particle diameter of about 70 μm, a second alumina filler having an average particle diameter of about 20 μm and a third alumina filler having an average particle diameter of about 2 μm, wherein the weight ratio (first alumina filler: second alumina filler: third alumina filler) between the fillers was about 12:4:10, was used.

[0231] The value of General Formula 1 above for the filler component is about 3, and the value of General Formula 2 above is about 0.4.

[0232] The main and curing agent compositions were prepared in the same manner as in Example 1 using the filler component, except that the filler component in an amount such that about 88.7 parts by weight of the filler component was present in 100 parts by weight of the resin composition in which the main and curing agent compositions were mixed, was divided into two equal weights and blended into each of the main and curing agent compositions.

Comparative Example 3

[0233] As the filler component, a mixture of a first alumina filler having an average particle diameter of about 40 μm, a second alumina filler having an average particle diameter of about 20 μm and a third alumina filler having an average particle diameter of about 2 μm, wherein the weight ratio (first alumina filler: second alumina filler: third alumina filler) between the fillers was about 3:1:1, was used.

[0234] The value of General Formula 1 above for the filler component is about 3, and the value of General Formula 2 above is about 1.

[0235] The main and curing agent compositions were prepared in the same manner as in Example 1 using the filler component, except that the filler component in an amount such that about 86.7 parts by weight of the filler component was present in 100 parts by weight of the resin composition in which the main and curing agent compositions were mixed, was divided into two equal weights and blended into each of the main and curing agent compositions.

Comparative Example 4

[0236] As the filler component, a mixture of a first alumina filler having an average particle diameter of about 40 μm, a second alumina filler having an average particle diameter of about 20 μm and a third alumina filler having an average particle diameter of about 2 μm, wherein the weight ratio (first alumina filler: second alumina filler: third alumina filler) between the fillers was about 13:10:10, was used.

[0237] The value of General Formula 1 above for the filler component is about 1.3, and the value of General Formula 2 above is about 1.

[0238] The main and curing agent compositions were prepared in the same manner as in Example 1 using the filler component, except that the filler component in an amount such that about 86.7 parts by weight of the filler component was present in 100 parts by weight of the resin composition in which the main and curing agent compositions were mixed, was divided into two equal weights and blended into each of the main and curing agent compositions.

Comparative Example 5

[0239] As the filler component, a mixture of a first alumina filler having an average particle diameter of about 70 μm and a third alumina filler having an average particle diameter of about 2 μm, wherein the weight ratio (first alumina filler: third alumina filler) between the fillers was about 7:3, was used.

[0240] The main and curing agent compositions were prepared in the same manner as in Example 1 using the filler component, except that the filler component in an amount such that about 87.6 parts by weight of the filler component was present in 100 parts by weight of the resin composition in which the main and curing agent compositions were mixed, was divided into two equal weights and blended into each of the main and curing agent compositions.

[0241] Physical properties measured for the resin compositions were summarized and described in Table 1 below.

TABLE-US-00001 TABLE 1 Average particle Solid matter diameter (μm) Thermal Load hardness (gf) First Second Third conductivity value Main Curing filler filler filler W.sub.A/W.sub.B W.sub.B/W.sub.C (W/mK) (kgf) agent agent Example 1 70 20 2 3 1 3.1 about 25 50 43 2 70 20 2 2 1.5 3.0 about 22 50 50 3 70 20 2 5 0.5 3.0 about 25 65 70 4 65 20 2 3 1 3.2 about 25 50 50 5 120 20 2 3 1 3.2 about 25 40 40 Comparative 1 70 20 2 1.3 1 3.0 about 25 47 139 Example 2 70 20 2 3 0.4 3.0 about 30 300 400 3 40 20 2 3 1 3.0 about 30 250 300 4 40 20 2 1.3 1 3.1 about 30 323 458 5 70 — 2 — — 3.1 about 50 50 43 W.sub.A: weight ratio (weight %) of the first filler in the component (based on 100 weight % of the total of the first to third fillers) W.sub.B: weight ratio (weight %) of the second filler in the filler component (based on 100 weight % of the total of the first to third fillers) W.sub.C: weight ratio (weight %) of the third filler in the filler component (based on 100 weight % of the total of the first to third fillers)

[0242] From Table 1, it could be seen that the resin compositions of Examples 1 to 5 comprising the filler component satisfying all the average particle diameters of the fillers and General Formulas 1 and 2 exhibited the high thermal conductivity and low load value, and the hardness of solid matters generated in the main and curing agent compositions was also maintained at a low level. On the other hand, in the case of Comparative Example 1, which did not satisfy the condition of General Formula 1, the hardness of the solid content in the curing agent was high, whereby it was confirmed that it could overload the equipment in the injection process.

[0243] In Comparative Example 2, which did not satisfy the condition of General Formula 2, the high thermal conductivity was ensured, but the load value was large, and the hardness of the main and curing agent compositions was also high.

[0244] In Comparative Example 3, which did not satisfy the particle diameter condition of the filler component, Comparative Example 4, which did not satisfy the particle diameter condition and the condition of General Formula 1, and Comparative Example 5, which included only two fillers as the fillers, the thermal conductivity was secured to some extent, but the load value and/or the hardness of the solid content showed poor results.