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 two or more fillers having different average particle diameters from each other, wherein the resin composition has a load value of less than 35 kgf, and wherein the resin composition has a thermal conductivity of 3.0 W/mK or more after being cured.

2. The resin composition according to claim 1, wherein it-the resin composition satisfies the following general formula 1:
25≤D.sub.50A/D.sub.50C≤300   [General Formula 1] wherein, D.sub.50A is a maximum average particle diameter of the fillers in the filler component, and the D.sub.50C is a minimum average particle diameter of the fillers in the filler component.

3. The resin composition according to claim 2, wherein the maximum average particle diameter (D.sub.50A) of the filler component is in a range of 60 μm to 200 μm.

4. The resin composition according to claim 2, wherein the minimum average particle diameter (D.sub.50C) of the filler component is in a range of 0.2 μm to 5 μm.

5. The resin composition according to claim 1, wherein the filler component comprises three fillers having different average particle diameters from each other.

6. The resin composition according to claim 1, wherein the two or more fillers of the filler component comprises: a first filler having an average particle diameter in the a range of 60 μm to 120 μm; a second filler having an average particle diameter of more than 5 μm and 40 μm or less; and a third filler having an average particle diameter in the a range of 0.2 μm to 5 μm.

7. The resin composition according to claim 1, wherein it-the resin composition comprises 91 weight % or less of the filler component.

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

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

10. The resin composition according to claim 1, wherein the filler component comprises fumed silica, clay, calcium carbonate (CaCO.sub.3), 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.

11. The resin composition according to claim 1, wherein the resin component is a polyol, an isocyanate compound, a urethane resin, an acrylic resin, an epoxy resin, an olefin resin or a silicone resin.

12. 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 which is a cured product of the resin composition according to claim 1, in contact with at least one of the plurality of battery cells and the bottom plate or the sidewalls.

13. A battery pack, comprising two or more battery modules of claim 12, wherein the battery modules are electrically connected to each other.

14. An automobile, comprising the battery module of claim 12.

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

Description

DESCRIPTION OF DRAWINGS

[0167] FIG. 1 is a diagram for exemplarily explaining a process of injecting a resin composition.

[0168] FIG. 2 shows an exemplary mixing machine, which can be applied in the present application.

[0169] FIG. 3 shows an exemplary module case, which can be applied in the present application.

[0170] FIG. 4 schematically shows a form in which battery cells are housed in a module case.

Explanation of Reference Numerals

[0171] 1: mixing machine

[0172] 2, 2a, 2b: cartridge

[0173] 3, 3a, 3b: pressurizing means

[0174] 4, 4a, 4b: first discharge part

[0175] 5: mixer

[0176] 6, 6a, 6b: receiving part

[0177] 7: second discharge part

[0178] 10: module case

[0179] 10a: bottom plate

[0180] 10b: sidewall

[0181] 10c: top plate

[0182] 20, 40: battery cell

[0183] 30: injection equipment

[0184] 20: inlet

MODE FOR INVENTION

[0185] Hereinafter, the present application will be described in detail through Examples, but the scope of the present application is not limited by Examples below.

[0186] 1. Evaluation of Thermal Conductivity

[0187] 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.

[0188] 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.

[0189] 2. Measurement of Load Value

[0190] 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.

[0191] 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.

[0192] 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.

[0193] 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).

[0194] 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.

[0195] 3. Measurement of Average Particle Diameter

[0196] 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.

[0197] 5. Sphericity Evaluation of Filler

[0198] 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.

[0199] 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.

[0200] <Circularity Equation>

Circularity=4πA/P.sup.2

[0201] In this specification, the sphericity is an average value of circularity measured by Marvern's particle shape analysis equipment (FPIA-3000).

Example 1

[0202] A resin composition was prepared in a two-component type using the following materials.

[0203] 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##

[0204] In addition, polyisocyanate (HDI, hexamethylene diisocyanate) was used as a curing agent.

[0205] As the filler component, a mixture obtained by mixing a first alumina filler (spherical, sphericity 0.95 or more) having an average particle diameter of about 70 μm or so, a second alumina filler (spherical, sphericity 0.95 or more) having an average particle diameter of about 20 μm or so and a third alumina filler (non-spherical, sphericity less than 0.9) having an average particle diameter of about 2 μm in a weight ratio of 4:3:3 (first alumina filler: second alumina filler: third alumina filler) was used.

[0206] Therefore, the ratio (D.sub.50A/D.sub.50C) of the maximum average particle diameter (D.sub.50A) to the minimum average particle diameter (D.sub.50C) in the filler component is about 35. 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.

[0207] 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.

[0208] 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 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.

Example 2

[0209] Main and curing agent compositions were prepared in the same manner as in Example 1, except that as the filler component, a first alumina filler (spherical, sphericity of 0.95 or more) having an average particle diameter of about 120 μm, a second alumina filler (spherical, sphericity of 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 1 μm were mixed in a weight ratio of 4:3:3 (first alumina filler: second alumina filler: third alumina filler) and used.

[0210] The ratio (D.sub.50A/D.sub.50C) of the maximum average particle diameter (D.sub.50A) to the minimum average particle diameter (D.sub.50C) in the filler component was about 120, and when the total weight of the filler component was set to 100 weight %, the ratio of the alpha phase was about 55 weight %. The alpha phase was obtained by performing the XRD analysis on the filler component.

Example 3

[0211] Main and curing agent compositions were prepared in the same manner as in Example 1, except that as the filler component, a first alumina filler (spherical, sphericity of 0.95 or more) having an average particle diameter of about 75 μm, a second alumina filler (spherical, sphericity of 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 0.5 μm were mixed in a weight ratio of 4:3:3 (first alumina filler: second alumina filler: third alumina filler) and used.

[0212] The ratio (D.sub.50A/D.sub.50C) of the maximum average particle diameter (D.sub.50A) to the minimum average particle diameter (D.sub.50C) in the filler component is about 150. In addition, when the total weight of the filler component was set to 100 weight %, the alpha phase was present in a ratio of about 55 weight %. The alpha phase was obtained by performing the XRD analysis on the filler component.

Example 4

[0213] Main and curing agent compositions were prepared in the same manner as in Example 1, except that as the filler component, a first alumina filler (spherical, sphericity of 0.95 or more) having an average particle diameter of about 65 μm, a second alumina filler (spherical, sphericity of 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 1 μm were mixed in a weight ratio of 4:3:3 (first alumina filler: second alumina filler: third alumina filler) and used. The ratio (D.sub.50A/D.sub.50C) of the maximum average particle diameter (D.sub.50A) to the minimum average particle diameter (D.sub.50C) in the filler component is about 65. When the total weight of the filler component was set to 100 weight %, the alpha phase was included in a ratio of about 55 weight %. The alpha phase was obtained by performing the XRD analysis on the filler component.

Example 5

[0214] Main and curing agent compositions were prepared in the same manner as in Example 1, except that as the filler component, a first alumina filler (spherical, sphericity of 0.95 or more) having an average particle diameter of about 120 μm, a second alumina filler (spherical, sphericity of 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 0.5 μm were mixed in a weight ratio of 4:3:3 (first alumina filler: second alumina filler: third alumina filler) and used.

[0215] The ratio (D.sub.50A/D.sub.50C) of the maximum average particle diameter (D.sub.50A) to the minimum average particle diameter (D.sub.50C) in the filler component is about 240. When the total weight of the filler component is set to 100 weight %, the alpha phase is present in the filler component in a ratio of about 55 weight %. The alpha phase was obtained by performing the XRD analysis on the filler component.

Example 6

[0216] Main and curing agent compositions were prepared in the same manner as in Example 1, except that as the filler component, a first alumina filler (spherical, sphericity of 0.95 or more) having an average particle diameter of about 70 μm, a second alumina filler (spherical, sphericity of 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 were mixed in a weight ratio of 4:3:3 (first alumina filler: second alumina filler: third alumina filler) and used.

[0217] The ratio (D.sub.50A/D.sub.50C) of the maximum average particle diameter (D.sub.50A) to the minimum average particle diameter (D.sub.50C) in the filler component is about 35. In addition, when the total weight of the filler component is set to 100 weight %, the ratio of the alpha phase is about 45 weight %. The alpha phase was obtained by performing the XRD analysis on the filler component.

Example 7

[0218] Main and curing agent compositions were prepared in the same manner as in Example 1, except that as the filler component, a first alumina filler (spherical, sphericity of 0.95 or more) having an average particle diameter of about 70 μm, a second alumina filler (spherical, sphericity of 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 were mixed in a weight ratio of 4:3:3 (first alumina filler: second alumina filler: third alumina filler) and used.

[0219] The ratio (D.sub.50A/D.sub.50C) of the maximum average particle diameter (D.sub.50A) to the minimum average particle diameter (D.sub.50C) in the filler component is about 35. In addition, when the total weight of the filler component is set to 100 weight %, the ratio of the alpha phase is about 65 weight %. The alpha phase was obtained by performing the XRD analysis on the filler component.

Comparative Example 1

[0220] Main and curing agent compositions were prepared in the same manner as in Example 1, except that as the filler component, 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 2μm were mixed in a weight ratio of 4:3:3 (first alumina filler: second alumina filler: third alumina filler) and used.

[0221] The ratio (D.sub.50A/D.sub.50C) of the maximum average particle diameter (D.sub.50A) to the minimum average particle diameter (D.sub.50C) in the filler component is about 20. In addition, the alpha phase is about 55 weight % based on 100 weight % of the total filler component.

Comparative Example 2

[0222] Main and curing agent compositions were prepared in the same manner as in Example 1, except that using the filler component of Comparative Example 2, the amount of the filler component was adjusted so that about 88.6 parts by weight was present in 100 parts by weight of the resin composition in which the main and curing agent compositions were mixed, and this filler component was divided into two equal weights and blended into each of the main and curing agent compositions.

Comparative Example 3

[0223] As the filler component, a first alumina filler (spherical, sphericity 0.9 or more) having an average particle diameter of about 70 μm, a second alumina filler (spherical, sphericity 0.9 or more) having an average particle diameter of about 20 μm and a third alumina filler (spherical, sphericity 0.9 or more) having an average particle diameter of about 2 μm were mixed in a weight ratio of 4:3:3 (first alumina filler: second alumina filler: third alumina filler) and used. The ratio (D.sub.50A/D.sub.50C) of the maximum average particle diameter (D50A) to the minimum average particle diameter (D.sub.50C) in the filler component is about 35. When the total weight of the filler component was set to 100 weight %, the alpha phase was included in about 35 weight %.

[0224] Main and curing agent compositions were prepared in the same manner as in Example 1, except that the filler component was used.

[0225] The results of measuring thermal conductivities and load values using the compositions of Examples and Comparative Examples are as shown in Table 1 below.

TABLE-US-00001 TABLE 1 Average particle diameter (μm) Alpha Thermal Load First Second Third phase conductivity value filler filler filler D.sub.50A/D.sub.50C (weight %) (W/mK) (kgf) Example 1 70 20 2 35 55 3.0 25 2 120 20 1 120 55 3.1 24 3 70 20 0.5 140 55 3.0 25 4 65 20 1 65 55 3.0 29 5 120 20 0.5 240 55 3.1 24 6 70 20 2 35 45 3.0 25 7 70 20 2 35 65 3.1 25 Comparative 1 40 20 2 20 55 2.8 31 Example 2 40 20 2 20 55 3.1 38 3 70 20 2 35 35 2.8 25 D.sub.50A: maximum average particle diameter (=average particle diameter of first filler) D.sub.50C: minimum average particle diameter (=average particle diameter of third filler)

[0226] As described in Table 1 above, all of the resin compositions of Examples were cured and exhibited a high thermal conductivity of 3.0 W/mK or more and simultaneously a low load value. In the case of the resin composition of Comparative Example 1, the maximum average particle size was small, and accordingly, even when the same amount of filler component as in Example was included, the thermal conductivity was low and the load value was high.

[0227] In the case of Comparative Example 2, the thermal conductivity was increased due to an increase in the content of the filler component, but the load value was significantly increased than that of Comparative Example 1. In Comparative Example 3, the ratio of the alpha phase was small, so that the thermal conductivity of 3.0 W/mK or more could not be ensured.