KR20220043766A - resin composition - Google Patents

Abstract

The application provides a resin composition which exhibits adequate viscosity, thixotropy, and/or thermal conductivity before and after curing and exhibits adequate adhesion to effectively maintain a plurality of battery modules before and after curing and re-workability to enable separation and reattachment of modules during an assembly process of a battery pack.

Description

resin composition

This application relates to a resin composition.

Thermal interface material (TIM) refers to any material interposed between two components to improve the thermal coupling between them. In general, a thermal interface material is used as a heat dissipation material. Among these heat dissipating materials, a resin composition in which a thermally conductive filler is blended with resin is known, and Patent Document 1 is known for a battery module to which a resin composition is applied.

Thermal interface materials may sometimes require low adhesion and room temperature hardenability.

A resin having such physical properties is, for example, a silicone resin. Silicone resin is mainly used as a heat dissipation material due to its low adhesive strength and room temperature curability and excellent heat resistance. However, when low molecular weight siloxane is used, there is a problem in that VOC (volatile organic compound) is pressed to the electrode and causes contact defects.

As an alternative to the poor contact problem, a urethane resin or an epoxy resin may be considered. However, both the urethane resin and the epoxy resin have high adhesion, and the epoxy resin has a problem that it takes a long time to cure at room temperature.

Republic of Korea Patent Publication No. 10-2016-0105354

The present application is to provide a resin composition as a thermal interface material that requires room temperature curing and has low adhesion (especially for PET interfaces).

An object of the present application is to provide a resin composition exhibiting an appropriate viscosity, thixotropy, and/or thermal conductivity before and after curing.

The present application relates to a resin composition that exhibits adequate adhesion to effectively maintain a plurality of battery modules before and after curing and re-workability to enable separation and reattachment of modules during the assembly process of a battery pack at the same time is intended to provide

Another object of the present application is to provide a resin composition that exhibits room temperature curability and rapid curability even with an excessive amount of filler.

The present application relates to a resin composition that requires room temperature curing and is a thermal interface material having low adhesion (especially, low adhesion to PET interface).

In the present application, a thiourethane reaction may be used as the resin composition, and a urethane reaction may be used in addition thereto. In this case, the main part including the polyfunctional thiol compound and the like and the curing agent part including the isocyanate compound may react at room temperature to be cured. That is, the resin composition of the present application may be a room temperature curing type.

The term "room temperature" used in this application is a temperature in a natural state that is not specially heated or reduced, and any one temperature within the range of about 10 ℃ to 30 ℃, for example, about 15 ℃ or more, about 18 ℃ or more, It may mean a temperature of about 20 °C or higher, or about 23 °C or higher, and about 27 °C or lower.

In an example of the present application, the resin composition is a one-component type in which the curing reaction occurs when the main part, the curing agent part, and a compound that inhibits their curing are mixed and certain conditions (eg, temperature and UV irradiation) are satisfied. It may be a composition.

In an example of the present application, the resin composition may be a two-component composition in which the main part and the curing agent are mixed without mixing, and the curing reaction is performed with the help of a catalyst or the like.

In an example of the present application, the resin composition may include a filler. For example, in order to secure thixotropy as needed in the process, and/or to ensure heat dissipation (thermal conductivity) within a battery module or battery pack, the composition of the present application contains an excess of filler as described below. may be included. When an excessive amount of filler is used, the viscosity of the composition increases and the processability of injecting the composition into the case of the battery module may deteriorate. Therefore, while containing an excess of filler, sufficient low-viscosity properties are required so as not to interfere with processability. In addition, if only low viscosity is shown, appropriate thixotropy is required because it is also difficult to secure fairness, and while curing, it may exhibit an appropriate desired adhesive strength, and curing itself may be required to proceed at room temperature.

Unless otherwise stated, the term alkyl group or alkylene group used in the present application has 1 to 20 carbon atoms, or 1 to 16 carbon atoms, or 1 to 12 carbon atoms, or 1 to 8 carbon atoms, or a straight chain or branched chain having 1 to 6 carbon atoms. A chain acyclic alkyl group or alkylene group, or a cyclic alkyl group or alkylene group having 3 to 20 carbon atoms, or 3 to 16 carbon atoms, or 3 to 12 carbon atoms, or 3 to 8 carbon atoms, or 3 to 6 carbon atoms, or an alkylene group, or a combination thereof It may be a saturated hydrocarbon group.

The term alkenyl group or alkenylene group used in the present application, unless otherwise specified, has 2 to 20 carbon atoms, or 2 to 16 carbon atoms, or 2 to 12 carbon atoms, or 2 to 8 carbon atoms, or 2 to 6 carbon atoms straight chain or branched. an acyclic alkenyl group or an alkenylene group in the chain; It may be a cyclic alkenyl group or alkenylene group having 3 to 20 carbon atoms, or 3 to 16 carbon atoms, or 3 to 12 carbon atoms, or 3 to 8 carbon atoms, or 3 to 6 carbon atoms, or an unsaturated hydrocarbon group to which they are bonded.

Unless otherwise stated, the alkynyl group or alkynylene group as used in the present application has 2 to 20 carbon atoms, or 2 to 16 carbon atoms, or 2 to 12 carbon atoms, or 2 to 8 carbon atoms, or 2 to 6 carbon atoms straight or branched. A chain alkynyl group or alkynylene group, or a cyclic alkynyl group or alkynyl group having 3 to 20 carbon atoms, or 3 to 16 carbon atoms, or 3 to 12 carbon atoms, or 3 to 8 carbon atoms, or 3 to 6 carbon atoms It may be a lene group or an unsaturated hydrocarbon group to which they are bonded.

An aryl group as a term used in the present application may mean an aromatic ring in which one hydrogen is removed from an aromatic hydrocarbon ring unless otherwise specified. The aryl group may be monocyclic or polycyclic.

The term heteroaryl group used in the present application, unless otherwise stated, as an atom forming a ring may mean a substituent including an aromatic ring containing one or more hetero atoms (eg, N, O, S, etc.) there is. The heteroaryl group may be monocyclic or polycyclic.

The alkyl group, alkylene group, alkenyl group, alkenylene group, alkynyl group, alkynylene group, aryl group or heteroaryl group may be optionally substituted with one or more substituents. In this case, as the substituent, halogen (chloro (Cl), iodine (I), bromo (Br), fluorine (F)), alkyl group, alkenyl group, alkynyl group, aryl group, heteroaryl group, ether group, carbonyl group , may be at least one selected from the group consisting of a carboxyl group and a hydroxyl group, but is not limited thereto.

Thermal conductivity, a term used in this application, is ASTM D5470 standard or ISO 22007-2 along the thickness direction of the sample in a state in which the resin composition is prepared as a sample (hardened product) having a diameter of 2 cm or more and a thickness of 4 mm. When measured according to the standard, it may mean a case of showing thermal conductivity of about 2.5 W/m·K or more.

In another example, the thermal conductivity may be about 2.6 W/m·K or more, 2.7 W/m·K or more, 2.8 W/m·K or more, 2.9 W/m·K or more, or 3.0 W/m·K or more. Since the higher the thermal conductivity, the higher the thermal conductivity, the upper limit thereof is not particularly limited. For example, the thermal conductivity is 20 W/m·K or less, 18 W/m·K or less, 16 W/m·K or less, 14 W/m·K or less, 12 W/m·K or less, 10 W /m·K or less, 8 W/m·K or less, 6 W/m·K or less, or 4 W/m·K or less.

The present application may provide a curable composition included in the main part of the resin composition. The curable composition according to the present application may include a polyfunctional thiol compound and a filler. By using the polyfunctional thiol compound, the curable composition according to the present application can form a cured product that can be cured at room temperature and shows a suitably low adhesion to ensure reworkability.

In the polyfunctional thiol compound according to the present application, "polyfunctional" means a compound containing two or more thiol groups (-SH), and is not particularly limited as long as there are two or more thiol groups at the end of the molecular structure. In another example, the "polyfunctional" may mean a compound including a thiol group (-SH) in the range of 2 to 10.

The polyfunctional thiol compound according to the present application may be a compound including two or more substituents of Formula 3 below. In addition, the polyfunctional thiol compound according to the present application may include 3 or more, 4 or more, or 5 or more substituents of Formula 3 below, and the polyfunctional thiol compound includes 10 or less substituents of Formula 3 below, 9 It may include no more than 8, 7 or less, or 6 or less.

In another example, the polyfunctional thiol compound according to the present application is an alkane having 1 to 20 carbon atoms, an alkene having 2 to 20 carbon atoms, or It may be an alkyne having 2 to 20 carbon atoms. In another example, the polyfunctional thiol compound is an alkane having 1 to 20 carbon atoms and 2 to 20 carbon atoms substituted with 10 or less, 9 or less, 8 or less, 7 or less, or 6 or less substituents of the following Chemical Formula 3 of an alkene or an alkyne having 2 to 20 carbon atoms. The carbon number of the alkane may be 1 to 16, 1 to 12, 1 to 8, 1 to 4, or 1 to 2, and the carbon number of the alkene and the alkyne is 2 to 16, 2 to 12, 2 to 8, 2 to 4 Or it may be 2-3.

[Formula 3]

In Formula 3, in Formula 3, L ₁ may be an alkylene group having 1 to 20 carbon atoms, an alkenylene group having 2 to 20 carbon atoms, or an alkynylene group having 2 to 20 carbon atoms. In order to form a cured product having an appropriate adhesive strength, L ₁ is preferably an alkylene group having 1 to 4 carbon atoms.

In Formula 3, Q may be a single bond, a carbonyl group, an ester group, or an amide group. In order to form a cured product having an appropriate adhesive strength, in addition to L ₁ , Q is preferably an ester group or a carbonyl group.

In Formula 3, L ₂ may be a single bond, an alkylene group having 1 to 20 carbon atoms, an alkenylene group having 2 to 20 carbon atoms, or an alkynylene group having 2 to 20 carbon atoms.

In Formula 3, "*" means a bond.

The polyfunctional thiol compound according to the present application has a molecular weight of 200 g/mol or more, 225 g/mol or more, 250 g/mol or more, 275 g/mol or more, 300 g/mol or more, 325 g/mol or more, 350 g/mol or more. It may be mol or more or 375 g/mol or more, and the polyfunctional thiol compound has a molecular weight of 600 g/mol or less, 575 g/mol or less, 550 g/mol or less, 525 g/mol or less, 500 g/mol or less, 475 g/mol or less, 450 g/mol or less, 425 g/mol or less, or 400 g/mol or less. The polyfunctional thiol compound according to the present application may include a substituent of Formula 3 in the range satisfying the molecular weight.

The curable composition according to the present application may include 5 parts by weight or more of the polyfunctional thiol compound based on 100 parts by weight of the filler. In another example, the curable composition may include 7 parts by weight or more or 9 parts by weight or more of the polyfunctional thiol compound based on 100 parts by weight of the filler.

The filler may be a thermally conductive filler, and the thermally conductive filler is a filler capable of forming a cured product having thermal conductivity as described above.

The thermal conductivity of the thermally conductive filler itself may be, for example, about 1 W/mK or more, about 5 W/mK or more, about 10 W/mK or more, or about 15 W/mK or more. In another example, the thermal conductivity of the thermally conductive filler itself may be, for example, about 400 W/mK or less, about 350 W/mK or less, or about 300 W/mK or less.

Examples of the thermally conductive filler include oxides such as aluminum oxide (alumina), magnesium oxide, beryllium oxide or titanium oxide; nitrides such as boron nitride, silicon nitride or aluminum nitride, and carbides such as silicon carbide; Hydrated metals, such as aluminum hydroxide or magnesium hydroxide, Metal fillers, such as copper, silver, iron, aluminum, or nickel; metal alloy fillers such as titanium; It may be a silicon powder such as quartz, glass or silica, but is not limited thereto.

In addition, if insulating properties can be secured, application of a carbon filler such as graphite may be considered. For example, the carbon filler may use activated carbon. The form or ratio of the filler included in the cured product is not particularly limited, and is selected in consideration of the viscosity of the curable composition, the possibility of sedimentation in the cured product, desired thermal resistance or thermal conductivity, insulation, filling effect or dispersibility, etc. can be

The shape of the thermally conductive filler may be appropriately selected from spherical and/or non-spherical (eg, needle-shaped and plate-shaped, etc.) as needed, and is not limited thereto.

The thermally conductive filler can use 1 type(s) or 2 or more types suitably selected as needed. In addition, even if the same type of thermally conductive filler is used, different shapes may be mixed and used, or those having different average particle diameters may be mixed and used. For example, aluminum hydroxide, aluminum, and alumina may be mixed and used as a thermally conductive filler, and their shapes and average particle diameters may be different from each other.

In general, the smaller the size of the thermally conductive filler, the higher the viscosity of the curable composition and the higher the likelihood that the thermally conductive filler will settle in the cured product of the curable composition. In addition, as the size of the filler increases, the thermal resistance tends to increase. Therefore, an appropriate type of filler may be selected in consideration of the above points, and if necessary, two or more types of fillers may be used.

In addition, it is advantageous to use a spherical thermally conductive filler in consideration of the amount to be filled, but a thermally conductive filler in a form such as a needle-shaped or plate-shaped filler in consideration of network formation or conductivity may also be used.

In one example, the curable composition may include a thermally conductive filler having an average particle diameter in the range of 0.001 μm to 80 μm. The average particle diameter of the thermally conductive filler may be 0.01 μm or more, 0.1 or more, 0.5 μm or more, 1 μm or more, 2 μm or more, 3 μm or more, 4 μm or more, 5 μm or more, or about 6 μm or more in another example. In another example, the average particle diameter of the thermally conductive filler is about 75 μm or less, about 70 μm or less, about 65 μm or less, about 60 μm or less, about 55 μm or less, about 50 μm or less, about 45 μm or less, about 40 μm or less , about 35 μm or less, about 30 μm or less, about 25 μm or less, about 20 μm or less, about 15 μm or less, about 10 μm or less, or about 5 μm or less.

In this case, the average particle diameter of the thermally conductive filler is a so-called D50 particle diameter (median particle diameter), and may mean a particle diameter at 50% cumulative by volume of the particle size distribution. That is, the particle size distribution is obtained on the basis of the volume, and the average particle diameter can be viewed as the particle diameter at the point where the cumulative value becomes 50% on the cumulative curve with 100% of the total volume. The D50 particle size as described above may be measured by a laser diffraction method.

According to the size of the thermally conductive filler, it can be divided into a large thermally conductive filler, a medium thermally conductive filler, and a small thermally conductive filler. The large thermally conductive filler may have an average particle diameter of 80 μm or less, 78 μm or less, 76 μm or less, 74 μm or less, or 72 μm or less. In another example, the large thermally conductive filler may have an average particle diameter of at least 60 μm, at least 62 μm, at least 64 μm, at least 66 μm, or at least 68 μm. The medium-sized thermally conductive filler may have an average particle diameter of 58 μm or less, 50 μm or less, 40 μm or less, or 25 μm or less. In another example, the medium-sized thermally conductive filler may have an average particle diameter of 10 μm or more, 12.5 μm or more, 15 μm or more, or 17.5 μm or more. The small thermally conductive filler may have an average particle diameter of 9 μm or less, 5 μm or less, or 3 μm or less. In another example, the small thermally conductive filler may have an average particle diameter of 0.001 μm or more, 0.01 μm or more, 0.05 μm or more, 0.1 μm or more, 0.2 μm or more, 0.4 μm or more, 0.8 μm or more, or 1 μm or more.

The thermally conductive filler may be used by selecting two or more of a large thermally conductive filler, a medium thermally conductive filler, and a small thermally conductive filler. In this case, the thermally conductive filler may satisfy the content ratio and/or particle size ratio within the following ranges so as to ensure fast curing at room temperature through an appropriate combination with each component included in the curable composition of the present application.

When the thermally conductive filler includes a large thermally conductive filler, the content of the large thermally conductive filler is 30% by weight or more, 37.5% by weight or more, 42.5% by weight or more, 47.5% by weight or more, 50% by weight relative to the total weight of the thermally conductive filler or more, 52.5 wt% or more, 55 wt% or more, or 57.5 wt% or more. In another example, the content of the large thermally conductive filler is 87.5% by weight or less, 80% by weight or less, 75% by weight or less, 72.5% by weight or less, 70% by weight or less, 67.5% by weight or less, 65% by weight or less, based on the total weight of the thermally conductive filler % or less or 62.5 wt% or less. Moreover, it is preferable that a large sized thermally conductive filler is a spherical particle.

When the thermally conductive filler includes a medium thermally conductive filler, the content of the medium thermally conductive filler is 5% by weight or more, 10% by weight or more, 12% by weight or more, 14% by weight or more, 16% by weight or more, based on the total weight of the thermally conductive filler or more, 18 wt% or more, or 20 wt% or more. In another example, the content of the medium-sized thermally conductive filler is 52.5% by weight or less, 50% by weight or less, 45% by weight or less, 40% by weight or less, 36% by weight or less, 32% by weight or less, 28% by weight or less, based on the total weight of the thermally conductive filler % or less, 24 wt% or less, or 20 wt% or less. Moreover, it is preferable that a medium-sized thermally conductive filler is a spherical particle.

When the thermally conductive filler includes a small thermally conductive filler, the content of the small thermally conductive filler is 5% by weight or more, 10% by weight or more, 12% by weight or more, 14% by weight or more, 16% by weight of the total weight of the thermally conductive filler or more, 18 wt% or more, or 20 wt% or more. In another example, the content of the small thermally conductive filler is 52.5% by weight or less, 50% by weight or less, 45% by weight or less, 40% by weight or less, 36% by weight or less, 32% by weight or less, 28% by weight or less, based on the total weight of the thermally conductive filler % or less, 24 wt% or less, or 20 wt% or less. In addition, it is preferable that the small-sized thermally conductive fillers are non-spherical (square-shaped, etc.) particles.

When the thermally conductive filler includes a large thermally conductive filler and a medium thermally conductive filler, the content of the medium thermally conductive filler is 25 parts by weight compared to 100 parts by weight of the large thermally conductive filler, considering the room temperature rapid curing of the curable composition according to the present application It is preferable that at least 26 parts by weight, at least 27 parts by weight, at least 28 parts by weight, at least 29 parts by weight, or at least 30 parts by weight. In another example, considering the room temperature rapid curing of the curable composition according to the present application, the content of the medium-sized thermally conductive filler is 45 parts by weight or less, 42.5 parts by weight or less, 40 parts by weight or less, 37.5 parts by weight compared to 100 parts by weight of the large thermally conductive filler. It is preferable that it is less than or equal to 35 parts by weight or less. In addition, the value of the average particle diameter (D1) of the large-sized thermally conductive filler / the average particle diameter (D2) of the medium-sized thermally conductive filler is preferably 2 or more, 2.25 or more, 2.5 or more, 2.75 or more, 3 or more, 3.25 or more, or 3.5 or more, It is preferable that they are 5 or less, 4.5 or less, 4.25 or less, 4 or less, 3.75 or less, or 3.5 or less. When the large-size and medium-sized thermally conductive fillers satisfy the above range, it is possible to secure room temperature fast curing of the curable composition according to the present application.

When the thermally conductive filler includes a large thermally conductive filler and a small thermally conductive filler, the content of the small thermally conductive filler is 25 parts by weight compared to 100 parts by weight of the large thermally conductive filler, considering the room temperature rapid curing of the curable composition according to the present application It is preferable that at least 26 parts by weight, at least 27 parts by weight, at least 28 parts by weight, at least 29 parts by weight, or at least 30 parts by weight. In another example, considering the room temperature rapid curing of the curable composition according to the present application, the content of the small thermal conductive filler is 45 parts by weight or less, 42.5 parts by weight or less, 40 parts by weight or less, 37.5 parts by weight compared to 100 parts by weight of the large thermal conductive filler. It is preferable that it is less than or equal to 35 parts by weight or less. In addition, the value of the average particle diameter (D1) of the large thermal conductive filler / the average particle diameter (D3) of the small thermal conductive filler is preferably 10 or more, 15 or more, 20 or more, 25 or more, 30 or more, or 32.5 or more, and 500 or less, It is preferably 100 or less, 90 or less, 80 or less, 70 or less, 60 or less, or 50 or less. When the large-size and small-sized thermally conductive fillers satisfy the above ranges, it is possible to secure room temperature fast curing of the curable composition according to the present application.

In the present application, it is most preferable to use a thermally conductive filler including all of a large thermally conductive filler, a medium thermally conductive filler, and a small thermally conductive filler. At this time, the content ratio of each particle and the average particle diameter ratio are as described above, and through the binder component and an appropriate combination thereof, it is possible to secure room temperature fast curing of the curable composition according to the present application.

The thermally conductive filler may include spherical and non-spherical particles. In the present application, the term spherical particle means a particle having a sphericity of about 0.95 or more, and a non-spherical particle means a particle having a sphericity of less than 0.95. The sphericity can be confirmed through particle shape analysis. Specifically, the sphericity of the filler, which is a three-dimensional particle, may be defined as a ratio (S'/S) of the surface area (S) of the particle to the surface area (S') of a sphere having the same volume of the particle. For real particles, we usually use circularity. The circularity is obtained by obtaining a two-dimensional image of an actual particle and expressed as a ratio of the boundary P of the image and the boundary of a circle having the same area (A) as the image, and is obtained by the following equation.

<Circularity formula>

Circularity=4πA/P ²

The circularity is expressed as a value from 0 to 1, a perfect circle has a value of 1, and irregularly shaped particles have a value lower than 1. The sphericity value in this specification was taken as the average value of the circularity measured with Marvern's vertical analysis equipment (FPIA-3000).

Considering appropriate viscosity and thixotropy of the curable composition according to the present application, the content of non-spherical particles is 10 parts by weight or more, 12.5 parts by weight or more, 15 parts by weight or more, 17.5 parts by weight or more, 20 parts by weight based on 100 parts by weight of the spherical particles. The amount may be at least 22.5 parts by weight, and in another example, 45 parts by weight or less, 40 parts by weight or less, 35 parts by weight or less, or 30 parts by weight or less.

In order to obtain excellent heat dissipation performance, it may be considered that a high content of the thermally conductive filler is used in the curable composition of the present application. In addition, in consideration of securing of low viscosity and appropriate thixotropy for securing fairness as well as securing excellent heat dissipation performance as described above, the content of the filler in the curable composition of the present application is 80% by weight or more, 82.5% by weight relative to the total weight or more, 85 wt% or more, or 90 wt% or more, and 95 wt% or less, 92.5 wt% or less, or 90 wt% or less.

In another example, the content of the filler in the curable composition of the present application is 800 parts by weight or more, 1,000 parts by weight or more, 1,300 parts by weight or more, 1,600 parts by weight or more, 1,900 parts by weight or more, or 2,100 parts by weight based on 100 parts by weight of the polyfunctional thiol compound. may be more, and in another example, the content of the filler is 5,000 parts by weight or less, 4,500 parts by weight or less, 4,000 parts by weight or less, 3,500 parts by weight or less, 3,000 parts by weight or less, or 2,500 parts by weight based on 100 parts by weight of the polyfunctional thiol compound. may be below.

The curable composition according to the present application may further include 150 parts by weight or less of a polyol based on 100 parts by weight of the polyfunctional thiol compound. In another example, the curable composition according to the present application is 140 parts by weight or less, 130 parts by weight or less, 120 parts by weight or less, 110 parts by weight or less, 100 parts by weight or less, 90 parts by weight or less, 80 parts by weight or less based on 100 parts by weight of the polyfunctional thiol compound. parts by weight or less, 70 parts by weight or less, 60 parts by weight or less, 50 parts by weight or less, 40 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, 5 parts by weight or less, 1 part by weight or less, 0.1 The polyol may be included in an amount of not more than 0.01 part by weight, or less than 0.001 part by weight. The curable composition according to the present application may form a cured product having adequate adhesion and high thermal conductivity by using a polyol within the above range.

When a polyol is used together with a thiol compound, the adhesion and thermal conductivity increase when the content of the polyol is increased. Therefore, in order to secure the desired thermal conductivity and reworkability, the content ratio of the polyol and the thiol compound is important. Considering this content ratio, as described above, the content of the polyol is preferably 150 parts by weight or less based on 100 parts by weight of the thiol compound. When the content of the polyol satisfies the above range, it is possible to secure the reworkability of the PET interface.

The polyol refers to a compound including two or more hydroxyl groups, and is not particularly limited. For example, (poly) ethylene glycol, diethylene glycol, (poly) propylene glycol, 1,2-butylene glycol, 2,3-butylene glycol, 1,3-propanediol, 1,3-butanediol, 1 ,4-butanediol, 1,6-hexanediol, neopentyl glycol, 1,2-ethylhexyldiol, 1,5-pentanediol, 1,9-nonanediol, 1,10-decanediol, 1,3-cyclo Hexanedimethanol and 1,4-cyclohexanedimethanol, (poly)ethylenetriol, diethylenetriol, (poly)propylenetriol, glycerin, 1,2,3-butanetriol, 1,2,4- Butanetriol, 1,3,4-hexanetriol, 1,3,6-hexanetriol unit, and may be exemplified by trimethylolpropane, but is not limited thereto.

In another example, the polyol may be a polyester polyol. The polyester polyol may include at least one of a carboxylic acid polyol and a caprolactone polyol. The carboxylic acid polyol may be formed by reacting a component containing a carboxyl group with a component containing a polyfunctional hydroxyl group, and the caprolactone polyol may be formed by reacting caprolactone with a component containing a polyfunctional hydroxyl group. In this case, the polyfunctional hydroxyl group compound, which is a component containing a polyfunctional hydroxyl group, refers to a compound containing two or more hydroxyl groups.

The polyester polyol according to the present application may include a carboxylic acid polyol represented by Formula 1 below. In addition, the polyester polyol according to the present application may include a caprolactone polyol represented by Formula 2 below.

[Formula 1]

[Formula 2]

In Formula 1, X is a unit derived from carboxylic acid, Y ₁ and Y ₂ are each independently a unit derived from a polyfunctional hydroxyl group compound, and n may be a number within the range of 1 to 20.

In Formula 1, the carboxylic acid-derived unit may be a unit formed by reacting carboxylic acid with a polyfunctional hydroxyl group compound, and the polyfunctional hydroxyl group-derived unit may be a unit formed by reacting the polyfunctional hydroxyl group compound with carboxylic acid.

In Formula 2, Y is a unit derived from a polyfunctional hydroxyl group compound, and m ₁ and m ₂ may each independently be a number within the range of 1 to 20. In addition, in Formula 2, the unit derived from the polyfunctional hydroxyl group compound is a unit formed by reacting the polyfunctional hydroxyl group compound with carboxylic acid or caprolactone.

That is, when the hydroxy group of the polyfunctional hydroxy group compound reacts with the carboxyl group of the carboxylic acid, an ester bond is formed while water (H ₂ O) molecules are separated by a condensation reaction. It refers to a portion excluding the ester bond portion after forming an ester bond by the reaction. In addition, Y ₁ and Y ₂ are portions excluding the ester bond after the polyfunctional hydroxyl group compound forms an ester bond by the condensation reaction.

In addition, Y in Formula 2 also represents a portion excluding the ester bond after the polyfunctional hydroxyl group compound forms an ester bond with caprolactone.

On the other hand, when at least one of Y ₁ and Y ₂ in Formula 1 is a unit derived from a polyfunctional hydroxyl group compound including three or more hydroxyl groups, a structure in which at least one of Y ₁ and Y ₂ is branched may be implemented. there is. Also, in the case where Y in Formula 2 is a unit derived from a polyfunctional hydroxyl group compound including three or more hydroxyl groups, a branched structure may be implemented in Y as well.

In Formula 1, the type of the carboxylic acid-derived unit of X is not particularly limited, but in order to secure desired physical properties, a phthalic acid unit, an isophthalic acid unit, a terephthalic acid unit, a trimellitic acid unit, a tetrahydrophthalic acid unit, a hexahydrophthalic acid unit, Tetrachlorophthalic acid unit, oxalic acid unit, adipic acid unit, azelaic acid unit, sebacic acid unit, succinic acid unit, malic acid unit, glataric acid unit, malonic acid unit, pimelic acid unit, suberic acid unit, 2,2-dimethyl succinic acid unit, 3,3-dimethylglutaric acid unit, 2,2-dimethylglutaric acid unit, maleic acid unit, fumaric acid unit, itaconic acid unit or fatty acid unit. In consideration of appropriate hardness, adhesiveness and reworkability, an aliphatic carboxylic acid-derived unit is preferable rather than an aromatic carboxylic acid-derived unit, and (CH ₂ ) _p (COOH) ₂ . A unit is more preferable (in this case, p may be any number, and may be an integer between 1 and 16).

On the other hand, in Formula 1, the type of the unit derived from the polyfunctional hydroxyl group compound of Y ₁ and Y ₂ is not particularly limited, but in order to secure the desired physical properties, each independently a (poly) ethylene glycol unit, a diethylene glycol unit, ( Poly) propylene glycol unit, 1,2-butylene glycol unit, 2,3-butylene glycol unit, 3-methyl-1,5-pentanediol unit, 1,3-propanediol unit, 1,3-butanediol unit , 1,4-butanediol unit, 1,6-hexanediol unit, neopentylglycol unit, 1,2-ethylhexyldiol unit, 1,5-pentanediol unit, 1,9-nonanediol unit, 1,10- Decanediol unit, 1,3-cyclohexanedimethanol unit, 1,4-cyclohexanedimethanol unit, (poly)ethylenetriol unit, diethylenetriol unit, (poly)propylenetriol unit, glycerin unit, 1 , may be a 2,3-butanetriol unit, a 1,2,4-butanetriol unit, a 1,3,4-hexanetriol unit, a 1,3,6-hexanetriol unit, or a trimethylolpropane unit. .

In addition, in Formula 2, the type of unit derived from the polyfunctional hydroxyl group compound of Y is not particularly limited, but in order to secure desired physical properties, each independently a (poly) ethylene glycol unit, a diethylene glycol unit, a (poly) propylene glycol unit , 1,2-butylene glycol unit, 2,3-butylene glycol unit, 3-methyl-1,5-pentanediol unit, 1,3-propanediol unit, 1,3-butanediol unit, 1,4- Butanediol unit, 1,6-hexanediol unit, neopentyl glycol unit, 1,2-ethylhexyldiol unit, 1,5-pentanediol unit, 1,9-nonanediol unit, 1,10-decanediol unit, 1 ,3-cyclohexanedimethanol unit, 1,4-cyclohexanedimethanol unit, (poly)ethylenetriol unit, diethylenetriol unit, (poly)propylenetriol unit, glycerin unit, 1,2,3- butanetriol unit, 1,2,4-butanetriol unit, 1,3,4-hexanetriol unit, 1,3,6-hexanetriol unit or trimethylolpropane unit.

In Formula 1, n may be selected in consideration of the desired physical properties of the curable composition or the cured product of the resin composition including the curable composition, and may be 1 or more, 4 or more, 8 or more, 12 or more, or 16 or more, In another example, it may be 20 or less, 16 or less, 12 or less, 8 or less, 4 or less, or 2 or less.

In addition, in Formula 2, m ₁ and m ₂ may be selected in consideration of desired physical properties of a curable composition or a cured product of a resin composition including the curable composition, and each independently 1 or more, 4 or more, 8 or more, 12 It may be more than or equal to 16, and in another example, each independently may be 20 or less, 16 or less, 12 or less, 8 or less, 4 or less, or 2 or less.

The molecular weight of the polyol may be adjusted in consideration of the low viscosity characteristics described below, durability or adhesiveness, etc., and is about 300 g/mol or more, 400 g/mol or more, 500 g/mol or more, 600 g/mol or more, 700 g/mol or more, 800 g/mol or more, 900 g/mol or more, 1,000 g/mol or more, 1,200 g/mol or more, 1,400 g/mol or more, 1,600 g/mol or more, or 1800 g/mol or more; , in another example about 2,000 g/mol or less, 1,800 g/mol or less, 1,600 g/mol or less, 1,400 g/mol or less, 1,200 g/mol or less, 1,000 g/mol or less, 900 g/mol or less, 800 g/mol or less mol or less, 700 g/mol or less, 600 g/mol or less, 500 g/mol or less, or 400 g/mol or less.

Unless otherwise specified, in the present application, the molecular weight may be a weight average molecular weight (M _w ) measured using Gel Permeation Chromatography (GPC). When the molecular weight of the polyol is within the above range, problems related to volatile components may be improved.

The curable composition according to the present application may further include a plasticizer. The type of the plasticizer is not particularly limited, but for example, a phthalic acid compound, a phosphoric acid compound, an adipic acid compound, a sebacic acid compound, a citric acid compound, a glycolic acid compound, a trimellitic acid compound, a polyester compound, epoxidized soybean oil, chlorinated Paraffin, chlorinated fatty acid ester, fatty acid compound, a compound having a saturated aliphatic chain substituted with a sulfonic acid group to which a phenyl group is bonded (eg, mesamoll manufactured by LANXESS), and vegetable oil may be selected and used.

The phthalic acid compound is dimethyl phthalate, diethyl phthalate, dibutyl phthalate, dihexyl phthalate, di-n-octyl phthalate, di-2-ethylhexyl phthalate, diisooctyl phthalate, dicapryl phthalate, dinonyl phthalate, diisononyl Phthalate, didecyl phthalate, diundecyl phthalate, dilauryl phthalate, ditridecyl phthalate, dibenzyl phthalate, dicyclohexyl phthalate, butyl benzyl phthalate, octyl decyl phthalate, butyl octyl phthalate, octyl benzyl phthalate, n-hexyl n- One or more of decyl phthalate, n-octyl phthalate and n-decyl phthalate may be used.

The phosphoric acid compound may be at least one of tricresyl phosphate, trioctyl phosphate, triphenyl phosphate, octyl diphenyl phosphate, cresyl diphenyl phosphate and trichloroethyl phosphate.

The adipic acid compound is dibutoxyethoxyethyl adipate (DBEEA), dioctyl adipate, diisooctyl adipate, di-n-octyl adipate, didecyl adipate, diisodecyl adipate, n-octyl One or more of n-decyl adipate, n-heptyl adipate and n-nonyl adipate may be used.

As the sebacic acid compound, one or more of dibutyl sebacate, dioctyl sebacate, diisooctyl sebacate, and butyl benzyl may be used.

As the citric acid compound, one or more of triethyl citrate, acetyl triethyl citrate, tributyl citrate, acetyl tributyl citrate and acetyl trioctyl citrate may be used.

As the glycolic acid compound, at least one of methyl phthalyl ethyl glycolate, ethyl phthalyl ethyl glycolate, and butyl phthalyl ethyl glycolate may be used.

As the trimellitic acid compound, at least one of trioctyl trimellitate and tri-n-octyl n-decyl trimellitate may be used.

The polyester compound includes butane diol, ethylene glycol, propane 1,2 diol, propane 1,3 diol, polyethylene glycol, glycerol, diacid (selected from adipic acid, succinic acid, succinic anhydride) and hydroxy acids (eg, hydroxystearic acid).

The content of the plasticizer may be 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 25 parts by weight or more, 30 parts by weight or more, or 35 parts by weight or more, based on 100 parts by weight of the polyfunctional thiol compound. The content may be 150 parts by weight or less, 140 parts by weight or less, 130 parts by weight or less, 120 parts by weight or less, or 110 parts by weight or less based on 100 parts by weight of the polyfunctional thiol compound. The content of the plasticizer in the curable composition of the present application may be appropriately determined according to the content ratio of the polyol and the polyfunctional thiol compound in order to secure appropriate viscosity and thixotropy.

In another example of the present application, the plasticizer further included in the curable composition may be an adipic acid compound. When the plasticizer is an adipic acid compound, the curable composition according to the present application may include 2 parts by weight or more of the polyfunctional thiol compound based on 100 parts by weight of the filler. In another example, the curable composition may include 3 parts by weight or more or 4 parts by weight or more of the polyfunctional thiol compound based on 100 parts by weight of the filler.

In addition, when the plasticizer is an adipic acid compound, when the curable composition further includes a polyol, the curable composition according to the present application is 300 parts by weight or less, 280 parts by weight or less, 260 parts by weight based on 100 parts by weight of the polyfunctional thiol compound. parts by weight or less, 240 parts by weight or less, 220 parts by weight or less, 200 parts by weight or less, 180 parts by weight or less, 160 parts by weight or less, 140 parts by weight or less, 120 parts by weight or less, 100 parts by weight or less, 80 parts by weight or less, 60 parts by weight or less parts by weight or less, 40 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, and 1 part by weight or less of the polyol.

As described above, when the polyol is used together with the thiol compound, the content ratio of the polyol and the thiol compound is important in order to secure desired thermal conductivity and reworkability. However, when the plasticizer is an adipic acid compound, the content of the polyol required to secure reworkability may be increased compared to that which does not. Through this, it is possible to secure a resin composition having higher thermal conductivity and securing reworkability.

The adipic acid compound may be represented by Formula 4 below.

[Formula 4]

In Formula 4, P ₁ and P ₂ may each independently represent an alkyl group having 2 to 20 carbon atoms having one or a plurality of ether bonds, or an alkyl group having 2 to 20 carbon atoms unsubstituted or substituted with an alkyl group.

The adipic acid compound of the present application is not particularly limited as long as it corresponds to Chemical Formula 4, for example, dibutoxyethoxyethyl adipate (DBEEA), dioctyl adipate, diisooctyl adipate, and di-n-octyl. One or more of adipate, didecyl adipate, diisodecyl adipate, n-octyl n-decyl adipate, n-heptyl adipate and n-nonyl adipate may be used.

The content of the adipic acid compound of the present application is 60% by weight or more, 65% by weight or more, 70% by weight or more, 75% by weight or more, 80% by weight or more, 85% by weight or more, 90% by weight or more, 95 wt% or more, 99 wt% or more, 99.9 wt% or more, or 100 wt%.

In an example of the present application, the resin composition may include a main part including the curable composition; and a curing agent part including an isocyanate component; may be a two-component composition comprising

The two-component composition according to the present application may form a cured product while the thiol group of the main part and the isocyanate group of the curing agent part cause a thiourethane reaction. In addition, when the polyol is additionally included in the main part, the thiol group and the hydroxyl group of the main part may cause thiourethane and urethane reactions with the isocyanate group of the curing agent, respectively, to form a cured product. Through the thiourethane and urethane reaction, the two-component composition may be cured at room temperature. That is, the resin composition according to the present application may be a room temperature curable two-component composition.

The curing agent part of the two-component composition according to the present application may include an isocyanate component, and the isocyanate component may include a bifunctional isocyanate compound and a trifunctional or higher polyfunctional isocyanate compound. In this case, the polyfunctional isocyanate compound means a compound containing three or more isocyanate groups. In addition, as the polyfunctional isocyanate compound, a trifunctional isocyanate compound, which is a compound containing three isocyanate groups, is suitable.

The kind in particular of a bifunctional isocyanate compound and a polyfunctional isocyanate compound is not restrict|limited. However, in order to secure the desired physical properties, a non-aromatic isocyanate compound that does not contain an aromatic group may be used. That is, it may be advantageous to use an aliphatic or cycloaliphatic series. When an aromatic polyisocyanate is used, since the reaction rate is excessively fast and the glass transition temperature of the cured product may be high, it may be difficult to secure processability and physical properties suitable for the use of the composition of the present application.

At least one of an aliphatic difunctional isocyanate compound and an alicyclic difunctional isocyanate compound may be used as the bifunctional isocyanate compound according to the present application. The aliphatic difunctional isocyanate compound may be exemplified by hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate, norbornane diisocyanate methyl, ethylene diisocyanate, propylene diisocyanate, and tetramethylene diisocyanate, and in particular, thereto. It is not limited. The alicyclic difunctional isocyanate compound may be exemplified by transcyclohexane-1,4-diisocyanate, isophorone diisocyanate, bis(isocyanatemethyl)cyclohexane diisocyanate and dicyclohexylmethane diisocyanate, and the like, and is particularly limited thereto. it is not In addition, 1 type or 2 or more types can be used for a bifunctional isocyanate compound.

The polyfunctional isocyanate compound according to the present application is not particularly limited as long as it is a compound containing three or more isocyanate groups. The polyfunctional isocyanate compound according to the present application may use, for example, a multimer or more of a trimer of the isocyanate compound, and a compound in the form of a biuret obtained by reacting the isocyanate compound with water may also be used. . That is, at least one selected from a multimer of an isocyanate compound and a biuret compound may be used as the polyfunctional isocyanate compound.

Specifically, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate, norbornane diisocyanate methyl, ethylene diisocyanate, propylene diisocyanate, tetramethylene diisocyanate, transcyclohexane-1,4-diisocyanate, Polymers, such as isophorone diisocyanate, bis(isocyanate methyl) cyclohexane diisocyanate, and dicyclohexylmethane diisocyanate, and the compound in the form of a biuret can be mentioned as an example of a polyfunctional isocyanate compound.

The isocyanate component of the present application is preferably a mixture of a bifunctional isocyanate compound and a trifunctional or more polyfunctional isocyanate compound in consideration of securing reworkability, and trifunctional based on the number of moles (M2) of the bifunctional isocyanate compound The ratio (M/M2) of the number of moles (M) of the above polyfunctional isocyanate compound may be in the range of 4 to 8 or 5 to 7.

In order to obtain excellent heat dissipation performance, it may be considered that a high content of the thermally conductive filler is used in the curing agent part. The content of the filler included in the curing agent may be 400 parts by weight or more, 450 parts by weight or more, 500 parts by weight or more, 550 parts by weight or more, 600 parts by weight or more, 650 parts by weight or more, or 700 parts by weight or more relative to 100 parts by weight of the isocyanate component. In another example, the content of the filler may be 1,800 parts by weight or less, 1,700 parts by weight or less, 1,600 parts by weight or less, 1,500 parts by weight or less, 1,400 parts by weight or less, or 1,300 parts by weight or less relative to 100 parts by weight of the isocyanate component.

In the resin composition according to the present application, the ratio (V1/V2) of the volume (V1) of the main part to the volume (V2) of the curing agent part may be in the range of 0.5 to 1.5 or 0.75 to 1.25. When the ratio (V1/V2) of the volume (V1) of the main part and the volume (V2) of the curing agent part satisfies the above range, the thiourethane reaction may be efficiently performed.

The content of the plasticizer of the present application is 1 wt% or more, 1.2 wt% or more, 1.4 wt% or more, 1.6 wt% or more, 1.8 wt% or more, 2 wt% or more, 2.2 wt% or more, or It may be 2.4 wt% or more, and in another example, the content of the plasticizer is 4 wt% or less, 3.75 wt% or less, 3.5 wt% or less, 3.25 wt% or less, 3 wt% or less, 2.75 wt%, based on the total weight of the two-component composition or less or 2.5% by weight or less. When the content of the plasticizer of the present application satisfies the above range, appropriate viscosity and thixotropy can be ensured before and after curing for the two-component composition.

The plasticizer used in the two-component composition of the present application may be included in at least one of the main part and the curing agent part to finally satisfy the above content range. In this case, the main part preferably includes a plasticizer, and the content of the plasticizer may be appropriately adjusted according to the content ratio of polyol and thiol in the main part.

In the two-component composition according to the present application, when the main part and the curing agent part are mixed, the content of the filler is 75 wt% or more, 76 wt% or more, 77 wt% or more, 78 wt% or more, 79 wt% based on the total weight of the mixture % or more, 80% or more, 81% or more, 82% or more, 83% or more, 84% or more, 85% or more, 86% or more, 87% or more, 88% or more, 89% or more % or more, 90 wt% or more, 91 wt% or more, 92 wt% or more, 93 wt% or more, 94 wt% or more, or 95 wt% or more. In another example, the content of the filler is 96 wt% or less, 95 wt% or less, 94 wt% or less, 93 wt% or less, 92 wt% or less, 91 wt% or less, 90 wt% or less, 89 wt% or less based on the total weight of the mixture % or less, 88% or less, 87% or less, 86% or less, 85% or less, 84% or less, 83% or less, 82% or less, 81% or less, 80% or less, 79 weight % or less, 78 weight % or less, 77 weight % or less, or 76 weight % or less.

The two-part composition according to the present application may include 1.2 parts by weight or more of the polyfunctional thiol compound based on 100 parts by weight of the filler. In another example, the two-component composition contains 1.5 parts by weight or more, 1.7 parts by weight or more, 1.9 parts by weight or more, 2.1 parts by weight or more, 2.4 parts by weight or more, 3 parts by weight or more, or 4 parts by weight or more, based on 100 parts by weight of the filler. It may contain a thiol compound.

The resin composition (curable composition or two-component composition, etc.) according to the present application is a viscosity modifier, for example, thixotropy, if necessary It may further include an agent, a diluent, a surface treatment agent, or a coupling agent. The thixotropic agent may adjust the viscosity according to the shear force of the resin composition. As the thixotropic agent that can be used, fumed silica and the like can be exemplified. The diluent is generally used to lower the viscosity of the resin composition, and various types of diluents known in the art may be used without limitation as long as they can exhibit the above action. The surface treatment agent is for surface treatment of the filler introduced into the cured product of the resin composition, and as long as it can exhibit the above action, various types known in the art may be used without limitation. In the case of the coupling agent, for example, it can be used to improve the dispersibility of the thermally conductive filler such as alumina, and if it can exhibit the above action, various types of known in the art can be used without limitation.

If necessary, the resin composition according to the present application may further include a flame retardant or a flame retardant auxiliary agent. The resin composition further including a flame retardant or a flame retardant auxiliary may be cured to form a flame retardant resin. As the flame retardant, various known flame retardants may be applied without particular limitation, for example, a flame retardant in the form of a solid filler or a liquid flame retardant may be applied. The flame retardant may include, for example, an organic flame retardant such as melamine cyanurate or an inorganic flame retardant such as magnesium hydroxide, but is not limited thereto. When the amount of the thermally conductive filler included in the resin composition is large, a liquid type flame retardant material (TEP, Triethyl phosphate or TCPP, tris(1,3-chloro-2-propyl)phosphate, etc.) may be used. In addition, a silane coupling agent capable of acting as a flame retardant synergist may be added.

The composition may include the composition as described above, and may be a solvent-based composition, an aqueous composition, or a solvent-free composition.

The resin composition may be cured to form a cured product, and may have at least one of the following physical properties. Each of the following physical properties is independent, and any one physical property does not take precedence over the other properties, and the cured product of the resin composition may satisfy at least one or two or more of the following physical properties. The cured product of the resin composition satisfying at least one or two or more of the following physical properties is caused by a combination of each component of the resin composition.

The resin composition is produced as a sample (cured product) having a diameter of 2 cm or more and a thickness of 4 mm, and is about 2.5 W/ It may have a thermal conductivity of m·K or more. In another example, the thermal conductivity may be about 2.6 W/m·K or more, 2.7 W/m·K or more, 2.8 W/m·K or more, 2.9 W/m·K or more, or 3.0 W/m·K or more. Since the higher the thermal conductivity, the higher the thermal conductivity, the upper limit thereof is not particularly limited. For example, the thermal conductivity is 20 W/m·K or less, 18 W/m·K or less, 16 W/m·K or less, 14 W/m·K or less, 12 W/m·K or less, 10 W /m·K or less, 8 W/m·K or less, 6 W/m·K or less, or 4 W/m·K or less.

The cured product of the resin composition must have a thermal resistance of about 5 K/W or less, about 4.5 K/W or less, about 4 K/W or less, about 3.5 K/W or less, about 3 K/W or less, or about 2.8 K/W or less. can When the heat resistance in this range is adjusted to appear, excellent cooling efficiency or heat dissipation efficiency can be secured. The heat resistance may be a numerical value measured according to ASTM D5470 standard or ISO 22007-2 standard, and the measuring method is not particularly limited.

The cured product of the resin composition has a normal temperature peeling force (or adhesion) to PET (polyethylene teraphtalate) of about 400 gf/cm or less, 300 gf/cm or less, 280 gf/cm or less, 260 gf/cm or less, 240 gf/cm Hereinafter, it may be 220 gf/cm or less or 210 gf/cm or less. In another example, the cured product of the resin composition has an adhesive strength of about 20 gf / cm or more, 22 gf / cm or more, 24 gf / cm or more, 26 gf / cm or more, 28 gf / cm or more, 30 gf / cm or more, 32 gf/cm or more or 35 gf/cm or more. The adhesive strength is about 4 cm in width and 10 cm in height on an aluminum substrate, and after coating the uncured resin composition to have a thickness of about 2 mm, PET (poly (poly() An aluminum pouch with an ethylene terephthalate) interface was attached. The aluminum pouch, which can be used when manufacturing a battery cell, was attached so that the PET interface and the coated resin composition were in contact. Thereafter, after curing at room temperature for about 24 hours, the adhesive force may be measured while peeling the aluminum pouch at a peeling rate of about 0.5 mm/s and a peeling angle of 180 degrees.

In addition, the adhesive force may be an adhesive force to any substrate or module case in contact with the cured product of the resin composition. If the adhesive force as described above can be secured, an appropriate adhesive force may appear with respect to various materials, for example, a case or a battery cell included in a battery module. In addition, when the adhesive force within this range is secured, volume change during charging and discharging of battery cells in the battery module, change in the use temperature of the battery module, peeling due to curing shrinkage, etc. are prevented, and excellent durability can be secured. In addition, re-workability capable of enabling the module to be detached and reattached during the assembly process of the battery pack may be secured.

의 저온에서 30분 유지한 후 다시 온도를 80

로 올려서 30분 유지하는 것을 하나의 사이클로 하여 상기 사이클을 100회 반복하는 열충격 시험 후에 배터리 모듈의 모듈 케이스 또는 배터리셀로부터 떨어지거나 박리되거나 혹은 크랙이 발생하지 않는 것을 의미할 수 있다.The cured product of the resin composition can secure durability to be applied to products requiring a long warranty period (in the case of automobiles, about 15 years or more), such as automobiles. Durability is about -40

After holding for 30 minutes at a low temperature of

It may mean that the battery module does not come off, peel, or crack from the module case or battery cell of the battery module after the thermal shock test of repeating the cycle 100 times as one cycle to keep it for 30 minutes.

The cured product of the resin composition may have electrical insulation properties of about 3 kV/mm or more, about 5 kV/mm or more, about 7 kV/mm or more, 10 kV/mm or more, 15 kV/mm or more, or 20 kV/mm or more. . The higher the dielectric breakdown voltage, the better the cured product of the resin composition exhibits excellent insulation, and about 50 kV/mm or less, 45 kV/mm or less, 40 kV/mm or less, 35 kV/mm or less, 30 kV/ mm or less, but is not particularly limited. In order to achieve the breakdown voltage as described above, an insulating filler may be applied to the resin composition. In general, among thermally conductive fillers, a ceramic filler is known as a component capable of securing insulation. The electrical insulation may be measured with a dielectric breakdown voltage measured according to ASTM D149 standard. In addition, if the cured product of the resin composition can ensure the electrical insulation as described above, stability can be secured while maintaining performance with respect to various materials, for example, a case or battery cell included in a battery module.

The cured product of the resin composition may have a specific gravity of 5 or less. The specific gravity may be 4.5 or less, 4 or less, 3.5 or less, or 3 or less in another example. The specific gravity of the cured product of the resin composition is advantageous in reducing the weight of the applied product as the numerical value is lower, so the lower limit is not particularly limited. For example, the specific gravity may be about 1.5 or more or 2 or more. In order for the cured product of the resin composition to exhibit a specific gravity in the above range, for example, a filler that can ensure desired thermal conductivity even at a low specific gravity when adding a thermally conductive filler, that is, a filler having a low specific gravity by itself A method of applying or applying a surface-treated filler may be used.

It is appropriate that the cured product of the resin composition does not contain volatile substances as much as possible. For example, the cured product of the resin composition may have a ratio of nonvolatile components of 90 wt% or more, 95 wt% or more, or 98 wt% or more. In the above, the ratio with the nonvolatile component can be defined in the following manner. That is, the non-volatile content may be defined as the portion remaining after the cured product of the resin composition is maintained at 100° C. for about 1 hour as the non-volatile content, and thus the ratio is the initial weight of the cured product of the resin composition and the initial weight of the resin composition at 100° C. It can be measured based on the ratio after holding for about 1 hour.

The cured product of the resin composition will have excellent resistance to deterioration, if necessary, and may be required to have stability that does not react chemically as much as possible.

It may be advantageous for the cured product of the resin composition to have a low shrinkage during or after curing. Through this, it is possible to prevent peeling or voids that may occur in the process of manufacturing or using various materials, for example, a case or a battery cell included in a battery module. The shrinkage rate may be appropriately adjusted within a range capable of exhibiting the above-described effects, and may be, for example, less than 5%, less than 3%, or less than about 1%. Since the shrinkage ratio is advantageous as the numerical value is lower, the lower limit thereof is not particularly limited.

The cured product of the resin composition may also advantageously have a low coefficient of thermal expansion (CTE). Through this, it is possible to prevent peeling or voids that may occur in the process of manufacturing or using various materials, for example, a case or a battery cell included in a battery module. The coefficient of thermal expansion may be appropriately adjusted within a range capable of exhibiting the above-described effects, for example, less than 300 ppm/K, less than 250 ppm/K, less than 200 ppm/K, less than 150 ppm/K or 100 ppm It can be less than /K. Since the coefficient of thermal expansion is advantageous as the numerical value is lower, the lower limit thereof is not particularly limited.

The cured product of the resin composition may have an appropriate tensile strength, and through this, excellent impact resistance and the like may be secured. The tensile strength may be adjusted, for example, in the range of about 1.0 MPa or more.

The cured product of the resin composition may also have a 5% weight loss temperature in thermogravimetric analysis (TGA) of 400° C. or more, or a residual amount of 800° C. of 70 wt% or more. Due to these characteristics, stability at high temperature may be further improved with respect to various materials, for example, a case or a battery cell included in a battery module. The remaining amount at 800 °C may be about 75 wt% or more, about 80 wt% or more, about 85 wt% or more, or about 90 wt% or more in another example. The remaining amount at 800°C may be about 99% by weight or less in another example. The thermogravimetric analysis (TGA) may be measured within the range of 25 °C to 800 °C at a temperature increase rate of 20 °C/min in a nitrogen (N ₂ ) atmosphere of 60 cm ³ /min. The thermogravimetric analysis (TGA) result can also be achieved by adjusting the composition of the cured product of the resin composition. For example, the remaining amount at 800°C is influenced by the type or ratio of the thermally conductive filler contained in the cured product of the resin composition, and when an excessive amount of the thermally conductive filler is included, the remaining amount increases. However, when the polymer and/or monomer used in the resin composition generally has high heat resistance compared to other polymers and/or monomers, the residual amount is higher, and the polymer and/or monomer component included in the cured product of the resin composition is also the same. affects hardness.

The resin composition of the present application may be formed by mixing each of the components listed above. In addition, the resin composition may be formed by mixing after adding a flame retardant to the mixture formed by mixing. The resin composition of the present application is not particularly limited with respect to the mixing order as long as all necessary components can be included.

The resin composition of the present application is an iron, washing machine, dryer, clothes manager, electric shaver, microwave oven, electric oven, electric rice cooker, refrigerator, dishwasher, air conditioner, electric fan, humidifier, air purifier, mobile phone, walkie-talkie, television, radio, computer , it is possible to dissipate heat generated by being used in various electric and electronic products such as laptops, or batteries such as secondary batteries. In particular, the resin composition of the present application may be used as a material for connecting battery modules in a battery car battery manufactured by gathering battery cells to form one battery module, and combining several battery modules to form one battery pack. . When the resin composition of the present application is used as a material for connecting the battery module, it may serve to dissipate heat generated in the battery cell and fix the battery cell from external shock and vibration.

The cured product of the resin composition of the present application may transfer heat generated from the exothermic element to the cooling portion. That is, the cured product of the resin composition may radiate heat generated from the exothermic element.

The cured product of the resin composition may be positioned between the exothermic element and the cooling portion to thermally contact them. Thermal contact means that the cured product of the resin composition is in direct physical contact with the exothermic element and the cooling part to radiate heat generated from the exothermic element to the cooling part, or the cured product of the resin composition is in direct contact with the exothermic element and the cooling part. / or to dissipate the heat generated by the exothermic element to the cooling area even without direct contact with the cooling portion (that is, there is a separate layer between the cured product of the resin composition and the exothermic element and/or the cooling portion) it means.

The present application may provide a resin composition as a thermal interface material that requires room temperature curing and has low adhesion (especially for PET interfaces).

The present application may provide a resin composition exhibiting appropriate viscosity, thixotropy, and/or thermal conductivity before and after curing.

The present application relates to a resin composition that exhibits adequate adhesion to effectively maintain a plurality of battery modules before and after curing and re-workability to enable separation and reattachment of modules during the assembly process of a battery pack at the same time can provide

The present application may also provide a resin composition that exhibits room temperature curability and rapid curability even with an excessive amount of filler.

Hereinafter, the present application will be described with reference to Examples and Comparative Examples, but the scope of the present application is not limited by the contents presented below.

<Method of measuring physical properties>

(1) Adhesive force measurement method

On an aluminum substrate (Al 6061), the uncured resin composition is coated to have a width of about 4 cm and a length of 10 cm and a thickness of about 2 mm, and then PET (poly An aluminum pouch with an (ethylene terephthalate)) interface was attached. The aluminum pouch, which can be used when manufacturing a battery cell, was attached so that the PET interface and the coated resin composition were in contact. Thereafter, after curing at room temperature for about 24 hours, the adhesive force was measured while peeling the aluminum pouch at a peeling rate of about 0.5 mm/s and a peeling angle of 180 degrees.

(2) Method of measuring thermal conductivity

Thermal conductivity was measured using a hot disk method. Specifically, thermal conductivity was measured according to ISO 22007-2 standard along the thickness direction of the sample in a state in which the resin composition was cured into a disk-shaped sample having a diameter of 4 cm and a thickness of 4 mm.

Example 1

A main part (P1) was prepared by mixing the polyester polyol (A), thiol (B) and filler (D1) in a weight ratio of 4.84:4.84:90.33. In this case, as the polyester polyol (A), bifunctional caprolactone polyol (A1, weight average molecular weight 450 g/mol, Perstorp's CAPA2043) was used, and as the thiol (B), TMMP (trimethylolpropane tris (3-mercaptopropionate)) was used. The filler (D1) was spherical aluminum oxide (D11) having an average particle size of about 70 μm, spherical aluminum oxide (D12) having an average particle size of about 20 μm, and non-spherical aluminum oxide having an average particle size of about 2 μm. It was used by mixing in a weight ratio of 6:2:2 (D11:D12:D13).

A curing agent part (P2) was prepared by mixing the curing agent (C) and the filler (D2) in a weight ratio of 10.87:89.13 (C:D2). In this case, as the curing agent (C), a trimer compound (LV2, trifunctional, Vencorex) based on hexamethylene diisocyanate (HDI) was used, and the filler (D2) was the same as that of the filler (D1).

The average particle diameter of the filler referred to in this specification is the D50 particle diameter, also called the so-called median particle diameter, and is the particle diameter (median diameter) at 50% of the cumulative volume-based cumulative curve of the particle size distribution. Such a particle size can be defined as the particle diameter at a point where the cumulative value becomes 50% on a cumulative curve in which the particle size distribution is calculated on a volume basis and the total volume is 100%. The D50 particle size can be measured using Marven's MASTERSIZER 3000 equipment based on ISO-13320, and Ethanol was used as a solvent.

The cured product was mixed with the main part (P1) and the curing agent part (P2) in a volume ratio of 1:1 (P1:P2), poured into a mold, and maintained at room temperature for 24 hours to have a diameter of 4 cm and a thickness of 4 mm. It was formed in the form of a disk (disk).

Example 2

Example 1 above, except that the main part (P1) was prepared by mixing the polyester polyol (A), thiol (B) and filler (D1) in a weight ratio of 2.23:6.70:91.07 (A:B:D1). In the same manner as described above, the main part (P1) and the curing agent part (P2) were stirred and mixed in a volume ratio of 1:1 (P1:P2), poured into a mold, and maintained at room temperature for 24 hours to have a diameter of 4 cm and a thickness of 4 mm. It was formed in the form of a disk (disk).

Example 3

The main part (P1) was prepared by mixing the thiol (B) and the filler (D1) in a weight ratio of 8.26:91.74 (B:D1) without using the polyester polyol (A), and the curing agent (C) and the filler (D2) was mixed in a weight ratio of 12.34:87.65 (C:D2) to prepare the curing agent portion (P2), except that the main portion (P1) and the curing agent portion (P2) were prepared in the same manner as in Example 1 above. was stirred and mixed at a volume ratio of 1:1 (P1:P2), poured into a mold, and maintained at room temperature for 24 hours to form a disk having a diameter of 4 cm and a thickness of 4 mm.

Comparative Example 1

The main part (P1) was prepared by mixing the polyester polyol (A) and the filler (D1) in a weight ratio of 11.35:88.65 (A:D1) without using the thiol (B), and the curing agent (C) and the filler (D2) was mixed in a weight ratio of 9.09:90.91 (C:D2) to prepare the curing agent portion (P2), except that the main portion (P1) and the curing agent portion (P2) were prepared in the same manner as in Example 1 above. was stirred and mixed at a volume ratio of 1:1 (P1:P2), poured into a mold, and maintained at room temperature for 24 hours to form a disk having a diameter of 4 cm and a thickness of 4 mm.

Comparative Example 2

Without using the thiol (B), the polyester polyol (A) and the filler (D1) were mixed in a weight ratio of 11.01:88.99 (A:D1), and the polyester polyol (A) was a bifunctional caprolactone polyol (A1) ) but not trifunctional caprolactone polyol (A2, weight average molecular weight 500 g/mol, Perstorp CAPA3050) was used to prepare the main part (P1), and the curing agent (C) and filler (D2) were added at 9.90:90.10 (C: In the same manner as in Example 1, except that the curing agent part P2 was prepared by mixing in a weight ratio of D2), the main part P1 and the curing agent part P2 were mixed in a volume of 1:1 (P1:P2) After stirring and mixing in a ratio, it was poured into a mold and maintained at room temperature for 24 hours to form a disk having a diameter of 4 cm and a thickness of 4 mm.

Comparative Example 3

Polyester polyol (A), thiol (B) and filler (D1) were mixed in a weight ratio of 9.77:1.08:89.15 (A:B:D1) to prepare a main part (P1), a curing agent (C) and a filler (D2) was mixed in a weight ratio of 9.34:90.65 (C:D2) to prepare the curing agent portion (P2), except that the main portion (P1) and the curing agent portion (P2) were prepared in the same manner as in Example 1 above. After stirring and mixing in a volume ratio of 1:1 (P1:P2), it was poured into a mold and maintained at room temperature for 24 hours to form a disk having a diameter of 4 cm and a thickness of 4 mm.

Comparative Example 4

Polyester polyol (A), thiol (B) and filler (D1) were mixed in a weight ratio of 7.20:3.08:89.72 (A:B:D1) to prepare a main part (P1), a curing agent (C) and a filler (D2) was mixed in a weight ratio of 10.20:89.80 (C:D2) to prepare the curing agent portion (P2), except that the main portion (P1) and the curing agent portion (P2) were prepared in the same manner as in Example 1 above. After stirring and mixing in a volume ratio of 1:1 (P1:P2), it was poured into a mold and maintained at room temperature for 24 hours to form a disk having a diameter of 4 cm and a thickness of 4 mm.

Example 4

Polyester polyol (A), thiol (B), plasticizer (E) and filler (D1) were mixed in a weight ratio of 5.49:2.35:2.48:89.67 (A:B:E:D1) to prepare the main part (P1). prepared. In this case, as the polyester polyol (A), bifunctional caprolactone polyol (A1, weight average molecular weight 450 g/mol, Perstorp's CAPA2043) was used, and as the thiol (B), TMMP (trimethylolpropane tris (3-mercaptopropionate)) was used. The filler (D1) was spherical aluminum oxide (D11) having an average particle size of about 70 μm, spherical aluminum oxide (D12) having an average particle size of about 20 μm, and non-spherical aluminum oxide having an average particle size of about 2 μm. It was used by mixing in a weight ratio of 6:2:2 (D11:D12:D13). In addition, as the plasticizer (E), DINA (diisononyl adipate) was used.

A curing agent part (P2) was prepared by mixing the curing agent (C), the plasticizer (E), and the filler (D2) in a weight ratio of 7.75:2.45:89.80 (C:E:D2). In this case, as the curing agent (C), a trimer compound (LV2, trifunctional, Vencorex) based on hexamethylene diisocyanate (HDI) was used, and the filler (D2) was the same as that of the filler (D1). In addition, as the plasticizer (E), DINA (diisononyl adipate) was used.

The cured product was mixed with the main part (P1) and the curing agent part (P2) in a volume ratio of 1:1 (P1:P2), poured into a mold, and maintained at room temperature for 24 hours to have a diameter of 4 cm and a thickness of 4 mm. It was formed in the form of a disk (disk).

Example 5

Polyester polyol (A), thiol (B), plasticizer (E) and filler (D1) were mixed in a weight ratio of 3.71:3.71:2.89:89.68 (A:B:E:D1) to prepare the main part (P1). and mixing the curing agent (C), the plasticizer (E) and the filler (D2) in a weight ratio of 8.16:2.04:89.80 (C:E:D2) to prepare the curing agent part (P2). In the same manner as in 4, the main part (P1) and the curing agent part (P2) were stirred and mixed in a volume ratio of 1:1 (P1:P2), poured into a mold, and maintained at room temperature for 24 hours, with a diameter of 4 cm and a thickness of 4 mm was formed in the form of a disk of

Example 6

Polyester polyol (A), thiol (B), plasticizer (E), and filler (D1) were mixed in a weight ratio of 4.06:4.06:2.42:89.45 (A:B:E:D1) to prepare a main part (P1) At this time, the polyester polyol (A) was a bifunctional caprolactone polyol (A1, weight average molecular weight 450 g/mol, Perstorp's CAPA2043) and adipate polyol (A3, weight average molecular weight 2,000 g/mol, Kuraray) Company P-2010) was mixed in a weight ratio of 1:1 (A1:A3), and the curing agent (C), plasticizer (E) and filler (D2) were used in 7.49:2.49:90.01 (C:E:D2) In the same manner as in Example 4, except that the curing agent part P2 was prepared by mixing in a weight ratio of After stirring and mixing, it was poured into a mold and maintained at room temperature for 24 hours to form a disk having a diameter of 4 cm and a thickness of 4 mm.

Example 7

Polyester polyol (A), thiol (B), plasticizer (E), and filler (D1) were mixed in a weight ratio of 4.42:4.42:1.69:89.46 (A:B:E:D1) to prepare a main part (P1) At this time, the polyester polyol (A) was an adipate polyol (A3, weight average molecular weight 2,000 g/mol, Kuraray's P-2010) was used, and the curing agent (P2) was prepared by mixing the curing agent (C), the plasticizer (E) and the filler (D2) in a weight ratio of 6.75:3.25:90.00 (C:E:D2). In the same manner as in Example 4, except for one thing, the main part (P1) and the curing agent part (P2) were stirred and mixed in a volume ratio of 1:1 (P1:P2), poured into a mold, and maintained at room temperature for 24 hours. It was formed in the form of a disk having a diameter of 4 cm and a thickness of 4 mm.

Example 8

Polyester polyol (A), thiol (B), plasticizer (E) and filler (D1) were mixed in a weight ratio of 3.92:3.92:2.69:89.46 (A:B:E:D1) to prepare a main part (P1) At this time, the polyester polyol (A) was not a bifunctional caprolactone polyol (A1, weight average molecular weight 450 g/mol, Perstorp's CAPA2043) but a polyol (A3, weight average molecular weight 2,000 g/mol, Kuraray's P-2010) ), and the curing agent (C) is a trimer compound (LV2, trifunctional, Vencorex) based on HDI (Hexamethylene diisocyanate) and a bifunctional isocyanate compound based on HDI (Hexamethylene diisocyanate) (C2, AE700-100, Asahi) Kasei) used a mixed isocyanate compound mixed in a molar ratio of 6:1, and the curing agent (C), plasticizer (E) and filler (D2) were mixed with 7.80:2.20:90.00 (C:E:D2) by weight. In the same manner as in Example 4, except that the curing agent part P2 was prepared by mixing in a ratio, the main part P1 and the curing agent part P2 were stirred and mixed in a volume ratio of 1:1 (P1:P2). Then, it was poured into a mold and maintained at room temperature for 24 hours to form a disk having a diameter of 4 cm and a thickness of 4 mm.

Example 9

Polyester polyol (A), thiol (B), plasticizer (E), and filler (D1) were mixed in a weight ratio of 3.50:3.49:2.92:90.08 (A:B:E:D1) to prepare a main part (P1) At this time, the polyester polyol (A) was a bifunctional caprolactone polyol (A1, weight average molecular weight 450 g/mol, Perstorp CAPA2043) and adipate polyol (A3, weight average molecular weight 2,000 g/mol, Kuraray Corporation) P-2010) was mixed in a weight ratio of 1:1 (A1:A3), and the curing agent (C) was a trimer compound (LV2, trifunctional, Vencorex) based on HDI (Hexamethylene diisocyanate) and HDI. (Hexamethylene diisocyanate)-based bifunctional isocyanate compound (C2, AE700-100, Asahi Kasei) was mixed in a molar ratio of 6:1, and the curing agent (C), plasticizer (E) and filler (D2) were 8.67 In the same manner as in Example 4, except that the curing agent part P2 was prepared by mixing in a weight ratio of :1.97:89.37 (C:E:D2), the main part P1 and the curing agent part P2 were 1 After stirring and mixing at a volume ratio of :1 (P1:P2), it was poured into a mold and maintained at room temperature for 24 hours to form a disk having a diameter of 4 cm and a thickness of 4 mm.

Example 10

Polyester polyol (A), thiol (B), plasticizer (E), and filler (D1) were mixed in a weight ratio of 3.11:3.11:3.68:90.09 (A:B:E:D1) to prepare a main part (P1) At this time, the polyester polyol (A) was an adipate polyol (A3, weight average molecular weight 2,000 g/mol, Kuraray's P-2010) was used, and the curing agent (C) was a HDI (Hexamethylene diisocyanate)-based difunctional isocyanate compound (C2), not a HDI (Hexamethylene diisocyanate)-based trimer compound (LV2, trifunctional, Vencorex). , AE700-100, Asahi Kasei), and mixing the curing agent (C), plasticizer (E) and filler (D2) in a weight ratio of 9.42:1.22:89.36 (C:E:D2) to the curing agent part ( Except for preparing P2), in the same manner as in Example 4, the main part (P1) and the curing agent part (P2) were stirred and mixed at a volume ratio of 1:1 (P1:P2), poured into a mold, and then poured into a mold at room temperature for 24 hours. It was maintained for a period of time to form a disk having a diameter of 4 cm and a thickness of 4 mm.

Example 11

Polyester polyol (A), thiol (B), plasticizer (E), and filler (D1) were mixed in a weight ratio of 2.50:2.50:4.90:90.09 (A:B:E:D1) to prepare a main part (P1) At this time, the curing agent (C) was not a HDI (Hexamethylene diisocyanate)-based trimer compound (LV2, trifunctional, Vencorex), but an HDI (Hexamethylene diisocyanate)-based bifunctional isocyanate compound (C2, AE700-100, Asahi Kasei), the curing agent (C) and the filler (D2) were mixed in a weight ratio of 10.64:89.36 (C:D2) to prepare the curing agent part (P2), except that Example 4 and the above subject matter Part (P1) and curing agent part (P2) were stirred and mixed at a volume ratio of 1:1 (P1:P2), poured into a mold, and maintained at room temperature for 24 hours to form a disk with a diameter of 4 cm and a thickness of 4 mm. formed.

Example 12

Without using polyester polyol (A), thiol (B), plasticizer (E) and filler (D1) were mixed in a weight ratio of 3.98:4.07:91.94 (B:E:D1) to prepare the main part (P1). The curing agent (C) was not an HDI (Hexamethylene diisocyanate)-based trimer compound (LV2, trifunctional, Vencorex) but an HDI (Hexamethylene diisocyanate)-based bifunctional isocyanate compound (C2, AE700-100, Asahi Kasei) company), and the curing agent part (P2) was prepared by mixing the curing agent (C), the plasticizer (E) and the filler (D2) in a weight ratio of 11.69:0.81:87.50 (C:E:D2). Example 4 and the main part (P1) and the curing agent part (P2) were stirred and mixed in a volume ratio of 1:1 (P1:P2), poured into a mold, and maintained at room temperature for 24 hours, with a diameter of 4 cm and a thickness of 4 mm was formed in the form of a disk of

Example 13

Without using polyester polyol (A), thiol (B), plasticizer (E) and filler (D1) were mixed in a weight ratio of 3.98:4.07:91.94 (B:E:D1) to prepare the main part (P1). The curing agent (C) was not an HDI (Hexamethylene diisocyanate)-based trimer compound (LV2, trifunctional, Vencorex) but an HDI (Hexamethylene diisocyanate)-based bifunctional isocyanate compound (C2, AE700-100, Asahi Kasei) ) was used, and the curing agent (P2) was prepared by mixing the curing agent (C), the plasticizer (E) and the filler (D2) in a weight ratio of 11.69:0.81:87.50 (C:E:D2), and the plasticizer In (E), the main part (P1) and the curing agent part (P2) were 1:1 (P1) in the same manner as in Example 4, except that DBEEA (Bis[2-(2-butoxyethoxy)ethyl] adipate) was used. :P2) was stirred and mixed in a volume ratio, poured into a mold, and maintained at room temperature for 24 hours to form a disk having a diameter of 4 cm and a thickness of 4 mm.

Example 14

Polyester polyol (A), thiol (B), plasticizer (E) and filler (D1) were mixed in a weight ratio of 4.42:4.42:1.69:89.46 (A:B:E:D1) to prepare the main part (P1). At this time, the polyester polyol (A) was an adipate polyol (A3, weight average molecular weight 2,000 g/ mol, Kuraray P-2010) was used, and the curing agent (P2) was mixed with a curing agent (C), a plasticizer (E) and a filler (D2) in a weight ratio of 6.75:3.25:90.00 (C:E:D2). was prepared, and the plasticizer (E) was the main part (P1) and the curing agent part (P2) in the same manner as in Example 4 except that DBEEA (Bis[2-(2-butoxyethoxy)ethyl] adipate) was used. was stirred and mixed at a volume ratio of 1:1 (P1:P2), poured into a mold, and maintained at room temperature for 24 hours to form a disk having a diameter of 4 cm and a thickness of 4 mm.

Example 15

Polyester polyol (A), thiol (B), plasticizer (E) and filler (D1) were mixed in a weight ratio of 5.14:5.14:0.63:89.09 (A:B:E:D1) to prepare the main part (P1). The curing agent part (P2) was prepared by mixing the curing agent (C), the plasticizer (E) and the filler (D2) in a weight ratio of 6.85:4.27:88.89 (C:E:D2), and the plasticizer (E) In the same manner as in Example 4, except that an alkylsulfonic acid containing a phenol group (Mesamoll, LANXESS) was used, the main part (P1) and the curing agent part (P2) were mixed in a volume ratio of 1:1 (P1: P2). After stirring and mixing, it was poured into a mold and maintained at room temperature for 24 hours to form a disk having a diameter of 4 cm and a thickness of 4 mm.

Comparative Example 5

Without using the thiol (B), the polyester polyol (A) and the filler (D1) were mixed in a weight ratio of 13.40:86.60 (A:D1) to prepare the main part (P1), at this time the polyester polyol ( A) was not a bifunctional caprolactone polyol (A1, weight average molecular weight 450 g/mol, Perstorp CAPA2043), but an adipate polyol (A3, weight average molecular weight 2,000 g/mol, Kuraray company P-2010) was used. , the curing agent (C), the plasticizer (E), and the filler (D2) were mixed in a weight ratio of 2.11:4.93:92.95 (C:E:D2) to prepare the curing agent part (P2). In the same manner, the main part (P1) and the curing agent part (P2) were stirred and mixed in a volume ratio of 1:1 (P1:P2), poured into a mold, and maintained at room temperature for 24 hours to have a disk with a diameter of 4 cm and a thickness of 4 mm. (disk) was formed in the form.

Comparative Example 6

Without using thiol (B), polyester polyol (A), plasticizer (E) and filler (D1) were mixed in a weight ratio of 8.20:1.80:89.68 (A:E:D1) to prepare the main part (P1). and mixing the curing agent (C), the plasticizer (E) and the filler (D2) in a weight ratio of 7.09:3.11:89.80 (C:E:D2) to prepare the curing agent part (P2). In the same manner as in 4, the main part (P1) and the curing agent part (P2) were stirred and mixed in a volume ratio of 1:1 (P1:P2), poured into a mold, and maintained at room temperature for 24 hours, with a diameter of 4 cm and a thickness of 4 mm was formed in the form of a disk of

Comparative Example 7

Polyester polyol (A), thiol (B), plasticizer (E) and filler (D1) were mixed in a weight ratio of 5.49:2.35:2.48:89.67 (A:B:E:D1) to prepare the main part (P1). The curing agent part (P2) was prepared by mixing the curing agent (C), the plasticizer (E) and the filler (D2) in a weight ratio of 7.75:2.45:89.80 (C:E:D2), and the plasticizer (E) In the same manner as in Example 4, except that an alkylsulfonic acid containing a phenol group (Mesamoll, LANXESS) was used, the main part (P1) and the curing agent part (P2) were mixed in a volume ratio of 1:1 (P1: P2). After stirring and mixing, it was poured into a mold and maintained at room temperature for 24 hours to form a disk having a diameter of 4 cm and a thickness of 4 mm.

The physical property measurement results of the Examples and Comparative Examples are shown in the table below.

division Thermal Conductivity (W/mK) Adhesion (gf/cm) Example 1 3.19 207 Example 2 3.12 164 Example 3 3.02 103 Comparative Example 1 3.18 645 Comparative Example 2 3.03 756 Comparative Example 3 3.49 660 Comparative Example 4 3.25 446 Example 4 3.24 51 Example 5 3.15 58 Example 6 2.91 57 Example 7 2.72 60 Example 8 2.87 40 Example 9 2.83 52 Example 10 2.87 64 Example 11 3.05 46 Example 12 2.85 37 Example 13 3.14 39 Example 14 2.81 60 Example 15 3.12 66 Comparative Example 5 2.73 839 Comparative Example 6 3.04 784 Comparative Example 7 3.25 446

In Table 1, Examples 1 to 3 and Comparative Examples 1 to 4 show the results of measuring physical properties after forming the resin composition without a plasticizer.

As shown in Table 1, Comparative Examples 1 and 2 containing only the polyol in the main part exhibited adhesion higher than 400 gf/cm, and compared to 100 parts by weight of the thiol compound, more than 150 parts by weight of the polyol was included. Examples 3 and 4 also showed adhesion higher than 400 gf/cm.

On the other hand, Examples 1 to 3 including the thiol compound and the polyol in the main part and 150 parts by weight or less of the polyol relative to 100 parts by weight of the thiol compound showed an adhesive force of 400 gf/cm or less to secure reworkability. showed that it could

In Table 1, Examples 4 to 15 and Comparative Examples 5 to 7 show the results of measuring physical properties after forming the resin composition including a plasticizer.

As shown in Table 1, Comparative Examples 5 and 6 containing only the polyol in the main part showed adhesion higher than 400 gf/cm, and compared to 100 parts by weight of the thiol compound, more than 150 parts by weight of the polyol Example 7 also showed adhesion higher than 400 gf/cm.

On the other hand, Examples 5 to 15, which included a thiol compound and a polyol in the main part and 150 parts by weight or less of a polyol relative to 100 parts by weight of the thiol compound, showed an adhesive force of 400 gf/cm or less to secure reworkability. showed that it could

In addition, Example 4 including a thiol compound and a polyol in the main part and containing 233 parts by weight of a polyol relative to 100 parts by weight of the thiol compound used an adipic acid compound as a dispersant to have a higher polyol content ratio than other examples. and showed that it can have an adhesive strength lower than 400 gf/cm. In addition, Example 4 showed that the thermal conductivity could be improved by increasing the polyol content.

Example 8 in which the trifunctional isocyanate compound and the bifunctional isocyanate compound were used simultaneously showed that it could have a lower adhesive strength than Example 7 in which only the trifunctional isocyanate compound was used under the same conditions. Similarly, Example 9 in which the trifunctional isocyanate compound and the bifunctional isocyanate compound were simultaneously used could have lower adhesion compared to Example 6 in which only the trifunctional isocyanate compound was used under the same conditions. Therefore, it can be seen that using a mixture of the bifunctional isocyanate compound and the polyfunctional isocyanate compound is more advantageous in terms of securing reworkability.

Claims (19)

It contains a polyfunctional thiol compound and a filler,
A curable composition that forms a cured product having a peeling force of 400 gf/cm or less at room temperature to the PET (poly(ethylene terephthalate)) interface, confirmed with a peeling rate of 0.5 mm/s and a peeling angle of 180 degrees.
The curable composition according to claim 1, wherein the polyfunctional thiol compound is an alkane, alkene or alkyne substituted with two or more substituents of the following formula (3):
[Formula 3]

In Formula 3, L ₁ is an alkylene group having 1 to 20 carbon atoms, an alkenylene group having 2 to 20 carbon atoms, or an alkynylene group having 2 to 20 carbon atoms, Q is a single bond, a carbonyl group, an ester group or an amide group, and L ₂ is a single bond, an alkylene group having 1 to 20 carbon atoms, an alkenylene group having 2 to 20 carbon atoms, or an alkynylene group having 2 to 20 carbon atoms, and "*" means a bond.
The curable composition according to claim 2, wherein Q in Formula 3 is an ester group or a carbonyl group.
The curable composition according to claim 2, wherein the polyfunctional thiol compound contains 2 to 10 substituents of the formula (3).
The curable composition according to claim 1, wherein the polyfunctional thiol compound has a molecular weight in the range of 200 to 600 g/mol.
The curable composition according to claim 1, comprising 5 parts by weight or more of polyfunctional thiol based on 100 parts by weight of the filler.
The curable composition of claim 1, further comprising 150 parts by weight or less of a polyol based on 100 parts by weight of the polyfunctional thiol compound.
8. The curable composition of claim 7, wherein the polyol is a polyester polyol.
The curable composition according to claim 8, wherein the polyester polyol is a carboxylic acid polyol of the following formula (1) or a caprolactone polyol of the following formula (2).
[Formula 1]

[Formula 2]

In Formula 1, X is a unit derived from carboxylic acid, Y ₁ and Y ₂ are each independently a unit derived from a polyfunctional hydroxyl group compound, n is a number within the range of 1 to 20,
In Formula 2, Y is a unit derived from a polyfunctional hydroxyl group compound, and m ₁ and m ₂ are each independently a number within the range of 1 to 20.
The curable composition according to claim 7, wherein the polyol has a weight average molecular weight in the range of 300 to 2,000 g/mol.
The curable composition of claim 1, further comprising 10 to 150 parts by weight of a plasticizer based on 100 parts by weight of the polyfunctional thiol compound.
12. The curable composition of claim 11, wherein the plasticizer is an adipic acid compound.
The curable composition according to claim 12, wherein the adipic acid compound is represented by the following formula (4):
[Formula 4]

In Formula 4, P ₁ and P ₂ are each independently an alkyl group having 2 to 20 carbon atoms having one or a plurality of ether bonds, or an alkyl group having 2 to 20 carbon atoms substituted or unsubstituted with an alkyl group.
A main part comprising the curable composition of any one of claims 1 and 13; and
A two-part composition comprising a curing agent part comprising an isocyanate component.
15. The two-part composition according to claim 14, wherein the isocyanate component comprises at least one of a difunctional isocyanate compound and a trifunctional or higher polyfunctional isocyanate compound.
The two-part composition according to claim 15, wherein the ratio (M/M2) of the number of moles (M) of the trifunctional or higher polyfunctional isocyanate compound based on the number of moles (M2) of the bifunctional isocyanate compound is in the range of 4 to 8.
The two-part composition according to claim 14, wherein the curing agent part further comprises a filler in an amount within the range of 400 to 1,800 parts by weight based on 100 parts by weight of the isocyanate component.
The two-part composition according to claim 12, which is room temperature curable.
exothermic elements; and a cooling site;
A device comprising a cured product of the curable composition of claim 1 or the two-component composition of claim 14, wherein the two are in thermal contact between the exothermic element and the cooling portion.