KR20220132878A - Curable compositon - Google Patents

Abstract

The present application relates to a curable composition of which a curing rate can be easily determined and the curing rate can be easily controlled, and to a method for producing the same. The curable composition contains a base material including a resin component and a filler component and a hardener.

Description

Curable composition {CURABLE COMPOSITON}

This application relates to a curable composition.

Recently, as ultra-high-speed and ultra-miniaturization technologies have remarkably developed, devices or machines to which the technology is applied have higher power and higher speed. However, on the other hand, more heat is generated and a thermal problem is caused, which increases the demand for a thermally conductive curable composition having a heat dissipation effect, which can effectively disperse or remove heat.

The thermally conductive curable composition should have an appropriate curing rate for operator convenience. For example, it is required that the curable composition not be cured until it spreads in the area requiring a heat dissipation effect in the applied article, and it is required to cure quickly so that subsequent operations can be performed after spreading.

Conventionally, in order to control the curing rate, a method of controlling the type or amount of a catalyst capable of controlling the reactivity of the curing agent with the main constituent constituting the curable composition has been used. However, when using the method as described above, it was difficult to achieve a desired level of curing speed. In particular, since the curing rate of the curable composition is very sensitively changed even when a small amount of the catalyst is used, it is difficult to accurately implement a desired curing rate.

Therefore, there is a need for a new method in which an operator can easily determine the curing rate of the curable composition and easily control the curing rate.

An object of the present application is to provide a curable composition that can easily determine the curing rate and can easily control the curing rate.

In addition, an object of the present application is to provide a method for preparing a curable composition that can achieve the above object.

In addition, an object of the present application is to provide a battery module including the curable composition as described above or a cured product thereof.

Of the physical properties mentioned in this specification, the physical properties in which the measured temperature affects the physical properties are properties measured at room temperature unless otherwise specified.

As used herein, the term “room temperature” refers to a natural temperature that is not heated or reduced, for example, any one temperature within the range of about 10° C. to 30° C., for example, about 15° C., about 18° C., about 20 It means a temperature of about ℃, about 23 ℃ or about 25 ℃. In addition, unless otherwise specified in this specification, the unit of temperature is °C.

Among the physical properties mentioned in this specification, when the measured pressure affects the result, unless otherwise specified, the corresponding physical property is a physical property measured at normal pressure. The term “atmospheric pressure” refers to a natural temperature that is not pressurized or depressurized, and usually about 1 atmosphere is referred to as atmospheric pressure.

The term "alkyl group" as used herein, unless otherwise stated, 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 or branched chain having 1 to 6 carbon atoms. may mean an acyclic alkyl group of

Unless otherwise stated, the terms "alkylene group" or "alkylidene group" as used herein are, for example, an alkylene group or alkylidene group having 1 to 12 carbon atoms, 4 to 10 carbon atoms, or 6 to 9 carbon atoms. may mean The alkylene group or alkylidene group may be, for example, linear, branched or cyclic, and may be optionally substituted by one or more substituents.

As used herein, the term "alkenyl group" or "alkenylene group" refers to 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 carbon atoms, unless otherwise specified. 6 may mean a straight or branched acyclic alkenyl group or an alkenylene group.

As used herein, the term "alkynyl group" or "alkynylene group" refers to 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 carbon atoms, unless otherwise specified. 6 may mean a straight-chain or branched acyclic alkynyl group or an alkynylene group.

Unless otherwise stated, the term "alkoxy group" as used herein is, for example, a linear or branched chain having 1 to 20 carbon atoms, 1 to 16 carbon atoms, 1 to 12 carbon atoms, 1 to 8 carbon atoms, or 1 to 4 carbon atoms. It may mean an alkyl group or, for example, a cycloalkyl group having 3 to 20 carbon atoms, 3 to 16 carbon atoms, or 4 to 12 carbon atoms. The alkyl group may be optionally substituted by one or more substituents.

As used herein, the term "aryl group" is, unless otherwise specified, a compound containing a benzene structure, a compound containing a structure in which two or more benzenes are connected by a linker, and two benzenes are each one or may refer to a monovalent moiety derived from a compound comprising a condensed or bonded structure while sharing two carbon atoms or a derivative of any one of the above-mentioned compounds. The scope of the aryl group as used in the present application may include a functional group commonly referred to as an aryl group, as well as a so-called aralkyl group or an arylalkyl group. The aryl group may be, for example, an aryl group having 6 to 25 carbon atoms, 6 to 21 carbon atoms, 6 to 18 carbon atoms, or 6 to 12 carbon atoms. Examples of the aryl group include a phenyl group, a dichlorophenyl group, a chlorophenyl group, a phenylethyl group, a phenylpropyl group, a benzyl group, a tolyl group, a xylyl group, or a naphthyl group.

In the present specification, the term “carboxylic acid-derived unit” used herein may mean a portion excluding a carboxyl group in a carboxylic acid compound. Similarly, as used herein, the term “polyol-derived unit” may refer to a portion of the polyol compound structure excluding a hydroxyl group.

In the present specification, the term “average particle size” is a so-called D50 particle size (median particle size), and may mean a particle diameter at 50% of the volume basis of the particle size distribution. It means the particle diameter at the point where the cumulative value is 50% on the cumulative curve that calculates the particle size distribution based on the volume and assumes 100% of the total volume. The D50 particle size as described above may be measured by a laser diffraction method.

The curable composition of the present application includes a main agent including a resin component and a filler component, and a curing agent.

The main agent and the curing agent included in the curable composition of the present application are mixed at room temperature and a relative humidity condition within the range of 40 to 60%, and the compressive force when maintained at the same temperature and relative humidity condition for 1 hour may be 7N or more. The compressive force means a compressive force measured in a state in which the main agent and the curing agent are mixed in a volume ratio of 1:1.

In one example, the curable composition may be a room temperature curable type. That is, the curing reaction may be initiated and proceeded at room temperature immediately after mixing the main agent and the curing agent included in the curable composition of the present application.

In one example, the main agent and the curing agent are mixed at room temperature and a relative humidity condition within the range of 40 to 60%, and the compressive force when maintained for 1 hour at the same temperature and relative humidity condition is 7.5N or more, 8N or more, 8.5N or more , 9 N or more, 9.5 N or more, 10 N or more, 10.5 N or more, 11 N or more, 11.5 N or more, 12 N or more, 12.5 N or more, 13 N or more, 13.5 N or more, or 14 N or more. The main agent and the curing agent are mixed at room temperature and a relative humidity condition within the range of 40 to 60%, and the upper limit of the compressive force when maintained for 1 hour at the same temperature and relative humidity condition is not particularly limited, but for example, 30N or less, 28N or less, 26 N or less, 24 N or less, 22 N or less, 20 N or less, 18 N or less, 16 N or less, 14 N or less, 12 N or less, or 11 N or less. The compressive force may be measured by a measuring method in an embodiment to be described later.

When the main agent and the curing agent in the curable composition are mixed at room temperature and 40 to 60% relative humidity conditions, and the compressive force when maintained for 1 hour appears in the above range, the workability and fairness required by the present application for the cured product of the curable composition It may have an initial curing rate that can satisfy , and it may be determined that the curing rate is improved.

The main agent and curing agent included in the curable composition of the present application are mixed at room temperature and a relative humidity condition within the range of 40 to 60%, and the compressive force when maintained at the same temperature and relative humidity condition for 2 hours may exceed 35N. The compressive force means a compressive force measured in a state in which the main agent and the curing agent are mixed in a volume ratio of 1:1.

In one example, the main agent and the curing agent are mixed at room temperature and a relative humidity condition within the range of 40 to 60%, and the compressive force when maintained at the same temperature and relative humidity condition for 2 hours is 36N or more, 38N or more, 40N or more, 42 N or more, 44 N or more, or 46 N or more, or 50 N or less, 45 N or less, 40 N or less, or 35 N or less. The compressive force may be measured by a measuring method in an embodiment to be described later. When the main agent and the curing agent in the curable composition are mixed at room temperature and 40 to 60% relative humidity conditions, and the compressive force when maintained for 2 hours appears in the above range, the workability and fairness required by the present application for the cured product of the curable composition It may have an initial curing rate that can satisfy , and it may be determined that the curing rate is improved.

The main agent and the curing agent included in the curable composition of the present application are mixed at room temperature and a relative humidity condition within the range of 40 to 60%, and the Shore A hardness when maintained at the same temperature and relative humidity condition for 3 hours may be 40 or more. The Shore A hardness means the Shore A hardness measured in a state in which the main agent and the curing agent are mixed in a volume ratio of 1:1.

In one example, the main agent and the curing agent are mixed at room temperature and a relative humidity condition within the range of 40 to 60%, and the Shore A hardness when maintained at the same temperature and relative humidity condition for 3 hours is 42 or more, 44 or more, 46 or more , 48 or more, 50 or more, 52 or more, 54 or more, 56 or more, 58 or more, 60 or more, 62 or more, or 64 or more, or 75 or less, 70 or less, 65 or less, or 60 or less. The Shore A hardness may mean Shore A hardness measured by the measurement method in Examples to be described later according to ASTM D 2240 standard. When the main agent and the curing agent in the curable composition are mixed at room temperature and 40 to 60% relative humidity conditions, and the compressive force when maintained for 3 hours appears in the above range, the workability and fairness required in the present application for the cured product of the curable composition It can be determined that the curing speed is improved to satisfy .

In one example, the curable composition of the present application may have a rate of change of Shore A hardness according to Equation 1 below 15/h. The rate of change of the Shore A hardness according to Equation 1 below means the rate of change of the Shore A hardness measured in a state in which the main agent and the curing agent are mixed in a volume ratio of 1:1.

[Equation 1]

Rate of change of Shore A hardness = 0.2 × (H ₈ -H ₃ )

In Equation 1, H ₈ is the Shore A hardness when the main agent and the curing agent are mixed at room temperature and a relative humidity condition within the range of 40 to 60%, and maintained at the same temperature and relative humidity condition for 8 hours, H ₃ is the main agent and Shore A hardness when the curing agent is mixed at room temperature and a relative humidity within the range of 40 to 60% and maintained at the same temperature and relative humidity for 3 hours.

Specifically, the rate of change of Shore A hardness according to Equation 1 is 14/h or less, 13/h or less, 12/h or less, 11/h or less, 10/h or less, 9/h or less, 8/h or less, 7 It may be less than or equal to /h or less than or equal to 6/h. The lower limit of the change rate of Shore A hardness according to Equation 1 is not particularly limited, but may be 2/h or more, 3/h or more, 4/h or more, 5/h or more, 6/h or more, or 7/h or more. . When the change rate of Shore A hardness according to Equation 1 satisfies the above range, it can be determined that the curing rate is improved so that the cured product of the curable composition can satisfy the workability and fairness required in the present application.

The curable composition of the present application may have a TA hardness of 0.5 kgf or more when the main agent and the curing agent are mixed at room temperature and a relative humidity condition within the range of 40 to 60%, and maintained at the same temperature and relative humidity condition for 1 hour. The TA hardness means the hardness measured by the measurement method in the following examples by the Texture Analyzer (TA).

Specifically, the main agent and the curing agent are mixed at room temperature and a relative humidity condition within the range of 40 to 60%, and the TA hardness when maintained for 1 hour at the same temperature and relative humidity condition is 0.6 kgf or more, 0.7 kgf or more, 0.8 kgf or more , 0.9 kgf or more, 1 kgf or more, 1.1 kgf or more, 1.2 kgf or more, 1.3 kgf or more, 1.4 kgf or more, 1.5 kgf or more, 1.6 kgf or more, 1.7 kgf or more, 1.8 kgf or more, 1.9 kgf or more, or 2 kgf or more . The upper limit of the TA hardness value when the main agent and the curing agent are mixed at room temperature and a relative humidity condition within the range of 40 to 60%, and maintained for 1 hour at the same temperature and relative humidity condition is not particularly limited, but 8 kgf or less, 7 kgf or less, 6 kgf or less, 5 kgf or less, 4 kgf or less, 3 kgf or less, 2 kgf or less, or 1.5 kgf or less. When the main agent and the curing agent are mixed at room temperature and a relative humidity condition within the range of 40 to 60%, and the TA hardness when maintained for 1 hour satisfies the above range, the cured product of the curable composition has workability and It may have an initial curing rate that can satisfy fairness, and it may be determined that the curing rate is improved.

The curable composition of the present application may have a rate of change of TA hardness of 5 kgf/h or more according to Equation 2 below. Mixing for measuring the rate of change of TA hardness according to Equation 2 may mean mixing the main agent and the curing agent in a volume ratio of 1:1.

[Equation 2]

Rate of change of TA hardness = 0.5 × (T ₃ -T ₁ )

In Equation 2, T ₃ is the TA hardness when the main agent and the curing agent are mixed at room temperature and a relative humidity condition within the range of 40 to 60%, and maintained at the same temperature and relative humidity condition for 3 hours, T ₁ is the main agent and the curing agent is the TA hardness when mixed at room temperature and a relative humidity condition within the range of 40 to 60%, and maintained at the same temperature and relative humidity condition for 1 hour.

Specifically, the rate of change of the TA hardness is 5.5 kgf/h or more, 6 kgf/h or more, 6.5 kgf/h or more, 7 kgf/h or more, 7.5 kgf/h or more, 8 kgf/h or more, 8.5 kgf/h or more , 9 kgf/h or more, 9.5 kgf/h or more, 10 kgf/h or more, 10.5 kgf/h or more, 11 kgf/h or more, or 11.5 kgf/h or more. The upper limit of the TA hardness change rate is not particularly limited, but for example, 20 kgf / h or less, 19 kgf / h or less, 18 kgf / h or less, 17 kgf / h or less, 16 kgf / h or less, 15 kgf / h or less, 14 kgf/h or less, 13 kgf/h or less, 12 kgf/h or less, 11 kgf/h or less, 10 kgf/h or less, or 9.5 kgf/h or less. When the rate of change of TA hardness according to Equation 2 satisfies the above range, it can be determined that the curing rate is improved so that the cured product of the curable composition can satisfy the workability and fairness required in the present application.

In one example, the resin composition of the present application may be a two-component resin composition including a main agent and a curing agent, and the subject may include a resin component and a filler component.

The subject included in the curable composition of the present application may have a moisture content of 200 ppm or more. The water content of the subject matter may be the water content measured by the Karl Fischer coulometric method and the measurement method in the following Examples.

Specifically, the moisture content of the subject matter is 210 ppm or more, 220 ppm or more, 230 ppm or more, 240 ppm or more, 250 ppm or more, 260 ppm or more, 270 ppm or more, 280 ppm or more, 290 ppm or more, 300 ppm or more, 310 ppm or more , 320 ppm or more, 330 ppm or more, 340 ppm or more, 350 ppm or more, 360 ppm or more, or 370 ppm or more. The upper limit of the moisture content of the subject matter may be 600 ppm or less, 550 ppm or less, 500 ppm or less, 450 ppm or less, 400 ppm or less, 350 ppm or less, 300 ppm or less, 250 ppm or less, or 220 ppm or less.

When the moisture content of the main agent in the curable composition of the present application satisfies the above range, the compressive force and Shore A hardness as described above when the main agent and the curing agent of the curable composition are mixed at room temperature and relative humidity within the range of 40 to 60% and TA hardness. Accordingly, it may have a curing rate that can satisfy the workability and processability required in the present application.

In one example, the curable composition of the present application may be a silicone-based resin composition, a urethane-based resin composition, an epoxy-based resin composition, or an acrylic resin composition. When the curable composition of the present application is a silicone-based resin composition, a silicone resin may be used as the subject and a siloxane compound may be used as the curing agent. When the curable composition of the present application is a urethane-based resin composition, a polyol resin is used as the subject and a curing agent may use an isocyanate compound. When the curable composition of the present application is an epoxy-based resin composition, an epoxy resin may be used as the subject and an amine compound may be used as the curing agent. When the curable composition of the present application is an acrylic resin composition, an acrylic resin is used as the subject, and An isocyanate compound can be used as a hardening|curing agent.

In one example, the curable composition of the present application may be a urethane-based resin composition. The urethane-based resin composition may be a two-part urethane resin composition, and the two-part urethane resin composition may include a main agent including a polyol and the like and a curing agent including a polyisocyanate compound.

The polyol means a compound containing two or more hydroxyl groups, (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-cyclohexanedimethanol 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 trimethylolpropane may be exemplified, but are not particularly limited thereto it is not

In one example, a polyester-based polyol may be used as the polyol of the present application. The polyester-based polyol may include a carboxylic acid-based polyol and/or a caprolactone-based polyol.

The carboxylic acid polyol may be formed by reacting a component containing a carboxylic acid and a polyol (eg, a diol or a triol), and the caprolactone polyol includes caprolactone and a polyol (eg, diol or triol). It can be formed by reacting the components. In this case, the carboxylic acid may be a dicarboxylic acid.

In one example, the polyol may be a polyol represented by the following Chemical Formula 1 or 2.

[Formula 1]

[Formula 2]

In Formulas 1 and 2, X is a carboxylic acid-derived unit, and Y is a polyol-derived unit. The polyol-derived unit may be, for example, a triol unit or a diol unit. Also, n and m may be arbitrary numbers. For example, n may be a number in the range of 2 to 10 or 2 to 5, and m may be a number in the range of 1 to 10 or 1 to 5. In Formulas 1 and 2, R ₁ and R ₂ are each independently an alkylene group, and specific types of the alkylene group are the same as those described in the introduction of the means for solving the problems of the present specification.

That is, when the hydroxyl group of the polyol and the carboxyl group of the carboxylic acid react, water (H ₂ O) molecules are desorbed by the condensation reaction, thereby forming an ester bond. As such, when the carboxylic acid forms an ester bond by the condensation reaction, the carboxylic acid-derived unit may mean a portion of the carboxylic acid structure that does not participate in the condensation reaction. In addition, the polyol-derived unit may refer to a portion of the polyol structure that does not participate in the condensation reaction.

In addition, Y in Formula 2 also represents a portion excluding the ester bond after the polyol forms an ester bond with caprolactone. That is, when the polyol-derived unit Y in Formula 2 forms an ester bond between the polyol and caprolactone, it may mean a portion of the polyol structure that does not participate in the ester bond. The ester bonds are shown in Formulas 1 and 2, respectively.

Meanwhile, when the polyol-derived unit in Formula Y is a unit derived from a polyol including three or more hydroxyl groups, such as a triol unit, a branched structure may be implemented in the Y portion in the Formula Y.

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, an aromatic compound having two or more carboxyl groups, an alicyclic compound having two or more carboxyl groups, and two or more carboxyl groups It may be a unit derived from one or more compounds selected from the group consisting of aliphatic compounds having.

The aromatic compound having two or more carboxyl groups may be, for example, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid or tetrachlorophthalic acid. The alicyclic compound having two or more carboxyl groups may be, for example, tetrahydrophthalic acid or hexahydrophthalic acid or tetrachlorophthalic acid. In addition, the aliphatic compound having two or more carboxyl groups is, for example, oxalic acid, adipic acid, azelaic acid, sebacic acid, succinic acid, malic acid, glutaric acid, malonic acid, pimelic acid, suberic acid, 2,2-dimethyl succinic acid, 3,3-dimethylglutaric acid, 2,2-dimethylglutaric acid, maleic acid, fumaric acid or itaconic acid.

Meanwhile, in Formulas 1 and 2, the type of the polyol-derived unit of Y is not particularly limited, but in order to secure desired physical properties, from the group consisting of an alicyclic compound having two or more hydroxyl groups and an aliphatic compound having two or more hydroxyl groups may be derived from one or more selected compounds.

The alicyclic compound having two or more hydroxyl groups may be, for example, 1,3-cyclohexanedimethanol or 1,4-cyclohexanedimethanol. In addition, the aliphatic compound having two or more hydroxyl groups is, for example, ethylene glycol, 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, glycerin or trimethylol It may be propane.

In one example, the filler component may be a thermally conductive filler. The thermal conductivity of the thermally conductive filler may be, for example, about 1 W/m·K or more, about 5 W/m·K or more, about 10 W/m·K or more, or about 15 W/m·K or more. In another example, the thermal conductivity of the thermally conductive filler may be about 400 W/m·K or less, about 350 W/m·K or less, or about 300 W/m·K or less.

As said thermally conductive filler, For example, 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, the 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 component is not particularly limited, and may be selected in consideration of the viscosity of the curable composition, the possibility of precipitation in the curable composition, desired thermal resistance or thermal conductivity, insulation, filling effect or dispersibility, and the like.

The shape of the filler component may be used by appropriately selecting a spherical and/or non-spherical shape (eg, needle-shaped and plate-shaped, etc.) as needed, but is not limited thereto.

The filler component may be prepared by mixing a filler component (C1) having a moisture content of 150 ppm or less and an average particle diameter of 10 μm or more and a filler component (C2) having a moisture content of 250 ppm or more and an average particle diameter of less than 10 μm.

Specifically, the moisture content of the filler component (C1) may be 145ppm or less, 140ppm or less, 135ppm or less, 130ppm or less, 125ppm or less, 120ppm or less, 115ppm or less, 110ppm or less, 105ppm or less, or 100ppm or less. The lower limit of the moisture content of the filler component (C1) is not particularly limited, but may be 0 ppm or more, 10 ppm or more, 30 ppm or more, 50 ppm or more, 70 ppm or more, or 90 ppm or more. The moisture content of the filler component (C1) may be the moisture content measured by the Karl Fischer coulometric method and the measurement method in the following Examples.

In one example, the filler component (C1) may be configured by mixing a first filler having an average particle diameter in a range of 30 μm to 100 μm, and a second filler having an average particle diameter in a range of 10 μm to 30 μm. In this case, the moisture content included in the filler component (C1) may be an average moisture content of the first and second fillers constituting the filler component (C1), and the moisture content of the first filler and the second filler is Each may be 150 ppm or less. In one example, the average particle diameter of the first filler is 31 μm or more, 32 μm or more, 33 μm or more, 34 μm or more, 35 μm or more, 36 μm or more, 37 μm or more, 38 μm or more, 39 μm or more, or 40 microns or more, 95 microns or less, 90 microns or less, 85 microns or less, 80 microns or less, 75 microns or less, 70 microns or less, 65 microns or less, 60 microns or less, 55 microns or less, 50 microns or less, 45 microns or less, or 40 microns or less may be below.

Also in one example, the average particle diameter of the second filler is 11 μm or more, 12 μm or more, 13 μm or more, 14 μm or more, 15 μm or more, 16 μm or more, 17 μm or more, 18 μm or more, 19 μm or more, or 20 μm or more, 29 μm or less, 28 μm or less, 27 μm or less, 26 μm or less, 25 μm or less, 24 μm or less, 23 μm or less, 22 μm or less, or 21 μm or less.

When the first filler and the second filler are mixed and used as the filler component (C1), the ratio (W1/W2) of the weight (W1) of the first filler and the weight (W2) of the second filler is 0.5 to 2 May be within range tomorrow. Specifically, the weight ratio (W1/W2) is 0.6 or more, 0.7 or more, 0.8 or more, 0.9 or more, 1 or more, 1.1 or more, 1.2 or more, or 1.3 or more, or 2 or less, 1.9 or less, 1.8 or less, 1.7 or less, 1.6 or less. , 1.5 or less or 1.4 or less.

The filler component (C2) (hereinafter, the third filler) may have a moisture content of 250 ppm or more. Specifically, the moisture content of the third filler may be 300 ppm or more, 350 ppm or more, 400 ppm or more, 450 ppm or more, or 500 ppm or more. When the third filler contains an excessive amount of moisture, aggregation of the filler component may occur and dispersibility may be deteriorated. Accordingly, there may occur a problem that the process time is increased or the quality of the cured product of the curable composition is deteriorated, so the upper limit of the moisture content of the third filler is 1300 ppm or less, 1200 ppm or less, 1100 ppm or less, 1000 ppm or less, 900 ppm or less, 800 It is preferable to set it so that it may become ppm or less, 700 ppm or less, 600 ppm or less, or 500 ppm or less. The water content of the third filler may be a water content measured by a Karl Fischer coulometric titration method and a measurement method in the following Examples.

The third filler having an average particle diameter of less than 10 μm has a larger specific surface area than a filler component (first filler or second filler) having an average particle diameter of 10 μm or more. Controlling the moisture content of the first filler or the second filler component having a relatively small specific surface area is more difficult than controlling the moisture content of the third filler component having a relatively large specific surface area. In the present application, by adjusting the moisture content of the third filler having a small particle size in the above range, the moisture content in the subject matter can be adjusted to be 200 ppm or more as described above, and thus, it is possible to satisfy the workability and fairness required in the present application. A curing rate of the curable composition may be realized.

Specifically, the third filler has an average particle diameter of 9.5 μm or less, 9 μm or less, 8.5 μm or less, 8 μm or less, 7.5 μm or less, 7 μm or less, 6.5 μm or less, 6 μm or less, 5.5 μm or less, 5 μm or less , 4.5 μm or less, 4 μm or less, 3.5 μm or less, or 3 μm or less. The lower limit of the average particle diameter of the third filler may be 0.001 μm or more, 0.01 μm or more, 0.1 μm or more, 0.5 μm or more, 1 μm or more, 1.5 μm or more, or 2 μm or more.

In one example, the third filler may be included in an amount of 10 to 50% by weight based on the total filler component. Specifically, the third filler is 12 wt% or more, 14 wt% or more, 16 wt% or more, 18 wt% or more, 20 wt% or more, 22 wt% or more, 24 wt% or more, 26 wt% or more, based on the total filler component. , 28 wt% or more, or 30 wt% or more, or 48 wt% or less, 46 wt% or less, 44 wt% or less, 42 wt% or less, 40 wt% or less, 38 wt% or less, 35 wt% or less or 33 wt% or less can

Moisture contained in the filler component according to the present application may activate the reaction of a catalyst capable of accelerating the curing reaction of the main agent and the curing agent in the curable composition, as will be described later. By adjusting the moisture content of the filler component included in the curable composition according to the present application to the above range, the curing rate of the curable composition may be appropriately adjusted.

In one example, the subject may include 100 parts by weight or more of the filler component based on 100 parts by weight of the resin component. Specifically, the filler component is 120 parts by weight or more, 140 parts by weight or more, 160 parts by weight or more, 180 parts by weight or more, 200 parts by weight or more, 220 parts by weight or more, 240 parts by weight or more, 260 parts by weight based on 100 parts by weight of the resin component. It may be included in parts by weight or more, 280 parts by weight or more, or 300 parts by weight or more. The upper limit of the content of the filler component is not particularly limited, but for example, about 900 parts by weight or less, 800 parts by weight or less, 700 parts by weight or less, 600 parts by weight or less, 500 parts by weight or less, 400 parts by weight or less, based on 100 parts by weight of the resin component. It may be included in parts by weight or less or 350 parts by weight or less. When the filler component of the present application is included in the above range relative to 100 parts by weight of the resin component, it is possible to provide a resin composition having an improved curing rate.

In one example, the subject may further comprise a catalyst. The catalyst may serve to promote a curing reaction between the main agent and the curing agent in the curable composition.

As the catalyst that can be used in the present application, a metal catalyst or an amine catalyst capable of accelerating the curing reaction of the curable composition may be used.

As the metal catalyst, an organometallic compound, for example, an organotin compound, an organobismuth compound, an organozirconium compound, or an organoaluminum compound may be applied, but an organotin compound is preferably used.

Examples of the organotin compound include dibutyltin dilaurate (DBTL), stannous octoacte, dibutyltin diacetate, or dibutyltin dimercaptide. Dialkyltin dicarboxylates may be applied.

In addition, as an amine catalyst, 1,4-diazabicyclo[2,2,2]octane (1,4-diazabicyclo[2,2,2]octane), bis(2-dimethylaminoethyl)ether (bis(2) -dimethylaminoethyl)ether), trimethylaminoethylethanolamine (trimethylaminoethylethanolamine), N,N,N',N',N''-pentamethyldiethylenetriamine (N,N,N',N',N''- pentamethyldiethylenetriamine), N,N'-dimethylethanolamine (N,N'-dimethylethanolamine), dimethylaminopropylamine, N-ethylmorpholine (N-ethylmorpholine), N,N-dimethylaminoethylmorpholine (N ,N-dimethylaminoethylmorpholine), N,N-dimethylcyclohexylamine (N,N-dimethylcyclohexylamine) or a tertiary amine such as 2-methyl-2-azanorbonrnane (2-methyl-2-azanorbonrnane) It may be applied, but is not limited thereto.

In one example of the present application, the weight ratio (B/A) of the catalyst (A) to the filler component (B) may be 2500 or less. Specifically, the weight ratio (B/A) is 2400 or less, 2300 or less, 2200 or less, 2100 or less, 2000 or less, 1900 or less, 1800 or less, 1700 or less, 1600 or less, 1500 or less, 1400 or less, 1300 or less, 1200 or less , 1100 or less, 1000 or less, 900 or less, or 800 or less. The lower limit of the weight ratio (B/A) may be 500 or more, 550 or more, 600 or more, 650 or more, 700 or more, or 750 or more. When the weight ratio (B/A) of the filler component (B) to the catalyst (A) is adjusted within the above range, the moisture contained in the filler component activates the reaction of the catalyst to set the curing rate of the curable composition within the desired range. can be appropriately adjusted.

In one example, the moisture content of the curing agent included in the curable composition of the present application may be 150 ppm or less. In another example, the water content of the curing agent may be 145 ppm or less, 140 ppm or less, 135 ppm or less, 130 ppm or less, 125 ppm or less, 120 ppm or less, or 115 ppm or less. The lower limit of the moisture content of the curing agent is not particularly limited, but may be 0 ppm or more, 10 ppm or more, 50 ppm or more, or 100 ppm or more. The water content may be a water content measured by a Karl Fischer coulometric titration method or a measurement method in Examples to be described later.

The curing agent may include a polyisocyanate compound. In one example, when the curing agent includes a polyisocyanate compound, it may include a trifunctional or more polyfunctional polyisocyanate compound and a bifunctional polyisocyanate compound.

The bifunctional polyisocyanate compound refers to a compound containing two isocyanate groups (-N = C = O) in one molecule, and the polyfunctional polyisocyanate compound refers to a compound containing three or more isocyanate groups . In another example, the polyfunctional polyisocyanate compound may include 3 to 10, 3 to 9, 3 to 7, 3 to 6, 3 to 5, or 3 to 4 isocyanate groups. can

As the bifunctional polyisocyanate compound of the present application, at least one or more of an aliphatic difunctional polyisocyanate compound and an aliphatic difunctional polyisocyanate compound may be used, but it is preferable to use an aliphatic difunctional polyisocyanate compound.

The aliphatic difunctional polyisocyanate compound may be exemplified by hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate, norbornane diisocyanate methyl, ethylene diisocyanate, propylene diisocyanate, and tetramethylene diisocyanate. However, it is not particularly limited thereto. The aliphatic cyclic difunctional polyisocyanate may be exemplified by transcyclohexane-1,4-diisocyanate, isophorone diisocyanate, bis(isocyanatemethyl)cyclohexane diisocyanate and dicyclohexylmethane diisocyanate, but is particularly limited thereto. it is not In addition, the said bifunctional polyisocyanate compound can use 1 type or 2 or more types.

The polyfunctional polyisocyanate compound according to the present application may use, for example, a multimer more than a trimer of the polyisocyanate compound, and a compound in the form of a biuret obtained by reacting the polyisocyanate compound with water. Can be used. That is, as the polyfunctional polyisocyanate compound, at least one selected from a multimer of the polyisocyanate compound and a biuret compound may be used.

Specifically, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate, norbornane diisocyanate methyl, ethylene diisocyanate, propylene diisocyanate, tetramethylene diisocyanate, transcyclohexane-1,4- Polymers such as diisocyanate, isophorone diisocyanate, bis(isocyanatemethyl)cyclohexane diisocyanate and dicyclohexylmethane diisocyanate, and biuret-form compounds can be exemplified as polyfunctional polyisocyanate compounds.

In one example of the present application, the polyfunctional polyisocyanate compound may be a trifunctional polyisocyanate compound including three isocyanate groups. The trifunctional polyisocyanate compound may be a compound represented by Formula 3 below.

[Formula 3]

In Formula 3, L ₇ , L ₈ , and L ₉ may each independently be an alkylene group, an alkenylene group, or an alkynyl group. Specific types of the alkylene group, alkenylene group, or alkynyl group in the definition of Chemical Formula 3 are the same as those described in the beginning of the means for solving the problems of the present specification.

When the curing agent includes a polyisocyanate compound including a trifunctional or higher polyfunctional polyisocyanate compound and a bifunctional polyisocyanate compound, the trifunctional or higher polyfunctional polyisocyanate compound is 20 wt% or more, 23 wt% of the total polyisocyanate compound % or more, 25 wt% or more, 27 wt% or more, 30 wt% or more, 32 wt% or more, 35 wt% or more, 37 wt% or more, 40 wt% or more, or 42 wt% or more, or 85 wt% or less, 80 Weight % or less, 75 wt% or less, 70 wt% or less, 65 wt% or less, 60 wt% or less, 55 wt% or less, 50 wt% or less, or 45 wt% or less.

In addition, the bifunctional polyisocyanate compound is 15 wt% or more, 17 wt% or more, 20 wt% or more, 22 wt% or more, 25 wt% or more, 28 wt% or more, 30 wt% or more, 32 wt% in the total polyisocyanate compound. % or more, 35% or more, 37% or more, 40% or more, 42% or more, 45% or more, 47% or more, 50% or more, 52% or more, 55% or more, or 57% or more % or less, or 80 wt% or less, 75 wt% or less, 70 wt% or less, 65 wt% or less, or 60 wt% or less.

In one example of the present application, the curing agent may further include a filler component. The filler component included in the curing agent may also be a thermally conductive filler. The same contents as those described in the filler component included in the subject matter may be applied to the thermal conductivity, type, and shape or ratio of the thermally conductive filler.

The particle diameter of the filler component included in the curing agent may be in the range of 0.001 μm to 100 μm. In another example, the average particle diameter of the filler may be 0.005 μm or more, 0.01 μm or more, 0.05 μm or more, 0.1 μm or more, 0.5 μm or more, 1 μm or more, 1.5 μm or more, or 2 μm or more. The upper limit of the average particle diameter of the filler component included in the curing agent is about 95 μm or less, about 85 μm or less, about 80 μm or less, 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 It may be 5 μm or less.

In one example, the curing agent may include 100 parts by weight or more of the filler component based on 100 parts by weight of the polyisocyanate compound. Specifically, the filler component may include 100 parts by weight or more of the filler component based on 100 parts by weight of the polyisocyanate compound, in one example, based on 100 parts by weight of the resin component. Specifically, the filler component is 200 parts by weight or more, 300 parts by weight or more, 400 parts by weight or more, 500 parts by weight or more, 600 parts by weight or more, 700 parts by weight or more, 800 parts by weight or more, 900 parts by weight based on 100 parts by weight of the resin component. It may be included in parts or more or 1000 parts by weight or more. The upper limit of the content of the filler component in the curing agent is not particularly limited, but for example, about 1500 parts by weight or less, 1450 parts by weight or less, 1400 parts by weight or less, 1350 parts by weight or less, 1300 parts by weight or less, based on 100 parts by weight of the polyisocyanate compound. , 1250 parts by weight or less, 1200 parts by weight or less, 1150 parts by weight or less, 1100 parts by weight or less, or 1050 parts by weight or less.

The curing agent may further include a desiccant. When the polyisocyanate included in the curing agent is directly in contact with moisture, an amine group and carbon dioxide are formed, which may cause problems such as surface hardening or viscosity increase of the curable composition. When the curing agent contains a moisture absorbent, storage stability of the curable composition can be secured, and problems such as surface hardening of the curable composition or increase in viscosity due to moisture can be solved.

The absorbent is, for example, methyldiphenylethoxysilane, molecular sieves, p-toluenesulfonyl isocyanate (PTSI), p-toluene-sulfonyl isocyanate (p-) toluene-sulfonyl isocyanate: TI), for example, acid anhydride esters such as diethyl malonate and dimethyl succinate, unsaturated silane compounds represented by the following Chemical Formula 4, and mixtures thereof can be

[Formula 4]

R ¹ SiR ² _(n) R ³ _(3-n)

In Formula 4, R ¹ may be an alkenyl group. In one example, R ¹ may be vinyl, allyl, propenyl, isopropenyl, butenyl, hexenyl, cyclohexenyl, or γ-methacryloxy propyl. In Formula 4, R ² and R ³ may each independently represent hydrogen, an alkyl group, an aryl group, an aralkyl group, a hydroxyl group, a halogen, an amine group, or —R ⁴ R ⁵ bonded to a silicon atom. In one example, R ⁴ is an oxygen or sulfur atom, R ⁵ is an alkyl group, an aryl group, an aralkyl group, an acyl group, or —R ⁶ R ⁷ , R ⁶ is an alkylene group or an alkylidene group, and R ⁷ is an alkoxy it can be a gimmick Also, in Formula 4, n may be an integer of 1 to 3.

In Chemical Formula 4, specific types of an alkenyl group, an alkyl group, an aryl group, an aralkyl group, an alkylene group, an alkylidene group, and an alkoxy group are the same as those described in the introduction of the means for solving the problems of the present specification.

In Formula 4, the acyl group is a functional group represented by RC=O, wherein R represents an alkyl group or an aryl group, and includes, for example, formyl, acetyl, propionyl or benzoyl, but is not limited thereto.

In one example of the present application, the unsaturated silane compound that can be used as a moisture absorbent is vinyltrimethoxysilane, vinyltriethoxysilane, vinyltripropoxysilane, vinyltriisopropoxysilane, vinyltributoxysilane, vinyltri It may be pentoxy silane, vinyltriphenoxy silane, vinyltriacetoxy silane, vinyltris(2-methoxyethoxy)silane, or a mixture of two or more thereof, but is not particularly limited thereto.

Since the moisture absorbent may react with moisture preferentially than the -NCO group in the polyisocyanate included in the curing agent, the storage stability of the curing agent and the curable composition including the same may be improved.

The desiccant may be included in an amount of 50 parts by weight or less based on 100 parts by weight of the polyisocyanate. In another example, the moisture absorbent may be included in an amount of 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, or 4 parts by weight or less, based on 100 parts by weight of polyisocyanate, or 1 It may be included in an amount of at least 2 parts by weight, at least 3 parts by weight, or at least 3.5 parts by weight.

In addition to this, the curable composition may contain a viscosity modifier, for example, a thixotropic agent, a diluent, a dispersant, a surface treating agent, or A coupling agent and the like may be further included.

In one example, fumed silica or the like may be used as the thixotropic agent. The diluent or dispersant is generally used to lower the viscosity of the curable composition, and various types known in the art may be used without limitation as long as it can exhibit the above action. The surface treatment agent is for surface treatment of the filler component, and various types known in the art may be used without limitation as long as it can perform the above-described action. In the case of the coupling agent, it may be used to improve the dispersibility of the filler component, and as long as it can act as described above, various types of known in the art may be used without limitation.

In addition, the curable composition may further include a flame retardant or a flame retardant auxiliary agent. In this case, a known flame retardant may be used without particular limitation, for example, a flame retardant in the form of a solid filler or a liquid flame retardant may be applied. For example, when the amount of an organic flame retardant such as melamine cyanurate, an inorganic flame retardant such as magnesium hydroxide, or a filler component included 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 present application is also an invention of a method for preparing a curable composition.

The manufacturing method of the curable composition of the present application includes preparing a main agent by mixing a resin component and a filler component, and controlling the water content in the filler component to control the water content of the main material to 200 ppm or more.

Specifically, the method for producing the curable composition of the present application controls the moisture content in the filler component to control the moisture content of the subject matter of 210 ppm or more, 220 ppm or more, 230 ppm or more, 240 ppm or more, 250 ppm or more, 260 ppm or more, 270 ppm or more. or more, 280 ppm or more, 290 ppm or more, 300 ppm or more, 310 ppm or more, 320 ppm or more, 330 ppm or more, 340 ppm or more, 350 ppm or more, 360 ppm or more, or 370 ppm or more, 600 ppm or less, 550 ppm or less, 500 ppm or less, 450 ppm or less, 400 ppm or less, 350 ppm or less, 300 ppm or less, 250 ppm or less, or 220 ppm or less.

In the method of manufacturing the curable composition, the content of the resin component and the filler component included in the subject matter may be the same as those described in the above-described curable composition.

The filler component may be prepared by mixing a filler component (C1) having a moisture content of 150 ppm or less and an average particle diameter of 10 μm or more and a filler component (C2) having a moisture content of 250 ppm or more and an average particle diameter of less than 10 μm.

Specifically, the moisture content of the filler component (C1) may be 145ppm or less, 140ppm or less, 135ppm or less, 130ppm or less, 125ppm or less, 120ppm or less, 115ppm or less, 110ppm or less, 105ppm or less, or 100ppm or less. The lower limit of the moisture content of the filler component (C1) is not particularly limited, but may be 0 ppm or more, 10 ppm or more, 30 ppm or more, 50 ppm or more, 70 ppm or more, or 90 ppm or more. The moisture content of the filler component (C1) may be a moisture content measured by a Karl Fischer coulometric method and a measurement method in the following Examples.

In one example, the filler component (C1) may include a first filler having an average particle diameter in a range of 30 μm to 100 μm, and a second filler having an average particle diameter in a range of 10 μm to 30 μm. In this case, the moisture content of the filler component (C1) may be an average moisture content of the first filler and the second filler constituting the filler component (C1), and the moisture content of the first filler and the second filler is 150 ppm, respectively. may be below.

In one example, the average particle diameter of the first filler is 31 μm or more, 32 μm or more, 33 μm or more, 34 μm or more, 35 μm or more, 36 μm or more, 37 μm or more, 38 μm or more, 39 μm or more, or 40 microns or more, 95 microns or less, 90 microns or less, 85 microns or less, 80 microns or less, 75 microns or less, 70 microns or less, 65 microns or less, 60 microns or less, 55 microns or less, 50 microns or less, 45 microns or less, or 40 microns or less may be below.

In addition, in one example, the average particle diameter of the second filler is 11 μm or more, 12 μm or more, 13 μm or more, 14 μm or more, 15 μm or more, 16 μm or more, 17 μm or more, 18 μm or more, 19 μm or more. Or 20 μm or more, 29 μm or less, 28 μm or less, 27 μm or less, 26 μm or less, 25 μm or less, 24 μm or less, 23 μm or less, 22 μm or less, or 21 μm or less.

When the first filler and the second filler are mixed and used as the filler component (C1), the ratio (W1/W2) of the weight (W1) of the first filler and the weight (W2) of the second filler is 0.5 to 2 May be within range tomorrow. Specifically, the weight ratio (W1/W2) is 0.6 or more, 0.7 or more, 0.8 or more, 0.9 or more, 1 or more, 1.1 or more, 1.2 or more, or 1.3 or more, or 2 or less, 1.9 or less, 1.8 or less, 1.7 or less, 1.6 or less. , 1.5 or less or 1.4 or less.

The filler component (C2) (third filler) may have a moisture content of 250 ppm or more. Specifically, the moisture content of the third filler may be 300 ppm or more, 350 ppm or more, 400 ppm or more, 450 ppm or more, or 500 ppm or more. When the third filler contains an excessive amount of moisture, aggregation of the filler component may occur and a problem of poor dispersibility may occur. Accordingly, since the process time may increase or the quality of the cured product of the curable composition may deteriorate, the upper limit of the water content of the third filler is 1300 ppm or less, 1200 ppm or less, 1100 ppm or less, 1000 ppm or less, 900 ppm or less, 800 ppm or less, It is preferable to make it 700 ppm or less, 600 ppm or less, or 500 ppm or less. The water content of the third filler may be a water content measured by a Karl Fischer coulometric titration method and a measurement method in the following Examples.

The third filler having an average particle diameter of less than 10 μm has a larger specific surface area than a filler component (first filler or second filler) having an average particle diameter of 10 μm or more. Controlling the moisture content of the first filler or the second filler component having a relatively small specific surface area is more difficult than controlling the moisture content of the third filler component having a relatively large specific surface area. In the manufacturing method of the present application, specifically, by adjusting the moisture content of the third filler having a small particle size to the above range, the moisture content in the subject matter can be adjusted to be 200 ppm or more, as described above, and thus the work required in the present application A curing rate of the curable composition that can satisfy property and fairness can be realized.

Specifically, the third filler has an average particle diameter of 9.5 μm or less, 9 μm or less, 8.5 μm or less, 8 μm or less, 7.5 μm or less, 7 μm or less, 6.5 μm or less, 6 μm or less, 5.5 μm or less, 5 μm or less , 4.5 μm or less, 4 μm or less, 3.5 μm or less, or 3 μm or less. The lower limit of the average particle diameter of the third filler may be 0.001 μm or more, 0.01 μm or more, 0.1 μm or more, 0.5 μm or more, 1 μm or more, 1.5 μm or more, or 2 μm or more.

In one example, the third filler may be included in an amount of 10 to 50% by weight based on the total filler component. Specifically, the third filler is 12 wt% or more, 14 wt% or more, 16 wt% or more, 18 wt% or more, 20 wt% or more, 22 wt% or more, 24 wt% or more, 26 wt% or more, based on the total filler component. , 28 wt% or more, or 30 wt% or more, or 48 wt% or less, 46 wt% or less, 44 wt% or less, 42 wt% or less, 40 wt% or less, 38 wt% or less, 35 wt% or less or 33 wt% or less can

In one example, the filler component may be included in an amount of 100 parts by weight or more based on 100 parts by weight of the resin component. Specifically, the filler component is 120 parts by weight or more, 140 parts by weight or more, 160 parts by weight or more, 180 parts by weight or more, 200 parts by weight or more, 220 parts by weight or more, 240 parts by weight or more, 260 parts by weight based on 100 parts by weight of the resin component. It may be included in parts by weight or more, 280 parts by weight or more, or 300 parts by weight or more. The upper limit of the content of the filler component is not particularly limited, but for example, about 900 parts by weight or less, 800 parts by weight or less, 700 parts by weight or less, 600 parts by weight or less, 500 parts by weight or less, 400 parts by weight or less, based on 100 parts by weight of the resin component. It may be included in parts by weight or less or 350 parts by weight or less. When the filler component of the present application is included in the above range relative to 100 parts by weight of the resin component, it is possible to provide a resin composition having an improved curing rate.

In one example, during the step of preparing the main agent, a catalyst may be further compounded. The catalyst may serve to promote a curing reaction between the main agent included in the curable composition and a curing agent to be described later.

The catalyst that may be formulated in the present application may be a metal catalyst or an amine catalyst capable of accelerating the curing reaction of the curable composition.

As the metal catalyst, an organometallic compound, for example, an organotin compound, an organobismuth compound, an organozirconium compound, or an organoaluminum compound may be applied, but an organotin compound is preferably used.

Examples of the organotin compound include dibutyltin dilaurate (DBTL), stannous octoacte, dibutyltin diacetate, or dibutyltin dimercaptide. Dialkyltin dicarboxylates may be applied.

In addition, as an amine catalyst, 1,4-diazabicyclo[2,2,2]octane (1,4-diazabicyclo[2,2,2]octane), bis(2-dimethylaminoethyl)ether (bis(2) -dimethylaminoethyl)ether), trimethylaminoethylethanolamine (trimethylaminoethylethanolamine), N,N,N',N',N''-pentamethyldiethylenetriamine (N,N,N',N',N''- pentamethyldiethylenetriamine), N,N'-dimethylethanolamine (N,N'-dimethylethanolamine), dimethylaminopropylamine, N-ethylmorpholine (N-ethylmorpholine), N,N-dimethylaminoethylmorpholine (N ,N-dimethylaminoethylmorpholine), N,N-dimethylcyclohexylamine (N,N-dimethylcyclohexylamine) or a tertiary amine such as 2-methyl-2-azanorbonrnane (2-methyl-2-azanorbonrnane) It may be applied, but is not limited thereto.

In one example, in the method for preparing the curable composition according to the present application, the content of the catalyst and the filler component can be controlled so that the weight ratio (B/A) of the catalyst (A) to the filler component (B) is 2500 or less. have. Specifically, the weight ratio (B/A) is 2400 or less, 2300 or less, 2200 or less, 2100 or less, 2000 or less, 1900 or less, 1800 or less, 1700 or less, 1600 or less, 1500 or less, 1400 or less, 1300 or less, 1200 or less , 1100 or less, 1000 or less, 900 or less, or 800 or less. The lower limit of the weight ratio (B/A) may be 500 or more, 550 or more, 600 or more, 650 or more, 700 or more, or 750 or more. When the weight ratio (B/A) of the filler component (B) to the catalyst (A) is adjusted within the above range, the moisture contained in the filler component activates the reaction of the catalyst to set the curing rate of the curable composition within the desired range. can be appropriately adjusted.

In one example, the method for preparing a curable composition according to the present application may further include a step of preparing a curing agent having a moisture content of 150 ppm or less by mixing a polyisocyanate compound and a moisture absorbent.

In the above step, the moisture absorbent may be included in an amount of 50 parts by weight or less based on 100 parts by weight of the polyisocyanate compound. In another example, the moisture absorbent may be included in an amount of 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, or 4 parts by weight or less, based on 100 parts by weight of polyisocyanate, or 1 weight part or less. It may be included in parts by weight or more, 2 parts by weight or more, 3 parts by weight or more, or 3.5 parts by weight or more.

For the details of the polyisocyanate compound and the moisture absorbent included in the curing agent, the description of the polyisocyanate compound and the moisture absorbent in the curing agent composition described above may be equally applied.

In addition, the curing agent may further include a filler component in addition to the polyisocyanate and the moisture absorbent, and the details of the filler component may be the same as that of the filler component in the curing agent composition described above.

In the present application, the water content of the curing agent may be prepared to be 150 ppm or less. In one example, the water content of the curing agent may be 145 ppm or less, 140 ppm or less, 135 ppm or less, 130 ppm or less, 125 ppm or less, 120 ppm or less, or 115 ppm or less. The lower limit of the moisture content of the curing agent is not particularly limited, but may be 0 ppm or more, 10 ppm or more, 50 ppm or more, or 100 ppm or more. When the polyisocyanate included in the curing agent is in direct contact with moisture, an amine group is formed and carbon dioxide is formed, which may cause problems such as surface hardening or viscosity increase of the curable composition. By adjusting the temperature, it is possible to solve problems such as surface hardening of the curable composition due to moisture or increase in viscosity. The moisture content of the curing agent may be implemented by adjusting the blending ratio of the polyisocyanate and the moisture absorbent included in the curing agent as described above.

The curable composition of the present application may be prepared by the manufacturing method as described above, and a cured product may be formed by a curing reaction of the main agent and the curing agent.

By the method for preparing the curable composition of the present application, when the main agent and the curing agent are mixed at room temperature and a relative humidity condition within the range of 40 to 60%, the properties of the compressive force, Shore A hardness and TA hardness as described above may be exhibited. According to the manufacturing method of the curable composition of the present application, it is possible to easily determine the curing rate so as to satisfy the workability and fairness required in the present application, and it is possible to derive an advantageous effect of easily controlling the curing rate.

The present application also relates to a battery module including the curable composition or a cured product thereof. The battery module includes a module case and a battery cell present inside the module case. The battery cell may be accommodated in the module case. One or more battery cells may exist in the module case, and a plurality of battery cells may be accommodated in the module case. The number of battery cells accommodated in the module case is not particularly limited as it is adjusted according to the use or the like. The battery cells accommodated in the module case may be electrically connected to each other.

The battery module of the present application may also include a resin layer in contact with the plurality of battery cells and the module case. The resin layer may include the above-described curable composition or a cured product thereof. The curable composition included in the resin layer may be a heat dissipation composition in one example. The heat dissipation composition means a composition capable of forming a cured product having heat dissipation performance. Heat dissipation performance, a term used in this application, is a thermal conductivity of about 2.5W/m·K or more when measured according to ASTM D5470 standard or ISO 22007-2 standard along the thickness direction of the cured product of the heat dissipation composition manufactured to a thickness of 4mm It may mean a case representing

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 also relates to a battery pack, for example, a battery pack including two or more of the aforementioned battery modules. In the battery pack, the battery modules may be electrically connected to each other. A method of configuring a battery pack by electrically connecting two or more battery modules is not particularly limited, and any known method may be applied.

The present application may provide a curable composition capable of easily controlling the curing rate by easily determining the curing rate, and a method for preparing the curable composition.

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

1. Determination of moisture content

Moisture content was measured by Karl Fischer coulometric titration using a measuring instrument (manufacturer: Metrohm, model name: 831KF Coulometer). In the Karl Fischer coulometric method, when the Karl Fischer reagent reacts with moisture in the sample, iodine ions present in the Karl Fischer reagent are generated into iodine molecules through electrolysis by the generator electrode of the measuring instrument to generate iodine molecules. This is a method of calculating the moisture content of a sample from the number of moles of electrons used.

As the Karl Fischer reagent, HYDRANAL-Coulomat AK reagent from SIGMA-ALDRICH was used.

Put about 0.1~1 g of sample into the vial of the measuring instrument, align the vial together with the blank vial on a Karl Fischer tray, then input 1 g of blank and the measured mass of the sample into the measuring instrument, and operate to heat the inside of the vial at 120 ° C. create an environment Thereafter, after measuring the amount of water consumed until the water vaporized from the sample and the Karl Fischer reagent no longer react, it is divided by the measured mass of the sample to determine the water content in ppm.

The moisture content (%) was calculated according to Equation 1 below, and converted into ppm units.

[Formula A]

Moisture content (%) = 100 Х amount of electricity consumed to produce iodine molecules/(10.72Х mass of sample (mg))

In Equation 1, 10.72 means the amount of electricity (C/mg) corresponding to 1 mg of water (H ₂ O).

When the sample to be measured is a liquid, about 20 drops (0.1 to 0.2 g) of the liquid sample is added to the Karl Fischer solution and reacted to obtain the same moisture content.

The moisture content of the composition as a whole can be calculated by measuring the moisture content of the individual components to be blended for the preparation of the composition in the above manner, and then based on the ratio of the ingredients to the composition.

2. filler particle size measurement

The average particle diameter of the filler is the D50 particle diameter, also called a so-called median particle diameter, and this particle diameter is the particle diameter (median particle diameter) at 50% cumulative of the volume-based cumulative curve of the particle size distribution. This particle size is defined as the particle diameter at the point where the cumulative value becomes 50% on the cumulative curve that calculates the particle size distribution on the basis of the volume and is 100% of the total volume.

The D50 particle size can be measured using Marven's MASTERSIZER 3000 equipment based on ISO-13320, and ethanol was used as a solvent in this case.

Example One.

filler manufacture of ingredients

The filler component is a filler component (C1) having an average particle diameter of about 10 μm or more (alumina having an average particle diameter (D50 particle diameter) of about 40 μm (first filler) and alumina having an average particle diameter (D50 particle diameter) of about 20 μm (second filler) ) and a filler component (C2) having an average particle diameter of less than 10 μm (alumina (third filler) having an average particle diameter (D50 particle diameter) of about 2 to 3 μm) was prepared by mixing.

Alumina has a large specific surface area, and pores exist depending on the crystal phase of the particles. The pores may contain a certain level of moisture, and the moisture contained in the alumina is recognized as adversely affecting the storage stability of the curable composition, and is usually removed and then blended into the composition.

In the preparation of the main filler component, the first and second fillers were used after removing moisture through a drying process, respectively. Specifically, the first filler and the second filler were dried at a temperature of 200° C. for about 24 hours to use a filler whose moisture content was adjusted to 100 ppm.

In the preparation of the main filler component, the third filler is dried at a temperature of 200° C. for about 24 hours, and alumina having a water content of about 200 ppm is moistened under humidified conditions (room temperature (25° C.) and relative humidity of 85% conditions) for 30 minutes. It was left to stand for a while, and the moisture content was adjusted to about 400 ppm. Specifically, about 1 kg of dried alumina is placed in a tray of about 30 cm × 20 cm × 5 cm and left in the humidification condition, then the alumina at the intermediate position and the middle height is collected, and the moisture content is measured in 30-minute increments and after 4 hours. The moisture content was measured and used.

The first and second fillers as described above and the third filler having a water content of 400 ppm are mixed in a weight ratio of 4:3:3 (first filler: second filler: third filler) to prepare a main filler component did.

As the filler component for a curing agent, the same first and second fillers as those for the main filler component were used, and the third filler was also used after removing moisture. That is, in the preparation of the filler component for the curing agent, the third filler was dried at a temperature of 200° C. for about 24 hours and an alumina filler having a moisture content of about 200 ppm was used.

These first to third fillers were mixed in a weight ratio of 4:3:3 (first filler: second filler: third filler) to prepare a filler component for a curing agent.

manufacture of the subject

Polyol, catalyst (DBTDL: dibutyltin dilaurate), the above main filler component, other additives (liquid and solid flame retardants and dispersants based on phosphoric acid) and colorant in a weight ratio of 30:0.121:93.15:9.31:0.028 (polyol:catalyst:filler) Ingredient: Additive: Colorant) to prepare a main ingredient.

The components are put in a paste mixer, mixed and dispersed twice for about 3 minutes under conditions of revolution 600 rpm and rotation 500 rpm, and after checking the generated heat, revolution 600 rpm and rotation 200 in a vacuum state (2.5 torr) The subject was prepared by defoaming for 4 minutes under the condition of rpm.

As the polyol, a polycaprolactone polyol obtained by reacting 1,4-butanediol and caprolactone in a weight ratio of 1:2.78 (1,4-butanediol:caprolactone) is used. did.

The moisture content (%) of the subject matter thus prepared was about 213 ppm.

Preparation of hardener

The curing agent contains a polyisocyanate compound, a curing agent filler component, a moisture absorbent (VTMO, vinyltrimethoxysilane), and other additives (a phosphoric acid-based liquid and solid flame retardant and dispersant) in a weight ratio of 8.54:88.36:0.3:2.8 (polyisocyanate compound: for curing agent). Filler components: desiccant: other additives) were prepared by mixing.

As the polyisocyanate compound, a mixture of hexamethylene diisocyanate trimer and 42.8:57.2 weight ratio of hexamethylene diisocyanate trimer and hexamethylene diisocyanate monomer (hexamethylene diisocyanate trimer: hexamethylene diisocyanate monomer) was used. , the mixing method of the components was the same as in the case of the subject.

The moisture content of this curing agent was about 100 ppm.

Example 2

A main agent and a curing agent were prepared in the same manner as in Example 1, except that alumina having a moisture content of about 500 ppm was used as the third filler in the preparation of the main filler component. As the third filler, alumina having the same average particle diameter (D50 particle diameter) as that used in Example 1 before the moisture content is adjusted at about 2 to 3 μm was used at room temperature (25° C.) and a humidification condition of 85% relative humidity. It was left for 1 hour to adjust the moisture content to about 500 ppm before use.

The moisture content of the subject matter thus prepared was about 240 ppm.

Example 3

A main agent and a curing agent were prepared in the same manner as in Example 1, except that alumina having a moisture content of about 600 ppm was used as the third filler in the preparation of the main filler component. As the third filler, alumina having the same average particle diameter (D50 particle diameter) as that used in Example 1 before the moisture content is adjusted at about 2 to 3 μm was used at room temperature (25° C.) and a humidification condition of 85% relative humidity. It was left for 2 hours to adjust the moisture content to about 600 ppm before use.

The moisture content of the subject matter thus prepared was about 266 ppm.

Example 4

A main agent and a curing agent were prepared in the same manner as in Example 1, except that alumina having a moisture content of about 700 ppm was used as the third filler in the preparation of the main filler component. As the third filler, alumina having the same average particle diameter (D50 particle diameter) as that used in Example 1 before the moisture content is adjusted at about 2 to 3 μm was used at room temperature (25° C.) and a humidification condition of 85% relative humidity. It was left for 5 hours to adjust the moisture content to about 700 ppm before use.

The water content of the subject matter thus prepared was about 293 ppm.

Example 5

A main agent and a curing agent were prepared in the same manner as in Example 1, except that alumina having a moisture content of about 1,000 ppm was used as the third filler in the preparation of the main filler component. As the third filler, alumina having the same average particle diameter (D50 particle diameter) as that used in Example 1 before the moisture content is adjusted at about 2 to 3 μm was used at room temperature (25° C.) and a humidification condition of 85% relative humidity. It was left for 24 hours to adjust the moisture content to about 1,000 ppm before use.

The moisture content of the subject matter thus prepared was about 373 ppm.

comparative example One

A main agent and a curing agent were prepared in the same manner as in Example 1, except that alumina having a moisture content of about 200 ppm was used as the third filler in the preparation of the main filler component. The third filler was also dried at a temperature of 200° C. for about 24 hours to use an alumina filler having an average particle diameter (D50 particle diameter) of about 2 to 3 μm with a moisture content of about 200 ppm.

The moisture content of the subject matter thus prepared was about 112 ppm.

Experimental example 1. Shore A hardness measurement

In a state where the temperature is maintained at about 25° C. and the relative humidity is maintained at about 40 to 60%, after mixing the subject and curing agent of each Example or Comparative Example in a volume ratio of 1:1, an hour interval from the time of mixing The hardness (Shore A hardness) was measured.

The main agent and the curing agent were respectively injected into the two-component cartridge in the above volume ratio, and the main agent and the curing agent were supplied and mixed in a static mixer to which the cartridge was applied using pneumatic pressure to mix the main agent and the curing agent.

The hardness was measured according to ASTM D 2240 standard.

Hardness (Shore A) was measured using ASKER's durometer hardness instrument. The surface of the mixture of the main agent and the curing agent was flattened, and a load of about 1.5 Kg was applied to the surface to measure the initial hardness, and after 5 seconds, the hardness was evaluated by confirming the stabilized measurement value.

The measured hardness (Shore A) is summarized in Table 1 below.

Example comparative example One 2 3 4 5 One 1hr 0 0 0 0 0 0 2hr 50 20 20 25 25 0 3hr 65 65 60 65 65 10 4hr 75 80 80 80 80 20 5hr 80 90 85 85 85 40 6hr 85 90 90 90 90 50 7hr 90 95 95 95 95 72 8hr 95 95 95 95 95 90

Experimental example 2. Hardness by Texture Analyzer ( TA hardness) measurement

In a state where the temperature is maintained at about 25° C. and the relative humidity is maintained at about 40 to 60%, after mixing the subject and curing agent of each Example or Comparative Example in a volume ratio of 1:1, an hour interval from the time of mixing The hardness was measured using the Texture Analyzer equipment (measurement of TA hardness).

At this time, the mixing of the main agent and the curing agent was carried out in the same manner as in Experimental Example 1.

Texture Analyzer (Stable Micro System, TAXT) plus) using the equipment, lower the pressing jig with a round bottom toward the mixture (1:1 volume ratio) of the main agent and curing agent at a speed of 1 mm/s, from the moment the pressing jig touches the surface of the mixture, from the surface The maximum force until pressing at a point of 3 mm in the vertical direction was recorded as the TA hardness.

The maximum force that the Texture Analyzer equipment used in the experiment can measure is about 30kgf, and when the value exceeds 30kgf, it was recorded as Over.

The measured TA hardness (unit: kgf) is summarized in Table 2 below.

Example comparative example One 2 3 4 5 One 1hr 1.1521 1.3879 1.7121 1.8618 2.0334 0.3152 2hr 10.3162 12.4486 13.6472 16.2188 16.4481 2.5499 3hr 19.4344 20.5811 22.6187 23.8833 25.4834 7.5567 4hr 29.7735 31.7756 Over Over Over 13.1195 5hr Over Over Over Over Over 18.7331 6hr Over Over Over Over Over 24.4642 7hr Over Over Over Over Over Over 8hr Over Over Over Over Over Over

Experimental example 3. Compression force measurement

In a state where the temperature is maintained at about 25° C. and the relative humidity is maintained at about 40 to 60%, after mixing the subject and curing agent of each Example or Comparative Example in a volume ratio of 1:1, an hour interval from the time of mixing to measure the compressive force.

At this time, the mixing method is the same as in Experimental Example 1.

The compressive force was measured three times by pressing the surface of the mixture (1:1 volume ratio) of the main agent and the curing agent with the bottom surface of the force sensor, and after recording the graph, the highest value was used as the compressive force. As a force sensor, Lab Quest's DFS-BTA was used, and the evaluation was conducted by connecting it to the interface, Lab Quest's LQ2-LE.

The maximum measured value of the force sensor was 35N, and when the measured compressive force exceeded the 35N range, it was indicated as Over.

The measured compressive force (unit: N) values are summarized in Table 3 below.

Example comparative example One 2 3 4 5 One 1hr 10.32 11.08 11.84 13.50 14.49 6.42 2hr Over Over Over Over Over 15.27 3hr Over Over Over Over Over 30.22 4hr Over Over Over Over Over Over 5hr Over Over Over Over Over Over 6hr Over Over Over Over Over Over 7hr Over Over Over Over Over Over 8hr Over Over Over Over Over Over

Claims (22)

It contains a main agent and a curing agent comprising a resin component and a filler component,
The main agent and the curing agent are mixed at room temperature and a relative humidity condition within the range of 40 to 60%, and a compressive force of 7N or more when maintained at the same temperature and relative humidity condition for 1 hour. The curable composition according to claim 1, wherein the main agent and the curing agent are mixed at room temperature and a relative humidity condition within a range of 40 to 60%, and the compressive force when maintained at the same temperature and relative humidity condition for 2 hours exceeds 35N. The curable composition according to claim 1, wherein the main agent and the curing agent have a Shore A hardness of 40 or more when mixed at room temperature and a relative humidity condition within a range of 40 to 60%, and maintained at the same temperature and relative humidity condition for 3 hours. The curable composition according to claim 1, wherein the rate of change of Shore A hardness according to the following formula (1) is 15/h or less:
[Equation 1]
Rate of change of Shore A hardness = 0.2 Х(H ₈ -H ₃ )
In Equation 1, H ₈ is the Shore A hardness when the main agent and the curing agent are mixed at room temperature and a relative humidity condition within the range of 40 to 60%, and maintained at the same temperature and relative humidity condition for 8 hours, H ₃ is the main agent and Shore A hardness when the curing agent is mixed at room temperature and a relative humidity condition within the range of 40 to 60%, and maintained at the same temperature and relative humidity condition for 3 hours. The curable composition according to claim 1, wherein the TA hardness when the main agent and the curing agent are mixed at room temperature and a relative humidity condition within the range of 40 to 60% and maintained at the same temperature and relative humidity condition for 1 hour is 0.5 kgf or more. The curable composition according to claim 1, wherein the rate of change of TA hardness according to the following formula (2) is 5 kgf/h or more:
[Equation 2]
Rate of change of TA hardness = 0.5 Х(T ₃ -T ₁ )
In Equation 2, T ₃ is the TA hardness when the main agent and the curing agent are mixed at room temperature and a relative humidity condition within the range of 40 to 60%, and maintained at the same temperature and relative humidity condition for 3 hours, T ₁ is the main agent and TA hardness when the curing agent is mixed at room temperature and a relative humidity condition within the range of 40 to 60%, and maintained at the same temperature and relative humidity condition for 1 hour. The curable composition according to claim 1, which is room temperature curable. The curable composition according to claim 1, wherein the subject has a moisture content of at least 200 ppm. The curable composition according to claim 1, wherein the resin component is a polyol. The curable composition according to claim 1, wherein the main agent comprises 100 parts by weight or more of the filler component based on 100 parts by weight of the resin component. The curable composition of claim 1 , wherein the subject further comprises a catalyst. The curable composition according to claim 11, wherein the weight ratio (B/A) of the catalyst (A) to the filler component (B) is 2500 or less. The curable composition according to claim 1, wherein the curing agent has a moisture content of 150 ppm or less. The curable composition of claim 1 , wherein the curing agent comprises a polyisocyanate compound. The curable composition according to claim 1, wherein the curing agent comprises a trifunctional or higher polyfunctional polyisocyanate compound and a bifunctional polyisocyanate compound. 15. The curable composition of claim 14, wherein the curing agent further comprises a filler component. 15. The curable composition of claim 14, wherein the curing agent further comprises a desiccant. Mixing a resin component and a filler component to prepare a base material,
A method for producing a curable composition by controlling the moisture content in the filler component to control the moisture content of the main ingredient to 200 ppm or more. The filler component according to claim 18, wherein the filler component is a mixture of a filler component (C1) having a moisture content of 150 ppm or less and an average particle diameter of about 10 μm or more, and a filler component (C2) having a moisture content of 250 ppm or more and an average particle diameter of less than 10 μm. A method for producing a curable composition prepared by 19. The method for producing a curable composition according to claim 18, wherein a catalyst is further incorporated in the preparation of the base material. The method for producing a curable composition according to claim 18, further comprising preparing a curing agent having a moisture content of 150 ppm or less by blending a polyisocyanate and a moisture absorbent. A battery module comprising the curable composition of claim 1 or a cured product thereof.