KR20230046132A - Curable composition - Google Patents

Abstract

The purpose of the present application is to provide a curable composition that can form a cured product having low specific gravity, excellent thermal conductivity performance, and excellent durability even at high temperatures. In addition, the purpose of the present application is to provide a curable composition that can maintain low hardness even at a high curing rate and form a cured product that can ensure re-workability. The curable composition comprises a resin composition containing a first polyorganosiloxane component, a linker, and a second polyorganosiloxane component; and a filler composition, and has an R_L value of 45 or less, wherein the R_L value is represented by the following general formula 1, R_L = L'/L.

Description

Curable composition {Curable composition}

This application relates to curable compositions.

Heat dissipation materials are used in various fields. For example, in a vehicle, a heat dissipation material may be used to handle heat generated from a battery module built into an electric vehicle capable of charging and discharging and an on-board charger (OBC) for charging the battery. Heat dissipation materials are also applied to parts that consume high power and generate a lot of heat, such as modules, to improve the lifespan of LED modules.

A resin composition in which a thermally conductive filler is blended with a resin is known and proposed as a countermeasure against heat dissipation, in order to thermally contact the heating element and the cooling portion and fix the heating element while dissipating heat emitted from the heating element. Patent Document 1 (Korean Patent Publication No. 10-2016-0105354) discloses a battery module to which the resin composition is applied.

The silicone-based resin composition has excellent heat resistance and can be used as a heat dissipation material. An inorganic hydroxide filler may be added to the silicone-based resin composition to realize excellent thermal conductivity and low specific gravity.

However, in order to realize excellent thermal conductivity, the content of the inorganic hydroxide filler needs to be increased. In this way, when the content of the silicone-based resin composition is reduced by increasing the content of the inorganic hydroxide filler, the binding effect of the silicone-based resin composition is reduced, thereby reducing the durability of the cured product at high temperature (cracking occurs inside). there was. In order to solve this problem, there is a method of increasing the curing rate, but as the curing rate increases, the hardness of the cured product increases, making it difficult to achieve low hardness physical properties.

In addition, when the content of the inorganic hydroxide filler is increased, the viscosity increases when mixed with the silicone-based resin composition, which is disadvantageous in processability. In order to solve this problem, there is a method using a low-viscosity silicone-based resin composition, but when a cured product is formed using these, there is a problem in that durability degradation occurs at high temperatures.

Therefore, a method capable of securing a curable composition having low specific gravity, excellent thermal conductivity, and excellent durability even at high temperatures has been required.

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

An object of the present application is to provide a curable composition capable of forming a cured product having low specific gravity, excellent thermal conductivity, and excellent durability even at high temperatures.

In addition, an object of the present application is to provide a curable composition capable of forming a cured product capable of maintaining low hardness and securing re-workability even at a high cure rate.

Among the physical properties mentioned in this application, if the measured temperature and pressure affect the physical properties, unless otherwise specified, the physical properties are measured at room temperature and atmospheric pressure (about 1 atm).

As used in this application, room temperature is a natural temperature that is not heated or cooled, for example, any temperature within the range of 10 ℃ to 30 ℃, for example, about 15 ℃ or more, about 18 ℃ or more, It may mean a temperature of about 20 ° C or higher, about 23 ° C or higher, about 27 ° C or lower, or 25 ° C.

The terms a to b used in this application mean within the range between a and b while including a and b. For example, including a to b parts by weight is the same as meaning included within the range of a to b parts by weight.

Relative humidity, a term used in this application, is expressed as a percentage (%) of the ratio of the amount of water vapor currently contained in air in a unit volume to the maximum saturated vapor pressure that air in a unit volume can contain, It can be expressed as RH%.

Weight average molecular weight (M _w ) and number average molecular weight (M _n ), which are terms used in this application, can be measured using GPC (Gel permeation chromatography), and can be specifically measured according to the following physical property measurement method. In addition, the polydispersity index (PDI), a term used in this application, is a value obtained by dividing the weight average molecular weight (M _w ) by the number average molecular weight (M _n ) (M _w /M _n ), and is the means distribution. Specifically, the number average molecular weight (M _n ) and weight average molecular weight (M _w ) are analyzed by putting the analysis object in a 20 mL vial, and diluting it in a THF (tetrahydrofuran) solvent to a concentration of about 20 mg/mL, and then , It can be measured after filtering the standard sample for calibration and the sample to be analyzed through a syringe filter (pore size: 0.2 ㎛). In addition, the analysis program can use ChemStation of Agilent technologies, and the number average molecular weight (M _n ) and weight average molecular weight (M _w ) can be obtained by comparing the elution time of the sample with a calibration curve. Here, the polydispersity index (PDI) may be a value obtained by dividing the measured weight average molecular weight (M _w ) by the number average molecular weight (M _n ).

<GPC measurement conditions>

Instrument: Agilent technologies' 1200 series

Column: TL Mix from Agilent technologies. Use A&B

Solvent: THF

Column temperature: 40 ℃

Sample concentration: 20 mg/mL, 10 μl injection

MP: 364000, 91450, 17970, 4910, 1300 used as standard samples

Excellent thermal conductivity, as a term used in this application, is a condition in which a curable composition is made of a cured product (sample) having a diameter of 2 cm or more and a thickness of 5 mm, ASTM D5470 standard or ISO 22007- 2 When measured according to the standard, it can mean that the measured thermal conductivity is about 1 W/mK or more, 1.1 W/mK or more, 1.2 W/mK or more, 1.3 W/mK or more, or 1.4 W/mK or more. there is.

Low hardness, a term used in this application, may mean a case in which the cured product of the curable composition has a Shore OO of 70 or less. In addition, the term low viscosity used in this application may refer to a case in which the composition including the resin composition and the filler composition has a viscosity of 400,000 cP or less measured at room temperature and at a shear rate of 1/s.

The low specific gravity of the cured material, which is a term used in this application, may mean a case in which the specific gravity of the cured material is 2 or less.

Viscosity, which is a term used in this application, may be a value measured at room temperature unless otherwise specified, and may be specifically measured according to the following viscosity measurement method. In addition, kinematic viscosity, which is a term used in this application, may be a value measured at 40 ° C. unless otherwise specified, and may be specifically measured according to the following kinematic viscosity measuring method.

[Viscosity measurement method]

Viscosity can be measured using a viscometer (manufacturer: Brookfield, model name: DV3T Rheometer) and a spindle CPA-52Z (selected according to the measurement range of viscosity), and after performing zero point adjustment of the viscometer A spindle, CPA-52Z, was attached to the spindle connection of the viscometer. A plate was mounted on the plate connection part of the viscometer, and was adjusted so that a certain gap between the spindle and the plate was formed through a control lever. The plate was separated, and a measurement target was applied to the center of the separated plate to have a thickness of 5 mm. Thereafter, the viscosity was measured while changing the shear rate from 0.1/s to 10.0/s at room temperature (25 ° C.). At this time, the viscosity measured at the shear rate of 1/s is the viscosity used in this application. can

[How to measure kinematic viscosity]

Kinematic viscosity, a term used in this application, may be a value measured using a kinematic viscometer at 40 ° C. After measuring the viscosity at 40 ° C. according to the [viscosity measurement method], the viscosity is divided by the density at the same temperature. can be a value

The content of a specific component, which is a term used in this application, may indicate the number of moles per unit mass.

Substitution, a term used in this application, means that a hydrogen atom bonded to a carbon atom of a compound is replaced with another substituent, and the position of substitution is not particularly limited as long as the hydrogen atom is substituted, i. In the case of more than one substitution, the substituents may be the same as or different from each other.

As used herein, the term substituent refers to an atom or group of atoms replacing one or more hydrogen atoms on the parent chain of a hydrocarbon. In addition, substituents are described below, but are not limited thereto, and the substituents may be further substituted with substituents described below or may not be substituted with any substituents unless otherwise specified in the present application.

An alkyl group or an alkylene group, which is a term used in this application, is a straight-chain or branched group having 1 to 20 carbon atoms, or 1 to 16 carbon atoms, or 1 to 12 carbon atoms, or 1 to 8 carbon atoms, or 1 to 6 carbon atoms, unless otherwise specified. It may be a chain alkyl group or an 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. Here, the cyclic alkyl group or alkylene group includes an alkyl group or alkylene group having only a cyclic structure and an alkyl group or alkylene group having a cyclic structure. For example, both a cyclohexyl group and a methyl cyclohexyl group correspond to a cyclic alkyl group. In addition, for example, an alkyl group or an alkylene group is specifically methyl (ene), ethyl (ene), n-propyl (ene), isopropyl (ene), n-butyl (ene), isobutyl ( (ene), tert-butyl (rene), sec-butyl (ene), 1-methyl-butyl (ene), 1-ethyl-butyl (ene), n-pentyl (ene), isopentyl (ene), neopentyl (ene), tert-pentyl (ene), n-hexyl (ene), 1-methylpentyl (ene), 2-methylpentyl (ene), 4-methyl-2-pentyl (ene), 3,3-dimethyl Butyl (ene), 2-ethylbutyl (ene), n-heptyl (ene), 1-methylhexyl (ene), n-octyl (ene), tert-octyl (ene), 1-methylheptyl (ene), 2-ethylhexyl(ene), 2-propylpentyl(ene), n-nonyl(ene), 2,2-dimethylheptyl(ene), 1-ethylpropyl(ene), 1,1-dimethylpropyl(ene) , Isohexyl (ene), 2-methylpentyl (ene), 4-methylhexyl (ene), 5-methylhexyl (ene), etc. may be exemplified, but are not limited thereto. In addition, the cycloalkyl group or cycloalkylene group is specifically cyclopropyl (ene), cyclobutyl (ene), cyclopentyl (ene), 3-methylcyclopentyl (ene), 2,3-dimethylcyclopentyl (ene), cyclo Hexyl (ene), 3-methylcyclohexyl (ene), 4-methylcyclohexyl (ene), 2,3-dimethylcyclohexyl (ene), 3,4,5-trimethylcyclohexyl (ene), 4-tert -Butylcyclohexyl (ene), cycloheptyl (ene), cyclooctyl (ene), etc. may be exemplified, but are not limited thereto.

An alkenyl group or alkenylene group, which is a term used in this application, is a straight chain or branched group having 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, unless otherwise specified. chain acyclic alkenyl or alkenylene groups; 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. Here, if a cyclic alkenyl group or alkenylene group is included, it corresponds to a cyclic alkenyl group or alkenylene group. Also, for example, ethenyl (ene), n-propenyl (ene), isopropenyl (ene), n-butenyl (ene), isobutenyl (ene), tert-butenyl (ene), sec -butenyl (rene), 1-methyl-butenyl (ene), 1-ethyl-butenyl (ene), n-pentenyl (ene), isopentenyl (ene), neopentenyl (ene), tert -Pentenyl (ene), n-hexenyl (ene), 1-methylpentenyl (ene), 2-methylpentenyl (ene), 4-methyl-2-pentenyl (ene), 3,3-dimethyl Butenyl (rene), 2-ethylbutenyl (ene), n-heptenyl (ene), 1-methylhexenyl (ene), n-octenyl (ene), tert-octenyl (ene), 1- Methylheptenyl (ene), 2-ethylhexenyl (ene), 2-propylpentenyl (ene), n-nonylenyl (ene), 2,2-dimethylheptenyl (ene), 1-ethylpropenyl ( Examples include 1,1-dimethylpropenyl (rene), isohexenyl (ene), 2-methylpentenyl (ene), 4-methylhexenyl (ene), and 5-methylhexenyl (ene). It can be, but is not limited to these. In addition, the cycloalkenyl group or cycloalkenylene group is specifically cyclopropenyl (ene), cyclobutenyl (ene), cyclopentenyl (ene), 3-methylcyclopentenyl (ene), 2,3-dimethylcyclophene tenyl(ene), cyclohexenyl(ene), 3-methylcyclohexenyl(ene), 4-methylcyclohexenyl(ene), 2,3-dimethylcyclohexenyl(ene), 3,4,5- Trimethylcyclohexenyl (ene), 4-tert-butylcyclohexenyl (ene), cycloheptenyl (ene), cyclooctenyl (ene) and the like may be exemplified, but are not limited thereto.

An alkynyl group or alkynylene group, which is a term used in this application, is a straight chain or branched group having 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, unless otherwise specified. Chain acyclic alkynyl group or alkynylene group, or a cyclic alkynyl group or alkynylene 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 can be Here, if a cyclic alkynyl group or alkynylene group is included, it corresponds to a cyclic alkynyl group or alkynylene group. Further, for example, ethynyl (rene), n-propynyl (ene), isopropynyl (ene), n-butynyl (ene), isobutynyl (ene), tert-butynyl (ene), sec-Butynyl (Rene), 1-methyl-Butynyl (Rene), 1-Ethyl-Butynyl (Rene), n-Pentynyl (Rene), Isopentynyl (Rene), Neopentynyl (Rene), tert-pentynyl(ene), n-hexynyl(ene), 1-methylpentynyl(ene), 2-methylpentynyl(ene), 4-methyl-2-pentynyl(ene), 3,3- dimethylbutynyl(ene), 2-ethylbutynyl(ene), n-heptynyl(ene), 1-methylhexynyl(ene), n-octynyl(ene), tert-octynyl(ene), 1-Methylheptynyl (Lene), 2-Ethylheptynyl (Lene), 2-Propylpentynyl (Lene), n-Nonynyl (Lene), 2,2-Dimethylheptynyl (Lene), 1-Ethylpropy Nyl (Rene), 1,1-dimethylpropynyl (Rene), isohexynyl (Rene), 2-methylpentynyl (Rene), 4-methylhexynyl (Rene), 5-methylhexynyl ( Ren) and the like may be exemplified, but are not limited thereto. In addition, the cycloalkynyl group or cycloalkynylene group is specifically cyclopropynyl (Lene), cyclobutynyl (Lene), cyclopentynyl (Lene), 3-methylcyclopentynyl (Lene), 2,3-dimethylcyclopentyl group. Nyl(ene), cyclohexynyl(ene), 3-methylcyclohexynyl(ene), 4-methylcyclohexynyl(ene), 2,3-dimethylcyclohexynyl(ene), 3, 4,5-trimethylcyclohexynyl (ene), 4-tert-butylcyclohexynyl (ene), cycloheptynyl (ene), cyclooctynyl (ene), etc. may be exemplified. Not limited to this.

The alkyl group, alkylene group, alkenyl group, alkenylene group, and alkynyl group may optionally be substituted with one or more substituents. In this case, substituents include halogen (chlorine (Cl), iodine (I), bromine (Br), fluorine (F)), aryl group, heteroaryl group, epoxy group, alkoxy group, cyano group, carboxyl group, acryl It may be at least one selected from the group consisting of a loyl group, a methacryloyl group, an acryloyloxy group, a methacryloyloxy group, a carbonyl group, and a hydroxyl group, but is not limited thereto.

As used herein, an aryl group refers to an aromatic ring in which one hydrogen is removed from an aromatic hydrocarbon ring, and the aromatic hydrocarbon ring may include a monocyclic or polycyclic ring. The aryl group is not particularly limited in carbon atoms, but unless otherwise specified, aryl having 6 to 30 carbon atoms, or 6 to 26 carbon atoms, or 6 to 22 carbon atoms, or 6 to 20 carbon atoms, or 6 to 18 carbon atoms, or 2 to 15 carbon atoms may be In addition, the term arylene group used in this application refers to an aryl group having two bonding sites, that is, a divalent group. The description of the aryl group described above may be applied except that each is a divalent group. The aryl group may be, for example, a phenyl group, a phenylethyl group, a phenylpropyl group, a benzyl group, a tolyl group, a xylyl group, or a naphthyl group, but is not limited thereto.

A heteroaryl group, a term used in this application, is an aromatic ring containing one or more heteroatoms other than carbon, and specifically, the heteroatoms are nitrogen (N), oxygen (O), sulfur (S), selenium (Se) and One or more atoms selected from the group consisting of nium (Te) may be included. At this time, atoms constituting the ring structure of the heteroaryl group can be referred to as a reducing group. In addition, heteroaryl groups may include monocyclic or polycyclic rings. The heteroaryl group is not particularly limited in carbon atoms, but has 2 to 30 carbon atoms, or 2 to 26 carbon atoms, or 2 to 22 carbon atoms, or 2 to 20 carbon atoms, or 2 to 18 carbon atoms, or 2 to 15 carbon atoms, unless otherwise specified. It may be a heteroaryl group. In another example, the number of reducing atoms of the heteroaryl group is not particularly limited, but may be a heteroaryl group having 5 to 30, 5 to 25, 5 to 20, 5 to 15, 5 to 10, or 5 to 8 reducing atoms. The heteroaryl group is, for example, a thiophene group, a furan group, a pyrrole group, an imidazolyl group, a thiazolyl group, an oxazolyl group, an oxadiazolyl group, a triazolyl group, a pyridyl group, and a bipyridyl group. , Pyrimidyl group, triazinyl group, acridyl group, pyridazinyl group, pyrazinyl group, quinolinyl group, quinazolinyl group, quinoxalinyl group, phthalazinyl group, pyridopyrimidinyl group, pyridopyrazinyl group , Pyrazinopyrazinyl group, isoquinolinyl group, indole group, carbazolyl group, benzoxazolyl group, benzimidazolyl group, benzothiazolyl group, benzocarbazolyl group, dibenzocarbazolyl group, benzothiophene group , Dibenzothiophene group, benzofuran group, dibenzofuran group, benzosilol group, dibenzosilol group, phenanthrolinyl group, isoxazolyl group, thiadiazolyl group, phenothiazinyl group, phenoxazine group And condensation structures thereof may be exemplified, but are not limited thereto.

In addition, the heteroarylene group, which is a term used in this application, means a heteroaryl group having two bonding sites, that is, a divalent group. The above description of the heteroaryl group may be applied except that each is a divalent group.

The aryl group or heteroaryl group may be optionally substituted with one or more substituents. In this case, substituents include halogen (chlorine (Cl), iodine (I), bromine (Br), fluorine (F)), aryl group, heteroaryl group, epoxy group, alkoxy group, cyano group, carboxyl group, acryl It may be at least one selected from the group consisting of a loyl group, a methacryloyl group, an acryloyloxy group, a methacryloyloxy group, a carbonyl group, and a hydroxyl group, but is not limited thereto.

curable composition

A curable composition according to an example of the present application may include a resin composition and a filler composition.

The curable composition, as a term used in this application, may include a component that can be converted into a resin through a curing reaction or a polymerization reaction, as well as a component generally known as a resin. In addition, the curable composition may be an adhesive composition, that is, an adhesive itself or a composition capable of forming an adhesive through a reaction such as a curing reaction.

In addition, the curable composition may be a solvent-type curable composition, a water-based curable composition, or a non-solvent type curable composition.

In addition, the curable composition may be an active energy ray (eg, ultraviolet ray) curing type, a moisture curing type, a thermosetting type, or a room temperature curing type, and preferably, the curable composition may be a room temperature curing composition. When the curable composition is an active energy ray curable type, curing of the curable composition is performed by irradiation with active energy rays such as ultraviolet rays, and when the curable composition is a moisture curable type, curing of the curable composition is performed by maintaining under appropriate moisture, In the case of a heat curable type, the curing of the curable composition is performed by applying appropriate heat, or in the case of a room temperature curing type, the curing of the curable composition may be performed by maintaining the curable composition at room temperature. .

The curable composition according to an example of the present application may be a one-component or two-component type. As used in this application, the one-component type refers to a form capable of forming a cured product in a state in which the main part and the curing agent part are mixed together, as is known in the art. In addition, the term two-component type used in this application means a type that is separated into a main part and a curing agent part as is well known, and can form a cured product by mixing and reacting them, and the main part includes a catalyst. may have been

In the curable composition according to an example of the present application, the volume ratio (V1/V2) of the main part (V1) and the curing agent part (V2) may be 0.5 or more, 0.6 or more, 0.7 or more, 0.8 or more, 0.9 or more, or 1 or more. In another example, the curable composition may have a volume ratio (V1/V2) of the main part (V1) and the curing agent part (V2) of 2 or less, 1.8 or less, 1.6 or less, 1.4 or less, or 1.2 or less. In the curable composition, the volume ratio (V1/V2) of the main part (V1) and the curing agent part (V2) may be included within a range formed by appropriately selecting the upper and lower limits listed above.

The resin composition, a term used in this application, may include a component that can be converted into a resin through a curing reaction or a polymerization reaction, as well as a component generally known as a resin. In addition, the resin composition may be an adhesive composition, that is, an adhesive itself or a composition capable of forming an adhesive through a reaction such as a curing reaction.

The curable composition according to an example of the present application contains 70% by weight or more, 72% by weight or more, 74% by weight or more, 76% by weight or more, 78% by weight or more, 80% by weight or more, or 82% by weight or more based on the total weight of the filler composition. can be included as In another example, the curable composition may include 99% by weight or less, 95% by weight or less, 90% by weight or less, or 85% by weight or less based on the total weight of the filler composition. The content ratio of the filler composition may be included within the range formed by appropriately selecting the upper and lower limits listed above. In addition, when the content ratio of the filler composition satisfies the above range, appropriate thixotropy and excellent thermal conductivity of a desired level may be secured.

The curable composition according to an example of the present application contains the resin composition in an amount of 5 parts by weight or more, 7.5 parts by weight or more, 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, or 20 parts by weight based on 100 parts by weight of the filler composition. It may contain more than one part by weight. In another example, the curable composition may include the resin composition in an amount of 50 parts by weight or less, 45 parts by weight or less, 40 parts by weight or less, 35 parts by weight or less, 30 parts by weight or less, or 25 parts by weight or less based on 100 parts by weight of the filler composition. there is. The content ratio of the resin composition may be included within the range formed by appropriately selecting the above-listed upper and lower limits. In addition, when the content ratio of the resin composition satisfies the above range, it is possible to secure a cured product having excellent durability even at a high temperature, maintaining low hardness even at a high curing rate, and having excellent reworkability.

The curable composition according to an example of the present application has an R _L value of 1 or more, 3 or more, 5 or more, 7 or more, 9 or more, 10 or more, 12 or more, 14 or more, 16 or more, 18 or more, 20 or more, 22 or more, 24 or more, 26 or more, or 28 or more may be satisfied. In another example, the curable composition may satisfy an R _L value of 45 or less, 44.5 or less, 44 or less, 43.5 or less, 43 or less, or 42.5 or less according to Formula 1 below. The R _L value according to the following general formula 1 of the curable composition may be included within the range formed by appropriately selecting the upper limit and the lower limit listed above. In addition, when the R _L value according to the following general formula 1 of the curable composition satisfies the above ratio, it is possible to form a cured product having low specific gravity and excellent thermal conductivity and excellent durability even at high temperatures, even at a high curing rate. Low hardness can be maintained and a cured product with excellent reworkability can be formed.

[Formula 1]

R _L = L'/L

In Formula 1, L' is the number of dialkylsiloxane repeating units of the curable composition as measured by ¹ H NMR and ²⁹ Si NMR. Specifically, L' may be a calculated value obtained according to Equation 1 below.

[Formula 1]

In Formula 1, n _A is the content of alkenyl groups contained in the first polyorganosiloxane component as measured by ¹ H NMR, and n _B is the amount of silicon-bonded hydrogen contained in the second polyorganosiloxane component as measured by ²⁹ Si NMR. is the content Also, m _A is the total weight of the first polyorganosiloxane component included in the curable composition, and m _B is the total weight of the second polyorganosiloxane component included in the curable composition. Here, the unit of n _A and n _B may be mmol/g, and the unit of m _A and m _B may be g. Also, the unit of the constant 27.03 in Equation 1 may be mmol/g, and the constant -2.5 may have no unit.

In addition, in Formula 1, L is a value according to Formula 2 below.

[Formula 2]

L = (p+q)/(q+1)

In Formula 2, p is the number of dialkylsiloxane repeating units of the linker as measured by ²⁹ Si NMR, and q is the number of monoalkylsiloxane repeating units of the linker as measured by ²⁹ Si NMR.

In the curable composition according to an example of the present application, the ratio (K ₁ /K ₂ ) of the total content of silicon-bonded hydrogen (K ₁ ) measured by ²⁹ Si NMR and the total content (K ₂ ) of alkenyl groups measured by ¹ H NMR ) may be 0.1 or more, 0.15 or more, 0.2 or more, 0.25 or more, 0.3 or more, 0.35 or more, or 0.4 or more. In another example, the curable composition has a ratio (K ₁ /K ₂ ) of the total content of silicon-bonded hydrogen (K ₁ ) measured by ²⁹ Si NMR and the total content (K ₂ ) of alkenyl groups measured by ¹ H NMR. 1 or less, 0.9 or less, 0.8 or less, 0.7 or less, or 0.65 or less. The ratio (K ₁ /K ₂ ) may be included within a range formed by appropriately selecting the upper and lower limits listed above. In addition, when the ratio (K ₁ /K ₂ ) satisfies the above range, low hardness can be maintained even at a high curing rate and a cured product having excellent reworkability can be secured.

The curable composition according to an example of the present application may have an R _N value of 1 or less, 0.9 or less, 0.8 or less, 0.7 or less, 0.6 or less, or 0.5 or less according to General Formula 3 below. In another example, the curable composition may have an R _N value of 0.01 or more, 0.025 or more, 0.05 or more, 0.075 or more, 0.1 or more, 0.2 or more, or 0.3 or more according to the following general formula 3. The R _N value according to the following general formula 3 of the curable composition may be included within the range formed by appropriately selecting the upper limit and the lower limit listed above. In addition, when the R _N value according to the following general formula 3 of the curable composition satisfies the above range, low hardness can be maintained even at a high curing rate and a cured product having excellent reworkability can be secured.

[Formula 3]

R _N = (N _A -N _H,2 )/N _H,1

In Formula 3, N _A is the number of moles of alkenyl groups contained in the first polyorganosiloxane component as measured by ¹ H NMR. In Formula 3, N _H,2 is the number of moles of silicon-bonded hydrogen contained in the second polyorganosiloxane component as measured by ²⁹ Si NMR. In Formula 3, N _H,1 is the number of moles of silicon-bonded hydrogen contained in the linker as measured by ²⁹ Si NMR.

In Formula 3, N _A may be a calculated value specifically obtained according to Equation 2 below.

[Formula 2]

In Equation 2, n _A is the content of alkenyl groups contained in the first polyorganosiloxane component as measured by ¹ H NMR, and m _A is the total weight of the first polyorganosiloxane component included in the curable composition.

In addition, N _H,1 in Formula 3 may be a calculated value specifically obtained according to Formula 3 below.

[Formula 3]

In Equation 3, n _H,1 is the content of silicon-bonded hydrogen contained in the linker measured by ²⁹ Si NMR, and m _H,1 is the total weight of the linker included in the curable composition.

In addition, N _H,2 in Formula 3 may be a calculated value specifically obtained according to Formula 4 below.

[Formula 4]

In Equation 4, n _H,2 is the content of silicon-bonded hydrogen contained in the second polyorganosiloxane component measured by ²⁹ Si NMR, and m _H,2 is the total weight of the second polyorganosiloxane component included in the curable composition. .

The curable composition according to an example of the present application may satisfy _HR of 110 or less, 109.5 or less, 109 or less, 108.5 or less, 108 or less, or 107.5 or less according to Formula 4 below. In another example, the curable composition has a _HR of 90 or more, 91 or more, 92 or more, 93 or more, 94 or more, 95 or more, 96 or more, 97 or more, 98 or more, 99 or more, 100 or more, or 101 or higher can be satisfied. The _HR value according to the following general formula 4 of the curable composition may be included within the range formed by appropriately selecting the upper limit and the lower limit listed above. In addition, when the _HR value according to Formula 4 of the curable composition satisfies the above ratio, a cured product having excellent durability even at a high temperature and maintaining low hardness even at a high curing rate can be formed.

[Formula 4]

H _R = H _f /H _{i ×} 100

In Formula 4, H _i is an initial Shore OO hardness measured immediately after the curable composition is cured, and H _f is a later Shore OO hardness measured after standing at 150 ° C. for 500 hours after measuring H _i .

The R _L value according to the general formula 1 and the HR _R value according to the general formula 4 are within the respective prescribed ranges by adjusting the types of components included in the curable composition according to an example of the present application and their content ratios, etc. can be included in

resin composition

The resin composition included in the curable composition according to an example of the present application may include a silicone resin. Here, the silicone resin may mean a resin having a polysiloxane main chain.

The resin composition included in the curable composition according to an example of the present application may include a first polyorganosiloxane component, a linker, and a second polyorganosiloxane component.

The resin composition included in the curable composition according to an example of the present application contains the first polyorganosiloxane component in an amount of 80% by weight or more, 82% by weight or more, 84% by weight or more, 86% by weight or more, or 88% by weight based on the total weight of the resin composition. % or more, 90% by weight or more, 92% by weight or more, or 94% by weight or more. In another example, the resin composition included in the curable composition contains the first polyorganosiloxane component in an amount of 99% by weight or less, 98.5% by weight or less, 98% by weight or less, 97.5% by weight or less, or 97% by weight or less based on the total weight of the resin composition. can be included with The content ratio of the first polyorganosiloxane component may be included within a range formed by appropriately selecting the upper and lower limits listed above. In addition, when the content ratio of the first polyorganosiloxane component satisfies the above range, it is possible to form a curable composition capable of securing a cured product having a low specific gravity while securing low viscosity characteristics.

The resin composition included in the curable composition according to an example of the present application contains a linker in an amount of 1.6 parts by weight or more, 1.7 parts by weight or more, 1.8 parts by weight or more, 1.9 parts by weight or more, 2 parts by weight based on 100 parts by weight of the first polyorganosiloxane component. or more or 2.1 parts by weight or more. In another example, the resin composition included in the curable composition contains a linker in an amount of 5 parts by weight or less, 4.5 parts by weight or less, 4 parts by weight or less, 3.5 parts by weight or less, or 3 parts by weight or less based on 100 parts by weight of the first polyorganosiloxane component. can include The content ratio of the linker may be included within the range formed by appropriately selecting the upper and lower limits listed above. In addition, when the content ratio of the linker satisfies the above range, a curable composition capable of securing a cured product having excellent durability even at high temperatures and maintaining low hardness even at a high curing rate can be formed.

The resin composition included in the curable composition according to an example of the present application includes the second polyorganosiloxane component in an amount of 0.1 part by weight or more, 0.25 part by weight or more, 0.5 part by weight or more, 0.75 part by weight based on 100 parts by weight of the first polyorganosiloxane component. or more or 1 part by weight or more. In another example, the resin composition included in the curable composition contains the second polyorganosiloxane component in an amount of 10 parts by weight or less, 8 parts by weight or less, 6 parts by weight or less, 4 parts by weight or less, based on 100 parts by weight of the first polyorganosiloxane component. It may contain 3 parts by weight or less. The content ratio of the second polyorganosiloxane component may be included within the range formed by appropriately selecting the upper and lower limits listed above. In addition, when the content ratio of the second polyorganosiloxane component satisfies the above range, it is possible to form a curable composition capable of securing a cured product having low specific gravity while securing low viscosity characteristics.

The first polyorganosiloxane component included in the resin composition of the curable composition according to an example of the present application may contain an alkenyl group at a terminal and include a dialkylsiloxane repeating unit.

The first polyorganosiloxane component may include a compound represented by Formula 1 below.

[Formula 1]

In Formula 1, R ₁ and R ₈ may each independently be an alkenyl group having 2 to 20 carbon atoms, 2 to 16 carbon atoms, 2 to 12 carbon atoms, 2 to 8 carbon atoms, or 2 to 4 carbon atoms.

In Formula 1, R ₂ , R ₃ , R ₄ , R ₅ , R ₆ and R ₇ each independently have 1 to 20 carbon atoms, 1 to 16 carbon atoms, 1 to 12 carbon atoms, 1 to 8 carbon atoms, and 1 to 8 carbon atoms. 4, it may be an alkyl group having 1 to 2 carbon atoms.

In Formula 1, m is 1 or more, 10 or more, 20 or more, 30 or more, 40 or more, 50 or more, 60 or more, 70 or more, 80 or more, 90 or more, 100 or more, 110 or more, 120 or more, 130 or more; It may be 140 or more, and in another example, m may be 200 or less, 190 or less, 180 or less, 170 or less, 160 or less, or 150 or less. The m may be included within the range formed by appropriately selecting the upper and lower limits listed above.

The first polyorganosiloxane component included in the resin composition of the curable composition according to an example of the present application includes the compound represented by Formula 1 in an amount of 55% by weight or more, 60% by weight or more, based on the total weight of the first polyorganosiloxane component, 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% by weight or more, or 99% by weight or more, and in another example, 100% by weight % can be included.

The first polyorganosiloxane component included in the resin composition of the curable composition according to an example of the present application has an alkenyl group content of 0.12 mmol/g or more, 0.13 mmol/g or more, or 0.14 mmol/g or more as measured by ¹ H NMR. , 0.15 mmol/g or more, 0.16 mmol/g or more, 0.17 mmol/g or more, or 0.18 mmol/g or more. In another example, the first polyorganosiloxane component has an alkenyl group content of 2 mmol/g or less, 1.8 mmol/g or less, 1.6 mmol/g or less, 1.4 mmol/g or less, 1.2 mmol/g or less, as measured by ¹ H NMR. g or less, 1 mmol/g or less, 0.8 mmol/g or less, 0.6 mmol/g or less, 0.4 mmol/g or less or 0.2 mmol/g or less. The content of the alkenyl group of the first polyorganosiloxane component may be included within the range formed by appropriately selecting the upper and lower limits listed above. In addition, when the content of the alkenyl group of the first polyorganosiloxane component satisfies the above range, a cured product having excellent durability even at high temperatures and maintaining low hardness even at a high curing rate can be secured.

The first polyorganosiloxane component included in the resin composition of the curable composition according to an example of the present application has a kinematic viscosity of less than 1,000 cSt, 900 cSt or less, 800 cSt or less, 700 cSt or less, 600 cSt or less, measured at 40 ° C. It may be less than cSt or less than 500 cSt. In another example, the first polyorganosiloxane component has a kinematic viscosity of 20 cSt or more, 60 cSt or more, 100 cSt or more, 140 cSt or more, 180 cSt or more, 220 cSt or more, 260 cSt or more measured at 40 ° C. or 300 cSt or greater. The kinematic viscosity of the first polyorganosiloxane component measured at 40° C. may be included within a range formed by appropriately selecting the upper and lower limits listed above. In addition, when the kinematic viscosity of the first polyorganosiloxane component, measured at 40 °C, satisfies the above range, low viscosity characteristics of the curable composition can be secured.

A linker included in the resin composition of the curable composition according to an example of the present application may control the aspect ratio of the crosslinked network of the cured product. The linker may include a dialkylsiloxane repeating unit and a monoalkylsiloxane repeating unit.

The linker may include a compound represented by Formula 2 below.

[Formula 2]

In Formula 2, R ₉ and R ₁₅ may each independently be hydrogen or an alkyl group having 1 to 20 carbon atoms, 1 to 16 carbon atoms, 1 to 12 carbon atoms, 1 to 8 carbon atoms, 1 to 4 carbon atoms, and 1 to 2 carbon atoms.

In Formula 2, R ₁₀ , R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₆ and R ₁₇ each independently have 1 to 20 carbon atoms, 1 to 16 carbon atoms, 1 to 12 carbon atoms, 1 to 8 carbon atoms, It may be an alkyl group having 1 to 4 carbon atoms and 1 to 2 carbon atoms.

In Formula 2, p may be 1 or more, 10 or more, 20 or more, 30 or more, or 40 or more, and in other examples, p may be 200 or less, 160 or less, 120 or less, 80 or less, or 60 or less. . The p may be included within the range formed by appropriately selecting the upper and lower limits listed above.

In Formula 2, q may be 1 or more, 2 or more, 3 or more, 4 or more, 5 or more, 6 or more, 7 or more, or 8 or more, and in other examples, q is 50 or less, 40 or less, 30 or less, 20 It may be less than or equal to 10. The q may be included within the range formed by appropriately selecting the upper and lower limits listed above.

The linker included in the resin composition of the curable composition according to an example of the present application contains the compound represented by Formula 2 in an amount of 55% by weight or more, 60% by weight or more, 65% by weight or more, 70% by weight or more, based on the total weight of the linker. 75% by weight or more, 80% by weight or more, 85% by weight or more, 90% by weight or more, 95% by weight or more, or 99% by weight or more, and in another example, 100% by weight.

The linker included in the resin composition of the curable composition according to an example of the present application has a silicon-bonded hydrogen content of 0.1 mmol/g or more, 0.25 mmol/g or more, 0.5 mmol/g or more, 0.75 mmol/g or more, as measured by ²⁹ Si NMR. g or more, 1 mmol/g or more, 1.25 mmol/g or more, 1.5 mmol/g or more or 1.75 mmol/g or more. In another example, the linker may have a silicon-bonded hydrogen content of 5 mmol/g or less, 4.8 mmol/g or less, 4.6 mmol/g or less, 4.4 mmol/g or less, or 4.2 mmol/g or less, as measured by ²⁹ Si NMR. . The content of silicon-bonded hydrogen in the linker may be contained within a range formed by appropriately selecting the upper and lower limits listed above. In addition, when the content of silicon-bonded hydrogen of the linker satisfies the above range, a cured product having excellent durability even at high temperatures and maintaining low hardness even at a high curing rate can be secured.

The linker included in the resin composition of the curable composition according to an example of the present application has an L value according to the following general formula 2 of 1 or more, 1.25. or more, 1.5 or more, 1.75 or more, 2 or more, 2.25 or more, 2.5 or more, 2.75 or more, or 3 or more may be satisfied. In another example, the linker may satisfy an L value of 20 or less, 18 or less, 16 or less, 14 or less, or 12 or less according to Formula 2 below. The L value according to the following general formula 2 of the linker may be included within the range formed by appropriately selecting the upper and lower limits listed above. In addition, when the L value of the linker according to Formula 2 below satisfies the above range, it is possible to form a curable composition capable of securing a cured product having excellent heat resistance during curing while securing low viscosity characteristics.

[Formula 2]

L = (p+q)/(q+1)

In Formula 2, p is the number of dialkylsiloxane repeating units of the linker as measured by ²⁹ Si NMR, and q is the number of monoalkylsiloxane repeating units of the linker as measured by ²⁹ Si NMR.

The linker included in the resin composition of the curable composition according to an example of the present application has a kinematic viscosity measured at 40 ° C. of less than 1,000 cSt, less than 900 cSt, less than 800 cSt, less than 700 cSt, less than 600 cSt, or less than 500 cSt. may be below. In another example, the linker may have a kinematic viscosity of 10 cSt or more, 50 cSt or more, 100 cSt or more, 150 cSt or more, 200 cSt or more, 250 cSt or more, or 300 cSt or more measured at 40 °C. The linker may have a kinematic viscosity measured at 40° C. within a range formed by appropriately selecting the upper and lower limits listed above. In addition, when the kinematic viscosity of the linker measured at 40 ° C. satisfies the above range, the low viscosity characteristic of the curable composition can be secured.

The second polyorganosiloxane component included in the resin composition of the curable composition according to an example of the present application may contain silicon-bonded hydrogen at the terminal and include dialkylsiloxane repeating units.

The second polyorganosiloxane component may include a compound represented by Chemical Formula 3 below.

[Formula 3]

In Formula 3, R ₁₈ , R ₁₉ , R ₂₀ , R ₂₁ , R ₂₂ and R ₂₃ each independently have 1 to 20 carbon atoms, 1 to 16 carbon atoms, 1 to 12 carbon atoms, 1 to 8 carbon atoms, 1 to 4 carbon atoms; It may be an alkyl group having 1 to 2 carbon atoms.

In Formula 3, r may be 1 or more, 2 or more, 3 or more, 4 or more, 5 or more, 6 or more, 7 or more, or 8 or more, and in other examples, r is 200 or less, 160 or less, 120 or less, It can be a number of 80 or less, 40 or less, or 20 or less. The r may be included within the range formed by appropriately selecting the upper and lower limits listed above.

The second polyorganosiloxane component included in the resin composition of the curable composition according to an example of the present application contains the compound represented by Formula 3 in an amount of 55% by weight or more, 60% by weight or more, based on the total weight of the second polyorganosiloxane component, 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% by weight or more, or 99% by weight or more, and in another example, 100% by weight % can be included.

The second polyorganosiloxane component included in the resin composition of the curable composition according to an example of the present application has a silicon-bonded hydrogen content of 0.1 mmol/g or more, 0.25 mmol/g or more, or 0.5 mmol/g, as measured by ²⁹ Si NMR. 0.75 mmol/g or more, 1 mmol/g or more, 1.25 mmol/g or more, 1.5 mmol/g or more, 1.75 mmol/g or more, 2 mmol/g or more, 2.25 mmol/g or more, 2.5 mmol/g or more, 2.75 mmol/g or more or 3 mmol/g or more. In another example, the second polyorganosiloxane component has a silicon-bonded hydrogen content of 5 mmol/g or less, 4.8 mmol/g or less, 4.6 mmol/g or less, 4.4 mmol/g or less, or 4.2 mmol as measured by ²⁹ Si NMR. /g or less, 4 mmol/g or less, 3.8 mmol/g or less, 3.6 mmol/g or less, 3.4 mmol/g or less, 3.2 mmol/g or less, or 3 mmol/g or less. The content of silicon-bonded hydrogen in the second polyorganosiloxane component may be included within a range formed by appropriately selecting the upper and lower limits listed above. In addition, when the content of silicon-bonded hydrogen of the second polyorganosiloxane component satisfies the above range, a cured product having excellent durability even at high temperatures and maintaining low hardness even at a high curing rate can be secured.

The second polyorganosiloxane component included in the resin composition of the curable composition according to an example of the present application has a kinematic viscosity of 500 cSt or less, 450 cSt or less, 400 cSt or less, 350 cSt or less, 300 cSt or less measured at 40 ° C. cSt or less, 250 cSt or less, 200 cSt or less, 150 cSt or less, 100 cSt or less, 90 cSt or less, 80 cSt or less, 70 cSt or less, 60 cSt or less, 50 cSt or less, 40 cSt or less, 30 cSt or less, or 20 cSt or less can In another example, the second polyorganosiloxane component may have a kinematic viscosity of 1 cSt or more, 1.5 cSt or more, 2 cSt or more, 2.5 cSt or more, 3 cSt or more, or 3.5 cSt or more measured at 40 ° C. The second polyorganosiloxane component may have a kinematic viscosity measured at 40° C. within a range formed by appropriately selecting the upper and lower limits listed above. In addition, when the kinematic viscosity of the second polyorganosiloxane component, measured at 40° C., satisfies the above range, the low viscosity characteristic of the curable composition can be secured.

filler composition

The type, shape, and size of the filler composition included in the curable composition according to an example of the present application are not particularly limited as long as they are used in the art. In addition, the filler composition may include one type or two or more types of filler particles. In addition, the filler composition may be a mixture of different shapes even though the same type of filler particles are used, or a mixture of filler particles having different average particle diameters. For example, the filler composition may be a mixture of aluminum hydroxide and aluminum oxide (alumina), and the shape and average particle diameter of the aluminum hydroxide and aluminum oxide may be different from each other.

The filler composition included in the curable composition according to an example of the present application may include filler particles with low specific gravity. Here, the low specific gravity filler particles may have a specific gravity of 3 or less, 2.9 or less, 2.8 or less, 2.7 or less, 2.6 or less, 2.5 or less, or 2.5 or less.

In addition, the filler composition may be a thermally conductive filler composition for processing (radiating heat) heat, and may include at least one thermally conductive filler particle. The thermally conductive filler particle may have a thermal conductivity of about 1 W/mK or more, 5 W/mK or more, 10 W/mK or more, or 15 W/mK or more, and in another example, about 400 W/mK or less, about 350 W / mK or less or about 300 W / mK or less may mean. The thermal conductivity of the thermally conductive filler particles that may be included in the filler composition is not particularly limited, but may be a value measured according to ASTM E1461.

The type of thermally conductive filler particles included in the filler composition is not particularly limited as long as its own thermal conductivity satisfies the above range, but examples include aluminum oxide (alumina), magnesium oxide, beryllium oxide, titanium oxide, etc. of metal oxides; metal nitrides such as boron nitride, silicon nitride or aluminum nitride; carbides such as silicon carbide; metal hydroxides such as aluminum hydroxide or magnesium hydroxide; metal fillers such as copper, silver, iron, aluminum or nickel; metal alloy fillers such as titanium; or mixtures thereof.

In addition, the low specific gravity filler particles may be the thermally conductive filler particles. By using such filler particles with low specific gravity, a curable composition capable of securing a cured product having low specific gravity and excellent heat dissipation performance can be formed. Examples of filler particles having low specific gravity and thermal conductivity include metal hydroxides such as aluminum hydroxide or magnesium hydroxide, but are not limited thereto.

Considering that the filler composition included in the curable composition according to an example of the present application may require insulation performance in contact with an electric or electronic device, it may not substantially include metal filler particles. Here, not substantially included means not intentionally added, and even if it exists naturally, it is included in 1% by weight or less, 0.5% by weight or less, 0.1% by weight or less, 0.01% by weight or less, or 0.001% by weight or less based on the total weight. It can mean that you are doing In addition, the metal filler particle is a filler particle that can be used as a conductor, for example, a metal filler such as copper, silver, iron, aluminum or nickel; and metal alloy fillers such as titanium, but are not limited thereto.

The filler composition included in the curable composition according to an example of the present application may include first low specific gravity filler particles and second low specific gravity filler particles.

The first low specific gravity filler particles may have an average particle diameter of 20 μm or more, 25 μm or more, 30 μm or more, 35 μm or more, 40 μm or more, 45 μm or more, 50 μm or more, or more. The upper limit of the average particle diameter of the first low specific gravity filler particles is not particularly limited, but may be 1,000 μm or less, 900 μm or less, 800 μm or less, or 500 μm or less.

The second low specific gravity filler particles have an average particle diameter of 10 μm or less, 9 μm or less, 8 μm or less, 7 μm or less, 6 μm or less, 5 μm or less, 4 μm or less, 3 μm or less, 2 μm or less, or 1 μm It can be less than or equal to. The lower limit of the average particle diameter of the second low specific gravity filler particles is not particularly limited, but may be 0.01 μm or more, 0.05 μm or more, or 0.1 μm or more.

The average particle diameter of the filler particles, which is a term used in this application, is a so-called D50 particle diameter (median particle diameter), and may mean a particle diameter at 50% cumulative volume based particle size distribution. That is, the particle size distribution is obtained on a volume basis, and the particle diameter at the point where the cumulative value is 50% in the cumulative curve with the total volume as 100% can be seen as the average particle diameter. The D50 particle diameter as described above can be measured by a laser diffraction method.

The first low specific gravity filler particles of the filler composition included in the curable composition according to an example of the present application are 30% by weight or more, 35% by weight or more, 40% by weight or more, 45% by weight or more, 50% by weight or more, based on the total weight of the filler composition. At least 55%, at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95% or 99 It may contain more than 100% by weight.

When the filler composition included in the curable composition according to an example of the present application includes first low specific gravity filler particles and second low specific gravity filler particles at the same time, the first low specific gravity filler particles are 30% of the total weight of the filler composition At least 35% by weight, at least 40% by weight, at least 45% by weight, at least 50% by weight, at least 55% by weight, at least 60% by weight, at least 65% by weight or at least 70% by weight. In another example, in the above case, the first low specific gravity filler particles may be included in 90% by weight or less, 85% by weight or less, 80% by weight or less, or 75% by weight or less based on the total weight of the filler composition. In this case, the weight ratio of the first low specific gravity filler particles may be included within the range formed by appropriately selecting the upper and lower limits listed above. In the above case, when the weight ratio of the first low specific gravity filler particles satisfies the above range, a curable composition capable of securing a cured product having low specific gravity and excellent heat dissipation performance may be formed.

When the filler composition included in the curable composition according to an example of the present application includes the first low specific gravity filler particles and the second low specific gravity filler particles at the same time, the first low specific gravity filler particles (F ₁ ) and the second low specific gravity filler The weight ratio (F ₁ /F ₂ ) of the particles (F ₂ ) may be 1 or more, 1.25 or more, 1.5 or more, 1.75 or more, 2 or more, or 2.25 or more. In another example, the weight ratio (F ₁ /F ₂ ) of the first low specific gravity filler particles (F ₁ ) and the second low specific gravity filler particles (F ₂ ) is 5 or less, 4.5 or less, 4 or less, 3.5 or less, or 3 may be below. The weight ratio (F ₁ /F ₂ ) of the first low specific gravity filler particles ( _F 1 ) and the second low specific gravity filler particles (F ₂ ) may be included within the range formed by appropriately selecting the upper and lower limits listed above. When the weight ratio (F ₁ /F ₂ ) of the first low specific gravity filler particles (F ₁ ) and the second low specific gravity filler particles (F ₂ ) satisfies the above range, a cured product having low specific gravity and excellent heat dissipation performance It is possible to form a curable composition capable of securing.

The filler composition included in the curable composition according to an example of the present application may further include hollow particles. The hollow particles may form a cured product having a low specific gravity by lowering the overall specific gravity of the filler composition, and may improve heat dissipation performance by forming a thermal network between the filler particles having a low specific gravity.

The hollow particles may have a specific gravity of 0.1 or more, 0.15 or more, 0.2 or more, or 0.25 or more, and in another example, may have a specific gravity of 1 or less, 0.95 or less, 0.9 or less, or 0.85 or less. The specific gravity of the hollow particles may be included within the range formed by appropriately selecting the upper and lower limits listed above. In addition, when the specific gravity of the hollow particles satisfies the above range, a cured product having a low specific gravity may be formed by lowering the overall specific gravity of the filler composition.

In addition, the hollow particles have an isostatic crash strength of 1 MPa or more, 5 MPa or more, 10 MPa or more, 15 MPa or more, 20 MPa or more, 25 MPa or more, 30 MPa or more, 35 MPa or more, or 40 MPa may be ideal In another example, the hollow particle may have an isostatic crushing strength of 200 MPa or less, 180 MPa or less, 160 MPa or less, 140 MPa or less, 120 MPa or less, 100 MPa or less, 80 MPa or less, or 60 MPa or less. The isostatic crushing strength of the hollow particles may be included within the range formed by appropriately selecting the upper and lower limits listed above. In addition, when the isostatic crushing strength of the hollow particles satisfies the above range, a durable cured product may be formed.

The filler composition included in the curable composition according to an example of the present application contains hollow particles in an amount of 1 part by weight or more, 1.5 parts by weight or more, based on 100 parts by weight of the sum of the weights of the first low specific gravity filler particles and the second low specific gravity filler particles. It may include 2 parts by weight or more or 2.5 parts by weight or more. In another example, the filler composition contains hollow particles in an amount of 10 parts by weight or less, 9 parts by weight or less, 8 parts by weight or less, 7 parts by weight or less, based on 100 parts by weight of the sum of the weights of the first low specific gravity filler particles and the second low specific gravity filler particles. parts by weight or less, 6 parts by weight or less, 5 parts by weight or less, or 4 parts by weight or less. The content ratio of the hollow particles may be included within the range formed by appropriately selecting the upper and lower limits listed above. In addition, when the content ratio of the hollow particles satisfies the above range, heat dissipation performance may be effectively improved by forming a thermal network between the low specific gravity filler particles.

added compound

The curable composition according to an example of the present application may further include one or two or more additives exemplified below in order to secure additional physical properties. However, the additives are sufficient as long as they are generally usable in the art, and are not necessarily limited to the additives exemplified below.

The curable composition according to an example of the present application may further include a metal catalyst to accelerate the progress of the cured product formation reaction. The metal catalyst may include, as a central metal element, at least one selected from the group consisting of aluminum, bismuth, lead, mercury, tin, zinc, platinum, silver, and zirconium. In addition, the metal catalyst may have a siloxane group, an ester group, an ether group, or a carboxy group bonded to the central metal element. The metal catalyst is, for example, Bis[1,3-bis(2-ethenyl)-1,1,3,3-tetramethyldisiloxane]platinum (CAS No. 81032-58-8), dibutyltin dilaurate or dimethyl Tin diacetate, but not particularly limited thereto, can be used without limitation as long as it is generally available in the art.

The metal catalyst preferably includes platinum (Pt) as a central metal element in consideration of components included in the curable composition. In addition, when the metal catalyst contains platinum (Pt), the curable composition contains the metal catalyst in an amount of 0.1 part by weight or more, 0.2 part by weight or more, 0.3 part by weight or more, or 0.4 part by weight or more based on 100 parts by weight of the first polyorganosiloxane component. , 0.5 parts by weight or more, 0.6 parts by weight or more, 0.7 parts by weight or more, 0.8 parts by weight or more, or 0.9 parts by weight or more. In another example, the curable composition contains a metal catalyst in an amount of 10 parts by weight or less, 9 parts by weight or less, 8 parts by weight or less, 7 parts by weight or less, 6 parts by weight or less, 5 parts by weight or less based on 100 parts by weight of the first polyorganosiloxane component. , 4 parts by weight or less, 3 parts by weight or less, 2 parts by weight or less, or 1 part by weight or less may be included. The content ratio of the metal catalyst may be included within the range formed by appropriately selecting the upper and lower limits listed above. In addition, when the content ratio of the metal catalyst satisfies the above range, it is possible to effectively progress the cured product formation reaction while reducing side reactions.

The curable composition according to an example of the present application may further include a dispersant. The dispersant is, for example, polyamideamine and its salt, polycarboxylic acid and its salt, modified polyurethane, modified polyester, modified poly(meth)acrylate, (meth)acrylic copolymer, naphthalenesulfonic acid formalin Condensates, polyoxyethylene alkyl phosphoric acid esters, polyoxyethylene alkylamines and pigment derivatives may be used, but any dispersant known in the art may be used without limitation. For example, Disperbyk-1799 (BYK Co.) and the like can be used.

In the curable composition according to an example of the present application, the dispersant is added in an amount of 0.01 parts by weight or more, 0.05 parts by weight or more, 0.1 parts by weight or more, 0.15 parts by weight or more, 0.2 parts by weight or more, 0.25 parts by weight or more, or 0.3 parts by weight based on 100 parts by weight of the filler composition. part or more, 0.35 parts by weight or more, 0.4 parts by weight or more, 0.45 parts by weight or more, or 0.5 parts by weight or more. In another example, the curable composition contains a dispersant in an amount of 1 part by weight or less, 0.95 parts by weight or less, 0.9 parts by weight or less, 0.85 parts by weight or less, 0.8 parts by weight or less, 0.75 parts by weight or less, 0.7 parts by weight or less, based on 100 parts by weight of the filler composition. , It may include 0.65 parts by weight or less, 0.6 parts by weight or less, or 0.55 parts by weight or less. The content ratio of the dispersant may be included within the range formed by appropriately selecting the upper limit and the lower limit listed above. When the content ratio of the dispersant satisfies the above range, excellent dispersibility between components in the curable composition may be secured.

The curable composition according to an example of the present application may further include a plasticizer. The type of plasticizer is not particularly limited, but examples include phthalic acid compounds, phosphoric acid compounds, adipic acid compounds, sebacic acid compounds, citric acid compounds, glycolic acid compounds, trimellitic acid compounds, polyester compounds, epoxidized soybean oil, chlorinated Paraffin, chlorinated fatty acid esters, fatty acid compounds, compounds having a saturated aliphatic chain substituted with a sulfonic acid group bound to a phenyl group (eg, LANXESS mesamoll), 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, octyldecyl 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. As the phosphoric acid compound, one or more of tricresyl phosphate, trioctyl phosphate, triphenyl phosphate, octyl diphenyl phosphate, cresyl diphenyl phosphate and trichloroethyl phosphate may be used. The adipic acid compound is dibutoxyethoxyethyl adipate (DBEEA), dioctyl adipate, diisooctyl adipate, di-n-octyl adipate, didecyl adipate, diisononyl adipate (DINA), One or more of diisodecyl adipate (DIDP), n-octyl n-decyl adipate, n-heptyl adipate and n-nonyl adipate may be used. The sebacic acid compound may use at least one of dibutyl sebacate, dioctyl sebacate, diisooctyl sebacate and butyl benzyl. 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, one or more of methyl phthalyl ethyl glycolate, ethyl phthalyl ethyl glycolate, and butyl phthalyl ethyl glycolate may be used. The trimellitic acid compound may use at least one of trioctyl trimellitate and tri-n-octyl n-decyl trimellitate. The polyester compound is butane diol, ethylene glycol, propane 1,2-diol, propane 1,3 diol, polyethylene glycol, glycerol, a diacid (selected from adipic acid, succinic acid, succinic anhydride) and a hydroxy acid (such as , hydroxystearic acid).

The curable composition according to an example of the present application may further include a peroxide compound, if necessary. The peroxide compound may be a material that initiates polymerization of the curable composition.

The peroxide compound is, for example, methyl ethyl ketone peroxide (MEKP), cyclohexanone peroxide, 3,3,5-trimethylcyclohexanone peroxide, methylcyclohexanone peroxide, methylacetate peroxide ketone peroxide compounds such as oxide and acetylacetone peroxide; tert-butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, paramenthane hydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide, and 1,1,3,3 -hydroperoxide compounds such as tetramethylbutylhydroperoxide and the like; Acetyl peroxide, isobutyl peroxide, octanoyl peroxide, decanoyl peroxide, laurinoyl peroxide, 3,3,5-trimethylhexanoyl peroxide, succinic acid peroxide, benzoyl peroxide, 2,4-dichloro benzoyl diacyl peroxide compounds such as peroxide and meth-toluoyl peroxide; An acyl peroxide compound such as benzoyl peroxide (BPO); may be, but is not limited thereto. In addition, 1 type or 2 or more types can be used for a peroxide compound.

The curable composition according to an example of the present application may further include a reaction accelerator if necessary. The reaction accelerator may perform a function of accelerating the polymerization reaction of the curable composition. The type of the reaction accelerator is not particularly limited, but for example, dimethyl-p-toluidine (DMPT) and the like may be used.

If necessary, the curable composition according to one embodiment of the present application is a viscosity modifier, for example, a thixotropy imparting agent, a diluent, a surface treatment agent for adjusting the viscosity, for example, to increase or decrease the viscosity or to adjust the viscosity according to shear force. Or a coupling agent may be further included. The thixotropy imparting agent can adjust the viscosity of the curable composition according to the shear force. As the thixotropy imparting agent that can be used, fumed silica and the like can be exemplified. The diluent is generally used to lower the viscosity of the curable composition, and various types of diluents known in the art may be used without limitation as long as they can exhibit the above function. The surface treatment agent is for surface treatment of the filler composition introduced into the cured product of the curable composition, and various types known in the art can be used without limitation as long as they can exhibit the above functions. In the case of the coupling agent, for example, it can be used to improve the dispersibility of thermally conductive filler particles (eg, alumina, etc.), and various types known in the industry can be used as long as they can exhibit the above effect. Can be used without restrictions.

The curable composition according to an example of the present application may further include a flame retardant or a flame retardant auxiliary, if necessary. A flame retardant cured product may be formed by curing the curable composition further including a flame retardant or a flame retardant auxiliary agent. As the flame retardant, various known flame retardants may be applied without particular limitation, and for example, a solid filler type flame retardant or a liquid flame retardant may be applied. Examples of the flame retardant include, but are not limited to, organic flame retardants such as melamine cyanurate and inorganic flame retardants such as magnesium hydroxide. When the amount of thermally conductive filler particles included in the curable 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.

Two-component curable composition

A two-component curable composition according to an example of the present application includes a main part including a first polyorganosiloxane component and a filler composition, and a first polyorganosiloxane component, a linker, a second polyorganosiloxane component and a filler composition (the filler of the main part). As independent of the composition, it may include a curing agent part including a filler component). Here, the first polyorganosiloxane component included in the main part and the first polyorganosiloxane component included in the curing agent part may be independent of each other, and may be identical to or different from each other.

In addition, the contents of the first polyorganosiloxane component, the linker, and the second polyorganosiloxane component included in the two-component curable composition according to an example of the present application are the same as those described above, and only the contents with differences will be described later. do.

In addition, unless specifically distinguished between a curable composition and a two-component curable composition in the present application, a curable composition may be a term including a two-component curable composition.

subject part

As described above, the main part of the two-component curable composition according to an example of the present application may include the first polyorganosiloxane component and the filler composition.

The filler composition included in the subject part is 70% by weight or more, 72% by weight or more, 74% by weight or more, 76% by weight or more, 78% by weight or more, 80% by weight or more, or 82% by weight or more based on the total weight of the subject part. can include In another example, the subject part may include the filler composition in an amount of 99 wt% or less, 95 wt% or less, 90 wt% or less, or 85 wt% or less based on the total weight of the subject part. The content ratio of the filler composition may be included within the range formed by appropriately selecting the upper and lower limits listed above.

The main part includes the first polyorganosiloxane component in an amount of 5 parts by weight or more, 7.5 parts by weight or more, 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, or 20 parts by weight or more, based on 100 parts by weight of the filler composition. can include more than In another example, the main part contains the first polyorganosiloxane component in an amount of 50 parts by weight or less, 45 parts by weight or less, 40 parts by weight or less, 35 parts by weight or less, 30 parts by weight or less, or 25 parts by weight or less based on 100 parts by weight of the filler composition. can be included with The content ratio of the first polyorganosiloxane component may be included within a range formed by appropriately selecting the upper and lower limits listed above. In addition, when the content ratio of the first polyorganosiloxane component satisfies the above range, a cured product having excellent durability even at a high temperature and maintaining low hardness even at a high curing rate can be secured.

In addition, the main part may further include a metal catalyst. In addition, one containing a metal catalyst may be the main part in the two-component curable composition. In the main part, the metal catalyst is added in an amount of 0.1 part by weight or more, 0.2 part by weight or more, 0.3 part by weight or more, 0.4 part by weight or more, 0.5 part by weight or more, or 0.6 part by weight based on 100 parts by weight of the first polyorganosiloxane component included in the main part. Or more, 0.7 parts by weight or more, 0.8 parts by weight or more or 0.9 parts by weight or more may be included. In another example, the main part contains the metal catalyst in an amount of 10 parts by weight or less, 9 parts by weight or less, 8 parts by weight or less, 7 parts by weight or less, 6 parts by weight or less, based on 100 parts by weight of the first polyorganosiloxane component included in the main part. It may include 5 parts by weight or less, 4 parts by weight or less, 3 parts by weight or less, 2 parts by weight or less, or 1 part by weight or less. The content ratio of the metal catalyst included in the main part may be included within a range formed by appropriately selecting the upper limit and the lower limit listed above. In addition, when the content ratio of the metal catalyst satisfies the above range, it is possible to effectively progress the cured product formation reaction while reducing side reactions.

In addition, the main part may further include one or two or more additives exemplified below in order to secure additional physical properties. Specifically, the subject part may further include a dispersing agent. In addition, the main part contains the dispersant in an amount of 0.01 parts by weight or more, 0.05 parts by weight or more, 0.1 parts by weight or more, 0.15 parts by weight or more, 0.2 parts by weight or more, 0.25 parts by weight or more, 0.3 parts by weight or more, 0.35 parts by weight or more, based on 100 parts by weight of the filler composition. It may include at least 0.4 parts by weight, at least 0.45 parts by weight, or at least 0.5 parts by weight. In another example, the main part contains the dispersant in an amount of 1 part by weight or less, 0.95 parts by weight or less, 0.9 parts by weight or less, 0.85 parts by weight or less, 0.8 parts by weight or less, 0.75 parts by weight or less, 0.7 parts by weight or less, based on 100 parts by weight of the filler composition. , It may include 0.65 parts by weight or less, 0.6 parts by weight or less, or 0.55 parts by weight or less. The content ratio of the dispersant may be included within the range formed by appropriately selecting the upper limit and the lower limit listed above.

The main part of the two-component curable composition according to an example of the present application may have a viscosity of 400,000 cP or less, 390,000 cP or less, 380,000 cP or less, or 370,000 cP or less measured at room temperature and at a shear rate of 1/s. In another example, the subject part may have a viscosity of 10,000 cP or more, 50,000 cP or more, 100,000 cP or more, 150,000 cP or more, or 200,000 cP or more measured at room temperature and at a shear rate of 1/s. The viscosity measured at room temperature and at a shear rate of 1/s of the subject part may be included within the range formed by appropriately selecting the upper and lower limits listed above.

hardener part

As described above, the curing agent part of the two-component curable composition according to an example of the present application may include a first polyorganosiloxane component, a linker, a second polyorganosiloxane component, and a filler composition. Here, the filler composition is independent of the filler composition of the main part, and may also be referred to as a filler component.

The filler composition (or may be referred to as a filler component) included in the curing agent part is 70% by weight or more, 72% by weight or more, 74% by weight or more, 76% by weight or more, 78% by weight or more, 80% by weight or more based on the total weight of the curing agent part. It may contain at least 82% by weight or more than 82% by weight. In another example, the curing agent part may include the filler composition in an amount of 99 wt% or less, 95 wt% or less, 90 wt% or less, or 85 wt% or less based on the total weight of the curing agent part. The content ratio of the filler composition may be included within the range formed by appropriately selecting the upper and lower limits listed above.

The first polyorganosiloxane component included in the curing agent part is independent of the first polyorganosiloxane component included in the main part, and a third polyorganosiloxane component to be distinguished from the first polyorganosiloxane component included in the main part. can also be said The curing agent part contains the first polyorganosiloxane component (or may be referred to as the third polyorganosiloxane component) in an amount of 5 parts by weight or more, 7.5 parts by weight or more, 10 parts by weight based on 100 parts by weight of the filler composition (or may be referred to as a filler component). It may include at least 12.5 parts by weight, at least 15 parts by weight, at least 17.5 parts by weight, or at least 20 parts by weight. In another example, the curing agent part contains the first polyorganosiloxane component in an amount of 50 parts by weight or less, 45 parts by weight or less, 40 parts by weight or less, 35 parts by weight or less, 30 parts by weight or less, or 25 parts by weight or less based on 100 parts by weight of the filler composition. can be included with The content ratio of the first polyorganosiloxane component may be included within a range formed by appropriately selecting the upper and lower limits listed above. In addition, when the content ratio of the first polyorganosiloxane component satisfies the above range, a cured product having excellent durability even at a high temperature and maintaining low hardness even at a high curing rate can be secured.

The curing agent part contains a linker in an amount of 0.1 part by weight or more, 0.15 part by weight or more, 0.2 part by weight or more, 0.25 part by weight or more, 0.3 part by weight or more, 0.35 part by weight or more based on 100 parts by weight of the filler composition (or filler component). Or it may contain 0.4 parts by weight or more. In another example, the curing agent part is a linker filler composition 100 parts by weight of 5 parts by weight or less, 4.5 parts by weight or less, 4 parts by weight or less, 3.5 parts by weight or less, 3 parts by weight or less, 2.5 parts by weight or less, 2 parts by weight or less or 1.5 parts by weight or less. The content ratio of the linker may be included within the range formed by appropriately selecting the upper and lower limits listed above. In addition, when the content ratio of the linker satisfies the above range, a curable composition capable of securing a cured product having excellent durability even at high temperatures and maintaining low hardness even at a high curing rate can be formed.

The curing agent part contains the second polyorganosiloxane component in an amount of 0.1 parts by weight or more, 0.2 parts by weight or more, 0.3 parts by weight or more, 0.4 parts by weight or more, or 0.5 parts by weight or more based on 100 parts by weight of the filler composition (or may be referred to as a filler component). can be included as In another example, the curing agent part may include the second polyorganosiloxane component in an amount of 10 parts by weight or less, 8 parts by weight or less, 6 parts by weight or less, 4 parts by weight or less, or 3 parts by weight or less based on 100 parts by weight of the filler composition. . The content ratio of the second polyorganosiloxane component may be included within the range formed by appropriately selecting the upper and lower limits listed above. In addition, when the content ratio of the second polyorganosiloxane component satisfies the above range, it is possible to form a curable composition capable of securing a cured product having low specific gravity while securing low viscosity characteristics.

In addition, the curing agent part may further include one or two or more additives exemplified below in order to secure additional physical properties. Specifically, the curing agent part may further include a dispersing agent. In addition, the curing agent part contains a dispersing agent in an amount of 0.01 parts by weight or more, 0.05 parts by weight or more, 0.1 parts by weight or more, 0.15 parts by weight or more, 0.2 parts by weight or more, 0.25 parts by weight or more based on 100 parts by weight of the filler composition (or filler component). 0.3 parts by weight or more, 0.35 parts by weight or more, 0.4 parts by weight or more, 0.45 parts by weight or more, or 0.5 parts by weight or more. In another example, the curing agent part contains a dispersing agent in an amount of 1 part by weight or less, 0.95 parts by weight or less, 0.9 parts by weight or less, 0.85 parts by weight or less, 0.8 parts by weight or less, based on 100 parts by weight of the dispersing agent. 0.75 parts by weight or less, 0.7 parts by weight or less, 0.65 parts by weight or less, 0.6 parts by weight or less, or 0.55 parts by weight or less. The content ratio of the dispersant may be included within the range formed by appropriately selecting the upper limit and the lower limit listed above.

The curing agent part of the two-component curable composition according to an example of the present application may have a viscosity of 400,000 cP or less, 390,000 cP or less, 380,000 cP or less, 370,000 cP, or 360,000 cP or less measured at room temperature and at a shear rate of 1/s. In another example, the curing agent part may have a viscosity of 10,000 cP or more, 50,000 cP or more, 100,000 cP or more, 150,000 cP or more, or 200,000 cP or more measured at room temperature and at a shear rate of 1/s. The viscosity measured at room temperature and at a shear rate of 1/s of the curing agent part may be included within the range formed by appropriately selecting the upper and lower limits listed above.

All omissions about the two-component curable composition according to an example of the present application may refer to the description of the curable composition according to an example of the present application.

Cured product of curable composition

The curable composition according to an example of the present application may be cured to form a cured product, and may have at least one or more of the following physical properties. Each physical property described below is independent, and any one physical property does not give priority to other physical properties, and the cured product of the curable composition may satisfy at least one or two or more of the physical properties described below. A cured product of a curable composition satisfying at least one or two or more of the physical properties described below is caused by a combination of each component included in the curable composition.

The cured product of the curable composition according to an example of the present application may satisfy _HR of 110 or less, 109.5 or less, 109 or less, 108.5 or less, 108 or less, or 107.5 or less according to Formula 4 below. In another example, the cured product of the curable composition has _HR according to Formula 4 of 90 or more, 91 or more, 92 or more, 93 or more, 94 or more, 95 or more, 96 or more, 97 or more, 98 or more, 99 or more, 100 above or above 101 can be satisfied. The cured product of the curable composition may have an _HR value according to the following general formula 4 within a range formed by appropriately selecting the upper and lower limits listed above. In addition, when the _HR value according to Formula 4 satisfies the above ratio, the cured product of the curable composition has excellent durability even at a high temperature and can maintain low hardness even at a high curing rate.

[Formula 4]

H _R = H _f /H _{i ×} 100

In Formula 4, H _i is the initial Shore OO hardness measured immediately after the curable composition according to an example of the present application is cured, and H _f is measured after standing at 150 ° C. for 500 hours after measuring H _i One later is Shore OO hardness.

The cured product of the curable composition according to an example of the present application may have a Shore OO hardness of 70 or less, 69 or less, 68 or less, 67 or less, 66 or less, 65 or less, 64 or less, or 63 or less. In another example, the cured product of the curable composition may have a Shore OO hardness of 20 or more, 25 or more, 30 or more, 35 or more, 40 or more, 45 or more, or 50 or more. The Shore OO hardness of the cured product of the curable composition may be included within the range formed by appropriately selecting the upper and lower limits listed above. In addition, in the cured product of the curable composition according to an example of the present application, H _f and H _i in Formula 4 are 70 or less, 69 or less, 68 or less, 67 or less, 66 or less, 65 or less, 64 or less, or 63 It may be less than, and in other examples, it may be 20 or more, 25 or more, 30 or more, 35 or more, 40 or more, 45 or more, or 50 or more. In addition, when the cured product of the curable composition satisfies the hardness range, durability is excellent even at a high temperature and low hardness can be maintained even at a high curing rate.

The cured product of the curable composition according to an example of the present application may have thermal conductivity of 1 W/mK or more. The thermal conductivity is a value measured according to ASTM D5470 standard or ISO 22007-2 standard along the thickness direction of the sample in a state where the curable composition is made of a cured product (sample) having a diameter of 2 cm or more and a thickness of 5 mm. can In another example, the cured product of the curable composition may have a thermal conductivity of 1.1 W/mK or more, 1.2 W/mK or more, 1.3 W/mK or more, or 1.4 W/mK or more measured according to the measurement method. Since the higher the thermal conductivity, the higher the thermal conductivity, the upper limit is not particularly limited. For example, the thermal conductivity is 20 W / mK or less, 18 W / mK or less, 16 W / mK or less, 14 W / mK or less, 12 W / mK or less, 10 W / mK or less, 8 W / mK or less, It may be 6 W/mK or less or 4 W/mK or less.

The cured product of the curable composition according to an example of the present application may have a specific gravity of 2 or less, 1.95 or less, 1.9 or less, 1.85 or less, 1.8 or less, or 1.75 or less. The lower limit of the specific gravity of the cured product of the curable composition is not particularly limited, since the lower the specific gravity, the more advantageous the light weight of the applied product. For example, the specific gravity may be 0.1 or more, 0.5 or more, or 1 or more.

The cured product of the curable composition according to an example of the present application has 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, or about 3 K/W or less. or about 2.8 K/W or less. In the case of adjusting the thermal resistance in this range to appear, excellent cooling efficiency or heat dissipation efficiency can be secured. The thermal resistance may be a value measured according to the ASTM D5470 standard or the ISO 22007-2 standard, and the measurement method is not particularly limited.

The cured product of the curable composition according to an example of the present application may secure durability in order to be applied to products requiring a long warranty period (eg, about 15 years or more in the case of automobiles), such as automobiles. Durability is maintained at a low temperature of about -40 ° C for 30 minutes, then raised to 80 ° C and maintained for 30 minutes as one cycle, and after a thermal shock test in which the cycle is repeated 100 times, it is separated from the module case or battery cell of the battery module It may mean that it is peeled off or cracks do not occur.

The cured product of the curable composition according to an example of the present application has an electrical insulation 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. It may be kV/mm or higher. The higher the value of the dielectric breakdown voltage, the cured product of the curable composition exhibits excellent insulation, 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. It may be less than mm, but is not particularly limited. In order to achieve the above dielectric breakdown voltage, insulating filler particles may be applied to the curable composition. In general, among thermally conductive filler particles, ceramic filler particles are known as components capable of securing insulation. The electrical insulation may be measured by dielectric breakdown voltage measured according to the ASTM D149 standard. In addition, if the cured product of the curable composition can secure electrical insulation as described above, stability can be secured while maintaining performance with respect to various materials, for example, a case or a battery cell included in a battery module.

에서 1 시간 정도 유지한 후에 잔존하는 부분을 비휘발분으로 정의할 수 있고, 따라서 상기 비율은 상기 경화성 조성물의 경화물의 초기 중량과 상기 100

에서 1 시간 정도 유지한 후의 비율을 기준으로 측정할 수 있다.It is appropriate that the cured product of the curable composition according to an example of the present application does not contain a volatile material as much as possible. For example, the cured product of the curable composition may have a non-volatile component ratio of 90% by weight or more, 95% by weight or more, or 98% by weight or more. In the above, the ratio with the non-volatile component can be defined in the following manner. That is, the non-volatile content is 100% of the cured product of the curable composition.

The portion remaining after maintaining for about 1 hour can be defined as non-volatile matter, and therefore the ratio is the initial weight of the cured product of the curable composition and the 100

It can be measured based on the ratio after maintaining for about 1 hour at

The cured product of the curable composition according to an example of the present application will have excellent resistance to deterioration as needed, and stability that does not react chemically as much as possible may be required.

It may be advantageous for the cured product of the curable composition according to an example of the present application to have a low shrinkage during or after curing. Through this, it is possible to prevent peeling or generation of gaps that may occur in the course 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 effect, and may be, for example, less than 5%, less than 3%, or less than about 1%. Since the shrinkage rate is more advantageous as the value is lower, the lower limit is not particularly limited.

The cured product of the curable composition according to an example of the present application may advantageously have a low coefficient of thermal expansion (CTE). Through this, it is possible to prevent peeling or generation of gaps that may occur in the course of manufacturing or using various materials, for example, a case or a battery cell included in a battery module. The thermal expansion coefficient may be appropriately adjusted within a range capable of exhibiting the above-mentioned effect, 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 Can be less than /K. The lower limit of the thermal expansion coefficient is not particularly limited, since the lower the numerical value, the more advantageous it is.

The cured product of the curable composition according to an example of the present application may have appropriately adjusted tensile strength, and through this, excellent impact resistance and the like may be secured. Tensile strength can be adjusted in a range of about 1.0 MPa or more, for example.

The cured product of the curable composition according to an example of the present application may have a 5% weight loss temperature in thermogravimetric analysis (TGA) of 400°C or more, or a residual amount of 800°C or more of 70% by weight or more. Due to these characteristics, stability at high temperatures can be further improved for 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% by weight or more, about 80% by weight or more, about 85% by weight or more, or about 90% by weight 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 measure the temperature within the range of 25°C to 800°C at a heating rate of 20°C/min under a nitrogen (N2) 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 curable composition. For example, the remaining amount at 800°C depends on the type or ratio of the thermally conductive filler component contained in the cured product of the curable composition, and when an excessive amount of the thermally conductive filler component is included, the residual amount increases. However, when the polymer and/or monomer used in the curable composition has generally higher heat resistance than other polymers and/or monomers, the residual amount is higher, and the polymer and/or monomer component included in the cured product of the curable composition is also higher. affects hardness.

The curable composition according to an example of the present application may be formed by mixing the above-listed components. In addition, the curable composition is not particularly limited as to the order of mixing as long as all necessary components can be included.

Usage

An apparatus according to an example of the present application includes a heating element; and a cooling portion, and may include a cured product of the curable composition according to an example of the present application in which both the heating element and the cooling portion are brought into thermal contact.

Devices according to an example of the present application include, for example, an iron, a washing machine, a dryer, a clothes care machine, an electric shaver, a microwave oven, an electric oven, an electric rice cooker, a refrigerator, a dishwasher, an air conditioner, a fan, a humidifier, an air purifier, a mobile phone, and a walkie-talkie. , TVs, radios, computers, laptops, and other various electrical and electronic products, or batteries such as secondary batteries, and the cured product of the curable composition can dissipate heat generated in the device. In particular, the curable composition of the present application can be used as a material for connecting battery modules in an electric vehicle battery manufactured by gathering battery cells to form one battery module and forming a battery pack by gathering several battery modules. . When the curable composition of the present application is used as a material for connecting battery modules, it may play a role of dissipating heat generated from the battery cells and fixing the battery cells from external shock and vibration.

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

A cured product of the curable composition may be positioned between the heating element and the cooling portion to bring them into thermal contact. Thermal contact means that the cured product of the curable composition is in direct physical contact with the exothermic element and the cooling portion to radiate heat generated from the exothermic element to the cooling portion, or the cured product of the curable composition is in direct physical contact with the exothermic element and the cooling portion. / or even if it does not directly contact the cooling portion (ie, a separate layer exists between the cured product of the curable composition and the exothermic element and / or the cooling portion) to dissipate heat generated from the exothermic element to the cooling portion it means.

The present application can provide a curable composition capable of forming a cured product having low specific gravity, excellent thermal conductivity, and excellent durability even at high temperatures.

In addition, the present application can provide a curable composition capable of forming a cured product capable of maintaining low hardness and securing re-workability even at a high curing rate.

1 shows a cross section of a cured product in a heat resistance evaluation test of Comparative Example 1 and Examples 1 and 2 after being placed in an oven at 150 ° C. and left for about 144 hours (6 days) and a cross section after leaving it for about 500 hours (21 days). it is shown

Hereinafter, the present invention will be described through examples and comparative examples, but the scope of the present invention is not limited due to the contents presented below.

Example 1.

Manufacture of subject parts

The first polyorganosiloxane (PS1) including the compound represented by Formula 1A, the filler composition (FC1), and the catalyst (Cat) were mixed in a weight ratio of 9.9:46.3:0.1 (PS1:FC1:Cat). The filler composition (FC1) is obtained by adding aluminum hydroxide (FC11) having an average particle diameter of 50 μm and aluminum hydroxide (FC12) having an average particle diameter of 1 μm in a weight ratio of 7:3 (FC11:FC12), and hollow particles (FC13) glass bubbles (provider: 3M, product name: S32HS) were additionally added in an amount of about 2.89 parts by weight based on 100 parts by weight of the sum of the weights of FC11 and FC12, and then they were mixed. In addition, the catalyst (Cat) has a CAS No. A metal catalyst containing a platinum (Pt) element, 81032-58-8 (platinum content: 0.4% by weight), was used.

[Formula 1A]

In Formula 1A, m is 143.

The compound represented by Formula 1A had a viscosity of about 350 cP measured at room temperature, The alkenyl group content was 0.186 mmol/g.

A silicone-based dispersant (provider: BYK, product name: BYK-1799) was additionally added in an amount of 0.5 parts by weight based on 100 parts by weight of the filler composition (FC1). The above components were put in a paste mixer, stirred at 600 rpm in the orbital direction and 500 rpm in the rotation direction for 3 minutes, and then degassed for 4 minutes at 600 rpm in the orbital direction and 200 rpm in the rotation direction in a vacuum state to obtain room temperature viscosity A final subject part (M) was prepared with an A of about 310,000 cP.

Manufacture of curing agent parts

A first polyorganosiloxane (PS1) including a compound represented by Formula 1A, a linker (LK) including a compound represented by Formula 2B, and a second polyorganosiloxane including a compound represented by Formula 3A ( PS2) and the filler composition (FC2) were mixed in a weight ratio of 9.09:0.41:0.5:46.3 (PS1:LK:PS2:FC2). In the filler composition (FC2), aluminum hydroxide (FC21) having an average particle diameter of 50 μm and aluminum hydroxide (FC22) having an average particle diameter of 1 μm were added in a weight ratio of 7:3 (FC21:FC22), and hollow particles (FC23) glass bubbles (provider: 3M, product name: S32HS) were additionally added in an amount of about 2.89 parts by weight based on 100 parts by weight of the sum of the weights of FC21 and FC22, and then they were mixed.

[Formula 1A]

In Formula 1A, m is 143.

The compound represented by Formula 1A had a viscosity of about 350 cP measured at room temperature, The alkenyl group content was 0.186 mmol/g.

[Formula 2B]

In Formula 2B, p is 45 and q is 8 (L = 5.9), and the kinematic viscosity measured at 40 ° C. was 47.4 cSt.

The compound represented by Formula 2B had a silicon-bonded hydrogen content of 1.94 mmol/g.

[Formula 3A]

In Formula 3A, r is 8.

The compound represented by Formula 3A had a viscosity of about 4 cP measured at room temperature, The silicon-bonded hydrogen content was 2.9 mmol/g.

A silicone-based dispersant (provider: BYK, product name: BYK-1799) was additionally added in an amount of 0.5 parts by weight based on 100 parts by weight of the filler composition (FC2). The above components were put in a paste mixer, stirred at 600 rpm in the orbital direction and 500 rpm in the rotation direction for 3 minutes, and then degassed for 4 minutes at 600 rpm in the orbital direction and 200 rpm in the rotation direction in a vacuum state to obtain room temperature viscosity A final curing agent part (H) having an A of about 310,000 cP was prepared.

Preparation of curable composition

A final curable composition was prepared by mixing the final subject part (M) and the final curing agent part (H) prepared above in a volume ratio of 1:1 (M:H).

The final curable composition according to Example 1 was analyzed by ¹ H NMR and ²⁹ Si NMR. Measured and calculated according to Equation 1 above, L' was 250.5, and R _L according to Equation 1 was 42.5. In addition, the final curable composition according to Example 1 had a ratio (K ₁ /K ₂ ) of the total content of silicon-bonded hydrogen (K ₁ ) and the total content of alkenyl groups (K ₂ ) of 0.63, and the general formula 3 R _N was 0.38.

Example 2.

Manufacture of subject parts

The main part (M) was prepared in the same way as the main part of Example 1.

Manufacture of curing agent parts

A first polyorganosiloxane (PS1) used in the curing agent part of Example 1, a linker (LK) including a compound represented by Formula 2A, a second polyorganosiloxane (PS2) including a compound represented by Formula 3A, and A curing agent part (H) was prepared in the same manner as in Comparative Example 1, except that the filler composition (FC2) was mixed in a weight ratio of 9.3:0.5:0.2:46.3 (PS1:LK:PS2:FC2). The curing agent part (H) had a room temperature viscosity of about 360,000 cP.

Preparation of curable composition

A final curable composition was prepared in the same manner as in Example 1 above.

The final curable composition according to Example 2 was analyzed by ¹ H NMR and ²⁹ Si NMR. Measured and calculated according to Equation 1 above, L' was 172.8, and R _L according to Equation 1 was 29.3. In addition, the final curable composition according to Example 2 had a ratio (K ₁ /K ₂ ) of the total content of silicon-bonded hydrogen (K ₁ ) and the total content of alkenyl groups (K ₂ ) of 0.43, and in the general formula 3 R _N was 0.32.

Comparative Example 1.

Manufacture of subject parts

The main part (M) was prepared in the same way as the main part of Example 1.

Manufacture of curing agent parts

A first polyorganosiloxane (PS1) including a compound represented by Formula 1A, a linker (LK) including a compound represented by Formula 2A, and a second polyorganosiloxane including a compound represented by Formula 3A ( PS2) and the filler composition (FC2) were mixed in a weight ratio of 9.27:0.23:0.5:46.3 (PS1:LK:PS2:FC2). In the filler composition (FC2), aluminum hydroxide (FC21) having an average particle diameter of 50 μm and aluminum hydroxide (FC22) having an average particle diameter of 1 μm were added in a weight ratio of 7:3 (FC21:FC22), and hollow particles (FC23) glass bubbles (provider: 3M, product name: S32HS) were additionally added in an amount of about 2.89 parts by weight based on 100 parts by weight of the sum of the weights of FC21 and FC22, and then they were mixed.

[Formula 1A]

In Formula 1A, m is 143.

The compound represented by Formula 1A had a viscosity of about 350 cP measured at room temperature, The alkenyl group content was 0.186 mmol/g.

[Formula 2A]

In Formula 2A, p is 38 and q is 8 (L=5.11).

The compound represented by Formula 2A had a silicon-bonded hydrogen content of 2.94 mmol/g.

[Formula 3A]

In Formula 3A, r is 8.

The compound represented by Formula 3A had a viscosity of about 4 cP measured at room temperature, The silicon-bonded hydrogen content was 2.9 mmol/g.

A silicone-based dispersant (provider: BYK, product name: BYK-1799) was additionally added in an amount of 0.5 parts by weight based on 100 parts by weight of the filler composition (FC2). The above components were put in a paste mixer, stirred at 600 rpm in the orbital direction and 500 rpm in the rotation direction for 3 minutes, and then degassed for 4 minutes at 600 rpm in the orbital direction and 200 rpm in the rotation direction in a vacuum state to obtain room temperature viscosity A final curing agent part (H) having an A of about 260,000 cP was prepared.

Preparation of curable composition

A final curable composition was prepared by mixing the final subject part (M) and the final curing agent part (H) prepared above in a volume ratio of 1:1 (M:H).

The final curable composition according to Comparative Example 1 was analyzed by ¹ H NMR and ²⁹ Si NMR. L' calculated according to Equation 1 was measured and calculated according to Equation 1 above, and R _L according to Equation 1 was 48.8. In addition, the final curable composition according to Comparative Example 1 had a ratio (K ₁ /K ₂ ) of the total content of silicon-bonded hydrogen (K ₁ ) and the total content of alkenyl groups (K ₂ ) of 0.60, and in the general formula 3 R _N was 0.32.

Comparative Example 2.

Manufacture of subject parts

The main part (M) was prepared in the same way as the main part of Example 1.

Manufacture of curing agent parts

The first polyorganosiloxane (PS1), linker (LK), second polyorganosiloxane (PS2) and filler composition (FC2) used in the curing agent part of Comparative Example 1 were used, but they were 9.23: 0.27: 0.5: 46.3 ( A curing agent part (H) was prepared in the same manner as in Comparative Example 1, except for mixing in the weight ratio of PS1:LK:PS2:FC2). The curing agent part (H) had a room temperature viscosity of about 290,000 cP.

Preparation of curable composition

A final curable composition was prepared in the same manner as in Comparative Example 1.

The final curable composition according to Comparative Example 2 was analyzed by ¹ H NMR and ²⁹ Si NMR. Measured and calculated according to Equation 1 above, L' was 249.1, and R _L according to Equation 1 was 48.9. In addition, the final curable composition according to Comparative Example 2 had a ratio (K ₁ /K ₂ ) of the total content of silicon-bonded hydrogen (K ₁ ) and the total content of alkenyl groups (K ₂ ) of 0.63, and in the general formula 3 R _N was 0.38.

Comparative Example 3.

Manufacture of subject parts

The main part (M) was prepared in the same way as the main part of Example 1.

Manufacture of curing agent parts

The first polyorganosiloxane (PS1), linker (LK), second polyorganosiloxane (PS2) and filler composition (FC2) used in the curing agent part of Comparative Example 1 were used, but they were 9.2: 0.3: 0.5: 46.3 ( A curing agent part (H) was prepared in the same manner as in Comparative Example 1, except for mixing in the weight ratio of PS1:LK:PS2:FC2). The curing agent part (H) had a room temperature viscosity of about 330,000 cP.

Preparation of curable composition

A final curable composition was prepared in the same manner as in Comparative Example 1.

The final curable composition according to Comparative Example 3 was analyzed by ¹ H NMR and ²⁹ Si NMR. L' calculated according to Equation 1 by measurement was 249.4, and R _L according to Equation 1 was 48.9. In addition, the final curable composition according to Comparative Example 3 had a ratio (K ₁ /K ₂ ) of the total content of silicon-bonded hydrogen (K ₁ ) and the total content of alkenyl groups (K ₂ ) of 0.65, and in the general formula 3 R _N according to this was 0.42.

Physical properties presented in Examples and Comparative Examples were evaluated in the following manner.

<How to measure physical properties>

1. Hardness and hardness change rate (H _R ) measurement method

(1) Initial Shore OO hardness (H _i )

After applying each final curable composition prepared in Examples and Comparative Examples to a thickness of about 5 mm on a glass surface, it was left for about 24 hours at room temperature (about 25 ° C) and normal humidity (about 40% RH). A cured product was formed.

Shore OO hardness was measured at room temperature according to the ASTM D2240 standard using a hardness tester on the surface of the cured product. Specifically, when a load of about 1.5 kg is applied to the surface of the cured product in a flat state with an indenter capable of measuring Shore OO type hardness of the ASKER Durometer, and the stabbing force is maintained for about 15 seconds The hardness value displayed on the hardness measuring instrument was measured.

(2) Later Shore OO hardness (H _f )

After putting the cured product whose initial Shore OO hardness was measured into an oven at 150 ° C. and leaving it for about 500 hours, take it out of the oven and measure the Shore OO hardness at room temperature according to the ASTM D2240 standard using a hardness tester. was measured in Specifically, the surface of the cured product (cured product after being left in the oven) in a flat state is poked by applying a load of about 1.5 kg with an indenter capable of measuring the Shore OO type hardness of the ASKER Durometer, When the stabbing force was maintained for about 15 seconds, the hardness value displayed on the hardness measuring instrument was measured.

(3) hardness change rate

According to the following general formula 4, the hardness change rate, _HR , was measured.

[Formula 4]

H _R = H _f /H _{i ×} 100

In Formula 4, H _i is an initial Shore OO hardness measured immediately after the curable composition is cured, and H _f is a later Shore OO hardness measured after standing at 150 ° C. for 500 hours after measuring H _i .

2. Heat resistance evaluation method

After applying each final curable composition prepared in Examples and Comparative Examples to a thickness of about 5 mm on a glass surface, it was left for about 24 hours at room temperature (about 25 ° C) and normal humidity (about 40% RH). A cured product was formed.

After putting the cured product in an oven at 150° C. and leaving it for about 500 hours, it was taken out of the oven, and the cured product taken out of the oven was evaluated according to the following heat resistance evaluation criteria.

[Heat Resistance Evaluation Criteria]

PASS: When there is no crack when the cross section of the cured material is observed with the naked eye

NG: When there are cracks when the cross section of the cured material is observed with the naked eye

3. Thermal conductivity measurement method

Thermal conductivity was measured using the hot disk method. Specifically, the thermal conductivity of each of the final curable compositions prepared in Examples and Comparative Examples was left at room temperature (about 25 ° C) and normal humidity (about 40% RH) for 24 hours, and the diameter was 2 cm and the thickness was 5 mm. In a state in which it was cured into a disk-shaped sample, it was measured with a thermal constant analyzer according to the ISO 22007-2 standard along the thickness direction of the sample.

4. ²⁹ Si NMR analysis

²⁹ Si NMR analysis of the polyorganosiloxane component or linker was performed in a known manner. In ^{the 29} Si NMR analysis, chemical shift was expressed using TMS (dilute tetramethylsilane in CDCl ₃ ) as a reference compound. Through ²⁹ Si NMR analysis, the number of dialkylsiloxane repeating units, the number of monoalkylsiloxane repeating units, and the content or number of moles of silicon-bonded hydrogen in the polyorganosiloxane component or linker to be measured can be found.

5. ^One H NMR analysis

¹ H NMR analysis of the polyorganosiloxane component was performed in a known manner. In ^{the 1} H NMR analysis, chemical shifts were expressed using TMS (dilute tetramethylsilane in CDCl ₃ ) as a reference compound. Through ¹ H NMR analysis, the content or number of moles of alkenyl groups in the polyorganosiloxane component to be measured can be found.

6. Specific gravity measurement method

Each of the final curable compositions prepared in Examples and Comparative Examples was left at room temperature (about 25 ° C.) and normal humidity (about 40% RH) for about 24 hours to form a cured product, and then cut into pieces to prepare a sample, The specific gravity of the sample was measured using a pycnometer.

7. Re-work evaluation method

After applying each of the final curable compositions prepared in Examples and Comparative Examples to an aluminum module plate having a width of about 8 cm, a length of about 8 cm, and a thickness of about 2 mm, room temperature (about 25 ° C.) and normal humidity ( About 40% RH) for about 24 hours to form a cured product. The cured product was separated from the aluminum module plate using a silicon spatula and evaluated according to the following rework evaluation criteria.

[Reworkability Evaluation standard]

PASS: When the cured material can be separated from the aluminum module plate without residue

NG: When it is impossible to separate the hardened material from the aluminum module plate or a residue remains even after being separated

The results of the test data measured in the above Examples and Comparative Examples are summarized in Table 1 below.

division Shore OO type
Hardness Hardness
Rate of Change ( _HR ) heat resistance
evaluation thermal conductivity
(W/mK) reworkability
evaluation importance Comparative Example 1 57 110.5 NG 1.42 PASS 1.733 Comparative Example 2 68 111.8 NG 1.47 PASS 1.728 Comparative Example 3 74 110.8 PASS 1.48 PASS 1.729 Example 1 62 101.6 PASS 1.45 PASS 1.735 Example 2 56 107.1 PASS 1.44 PASS 1.738

Referring to Table 1, Examples 1 and 2 show a Shore OO type hardness of 70 or less, a hardness change rate ( _HR ) of 110 or less, and were evaluated as PASS in heat resistance evaluation.

In addition, Comparative Example 1 and Comparative Example 2 had a hardness change rate ( _HR ) of more than 110 and were evaluated as NG in heat resistance evaluation. In addition, Comparative Example 3 was evaluated as PASS in the heat resistance evaluation, but the Shore OO type hardness was over 70 and the hardness change rate ( _HR ) was over 110.

In addition, Figure 1 shows the cross section of the cured product in the heat resistance evaluation test of Comparative Example 1 and Examples 1 and 2 after putting it in an oven at 150 ° C. and leaving it for about 144 hours (6 days), and after leaving it for about 500 hours (21 days). section is shown. Referring to Figure 1, it can be seen that Examples 1 and 2 were evaluated as PASS in the heat resistance evaluation test, and Comparative Example 1 was left for about 144 hours and then left for about 500 hours. can

Claims (62)

A first polyorganosiloxane component containing an alkenyl group at the terminal and containing a dialkylsiloxane repeating unit, a linker containing a dialkylsiloxane repeating unit and a monoalkylsiloxane repeating unit, and a dialkylsiloxane repeating unit containing silicon-bonded hydrogen at the terminal. a resin composition comprising a second polyorganosiloxane component comprising units; and
a filler composition,
A curable composition having an R _L value of 45 or less according to the following general formula 1:
[Formula 1]
R _L = L'/L
In Formula 1,
L' is the number of dialkylsiloxane repeating units of the curable composition as measured by ¹ H NMR and ²⁹ Si NMR,
L is a value according to the following general formula 2,
[Formula 2]
L = (p+q)/(q+1)
In Formula 2, p is the number of dialkylsiloxane repeating units of the linker as measured by ²⁹ Si NMR, and q is the number of monoalkylsiloxane repeating units of the linker as measured by ²⁹ Si NMR. The curable composition according to claim 1, wherein the first polyorganosiloxane component comprises a compound represented by Formula 1 below:
[Formula 1]

In Formula 1, R ₁ and R ₈ are each independently an alkenyl group having 2 to 20 carbon atoms, and R ₂ , R ₃ , R ₄ , R ₅ , R ₆ and R ₇ are each independently an alkyl group having 1 to 20 carbon atoms, and , m is a number in the range of 1 to 200. The curable composition according to claim 1, wherein the first polyorganosiloxane component has an alkenyl group content in the range of 0.12 to 2 mmol/g. The curable composition according to claim 1 , wherein the first polyorganosiloxane component has a kinematic viscosity measured at 40° C. of less than 1,000 cSt. The curable composition according to claim 1, wherein the linker comprises a compound represented by Formula 2 below:
[Formula 2]

In Formula 2, R ₉ and R ₁₅ are each independently hydrogen or an alkyl group having 1 to 20 carbon atoms, and R ₁₀ , R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₆ and R ₁₇ each independently have 1 to 20 carbon atoms 20 alkyl group, p is a number within the range of 1 to 200, and q is a number within the range of 1 to 50. The curable composition according to claim 1, wherein the content of silicon-bonded hydrogen in the linker is in the range of 0.1 to 5 mmol/g. The curable composition according to claim 1, wherein L according to the general formula 2 of the linker is in the range of 1 to 20. The curable composition according to claim 1, wherein the linker has a kinematic viscosity measured at 40 °C in the range of 10 to 1,000 cSt. The curable composition according to claim 1, wherein the second polyorganosiloxane component comprises a compound represented by Formula 3:
[Formula 3]

In Formula 3, R ₁₈ , R ₁₉ , R ₂₀ , R ₂₁ , R ₂₂ and R ₂₃ are each independently an alkyl group having 1 to 20 carbon atoms, and r is a number in the range of 1 to 200. The curable composition according to claim 1, wherein the second polyorganosiloxane component has a silicon-bonded hydrogen content of 0.1 to 5 mmol/g or more. The curable composition according to claim 1, wherein the second polyorganosiloxane component has a kinematic viscosity measured at 40°C in the range of 1 to 500 cSt. The curable composition according to claim 1, wherein the filler composition includes filler particles with low specific gravity, and the filler particles with low specific gravity have a specific gravity of 3 or less. 13. The method of claim 12, wherein the filler composition comprises first low specific gravity filler particles and second low specific gravity filler particles,
The first low specific gravity filler particles have an average particle diameter of 20 μm or more, and the second low specific gravity filler particles have an average particle diameter of 10 μm or less,
The weight ratio (F ₁ /F ₂ ) of the first low specific gravity filler particles (F ₁ ) and the second low specific gravity filler particles (F ₂ ) is in the range of 1 to 5. Curable composition. 13. The curable composition of claim 12, wherein the low specific gravity filler particles comprise a metal hydroxide. 14. The method of claim 13, wherein the filler composition further comprises hollow particles,
The hollow particles have a specific gravity of 0.1 to 1, and an isostatic crushing strength in the range of 1 to 200 MPa. The curable composition according to claim 15, wherein the hollow particles are included in an amount of 1 to 10 parts by weight based on 100 parts by weight of the sum of the weights of the first low specific gravity filler particles and the second low specific gravity filler particles. The curable composition of claim 1 , wherein the filler composition is substantially free of metal filler particles. The curable composition according to claim 1, comprising 80 to 99% by weight of the first polyorganosiloxane component based on the total weight of the resin composition. According to claim 1, Curable composition comprising a linker within the range of 1.6 to 5 parts by weight based on 100 parts by weight of the first polyorganosiloxane component. The curable composition according to claim 1, comprising the second polyorganosiloxane component in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the first polyorganosiloxane component. The curable composition according to claim 1, comprising the filler composition in the range of 70 to 99% by weight based on the total weight. The curable composition according to claim 1, comprising the resin composition in an amount of 5 to 50 parts by weight based on 100 parts by weight of the filler composition. The curable composition according to claim 1, further comprising a dispersant, and containing the dispersant in an amount of 0.01 to 1 part by weight based on 100 parts by weight of the filler composition. The curable composition according to claim 1, wherein the ratio (K ₁ /K ₂ ) of the total content of silicon-bonded hydrogen (K ₁ ) and the total content of alkenyl groups (K ₂ ) is in the range of 0.1 to 1. The curable composition according to claim 1, wherein the R _N value according to formula 3 is 1 or less:
[Formula 3]
R _N = (N _A -N _H,2 )/N _H,1
In formula 3,
N _A is the number of moles of alkenyl groups contained in the first polyorganosiloxane component measured by ¹ H NMR;
N _H,2 is the number of moles of silicon-bonded hydrogen contained in the second polyorganosiloxane component as measured by ²⁹ Si NMR;
N _H,1 is the number of moles of silicon-bonded hydrogen contained in the linker as determined by ²⁹ Si NMR. The curable composition of claim 1 further comprising a metal catalyst. The curable composition according to claim 26, comprising a metal catalyst containing a platinum (Pt) element in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the first polyorganosiloxane component. The curable composition according to claim 1, which forms a cured product having a Shore OO hardness of 70 or less. The curable composition according to claim 1, which forms a cured product having a thermal conductivity of 1 W/mK or higher. The curable composition according to claim 1, which forms a cured product having a specific gravity of 2 or less. A first polyorganosiloxane component containing an alkenyl group at the terminal and containing a dialkylsiloxane repeating unit, a linker containing a dialkylsiloxane repeating unit and a monoalkylsiloxane repeating unit, and a dialkylsiloxane repeating unit containing silicon-bonded hydrogen at the terminal. a resin composition comprising a second polyorganosiloxane component comprising units; and
a filler composition,
A curable composition in which _HR satisfies 110 or less according to the following general formula 4:
[Formula 4]
H _R = H _f /H _i Х100
In Formula 4, H _i is an initial Shore OO hardness measured immediately after the curable composition is cured, and H _f is a later Shore OO hardness measured after standing at 150 ° C. for 500 hours after measuring H _i . The curable composition according to claim 31, wherein the R _L value according to the following general formula 1 is 45 or less:
[Formula 1]
R _L = L'/L
In Formula 1,
L' is the number of dialkylsiloxane repeating units of the curable composition as measured by ¹ H NMR and ²⁹ Si NMR,
L is a value according to the following general formula 2,
[Formula 2]
L = (p+q)/(q+1)
In Formula 2, p is the number of dialkylsiloxane repeating units of the linker as measured by ²⁹ Si NMR, and q is the number of monoalkylsiloxane repeating units of the linker as measured by ²⁹ Si NMR. 32. The curable composition according to claim 31, wherein the first polyorganosiloxane component comprises a compound represented by Formula 1:
[Formula 1]

In Formula 1, R ₁ and R ₈ are each independently an alkenyl group having 2 to 20 carbon atoms, and R ₂ , R ₃ , R ₄ , R ₅ , R ₆ and R ₇ are each independently an alkyl group having 1 to 20 carbon atoms, and , m is a number in the range of 1 to 200. The curable composition according to claim 31, wherein the first polyorganosiloxane component has an alkenyl group content within a range of 0.12 to 2 mmol/g. 32. The curable composition of claim 31, wherein the first polyorganosiloxane component has a kinematic viscosity measured at 40°C of less than 1,000 cSt. The curable composition according to claim 31, wherein the linker comprises a compound represented by Formula 2:
[Formula 2]

In Formula 2, R ₉ and R ₁₅ are each independently hydrogen or an alkyl group having 1 to 20 carbon atoms, and R ₁₀ , R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₆ and R ₁₇ each independently have 1 to 20 carbon atoms 20 alkyl group, p is a number within the range of 1 to 200, and q is a number within the range of 1 to 50. The curable composition according to claim 31, wherein the content of silicon-bonded hydrogen in the linker is in the range of 0.1 to 5 mmol/g. 32. The curable composition according to claim 31, wherein L in the linker according to formula 2 is in the range of 1 to 20. The curable composition according to claim 31, wherein the linker has a kinematic viscosity measured at 40 °C in the range of 10 to 1,000 cSt. 32. The curable composition according to claim 31, wherein the second polyorganosiloxane component comprises a compound represented by Formula 3:
[Formula 3]

In Formula 3, R ₁₈ , R ₁₉ , R ₂₀ , R ₂₁ , R ₂₂ and R ₂₃ are each independently an alkyl group having 1 to 20 carbon atoms, and r is a number in the range of 1 to 200. The curable composition according to claim 31, wherein the second polyorganosiloxane component has a silicon-bonded hydrogen content of 0.1 to 5 mmol/g or more. 32. The curable composition according to claim 31, wherein the second polyorganosiloxane component has a kinematic viscosity measured at 40°C in the range of 1 to 500 cSt. 32. The curable composition of claim 31, wherein the filler composition comprises low specific gravity filler particles, wherein the low specific gravity filler particles have a specific gravity of 3 or less. 44. The method of claim 43, wherein the filler composition comprises first low specific gravity filler particles and second low specific gravity filler particles,
The first low specific gravity filler particles have an average particle diameter of 20 μm or more, and the second low specific gravity filler particles have an average particle diameter of 10 μm or less,
The weight ratio (F ₁ /F ₂ ) of the first low specific gravity filler particles (F ₁ ) and the second low specific gravity filler particles (F ₂ ) is in the range of 1 to 5. Curable composition. 44. The curable composition of claim 43, wherein the low specific gravity filler particles comprise a metal hydroxide. 44. The method of claim 43, wherein the filler composition further comprises hollow particles,
The hollow particles have a specific gravity of 0.1 to 1, and an isostatic crushing strength in the range of 1 to 200 MPa. The curable composition according to claim 46, wherein the hollow particles are included in an amount of 1 to 10 parts by weight based on 100 parts by weight of the sum of the weights of the first low specific gravity filler particles and the second low specific gravity filler particles. 32. The curable composition of claim 31, wherein the filler composition is substantially free of metal filler particles. The curable composition according to claim 31, comprising an alkenyl group-containing polyorganosiloxane component in an amount of 80 to 99% by weight based on the total weight of the resin composition. The curable composition according to claim 31, comprising the linker in an amount of 1.6 to 5 parts by weight based on 100 parts by weight of the first polyorganosiloxane component. The curable composition according to claim 31, comprising the second polyorganosiloxane component in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the first polyorganosiloxane component. The curable composition according to claim 31, comprising the filler composition in the range of 70 to 99% by weight based on the total weight. The curable composition according to claim 31, comprising the resin composition in an amount of 5 to 50 parts by weight based on 100 parts by weight of the filler composition. The curable composition according to claim 31, further comprising a dispersing agent, comprising the dispersing agent in an amount of 0.01 to 1 part by weight based on 100 parts by weight of the filler composition. 32. The curable composition according to claim 31, wherein the ratio (K ₁ /K 2 ) of the total content of silicon-bonded hydrogen ( _K 1 ) and the total content of alkenyl groups (K _{2 )} is in the range of 0.1 to 1. 32. The curable composition according to claim 31, wherein the R _N value according to formula 3 is 1 or less:
[Formula 3]
R _N = (N _A -N _H,2 )/N _H,1
In formula 3,
N _A is the number of moles of alkenyl groups contained in the first polyorganosiloxane component measured by ¹ H NMR;
N _H,2 is the number of moles of silicon-bonded hydrogen contained in the second polyorganosiloxane component as measured by ²⁹ Si NMR;
N _H,1 is the number of moles of silicon-bonded hydrogen contained in the linker as determined by ²⁹ Si NMR. 32. The curable composition of claim 31 further comprising a metal catalyst. The curable composition according to claim 57, comprising a metal catalyst containing platinum (Pt) in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the first polyorganosiloxane component. 32. The curable composition according to claim 31, which forms a cured product having a Shore OO hardness of 70 or less. The curable composition according to claim 31, which forms a cured product having a thermal conductivity of 1 W/mK or higher. The curable composition according to claim 31, which forms a cured product having a specific gravity of 2 or less. exothermic element; and a cooling portion;
An apparatus in which the curable composition of claim 1 or a cured product of claim 31 thermally contacts the heating element and the cooling portion.

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