KR20240050124A - A laminate - Google Patents

Abstract

The present application can provide a laminate that has excellent adhesion performance, excellent heat dissipation properties, no brittleness after curing, and appropriate surface hardness. Additionally, the present application can provide a battery assembly and a battery pack including the above laminate.

Description

Laminate {A laminate}

This application relates to a laminate and applications of the laminate, and specifically to a laminate that adheres battery cells in a battery assembly and dissipates heat generated from the battery cells.

As the treatment of heat generated from batteries such as electrical products, electronic products, or secondary batteries has become an important issue, various heat dissipation measures have been proposed. Among the thermally conductive materials used for heat dissipation measures, a resin composition containing a thermally conductive filler mixed with a resin is known. The resin composition can be used to dissipate heat emitted from the heating element while making thermal contact between the heating element and the cooling portion and fixing the heating element. Patent Document 1 discloses a battery module using the above resin composition.

The resin composition may have heat dissipation performance and have a certain level of adhesion by itself or by curing in order to fix the battery cell. Battery assemblies (also called battery modules) are generally manufactured by attaching battery cells to an adhesive with heat dissipation properties. Among the methods to demonstrate the adhesive properties of the adhesive, there was a method through heat curing, but there were cases where other components, such as battery cells, were damaged by heat due to the high temperature environment. In addition, one of the methods to demonstrate the adhesive properties of the adhesive was a method using active energy rays, but there was a problem that the degree of curing was different depending on the location due to the problem that the active energy rays were not evenly transmitted to the adhesive. In addition, one of the methods to demonstrate the adhesive properties of the adhesive was to cure it at room temperature, but there was a problem in that the curing time to demonstrate sufficient adhesive properties was long, which adversely affected the overall manufacturing efficiency.

Therefore, there was a need for a method that could be applied as an adhesive with heat dissipation properties while ensuring overall manufacturing efficiency through rapid curing.

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

The purpose of this application is to provide a laminate and applications or uses of the laminate. The application or use of the laminate may mean application or use in a battery assembly or battery pack. One purpose of the present application is to provide a laminate that has excellent adhesion performance, excellent heat dissipation properties, no brittleness after curing, and appropriate surface hardness.

Among the physical properties mentioned in this application, in cases where the measurement temperature affects the physical properties, the physical properties are those measured at room temperature, unless otherwise specified.

Room temperature, the term used in this application, is a natural temperature that is not heated or cooled, for example, any temperature in the range of 10 ℃ to 30 ℃, for example, about 15 ℃ or higher, about 18 ℃ or higher, It may mean a temperature of about 20°C or higher, about 23°C or higher, about 27°C or lower, or 25°C. Unless specifically specified in this specification, the unit of temperature is Celsius (℃).

Among the physical properties mentioned in this application, in cases where the measurement pressure affects the physical properties, unless otherwise specified, the physical properties are those measured at normal pressure.

The term atmospheric pressure used in this application refers to natural pressure that is not pressurized or depressurized, and atmospheric pressure in the range of about 700 mmHg to 800 mmHg is usually referred to as atmospheric pressure.

The terms a to b used in this application include a and b and mean within the range between a and b. For example, including a to b parts by weight is the same as including 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 a unit volume of air to the saturated water vapor pressure that a unit volume of air can contain at its maximum. It can be expressed as RH%.

Weight average molecular weight (M _w ), a term used in this application, can be measured using GPC (Gel permeation chromatography), and can be specifically measured according to the physical property measurement method below. In addition, the polydispersity index (PDI), a term used in this application, is the weight average molecular weight (M _w ) divided by the number average molecular weight (M _n ) (M _w /M _n ), and is the value of the molecular weight of the polymer. It means distribution. The number average molecular weight (M _n ) can also be measured using GPC (Gel permeation chromatography) if necessary.

Excellent thermal conductivity, a term used in this application, means that when measured in accordance with the physical property measurement method below, the measured thermal conductivity is 1.0 W/mK or more, 1.2 W/mK or more, 1.4 W/mK or more, and 1.6 W/mK. It may mean more than 1.8 W/mK, more than 2 W/mK, more than 2.2 W/mK, more than 2.4 W/mK, more than 2.6 W/mK, more than 2.8 W/mK, or more than 3 W/mK.

Viscosity, a term used in this application, may be a value measured at 25°C unless otherwise specified, and may be specifically measured according to the physical property measurement method below.

As used in this application, the term “substantially does not contain a specific material” means that the specific material is not intentionally included. However, if it naturally contains the above-mentioned specific substance, unless otherwise specified, it can be said to not substantially contain it if it contains 0.1% by weight or less, 0.05% by weight or less, or 0.01% by weight or less relative to the total weight.

The resin component, a term used in this application, can be defined as containing at least 10% by weight of resin based on the total weight of the resin component. In another example, the resin component may contain 15% by weight or more, 20% by weight, 25% by weight, or 30% by weight based on the total weight of the resin component.

Acrylic polymer, the term used in this application, can be defined as containing units derived from (meth)acrylate in an amount of at least 50% by weight or more based on the total weight of the acrylic polymer. In another example, the acrylic polymer contains units derived from (meth)acrylate in an amount of at least 55% by weight, at least 60% by weight, at least 65% by weight, at least 70% by weight, at least 75% by weight, and at least 80% by weight, based on the total weight of the acrylic polymer. It may contain more than % by weight, more than 85% by weight, more than 90% by weight, more than 95% by weight, more than 99% by weight, or more than 100% by weight.

Acrylic monomer, a term used in this application, may mean (meth)acrylate itself, or may mean one type of (meth)acrylate.

The acrylic monomer component, a term used in this application, may be defined as containing the above-described acrylic monomer in an amount of 50% by weight or more relative to the total weight of the acrylic monomer component. In another example, the acrylic monomer component includes the above-described acrylic monomer in an amount of at least 55% by weight, at least 60% by weight, at least 65% by weight, at least 70% by weight, at least 75% by weight, and at least 80% by weight, based on the total weight of the acrylic monomer component. , it may contain 85% by weight or more, 90% by weight or more, 95% by weight or more, 99% by weight or more, or 100% by weight.

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

The term halogen or halogen element used in this application refers to a group 17 element on the periodic table, and in this application, chlorine (Cl), iodine (I), bromine (Br), and fluorine ( F) may refer to a group consisting of

The term substituent used in this application refers to an atom or atom group that replaces one or more hydrogen atoms on the parent chain of a hydrocarbon. In addition, the substituent is described below, but is not limited thereto, and the substituent may be further substituted with a substituent described below or may not be substituted with any substituent, unless specifically stated in the present application.

Unless otherwise specified, the term alkyl group or alkylene group used in this application refers to a straight 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. It may be a chain alkyl or alkylene group, or a cyclic alkyl 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 ring structure and an alkyl group or alkylene group containing a ring structure. For example, both cyclohexyl group and methyl cyclohexyl group correspond to cyclic alkyl groups. Additionally, for example, an alkyl group or an alkylene group may specifically include methyl (lene), ethyl (lene), n-propyl (lene), isopropyl (lene), n-butyl (lene), isobutyl ( ren), tert-butyl(ren), sec-butyl(ren), 1-methyl-butyl(ren), 1-ethyl-butyl(ren), n-pentyl(ren), isopentyl(ren), neopentyl (lene), tert-pentyl (lene), n-hexyl (lene), 1-methylpentyl (lene), 2-methylpentyl (lene), 4-methyl-2-pentyl (lene), 3,3-dimethyl Butyl (lene), 2-ethylbutyl (lene), n-heptyl (lene), 1-methylhexyl (lene), n-octyl (lene), tert-octyl (lene), 1-methylheptyl (lene), 2-ethylhexyl(ren), 2-propylpentyl(ren), n-nonyl(ren), 2,2-dimethylheptyl(ren), 1-ethylpropyl(ren), 1,1-dimethylpropyl(ren) , isohexyl (lene), 2-methylpentyl (lene), 4-methylhexyl (lene), 5-methylhexyl (lene), etc., but is not limited to these. In addition, the cycloalkyl group or cycloalkylene group is specifically cyclopropyl (lene), cyclobutyl (lene), cyclopentyl (lene), 3-methylcyclopentyl (lene), 2,3-dimethylcyclopentyl (lene), cyclo Hexyl(ren), 3-methylcyclohexyl(ren), 4-methylcyclohexyl(ren), 2,3-dimethylcyclohexyl(ren), 3,4,5-trimethylcyclohexyl(ren), 4-tert -Butylcyclohexyl(lene), cycloheptyl(lene), cyclooctyl(lene), etc. may be exemplified, but are not limited thereto.

Unless otherwise specified, the term alkenyl group or alkenylene group used in this application refers to a straight 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. Chain acyclic alkenyl group or alkenylene group; It may be a cyclic alkenyl group or an 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 it contains a cyclic alkenyl group or alkenylene group, it corresponds to a cyclic alkenyl group or alkenylene group. Also, for example, ethenyl (lene), n-propenyl (lene), isopropenyl (lene), n-butenyl (lene), isobutenyl (lene), tert-butenyl (lene), sec -Butenyl (lene), 1-methyl-butenyl (lene), 1-ethyl-butenyl (lene), n-pentenyl (lene), isopentenyl (lene), neopentenyl (lene), tert -Pentenyl (ren), n-hexenyl (len), 1-methylpentenyl (len), 2-methylpentenyl (len), 4-methyl-2-pentenyl (len), 3,3-dimethyl Butenyl (lene), 2-ethylbutenyl (lene), n-heptenyl (lene), 1-methylhexenyl (lene), n-octenyl (lene), tert-octenyl (lene), 1- Methylheptenyl (lene), 2-ethylhexenyl (lene), 2-propylpentenyl (lene), n-nonylenyl (lene), 2,2-dimethylheptenyl (lene), 1-ethylpropenyl ( Examples include ren), 1,1-dimethylpropenyl (ren), isohexenyl (ren), 2-methylpentenyl (ren), 4-methylhexenyl (ren), 5-methylhexenyl (ren), etc. It may be possible, but it is not limited to these. In addition, the cycloalkenyl group or cycloalkenylene group is specifically cyclopropenyl (lene), cyclobutenyl (lene), cyclopentenyl (lene), 3-methylcyclopentenyl (lene), and 2,3-dimethylcyclophene. Tenyl(ren), cyclohexenyl(ren), 3-methylcyclohexenyl(ren), 4-methylcyclohexenyl(ren), 2,3-dimethylcyclohexenyl(ren), 3,4,5- Trimethylcyclohexenyl(ren), 4-tert-butylcyclohexenyl(ren), cycloheptenyl(ren), cyclooctenyl(ren), etc. may be exemplified, but are not limited thereto.

Unless otherwise specified, the term alkynyl group or alkynylene group used in this application refers to a straight 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. A chain acyclic alkynyl or alkynylene group, or a cyclic alkynyl group or alkynylene 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 could be a sign. Here, if it contains a cyclic alkynyl group or alkynylene group, it corresponds to a cyclic alkynyl group or alkynylene group. Also, for example, ethynyl (lene), n-propynyl (lene), isopropynyl (lene), n-butynyl (lene), isobutynyl (lene), tert-butynyl (lene), sec-butynyl (lene), 1-methyl-butynyl (lene), 1-ethyl-butynyl (lene), n-pentynyl (lene), isopentinyl (lene), neopentynyl (lene), tert-pentynyl(ren), n-hexynyl(ren), 1-methylpentynyl(ren), 2-methylpentynyl(ren), 4-methyl-2-pentynyl(ren), 3,3- Dimethylbutynyl (lene), 2-ethylbutynyl (lene), n-heptynyl (lene), 1-methylhexynyl (lene), n-octinyl (lene), tert-octinyl (lene), 1-methylheptynyl (lene), 2-ethylhexynyl (lene), 2-propylpentynyl (lene), n-noninyl (lene), 2,2-dimethylheptynyl (lene), 1-ethylpropy Nyl(ren), 1,1-dimethylpropynyl(ren), isohexynyl(ren), 2-methylpentynyl(ren), 4-methylhexynyl(ren), 5-methylhexynyl( ren), etc. may be exemplified, but are not limited to these. In addition, the cycloalkynyl group or cycloalkynylene group is specifically cyclopropynyl (lene), cyclobutynyl (lene), cyclopentynyl (lene), 3-methylcyclopentynyl (lene), and 2,3-dimethylcyclopentylene. Nyl (lene), cyclohexynyl (lene), 3-methylcyclohexynyl (lene), 4-methylcyclohexynyl (lene), 2,3-dimethylcyclohexynyl (lene), 3, Examples include 4,5-trimethylcyclohexynyl (lene), 4-tert-butylcyclohexynyl (lene), cycloheptinyl (lene), and cyclooctynyl (lene). It is not limited to this.

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

Aryl group, a term used in this application, 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 number of carbon atoms of the aryl group is not particularly limited, but unless otherwise specified, the aryl group is an aryl group 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 6 to 15 carbon atoms. It may be. Additionally, the term arylene group used in this application refers to an aryl group having two bonding positions, that is, a bivalent group. The description of the aryl group described above can be applied, except that each of these is a divalent group. The aryl group may include, for example, a phenyl group, phenylethyl group, phenylpropyl group, benzyl group, tolyl group, xylyl group, or naphthyl group, but is not limited thereto.

Heteroaryl group, the term used in this application, is an aromatic ring containing one or more heteroatoms other than carbon. Specifically, the heteroatoms include nitrogen (N), oxygen (O), sulfur (S), selenium (Se), and tele It may contain one or more atoms selected from the group consisting of nium (Te). At this time, the atoms constituting the ring structure of the heteroaryl group may be referred to as reducers. Additionally, the heteroaryl group may include a monocyclic or polycyclic ring. The number of carbon atoms of the heteroaryl group is not particularly limited, but unless otherwise specified, the heteroaryl group may have 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. 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 a reducing number of 5 to 30, 5 to 25, 5 to 20, 5 to 15, 5 to 10, or 5 to 8. The heteroaryl group includes, for example, thiophene group, furan group, pyrrole group, imidazolyl group, thiazolyl group, oxazolyl group, oxadiazolyl group, triazolyl group, pyridyl group, and 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, but are not limited thereto.

In addition, the term heteroarylene group used in this application refers to a heteroaryl group having two bonding positions, that is, a bivalent group. The description of the heteroaryl group described above can be applied, except that each of these is a divalent group.

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

The term (meth)acrylate used in this application refers to a compound containing a (meth)acrylate group. The (meth)acrylate is a concept that includes both methacrylate and acrylate. In addition, the methacrylate is a concept that includes both methacrylic acid and derivatives of methacrylic acid, and the acrylate is a concept that includes both acrylic acid and derivatives of acrylic acid.

In the present application, a composition that forms a cured product through a curing reaction can be referred to as a curable composition. In the present application, whether curing has been appropriately completed by the curing reaction can be confirmed by Fourier Transform Infrared (FT-IR), Differential Thermal Analysis (DSC), and Dynamic Mechanical Analysis (DMA) measurements. For example, it can be confirmed by Fourier Transform Infrared (FT-IR), Differential Thermal Analysis (DSC), and Dynamic Mechanical Analysis (DMA) measurements. For example, in the case of a composition containing one or more (meth)acrylates, it can be confirmed that the conversion based on the C=C peak around 1635 cm ^-1 confirmed by FT-IR analysis is 80% or more. You can. In addition, curing in the present application may mean the same as attempting to perform a curing reaction and appropriately completing the curing as described above.

The laminate according to an example of the present application may include a first layer and a second layer. Additionally, the first layer may include a cured product of the first composition, and the second layer may include a cured product of the second composition.

The first composition and the second composition according to an example of the present application may be a curable composition or a resin composition containing a resin. The term resin composition used in this application refers to a composition containing a component known in the industry as a resin or a composition that does not contain a resin but includes a component that can form a resin through a curing reaction or the like. Accordingly, the scope of the term resin or resin component in this application includes components that are generally known as resins as well as components that can form a resin through curing and/or polymerization reactions.

The first composition and the second composition according to an example of the present application may be a one-component or two-component composition. The one-component composition, a term used in this application, refers to a curable composition in which components participating in curing are contained in a state in which they are physically in contact with each other. In addition, the two-component composition, a term used in the present application, may refer to a curable composition in which at least some of the components participating in curing are physically separated and included.

The first composition and the second composition according to an example of the present application may be a solvent type or a non-solvent type. When considering application efficiency or environmental load, a solvent-free formulation may be appropriate.

The first composition and the second composition according to an example of the present application may each independently be an acrylic composition. That is, the first composition may be a first acrylic composition, and the second composition may be a second acrylic composition. The term acrylic composition used in this application means that it contains at least 50% by weight of at least one selected from the group consisting of (meth)acrylate and a polymer formed from the (meth)acrylate, based on the total weight of the acrylic composition. You can.

The laminate according to an example of the present application may have at least one of the following physical properties. Each physical property listed below is independent, and one physical property does not take precedence over the other physical properties, and can satisfy at least one or two of the physical properties listed below. The physical properties described below are due to the combination of components included in the curable composition or its cured product.

The laminate according to an example of the present application can exhibit excellent adhesion to a specific adherend. The laminate may have these properties due to the first layer and the second layer formed from the first composition and the second composition, respectively. The laminate has an adhesion (or peel force) of 100 gf/10mm or more, 150 gf/10mm or more, and 200 gf/25°C measured at a peeling speed of 0.3 mm/min and a peeling angle of 180 degrees to PET (polyethylene terephthalate). 10 mm or greater, 250 gf/10mm or greater, 300 gf/10mm or greater, 350 gf/10mm or greater, 400 gf/10mm or greater, 450 gf/10mm or greater, 500 gf/10mm or greater, 550 gf/10mm or greater, 600 gf/10mm or greater , 650 gf/10mm or more, 700 gf/10mm or more, or 750 gf/10mm or more, or 3,000 gf/10mm or less, 2,800 gf/10mm or less, 2,600 gf/10mm or less, 2,400 gf/10mm or less, 2,200 gf/10mm or less, 2,000 gf/10mm or less, 1,800 gf/10mm or less, 1,600 gf/10mm or less, 1,400 gf/10mm or less, 1,200 gf/10mm or less, 1,000 gf/10mm or less, or 900 gf/10mm or less, or by appropriately selecting the upper and lower limits above. It may be within the established range. The adhesive force (or peel force) can be specifically measured according to the physical property measurement method below. Additionally, specifically, the adhesive force may be for the second layer of the laminate (more specifically, the surface of the second layer).

Additionally, the adhesive force may be the adhesive force to any substrate or module case with which the laminate is in contact. If the above adhesion can be secured, appropriate adhesion can be achieved for various materials, for example, cases or battery cells included in the battery assembly. In addition, when adhesive strength in this range is secured, excellent durability can be secured by preventing volume changes during charging and discharging of battery cells in the battery assembly, peeling due to changes in use temperature of the battery assembly, or curing shrinkage.

It may be advantageous for the laminate according to an example of the present application to exhibit appropriate hardness. For example, if the hardness of the laminate is too high, the laminate may brittle, which may adversely affect reliability. In addition, by adjusting the hardness of the laminate, impact resistance and vibration resistance can be secured, and durability of the product can also be secured. The cured product of the above-described laminate is, for example, shore A type with a thickness of 10 or more, 20 or more, 30 or more, 40 or more, 50 or more, 60 or more, 62 or more, 64 or more, 66 or more, 68 or more, 70 or more. , 72 or more, 74 or more, 76 or more, 78 or more, or 80 or more, or 100 or less, 98 or less, 96 or less, 94 or less, 92 or less, or 90 or less. The hardness of the laminate may generally be influenced by the type or content ratio of the filler component contained in one layer of the laminate, and the polymer component contained in each layer of the laminate may also affect the hardness. Additionally, specifically, the hardness may be for the surface of the first layer or the second layer of the laminate, and more specifically, the hardness may be for the surface of the first layer of the laminate.

When the laminate according to an example of the present application is measured according to the physical property measurement method below, the measured thermal conductivity is 1.0 W/mK or more, 1.2 W/mK or more, 1.4 W/mK or more, and 1.6 W/mK or more. , may be greater than or equal to 1.8 W/mK, greater than or equal to 2 W/mK, greater than or equal to 2.2 W/mK, greater than or equal to 2.4 W/mK, greater than or equal to 2.6 W/mK, greater than or equal to 2.8 W/mK, or greater than or equal to 3 W/mK. Since the higher the thermal conductivity value, 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 less than 6 W/mK or less than 4 W/mK. Additionally, the thermal conductivity may be within a range that appears when the above-described lower and upper limits are appropriately selected.

The laminate 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, about 3 K/W or less, or about 2.8 K/W or less. It may be less than K/W. If the thermal resistance is adjusted to appear in this range, excellent cooling efficiency and 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. Additionally, specifically, the thermal resistance may be for the first layer and/or the second layer of the laminate.

The laminate according to an example of the present application can secure durability for application to products that require a long warranty period (about 15 years or more in the case of automobiles), such as automobiles. Durability is determined by maintaining the temperature at a low temperature of about -40℃ for 30 minutes, then raising the temperature to 80℃ and maintaining it for 30 minutes. After a thermal shock test in which the cycle is repeated 100 times, the temperature is not separated from the module case of the battery assembly or the battery cell. This may mean that no peeling or cracking occurs.

The laminate 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. It could be more than that. The higher the value of the dielectric breakdown voltage, the better the insulation properties of the laminate. It may be about 50 kV/mm or less, 45 kV/mm or less, 40 kV/mm or less, 35 kV/mm or less, and 30 kV/mm or less. There is no particular limitation. Additionally, specifically, the breakdown voltage may be for the first layer and/or the second layer of the laminate. In order to achieve the above dielectric breakdown voltage, insulating filler particles may be applied to some or all of the layers included in the laminate. In general, among thermally conductive filler particles, ceramic filler particles are known as a component that can secure insulation properties. The electrical insulation can be measured by dielectric breakdown voltage measured according to the ASTM D149 standard. In addition, if the laminate can secure the electrical insulation properties described above, stability can be secured while maintaining performance for various materials, such as cases or battery cells included in a battery assembly.

The laminate according to an example of the present application may have a specific gravity of 5 or less. In other examples, the specific gravity may be 4.5 or less, 4 or less, 3.5 or less, or 3 or less. The lower the specific gravity of the laminate is, the more advantageous it is to reduce the weight of the applied product, so the lower limit is not particularly limited. For example, the specific gravity may be about 1.5 or more or 2 or more. In order for the laminate to have a specific gravity in the above range, for example, when adding thermally conductive filler particles, a filler that can ensure the desired thermal conductivity even at as low a specific gravity as possible, that is, a filler particle that has a low specific gravity itself, is added. A method of applying filler particles or applying surface-treated filler particles may be used.

It is appropriate that the laminate according to an example of the present application does not contain volatile substances as much as possible. For example, the laminate 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. In other words, the non-volatile content can be defined as the non-volatile content remaining after the laminate is maintained at 100 ° C. for about 1 hour. Therefore, the ratio is the initial weight of the laminate and the weight of the laminate maintained for about 1 hour at 100 ° C. It can be measured based on the ratio afterward.

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

It may be advantageous for the laminate according to an example of the present application to have a low shrinkage rate during or after curing. Through this, it is possible to prevent delamination or voids that may occur during the manufacturing or use of various materials, such as cases or battery cells included in a battery assembly. The shrinkage rate may be appropriately adjusted within a range that can produce the above-described effects, and may be, for example, less than 5%, less than 3%, or less than about 1%. Since the lower the shrinkage value, the more advantageous, the lower limit is not particularly limited.

It may be advantageous for the laminate according to an example of the present application to have a low coefficient of thermal expansion (CTE). Through this, it is possible to prevent delamination or voids that may occur during the manufacturing or use of various materials, such as cases or battery cells included in a battery assembly. The thermal expansion coefficient may be appropriately adjusted in a range capable of producing the above-described effects, for example, less than 300 ppm/K, less than 250 ppm/K, less than 200 ppm/K, less than 150 ppm/K or 100 ppm. It may be less than /K. Since the lower the value of the thermal expansion coefficient, the more advantageous, the lower limit is not particularly limited.

The tensile strength of the laminate according to an example of the present application can be appropriately adjusted, and through this, excellent impact resistance, etc. can be secured. The tensile strength can be adjusted, for example, in a range of about 1.0 MPa or more.

The laminate according to an example of the present application may have a 5% weight loss temperature of 400°C or more in thermogravimetric analysis (TGA) or a residual weight of 800°C of 70% by weight or more. Due to these characteristics, stability at high temperatures can be further improved for various materials, such as cases or battery cells included in a battery assembly. In other examples, 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. The thermogravimetric analysis (TGA) can be measured within the range of 25°C to 800°C at a temperature increase rate of 20°C/min under a nitrogen (N ₂ ) atmosphere of 60 cm ³ /min. The thermogravimetric analysis (TGA) results can also be achieved by controlling the composition of the laminate.

In the laminate according to an example of the present application, the first layer may include a cured product of the first composition including a first resin component and a filler component. Additionally, the second layer may include a cured product of the second composition containing the second resin component.

In the laminate according to an example of the present application, the first composition contains a filler component of at least 70% by weight, at least 72% by weight, at least 74% by weight, at least 76% by weight, at least 78% by weight, based on the total weight of the first composition. 80% by weight or more, 82% by weight or more, or 84% by weight or more, or 98% by weight or less, 97% by weight or less, 96% by weight or less, 95% by weight or less, 94% by weight or less, 93% by weight or less, 92% by weight or less. , it may be 91% by weight or less, or 90% by weight or less, or within a range formed by appropriately selecting the upper and lower limits. When the content of the filler component satisfies the above range, excellent thermal conductivity and hardness at the desired level can be secured.

The type, shape, size, etc. of the filler component included in the first composition according to an example of the present application are not particularly limited as long as it is used in the art. Additionally, the filler component may include one or two or more types of filler particles. In addition, the filler component may be a mixture of filler particles of the same type with different shapes or with different average particle diameters. For example, the filler component may be a mixture of aluminum hydroxide and aluminum oxide (alumina), and the shapes and average particle sizes of the aluminum hydroxide and aluminum oxide may be different from each other. The first composition according to an example of the present application can secure a cured product having excellent thermal conductivity at a desired level by including a filler component.

The filler component included in the first composition according to an example of the present application may include filler particles having an average particle diameter of 70 ㎛ or more. In other examples, the average particle diameter of the filler is 75 ㎛ or more, 80 ㎛ or more, 85 ㎛ or more, 90 ㎛ or more, 95 ㎛ or more, 100 ㎛ or more, 105 ㎛ or more, 110 ㎛ or more, 115 ㎛ or more, 120 ㎛ or more. It can have sizes larger than that. Filler particles having an average particle diameter in the above range can be referred to as A filler particles in the present application, and the type and number of the A filler particles are not particularly limited as long as the average particle diameter is 70 ㎛ or more.

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

The shape of the A-pillar particles may be spherical and/or non-spherical (e.g., needle-shaped, plate-shaped, etc.) as appropriate, but is not limited thereto. However, in order to secure the desired level of thermal conductivity and hardness, the A-pillar particles may have a spherical shape.

As a term used in this application, spherical shape of the filler particle may mean that the sphericity is about 0.9 or more, and non-spherical shape may mean that the sphericity is less than about 0.9.

The sphericity can be confirmed through particle shape analysis of the filler particles. Specifically, the sphericity of a filler, which is a three-dimensional particle, can be defined as the ratio (S'/S) between the surface area of the particle (S) and the surface area of a sphere (S') having the same volume of the particle. For real particles, circularity is generally used. The circularity is obtained by obtaining a two-dimensional image of an actual particle and expressed as the ratio of the boundary (P) of the image to the boundary of a circle having the same area (A) as the same image, and is obtained by the following formula.

[Circularity formula]

Circularity=4πA/P ²

The circularity is expressed as a value from 0 to 1, with a perfect circle having a value of 1, and the more irregularly shaped particles have a value lower than 1. The sphericity value in this application can be measured as the average value of circularity measured with Marvern's particle shape analysis equipment (FPIA-3000).

The filler component included in the first composition according to an example of the present application includes the A filler particles in an amount of 10% by weight, 15% by weight, 20% by weight, 25% by weight, or 30% by weight based on the total weight of the filler component. It may contain more than 35% by weight or more than 40% by weight. In addition, in another example, the filler component contains the A filler particles in an amount of 100% by weight or less, 99.5% by weight or less, 90% by weight or less, 80% by weight or less, 70% by weight or less, 60% by weight or less, 50% by weight or less, 40% by weight or less. It may be included in less than 30% by weight or less than 30% by weight. The A-pillar particles may be included within the range formed by appropriately selecting the upper and lower limits listed above.

The filler component included in the first composition according to an example of the present application may include filler particles having an average particle diameter of more than 10 ㎛, 15 ㎛ or more, or 20 ㎛ or more. Additionally, in another example, the filler component may include filler particles having an average particle diameter of less than 70 ㎛, 65 ㎛ or less, 60 ㎛ or less, 55 ㎛ or less, or 50 ㎛ or less. Filler particles having an average particle diameter in the above range may be referred to as B filler particles in this application. The B-pillar particles are not particularly limited in type and number as long as the average particle diameter satisfies the above range.

The shape of the B-pillar particles may be spherical and/or non-spherical (for example, needle-shaped, plate-shaped, etc.) as appropriate, but is not limited thereto. However, in order to secure the desired level of thermal conductivity and hardness, the shape of the B pillar particles may be spherical.

The filler component included in the first composition according to an example of the present application includes the B filler particles in an amount of 5% by weight, 7.5% by weight, 10% by weight, 12.5% by weight, or 15% by weight based on the total weight of the filler component. It may contain more than 17.5% by weight or more than 20% by weight. In another example, the first filler component contains the B filler particles in an amount of 100% by weight or less, 90% by weight or less, 80% by weight or less, 70% by weight or less, 60% by weight or less, 50% by weight or less, It may contain less than 40% by weight or less than 30% by weight. The B pillar particles may be included within the range formed by appropriately selecting the upper and lower limits listed above.

Additionally, the filler component included in the first composition according to an example of the present application may include A-pillar particles and B-pillar particles.

When the filler component included in the first composition according to an example of the present application includes A filler particles and B filler particles, the first composition contains B filler particles in an amount of 10 parts by weight or more, 15 parts by weight, based on 100 parts by weight of A filler particles. It may contain at least 20 parts by weight, at least 25 parts by weight, at least 30 parts by weight, at least 35 parts by weight, at least 40 parts by weight, or at least 45 parts by weight. In addition, in another example, the first composition contains B filler particles in an amount of 200 parts by weight or less, 180 parts by weight or less, 160 parts by weight or less, 140 parts by weight or less, 120 parts by weight or less, and 100 parts by weight or less compared to 100 parts by weight of A filler particles. , may be included in 80 parts by weight or less or 60 parts by weight or less. In addition, by adjusting the content ratio of the A filler and B filler particles in the filler component within the above range, a first composition having an appropriate viscosity can be formed, and when cured, excellent thermal conductivity can be secured.

When the filler component included in the first composition according to an example of the present application includes A filler particles and B filler particles, the ratio of the diameter ( _DA ) of the A filler particles and the diameter ( _DB ) of the B filler particles ( _DA /D _B ) may be 2 or more, 2.2 or more, 2.4 or more, 2.6 or more, 2.8 or more, 3 or more, 3.2 or more, or 3.4 or more, and in other examples, the ratio (D _A /D _B ) is 5 or less, It may be 4.8 or less, 4.6 or less, 4.4 or less, 4.2 or less, or 4 or less. The ratio (D _A /D _B ) of the diameter ( _DA ) of the A filler particles and the diameter (DB ₎ of the B filler particles may be within a range formed by appropriately selecting the upper and lower limits listed above. In addition, when the ratio ( _DA /D _B ) of the diameter ( _DA ) of the A filler particles and the diameter (DB) of the B filler particles satisfies the above range, rapid curing of the first composition can be secured _. .

The filler component included in the first composition according to an example of the present application has an average particle diameter of 10 ㎛ or less, 9 ㎛ or less, 8 ㎛ or less, 7 ㎛ or less, 6 ㎛ or less, 5 ㎛ or less, 4 ㎛ or less, or 3 ㎛. It may contain the following filler particles. In addition, in other examples, the filler component may include filler particles having an average particle diameter of 0.01 ㎛ or more, 0.05 ㎛ or more, 0.1 ㎛ or more, 0.2 ㎛ or more, 0.4 ㎛ or more, 0.8 ㎛ or more, 1 ㎛ or more, or 2 ㎛ or more. there is. Filler particles having an average particle diameter in the above range may be referred to as C filler particles in this application. The C-pillar particles are not particularly limited in type and number as long as the average particle diameter satisfies the above range.

The shape of the C-pillar particles may be spherical and/or non-spherical (e.g., needle-shaped, plate-shaped, etc.) as appropriate, but is not limited thereto. However, in order to secure the desired level of thermal conductivity and hardness, the C-pillar particles may have a non-spherical shape.

The filler component included in the first composition according to an example of the present application includes the C filler particles in an amount of 10% by weight, 15% by weight, 20% by weight, 25% by weight, or 30% by weight based on the total weight of the filler component. It may contain more than 35% by weight or more than 40% by weight. In addition, in another example, the filler component contains the C filler particles in an amount of 100% by weight or less, 99% by weight or less, 90% by weight or less, 80% by weight or less, 70% by weight or less, 60% by weight or less, 50% by weight or less, 40% by weight or less. It may be included in less than 30% by weight or less than 30% by weight. The C-pillar particles may be included within the range formed by appropriately selecting the upper and lower limits listed above.

The filler component included in the first composition according to an example of the present application may include one or more selected from the group consisting of A-pillar particles, B-pillar particles, and C-pillar particles. Additionally, the filler component included in the first composition according to an example of the present application may include at least one selected from the group consisting of A-pillar particles and B-pillar particles and C-pillar particles.

The filler component included in the first composition according to an example of the present application may include A-pillar particles and C-pillar particles. When the filler component included in the first composition according to an example of the present application includes A-pillar particles and C-pillar particles (i.e., including cases where it includes B-pillar particles), the first composition contains C-pillar particles It may be included in an amount of at least 50 parts by weight, at least 60 parts by weight, at least 70 parts by weight, at least 80 parts by weight, at least 90 parts by weight, and at least 100 parts by weight, based on 100 parts by weight of the A filler particles. In addition, in another example, the first composition contains C filler particles in an amount of 300 parts by weight or less, 280 parts by weight or less, 260 parts by weight or less, 240 parts by weight or less, 220 parts by weight or less, and 200 parts by weight or less compared to 100 parts by weight of A filler particles. , may include 180 parts by weight or less, 160 parts by weight or less, 140 parts by weight or less, or 120 parts by weight or less. In addition, by adjusting the content ratio of the A filler and C filler particles in the filler component within the above range, a first composition having an appropriate viscosity can be formed, and when cured, excellent thermal conductivity can be secured.

The filler component included in the first composition according to an example of the present application may not include A-pillar but may include B-pillar particles and C-pillar particles. When the filler component included in the first composition according to an example of the present application does not include A filler but includes B-pillar particles and C-pillar particles, the first composition contains C-pillar particles in 100 parts by weight of B-pillar particles. It may contain 100 parts by weight or more, 120 parts by weight or more, 140 parts by weight or more, 160 parts by weight, 180 parts by weight or more, or 200 parts by weight or more. In addition, in another example, the first composition contains C filler particles in an amount of 500 parts by weight or less, 475 parts by weight or less, 450 parts by weight or less, 425 parts by weight or less, 400 parts by weight or less, and 375 parts by weight or less. , may include 350 parts by weight or less, 325 parts by weight or less, 300 parts by weight or less, 275 parts by weight or less, or 250 parts by weight or less. In addition, by adjusting the content ratio of the B-filler and C-filler particles in the filler component within the above range, a first composition having an appropriate viscosity can be formed and, when cured, excellent thermal conductivity can be secured.

The filler component included in the first composition according to an example of the present application may be a thermally conductive filler component for treating heat generated from a battery, etc., and may include at least one thermally conductive filler particle. The thermally conductive filler particles may have their own 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 other examples, about 400 W/mK or less, about 350 W. This may mean less than /mK or less than about 300 W/mK. The thermal conductivity of the thermally conductive filler particles that may be included in the filler component 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 component is not particularly limited as long as the thermal conductivity of the thermal conductivity described above satisfies the above range, but for example, aluminum oxide (alumina), magnesium oxide, beryllium oxide, or titanium oxide, etc. oxidation logistics; nitrides such as boron nitride, silicon nitride, or aluminum nitride; Carbide substances such as silicon carbide; Hydrated metals such as aluminum hydroxide or magnesium hydroxide; Metal fillers such as copper, silver, iron, aluminum or nickel; Metal alloy fillers such as titanium; Or it may be a mixture thereof.

The filler component included in the first composition according to an example of the present application may include a spherical filler and a non-spherical filler. Since the filler component includes a spherical filler and a non-spherical filler, a first composition having an appropriate viscosity can be formed and, when cured, excellent thermal conductivity can be secured.

Additionally, the filler component included in the first composition according to an example of the present application is a thermally conductive filler component, and the thermally conductive filler component may include a spherical filler and a non-spherical filler. Since the thermally conductive filler component includes a spherical filler and a non-spherical filler, a first composition having an appropriate viscosity can be formed and, when cured, excellent thermal conductivity can be secured.

The filler component included in the first composition according to an example of the present application has a weight ratio (OF/NF) of spherical filler (OF) and non-spherical filler (NF) of 0.1 or more, 0.2 or more, 0.3 or more, 0.4 or more, and 0.5. or more, 0.6 or more, 0.7 or more, 0.8 or more, 0.9 or more, 1 or more, 1.2 or more, 1.3 or more, 1.4 or more, or 1.5 or more, or 5 or less, 4.5 or less, 4 or less, 3.5 or less, 3 or less, 2.5 or less, 2 or less. Alternatively, it may be 1.5 or less, or within a range formed by appropriately selecting the above-mentioned upper and lower limits. By combining a spherical filler and a non-spherical filler as described above, the first composition can be formed with an appropriate viscosity, and when cured, excellent thermal conductivity can be secured.

The second composition according to an example of the present application may not substantially contain the above-mentioned filler component. Here, not included means that it is not artificially added, and may mean that it is present at 1% by weight or less, 0.5% by weight, 0.1% by weight or less, or 0.05% by weight or less relative to the total weight. Since the second composition does not substantially contain filler components, excellent adhesive properties can be secured. Specifically, the second composition substantially does not contain a filler component, thereby increasing the ratio of acrylic monomers participating in the photo-initiated reaction, thereby ensuring excellent adhesion.

In the laminate according to an example of the present application, the first composition forming the first layer may be cured by a thermal curing method. That is, the first layer can be formed by thermal curing. The first composition may further include a thermal initiator to perform a curing reaction through thermal curing.

The type of the thermal initiator is not particularly limited as long as it can initiate curing or polymerization of the first composition by heat. In addition, the thermal initiator is 70 ℃ or higher, 71 ℃ or higher, 72 ℃ or higher, 73 ℃ or higher, 74 ℃ or higher, 75 ℃ or higher, 76 ℃ or higher, 77 ℃ or higher, 78 ℃ or higher, 79 ℃ or higher, or 80 ℃ or higher. , inducing the activity of curing or polymerization reaction at a temperature of 100 ℃ or lower, 98 ℃ or lower, 96 ℃ or lower, 94 ℃ or lower, 92 ℃ or lower, or 90 ℃ or lower, or within an appropriately selected range of the above-mentioned upper and lower limits. can do.

The thermal initiator is, for example, 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile) (V-70, Wako (manufactured by)), 2,2-azobis-2, 4-dimethylvaleronitrile (V-65, Wako (manufactured)), 2,2-azobisisobutyronitrile (V-60, Wako (manufactured)) or 2,2-azobis-2-methylbutyro Azo-based initiators such as nitrile (V-59, Wako); Dipropyl peroxydicarbonate (Peroyl NPP, NOF (made)), diisopropyl peroxy dicarbonate (Peroyl IPP, NOF (made)), bis-4-butylcyclohexyl peroxy dicarbonate (Peroyl TCP, NOF (made) )), diethoxyethyl peroxy dicarbonate (Peroyl EEP, NOF (made)), diethoxyhexyl peroxy dicarbonate (Peroyl OPP, NOF (made)), hexyl peroxy dicarbonate (Perhexyl ND, NOF (made)) ), dimethoxybutyl peroxy dicarbonate (Peroyl MBP, NOF (made)), bis (3-methoxy-3-methoxybutyl) peroxy dicarbonate (Peroyl SOP, NOF (made)), hexyl peroxy pival Perhexyl PV (NOF), amyl peroxy pivalate (Luperox 546M75, Atofina), butyl peroxy pivalate (Perbutyl, NOF) or trimethylhexanoyl peroxide (Peroyl 355, NOF) Peroxyester compounds such as (No.)); Dimethyl hydroxybutyl peroxaneodecanoate (Luperox 610M75, Atofina), amyl peroxy neodecanoate (Luperox 546M75, Atofina) or butyl peroxy neodecanoate (Luperox 10M75, Atofina) peroxy dicarbonate compounds such as (a)); Acyl peroxides such as 3,5,5-trimethylhexanoyl peroxide, lauryl peroxide, or dibenzoyl peroxide; ketone peroxide; dialkyl peroxide; peroxy ketal; Alternatively, one or two or more types of peroxide initiators such as hydroperoxide may be used. In terms of securing the appropriate physical properties targeted in this application, it may be appropriate to apply the azo-based initiator above.

Meanwhile, the thermal initiator may be added together with the first resin component included in the first composition, or the first resin component may be first introduced into the reactor, the reaction temperature may be set to the above-mentioned temperature, and then the reaction will proceed. It may be administered by adding an appropriate amount at the time of initiation. That is, the initiation reaction may proceed while the thermal initiator is added. However, the first composition of the present application may not contain a separate solvent, and in this case, the reactor temperature may rapidly increase depending on the reaction rate of the polymerization reaction. Additionally, the desired physical properties may vary depending on the amount of thermal initiator applied. Therefore, from the viewpoint of securing the desired physical properties and preventing safety problems in the polymerization reaction, the amount and frequency of use of the thermal initiator can be appropriately adjusted.

The first composition according to an example of the present application contains a thermal initiator in an amount of 0.1 part by weight, 0.2 part by weight, 0.3 part by weight, 0.4 part by weight, 0.5 part by weight, or 0.6 part by weight, based on 100 parts by weight of the filler component. or more than 0.7 parts by weight, or more than 0.8 parts by weight, or less than 5 parts by weight, less than 4 parts by weight, less than 3 parts by weight, less than 2 parts by weight, or less than 1 part by weight, or a range appropriately selected from the above-mentioned upper and lower limits. It can be included within. When the thermal initiator is included in the above-mentioned ratio, the desired physical properties can be secured and safety problems in the polymerization reaction can be prevented.

In the laminate according to an example of the present application, the second composition forming the second layer may be cured by an active energy ray curing method. That is, the second layer can be formed by active energy ray curing. The second composition may further include a photoinitiator to perform a curing reaction according to active energy ray curing. The term active energy ray used in this application refers to light having a specific wavelength range, and the active energy ray curing method refers to the generation of initiation-causing substances such as radicals or cations by light having the specific wavelength range, This means that curing or polymerization is performed with these materials. The active energy rays include, for example, ultraviolet rays, infrared rays, or X-rays, and ultraviolet rays may be appropriately used.

The photoinitiator includes, for example, a radical initiator that generates a radical, and a cationic initiator that generates a cation (to be exact, a hydrogen ion). In the present application, a radical initiator may be more suitably used.

The radical initiator is intended to improve the curing speed by promoting radical polymerization, and as the radical initiator, radical initiators commonly used in the art may be used without limitation. For example, the radical initiator may include inorganic peroxides such as sodium persulfate, potassium persulfate, ammonium persulfate, potassium perphosphate, and hydrogen peroxide; t-butyl peroxide, cumene hydroperoxide, p-menthane hydroperoxide, di-t-butyl peroxide, t-butylcumyl peroxide, acetyl peroxide, isobutyl peroxide, octanoyl peroxide, dibenzoyl peroxide Organic peroxides such as oxide, 3,5,5-trimethylhexanol peroxide, and t-butyl peroxy isobutyrate; It may be one or more selected from the group consisting of azobisisobutyronitrile, azobis-2,4-dimethylvaleronitrile, azobiscyclohexanecarbonitrile, and methyl azobisisobutyric acid (butyric acid).

The cationic initiator is a compound that generates positive ions (H ⁺ ) by active energy rays. In the present application, cationic initiators commonly used in the art may be used without limitation. For example, the cationic initiator may preferably include, for example, a sulfonium salt or an iodonium salt. Specific examples of cationic initiators containing sulfonium salts or iodonium salts include, for example, diphenyl (4-phenylthio) phenylsulfonium hexafluoroantimonate (Diphenyl (4-phenylthio) )phenylsulfonium hexafluoroantimonate), diphenyl(4-phenylthio)phenylsulfonium hexafluorophosphate), (phenyl)[4-(2-methylpropyl)phenyl]-iodonium hexafluorophosphate Lophosphate ((phenyl)[4-(2-methylpropyl) phenyl]-Iodonium hexafluorophosphate), (Thiodi-4,1-phenylene)bis(diphenylsulfonium) dihexafluoroantimonate ((Thiodi-4 ,1-phenylene)bis(diphenylsulfonium) dihexafluoroantimonate) and (Thiodi-4,1-phenylene)bis(diphenylsulfonium) dihexafluorophosphate ) may be one or more selected from the group consisting of

Meanwhile, the photoinitiator may be added together with the second resin component included in the second composition, or may be added separately. The initiation reaction can be promoted by irradiating light with a wavelength range at which the photoinitiator can be active at an appropriate amount of energy or more.

The second composition according to an example of the present application contains the photoinitiator in an amount of 0.5 parts by weight or more, 0.6 parts by weight, 0.7 parts by weight or more, 0.8 parts by weight or more, 0.9 parts by weight or more, 1 part by weight or more, 1.2 parts by weight or more, 1.4 parts by weight or more, 1.6 parts by weight or more, 1.8 parts by weight or more, 2 parts by weight or more, 2.2 parts by weight or more, 2.4 parts by weight or more, or 2.5 parts by weight or more, or 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, 4 parts by weight or less, or 3 parts by weight or less, or within an appropriately selected range of the above-mentioned upper and lower limits. It can be included. When the photoinitiator satisfies the content ratio within the above-mentioned range, rapid curing is possible and desired physical properties can be secured.

As described above, the first composition according to an example of the present application includes a first resin component, and the second composition includes a second resin component. Additionally, the first resin component may include a first acrylic polymer. Additionally, the second resin component may include a second acrylic polymer.

The first composition according to an example of the present application contains the first resin component in an amount of 1 part by weight or more, 2 parts by weight or more, 3 parts by weight or more, 4 parts by weight or more, 5 parts by weight or more, 6 parts by weight or more, based on 100 parts by weight of the filler component. At least 7 parts by weight, at least 8 parts by weight, at least 9 parts by weight, or at least 10 parts by weight, or at most 100 parts by weight, at most 90 parts by weight, at most 80 parts by weight, at most 70 parts by weight, and at most 60 parts by weight, It may be 50 parts by weight or less, 40 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, or 15 parts by weight or less, or within an appropriately selected range of the above-mentioned upper and lower limits. When the first composition contains the first resin component in the above-mentioned range, excellent thermal conductivity and hardness can be secured.

The first resin component according to an example of the present application includes the first acrylic polymer in an amount of 10% by weight or more, 12% by weight or more, 14% by weight or more, 16% by weight or more, and 18% by weight or more relative to the total weight of the first resin component. , 20% by weight or more, 22% by weight or more, 24% by weight or more, 26% by weight or more, 28% by weight or more, 30% by weight or more, or 32% by weight or more, or 50% by weight or less, 48% by weight or less, 46% by weight. Hereinafter, it may be 44% by weight or less, 42% by weight or less, 40% by weight or less, 38% by weight or less, 36% by weight or less, or 34% by weight or less, or may include the above-mentioned upper and lower limits within an appropriately selected range. . When the first resin component contains the first acrylic polymer within the above range, it has a viscosity that is easy to handle and, after curing, excellent thermal conductivity and hardness can be secured.

The second composition according to an example of the present application contains the second resin component in an amount of 70% by weight, 72% by weight, 74% by weight, 76% by weight, 78% by weight, or 80% by weight, based on the total weight of the second composition. % or more, 82% or more, 84% or more, 86% or more or 88% or more, or 99% or less, 98% or less, 97% or less, 96% or less, 95% or less, 94% by weight. It may be less than 93% by weight, less than 93% by weight, or less than 92% by weight, or it may be included within an appropriately selected range of the above-mentioned upper and lower limits. When the second composition contains the second resin component in the above-described range, an excellent level of adhesion can be secured.

The second resin component according to an example of the present application contains a second acrylic polymer in an amount of 10% by weight or more, 12% by weight, 14% by weight, 16% by weight or more, and 18% by weight or more based on the total weight of the second resin component. , 20% by weight or more, 22% by weight or more, 24% by weight or more, 26% by weight or more, 28% by weight or more, 30% by weight or more, or 32% by weight or more, or 50% by weight or less, 48% by weight or less, 46% by weight. Hereinafter, it may be 44% by weight or less, 42% by weight or less, 40% by weight or less, 38% by weight or less, 36% by weight or less, or 34% by weight or less, or may include the above-mentioned upper and lower limits within an appropriately selected range. . When the second resin component contains the second acrylic polymer within the above range, it has a viscosity that is easy to handle and can secure excellent adhesion after curing.

The first acrylic polymer and the second acrylic polymer according to an example of the present application each independently include a (meth)acrylate unit containing an alkyl group (AA ₁ ) and a (meth)acrylate unit containing a hydroxy group (HA ₁ ). It can be included. In the (meth)acrylate unit (AA ₁ ) containing the alkyl group, the alkyl group has 1 to 20 carbon atoms, 1 to 18, 1 to 16, 1 to 14, 1 to 12, 1 to 10, 1 to 8, 1 It may range from 6, 1 to 4, 1 to 3, or 1 to 2. In the (meth)acrylate unit (HA ₁ ) containing the hydroxy group, the hydroxy group is 10 or less, 9 or less, 8 or less, 7 or less, 6 or less, 5 or less, 4 or less, 3 or less. There may be no more than one, two or less, or one.

The first acrylic polymer and the second acrylic polymer each independently contain an alkyl group-containing (meth)acrylate unit (AA ₁ ) in an amount of at least 50% by weight, at least 55% by weight, and at least 60% by weight based on the total weight of each acrylic polymer. or more than 65% by weight, more than 70% by weight, more than 75% by weight or more than 80% by weight, or less than 95% by weight, less than 90% by weight, or less than 85% by weight, or a range appropriately selected from the above-mentioned upper and lower limits. It can be included within. The first acrylic polymer and the second acrylic polymer each independently contain an alkyl group-containing (meth)acrylate unit (AA ₁ ) within the above-mentioned range, thereby ensuring the desired physical properties.

The first acrylic polymer and the second acrylic polymer each independently have a weight ratio (AA ₁ ) of a (meth)acrylate unit containing an alkyl group (AA ₁ ) and a (meth)acrylate unit (HA ₁ ) containing a hydroxy group. /HA ₁ ) is 1 or more, 1.5 or more, 2 or more, 2.5 or more, 3 or more, 3.5 or more, or 4 or more, or 10 or less, 9 or less, 8 or less, 7 or less, 6 or less, 5 or less, or 4.5 or less, or The above-mentioned upper and lower limits may be included within an appropriately selected range. The weight ratio (AA ₁ /HA ₁ ) of the first acrylic polymer and the second acrylic polymer is each independently included within the above-mentioned range, thereby ensuring the desired physical properties.

The first acrylic polymer and the second acrylic polymer are each independently a (meth)acrylate unit (AA ₁ ) containing an alkyl group, a (meth)acrylate unit (AA _{1_1} ) containing a straight or branched chain alkyl group, and It may include a (meth)acrylate unit (AA _{1_2} ) containing a cyclic alkyl group. In the (meth)acrylate unit (AA _{1_1} ) containing the straight-chain or branched-chain alkyl group, the straight-chain or branched alkyl group has 1 to 20 carbon atoms, 1 to 18, 1 to 16, 1 to 14, 1 to 12, It may range from 1 to 10 or 1 to 8. In addition, when it contains a branched chain alkyl group, the ratio (C ₁ /C ₂ ) of the number of carbon atoms in the main chain (C ₁ ) and the number of carbon atoms (C ₂ ) in the branch chain is 1 or more, It is 1.5 or more, 2 or more, 2.5 or more, 3 or more, 3.5 or more, or 4 or more, or 10 or less, 9 or less, 8 or less, 7 or less, 6 or less, 5 or less, or 4.5 or less, or the above-mentioned upper and lower limits as appropriate. It can be included within the selected range. If the first acrylic polymer and the second acrylic polymer include a (meth)acrylate unit (AA _{1_1} ) containing a straight-chain or branched-chain alkyl group as described above, the desired physical properties can be secured. In the (meth)acrylate unit (AA _{1_2} ) containing a cyclic alkyl group, the cyclic alkyl group has a carbon number of 1 to 20, 1 to 18, 1 to 16, 1 to 14, 1 to 12, or 1 to 10. It can be done tomorrow. . If the first acrylic polymer and the second acrylic polymer include a (meth)acrylate unit (AA _{1_2} ) containing a cyclic alkyl group as described above, the desired physical properties can be secured.

The first acrylic polymer and the second acrylic polymer are each independently a (meth)acrylate unit containing a straight-chain or branched alkyl group (AA _{1_1} ) and a (meth)acrylate unit containing a cyclic alkyl group (AA _{1_2} ) The weight ratio (AA _{1_1} /AA _{1_2} ) is 0.1 or more, 0.2 or more, 0.3 or more, 0.4 or more, 0.5 or more, 0.6 or more, 0.7 or more, 0.8 or more, 0.9 or more, 1 or more, 1.1 or more, 1.2 or more, 1.3 or more, 1.4 or more, 1.5 or more, 1.6 or more, 1.7 or more, or 1.8 or more, or 5 or less, 4.5 or less, 4 or less, 3.5 or less, 3 or less, 2.5 or less, or 2 or less, or within the appropriately selected range of the foregoing upper and lower limits. can be included in The weight ratio (AA _{1_1} /AA _{1_2} ) of the first acrylic polymer and the second acrylic polymer is each independently contained within the above-mentioned range, thereby securing the desired physical properties.

The first acrylic polymer and the second acrylic polymer each independently have a weight average molecular weight of 5,000 g/mol or more, 10,000 g/mol or more, 20,000 g/mol or more, 30,000 g/mol or more, 40,000 g/mol or more, or 50,000 g/mol or more. g/mol or more, 60,000 g/mol or more, 70,000 g/mol or more, 80,000 g/mol or more, 90,000 g/mol or more, 100,000 g/mol or more, 110,000 g/mol or more, 120,000 g/mol or more, 130,000 g/mol or more mol or more or 140,000 g/mol or more or 5,000,000 g/mol or less, 4,000,000 g/mol or less, 3,000,000 g/mol or less, 2,000,000 g/mol or less, 1,000,000 g/mol or less, 900,000 g/mol or less, 800,000 g/mol or less than or equal to 700,000 g/mol, less than or equal to 600,000 g/mol, less than or equal to 500,000 g/mol, less than or equal to 400,000 g/mol, less than or equal to 300,000 g/mol, less than or equal to 200,000 g/mol, or less than or equal to 180,000 g/mol, or the upper limit set forth above. and the lower limit may be included within an appropriately selected range. In addition, the first acrylic polymer and the second acrylic polymer each independently have a polydispersity index (PDI) of 1 or more, 1.2 or more, 1.4 or more, 1.6 or more, 1.8 or more, 2 or more, or 2.2 or more, or 5 or less, or 4.5 or more. or less, 4 or less, 3.5 or less, 3 or less, or 2.5 or less, or may be included within an appropriately selected range of the above-mentioned upper and lower limits. The first acrylic polymer and the second acrylic polymer each independently have a weight average molecular weight and a polydispersity index within the above-mentioned ranges, thereby securing the desired physical properties.

The first composition according to an example of the present application may further include a first acrylic monomer component. Additionally, the second composition according to an example of the present application may further include a second acrylic monomer component.

The first resin component according to an example of the present application includes the first acrylic monomer component in an amount of 100 parts by weight or more, 120 parts by weight, 140 parts by weight, 160 parts by weight, or 180 parts by weight, based on 100 parts by weight of the first acrylic polymer. Or it may be 200 parts by weight or more, 1,000 parts by weight or less, 800 parts by weight or less, 600 parts by weight or less, or 400 parts by weight or less, or within an appropriately selected range of the above-mentioned upper and lower limits. By controlling the content ratio of the first acrylic monomer component and the first acrylic polymer as described above, the desired physical properties can be secured.

The second resin component according to an example of the present application includes the second acrylic monomer component in an amount of 100 parts by weight or more, 120 parts by weight, 140 parts by weight, 160 parts by weight or more, and 180 parts by weight or more compared to 100 parts by weight of the first acrylic polymer. Or it may be 200 parts by weight or more, 1,000 parts by weight or less, 800 parts by weight or less, 600 parts by weight or less, or 400 parts by weight or less, or within an appropriately selected range of the above-mentioned upper and lower limits. By controlling the content ratio of the second acrylic monomer component and the second acrylic polymer as described above, the desired physical properties can be secured.

The first acrylic monomer component and the second acrylic monomer component according to an example of the present application may each independently include one or more acrylic monomers, that is, (meth)acrylate. In addition, the first acrylic monomer component and the second acrylic monomer component may each independently include (meth)acrylate (AA ₁ ) containing an alkyl group and (meth)acrylate (HA ₁ ) containing a hydroxy group. . In the (meth)acrylate (AA ₁ ) containing the alkyl group, the alkyl group has 1 to 20 carbon atoms, 1 to 18, 1 to 16, 1 to 14, 1 to 12, 1 to 10, 1 to 8, and 1 to It may be in the range of 6, 1 to 4, 1 to 3 or 1 to 2. In the (meth)acrylate (HA ₁ ) containing the hydroxy group, the hydroxy group is 10 or less, 9 or less, 8 or less, 7 or less, 6 or less, 5 or less, 4 or less, 3 or less. , there may be 2 or less or 1.

The first acrylic monomer component and the second acrylic monomer component each independently contain an alkyl group-containing (meth)acrylate (AA ₁ ) in an amount of at least 50% by weight, at least 55% by weight, and at least 60% by weight based on the total weight of each acrylic monomer component. % or more, 65% or more, 70% or more, 75% or more, or 80% or more by weight, or 95% or less, 90% or less, or 85% or less by weight, or appropriately selected the upper and lower limits above. It can be included within the scope. When the first acrylic monomer component and the second acrylic monomer component each independently contain (meth)acrylate (AA ₁ ) containing an alkyl group within the above-mentioned range, the desired physical properties can be secured.

The first acrylic monomer component and the second acrylic monomer component each independently have a weight ratio (AA ₁ ) of (meth)acrylate (AA ₁ ) containing an alkyl group and (meth)acrylate (HA ₁ ) containing a hydroxy group. /HA ₁ ) is 1 or more, 1.5 or more, 2 or more, 2.5 or more, 3 or more, 3.5 or more, or 4 or more, or 10 or less, 9 or less, 8 or less, 7 or less, 6 or less, 5 or less, or 4.5 or less, or The above-described upper and lower limits may be included within an appropriately selected range. The first acrylic monomer component and the second acrylic monomer component are each independently included in the weight ratio (AA ₁ /HA ₁ ) within the above-mentioned range, thereby ensuring the desired physical properties.

The first acrylic monomer component and the second acrylic monomer component are each independently (meth)acrylate (AA ₁ ) containing an alkyl group, (meth)acrylate (AA _{1_1} ) containing a straight-chain or branched-chain alkyl group, and It may include (meth)acrylate (AA _{1_2} ) containing a cyclic alkyl group. In the (meth)acrylate (AA _{1_1} ) containing the straight-chain or branched alkyl group, the straight-chain or branched alkyl group has 1 to 20 carbon atoms, 1 to 18, 1 to 16, 1 to 14, 1 to 12, 1 It may range from 10 to 10 or from 1 to 8. In addition, when it contains a branched chain alkyl group, the ratio (C ₁ /C ₂ ) of the number of carbon atoms in the main chain (C ₁ ) and the number of carbon atoms (C ₂ ) in the branch chain is 1 or more, It is 1.5 or more, 2 or more, 2.5 or more, 3 or more, 3.5 or more, or 4 or more, or 10 or less, 9 or less, 8 or less, 7 or less, 6 or less, 5 or less, or 4.5 or less, or the above-mentioned upper and lower limits as appropriate. It can be included within the selected range. If the first acrylic polymer and the second acrylic polymer include (meth)acrylate (AA _{1_1} ) containing a straight-chain or branched-chain alkyl group as described above, the desired physical properties can be secured. In (meth)acrylate (AA _{1_2} ) containing a cyclic alkyl group, the cyclic alkyl group has a carbon number of 1 to 20, 1 to 18, 1 to 16, 1 to 14, 1 to 12, or 1 to 10. You can. If the first acrylic monomer component and the second acrylic monomer component include (meth)acrylate (AA _{1_2} ) containing a cyclic alkyl group as described above, the desired physical properties can be secured.

The first acrylic monomer component and the second acrylic monomer component are each independently selected from the group consisting of (meth)acrylate (AA _{1_1} ) containing a straight or branched chain alkyl group and (meth)acrylate (AA _{1_2} ) containing a cyclic alkyl group. The weight ratio (AA _{1_1} /AA _{1_2} ) is 0.1 or more, 0.2 or more, 0.3 or more, 0.4 or more, 0.5 or more, 0.6 or more, 0.7 or more, 0.8 or more, 0.9 or more, 1 or more, 1.1 or more, 1.2 or more, 1.3 or more, 1.4 or more, 1.5 or more, 1.6 or more, 1.7 or more, or 1.8 or more, or 5 or less, 4.5 or less, 4 or less, 3.5 or less, 3 or less, 2.5 or less, or 2 or less, or within the appropriately selected range of the foregoing upper and lower limits. can be included in When the first acrylic monomer component and the second acrylic monomer component are each independently included in the weight ratio (AA _{1_1} /AA _{1_2} ) within the above-mentioned range, the desired physical properties can be secured.

The first resin component and the second resin component according to an example of the present application each independently have a glass transition temperature (T _g ) measured by DSC (Differential Scanning Calorimetry) of -50 ℃ or higher, -45 ℃ or higher, and -40 ℃ or higher. ℃ or higher, -35 ℃ or higher, -30 ℃ or higher or -25 ℃ or lower, 0 ℃ or lower, -5 ℃ or lower, -10 ℃ or lower, -15 ℃ or lower or -20 ℃ or lower, or the above-mentioned upper limit and The lower limit can be included within an appropriately selected range. The first resin component and the second resin component each independently satisfy a glass transition temperature within the above-mentioned range, making it easy to handle and ensuring flexible properties. The glass transition temperature may be a value measured according to the physical property measurement method below.

The first resin component and the second resin component according to an example of the present application each independently have a viscosity measured at 25° C. and 20 rpm of 1,000 cPs or more, 1,050 cPs or more, or 1,100 cPs or more, or 3,000 cPs or less, or 2,500 cPs or more. It may be cPs or less, 2,000 cPs or less, or 1,500 cPs or less, or may be included within an appropriately selected range of the above-mentioned upper and lower limits. Since the first resin component and the second resin component each independently satisfy the viscosity within the above-mentioned range, handling is easy and process efficiency can be improved by securing particularly excellent coating properties.

The first resin component and the second resin component according to an example of the present application can each independently be manufactured by heat-initiating an acrylic precursor composition. The term acrylic precursor composition used in this application may refer to a precursor composition capable of producing the above-described first resin component and second resin component. The acrylic precursor composition for producing the first resin component and the second resin component may have the same monomers and their content ratios, but may also be different. The acrylic precursor composition may include one or more, two or more, or three or more (meth)acrylates. The acrylic precursor composition may include (meth)acrylate (AA ₁ ) containing an alkyl group and (meth)acrylate (HA ₁ ) containing a hydroxy group. In the (meth)acrylate (AA ₁ ) containing the alkyl group, the alkyl group has 1 to 20 carbon atoms, 1 to 18, 1 to 16, 1 to 14, 1 to 12, 1 to 10, 1 to 8, and 1 to It may be in the range of 6, 1 to 4, 1 to 3 or 1 to 2. In the (meth)acrylate (HA ₁ ) containing the hydroxy group, the hydroxy group is 10 or less, 9 or less, 8 or less, 7 or less, 6 or less, 5 or less, 4 or less, 3 or less. , there may be 2 or less or 1.

In the acrylic precursor composition, (meth)acrylate (AA ₁ ) containing an alkyl group is included in an amount of at least 50% by weight, at least 55% by weight, at least 60% by weight, at least 65% by weight, and at least 70% by weight based on the total weight of each acrylic monomer component. % or more, 75% or more or 80% by weight or more, 95% or less, 90% or less, or 85% by weight or less, or may be included within an appropriately selected range of the above-mentioned upper and lower limits. By including (meth)acrylate (AA ₁ ) containing the alkyl group within the above-mentioned range, the desired physical properties can be secured.

In the acrylic precursor composition, the weight ratio (AA ₁ /HA ₁ ) of (meth)acrylate (AA ₁ ) containing an alkyl group and (meth)acrylate (HA ₁ ) containing a hydroxy group is 1 or more, 1.5 or more, 2 or more, 2.5 or more, 3 or more, 3.5 or more, or 4 or more, or 10 or less, 9 or less, 8 or less, 7 or less, 6 or less, 5 or less, or 4.5 or less, or within an appropriately selected range of the foregoing upper and lower limits. can be included in By keeping the weight ratio (AA ₁ /HA ₁ ) within the above-mentioned range, the desired physical properties can be secured.

In the acrylic precursor composition, (meth)acrylate (AA ₁ ) containing an alkyl group, (meth)acrylate (AA _{1_1} ) containing a straight or branched chain alkyl group, and (meth)acrylate containing a cyclic alkyl group. It may include (AA _{1_2} ). In the (meth)acrylate (AA _{1_1} ) containing the straight-chain or branched-chain alkyl group, the straight-chain or branched alkyl group has 1 to 20 carbon atoms, 1 to 18, 1 to 16, 1 to 14, 1 to 12, 1 It may range from 10 to 10 or from 1 to 8. In addition, when it contains a branched chain alkyl group, the ratio (C ₁ /C ₂ ) of the number of carbon atoms in the main chain (C ₁ ) and the number of carbon atoms (C ₂ ) in the branch chain is 1 or more, It is 1.5 or more, 2 or more, 2.5 or more, 3 or more, 3.5 or more, or 4 or more, or 10 or less, 9 or less, 8 or less, 7 or less, 6 or less, 5 or less, or 4.5 or less, or the above-mentioned upper and lower limits as appropriate. It can be included within the selected range. By including (meth)acrylate (AA _{1_1} ) containing a straight-chain or branched-chain alkyl group as described above, the desired physical properties can be secured. In (meth)acrylate (AA _{1_2} ) containing a cyclic alkyl group, the cyclic alkyl group has a carbon number of 1 to 20, 1 to 18, 1 to 16, 1 to 14, 1 to 12, or 1 to 10. You can. By including (meth)acrylate (AA _{1_2} ) containing a cyclic alkyl group as described above, the desired physical properties can be secured.

In the acrylic precursor composition, the weight ratio (AA _{1_1} /AA _{1_2} ) of (meth)acrylate (AA _{1_1} ) containing a straight or branched chain alkyl group and (meth)acrylate (AA _{1_2} ) containing a cyclic alkyl group is 0.1 or more, 0.2 or more, 0.3 or more, 0.4 or more, 0.5 or more, 0.6 or more, 0.7 or more, 0.8 or more, 0.9 or more, 1 or more, 1.1 or more, 1.2 or more, 1.3 or more, 1.4 or more, 1.5 or more, 1.6 or more, 1.7 or more Or it may be 1.8 or more, 5 or less, 4.5 or less, 4 or less, 3.5 or less, 3 or less, 2.5 or less, or 2 or less, or may be included within an appropriately selected range of the above-mentioned upper and lower limits. When the first acrylic monomer component and the second acrylic monomer component are each independently included in the weight ratio (AA _{1_1} /AA _{1_2} ) within the above-mentioned range, the desired physical properties can be secured.

The acrylic precursor composition contains the acrylic monomer as described above in an amount of at least 80% by weight, at least 81% by weight, at least 82% by weight, at least 83% by weight, at least 84% by weight, at least 85% by weight, 86% by weight, based on the total weight of the acrylic precursor composition. Included as % or more by weight, 87% or more, 88% or more, 89% or more, 90% or more, 91% or more, 92% or more, 93% or more, 94% or more, or 95% or more by weight. Alternatively, it may be less than 100% by weight, less than 99% by weight, less than 98% by weight, less than 97% by weight, less than 96% by weight, or less than 95% by weight, or it may be included within an appropriately selected range of the above-mentioned upper and lower limits.

The first resin component and the second resin component according to an example of the present application may each independently additionally include a thermal initiator in the acrylic precursor composition to induce a thermal initiation reaction. The type of the thermal initiator is not particularly limited as long as it can initiate curing or polymerization of the acrylic precursor composition by heat. In addition, the thermal initiator is 70 ℃ or higher, 71 ℃ or higher, 72 ℃ or higher, 73 ℃ or higher, 74 ℃ or higher, 75 ℃ or higher, 76 ℃ or higher, 77 ℃ or higher, 78 ℃ or higher, 79 ℃ or higher, or 80 ℃ or higher. , inducing the activity of curing or polymerization reaction at a temperature of 100 ℃ or lower, 98 ℃ or lower, 96 ℃ or lower, 94 ℃ or lower, 92 ℃ or lower, or 90 ℃ or lower, or within an appropriately selected range of the above-mentioned upper and lower limits. can do.

The thermal initiator is, for example, 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile) (V-70, Wako (manufactured by)), 2,2-azobis-2, 4-dimethylvaleronitrile (V-65, Wako (manufactured)), 2,2-azobisisobutyronitrile (V-60, Wako (manufactured)) or 2,2-azobis-2-methylbutyro Azo-based initiators such as nitrile (V-59, Wako); Dipropyl peroxydicarbonate (Peroyl NPP, NOF (made)), diisopropyl peroxy dicarbonate (Peroyl IPP, NOF (made)), bis-4-butylcyclohexyl peroxy dicarbonate (Peroyl TCP, NOF (made) )), diethoxyethyl peroxy dicarbonate (Peroyl EEP, NOF (made)), diethoxyhexyl peroxy dicarbonate (Peroyl OPP, NOF (made)), hexyl peroxy dicarbonate (Perhexyl ND, NOF (made)) ), dimethoxybutyl peroxy dicarbonate (Peroyl MBP, NOF (made)), bis (3-methoxy-3-methoxybutyl) peroxy dicarbonate (Peroyl SOP, NOF (made)), hexyl peroxy pival Perhexyl PV (NOF), amyl peroxy pivalate (Luperox 546M75, Atofina), butyl peroxy pivalate (Perbutyl, NOF) or trimethylhexanoyl peroxide (Peroyl 355, NOF) Peroxyester compounds such as (No.)); Dimethyl hydroxybutyl peroxaneodecanoate (Luperox 610M75, Atofina), amyl peroxy neodecanoate (Luperox 546M75, Atofina) or butyl peroxy neodecanoate (Luperox 10M75, Atofina) peroxy dicarbonate compounds such as (a)); Acyl peroxides such as 3,5,5-trimethylhexanoyl peroxide, lauryl peroxide, or dibenzoyl peroxide; ketone peroxide; dialkyl peroxide; peroxy ketal; Alternatively, one or two or more types of peroxide initiators such as hydroperoxide may be used. In terms of securing the appropriate physical properties targeted in this application, it may be appropriate to apply the azo-based initiator above.

Meanwhile, the thermal initiator may be added together with all acrylic monomers included in the acrylic precursor composition, or all of the acrylic monomers may be first introduced into the reactor, the reaction temperature is set to the above-mentioned temperature, and then the reaction is initiated. It can also be administered by adding an appropriate amount at the right time. That is, the initiation reaction may proceed while the thermal initiator is added. From the viewpoint of securing the desired physical properties and preventing safety problems in the polymerization reaction, the amount and frequency of use of the thermal initiator may be appropriately adjusted.

The acrylic precursor composition does not particularly limit the content of the thermal initiator, and may be appropriately included in consideration of appropriate physical properties and problems that may occur during the polymerization reaction as described above. However, for example, the acrylic precursor composition contains the thermal initiator in an amount of 1 ppm or more, 2 ppm or more, 3 ppm or more, 4 ppm or more, 5 ppm or more, 6 ppm or more, 7 ppm or more, based on the total weight of all acrylic monomers. ppm or higher, 8 ppm or higher, 9 ppm or higher, 10 ppm or higher, 11 ppm or higher, 12 ppm or higher, 13 ppm or higher, 14 ppm or higher, or 15 ppm or higher, or 100 ppm or lower, 90 ppm or lower, 80 ppm or lower, or 70 ppm Hereinafter, it may be 60 ppm or less, 50 ppm or less, 40 ppm or less, 30 ppm or less, or 20 ppm or less, or may include the above-mentioned upper and lower limits within an appropriately selected range. When the thermal initiator is included according to the above-mentioned ratio, it is advantageous to secure the desired physical properties and prevent safety problems in the polymerization reaction.

The acrylic precursor composition has a solid content of about 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, 28% or more under the above-mentioned conditions. or more, 30% or more, or 32% or more, or 50% or less, 48% or less, 46% or less, 44% or less, 42% or less, 40% or less, 38% or less, 36% or less, or 34% or less, or the above The reaction can be carried out until the above-mentioned upper and lower limits are within appropriately selected ranges.

The first composition and the second composition according to an example of the present application may each independently further include a crosslinking agent. The crosslinking agent can form a cured product having appropriate adhesion and hardness by implementing the composition and crosslinking structure included in each of the first composition and the second composition.

The crosslinking agent may be, for example, a urethane crosslinking agent, an aliphatic isocyanate crosslinking agent, an epoxy crosslinking agent, an aziridine crosslinking agent, and a metal chelate crosslinking agent, but is not limited thereto. Additionally, one or two or more types of crosslinking agents may be used. The urethane-based acrylate crosslinking agent is a compound that has multiple urethane bonds (-NHCOO-) in the molecular chain and an acrylic group that can react to ultraviolet rays at the end of the molecule, and is commercially available as PU-330 (Miwon Corporation) and PU-256. (Miwon Sangsa), PU-610 (Miwon Sangsa) and PU-340 (Miwon Sangsa) can be used. The aliphatic isocyanate crosslinking agent is, for example, an isocyanate compound such as isophorone diisocyanate, methylene dicyclohexyl diisocyanate, or cyclohexane diisocyanate, or a dimer thereof or Derivatives such as trimers can be used. The epoxy crosslinking agent is, for example, ethylene glycol diglycidyl ether, triglycidyl ether, trimethylolpropane triglycidyl ether, N,N,N',N'-tetraglycidyl ethylenediamine or glycerin diglycidyl. Dil ether, etc. can be used. The aziridine crosslinking agent is, for example, N,N'-toluene-2,4-bis(1-aziridinecarboxamide), N,N'-diphenylmethane-4,4'-bis(1-aziridine) Dincarboxamide), triethylene melamine, bisisoprotaloyl-1-(2-methylaziridine), or tri-1-aziridinylphosphine oxide can be used. For example, the metal chelate crosslinking agent may be a metal chelate component, which is a compound in which a multivalent metal such as aluminum, iron, zinc, tin, titanium, antimony, magnesium and/or vanadium is coordinated to acetylacetone or ethyl acetoacetate, etc. there is. In the present application, in order to form a cured product with appropriate adhesion and hardness, it may be appropriate to apply a urethane crosslinking agent considering the combination of the acrylic polymer and monomer components.

The first composition according to an example of the present application contains a crosslinking agent in an amount of 0.1 parts by weight or more, 0.5 parts by weight, 1 part by weight, 1.5 parts by weight or more, or 2 parts by weight or more, or 10 parts by weight, based on 100 parts by weight of the first resin component. Hereinafter, it may be 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, or 4 parts by weight or less, or may include the above-mentioned upper and lower limits within an appropriately selected range.

The second composition according to an example of the present application contains a crosslinking agent in an amount of 0.1 parts by weight or more, 0.5 parts by weight, 1 part by weight, 1.5 parts by weight or more, or 2 parts by weight or more, or 10 parts by weight, based on 100 parts by weight of the second resin component. Hereinafter, it may be 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, or 4 parts by weight or less, or may include the above-mentioned upper and lower limits within an appropriately selected range.

The first composition and the second composition can each independently contain a curing agent within the above range to form a cured product having appropriate adhesion and hardness.

The first 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 phosphate esters, polyoxyethylene alkylamines, pigment derivatives, etc. can be used, but dispersants known in the art can be used without limitation. Preferably, the dispersant may include a modified polyester dispersant, for example, Disperbyk-111 (BYK) and Solsperse 41000 (Lubrizol).

The first composition according to an example of the present application contains a dispersant in an amount of 1 part by weight or more, 2 parts by weight or more, 3 parts by weight or more, 4 parts by weight or more, or 5 parts by weight or more, or 20 parts by weight, based on 100 parts by weight of the first resin component. Hereinafter, it may be 15 parts by weight or less, 10 parts by weight or less, 8 parts by weight or less, or 6 parts by weight or less, or may include the above-mentioned upper and lower limits within an appropriately selected range. By including the dispersant within the above-mentioned content range, the dispersibility between the filler component and the first resin component can be improved to ensure uniform physical properties that do not change depending on the location.

The second composition according to an example of the present application may additionally include a dispersant as needed. 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 phosphate esters, polyoxyethylene alkylamines, pigment derivatives, etc. can be used, but dispersants known in the art can be used without limitation. Preferably, the dispersant may include a modified polyester dispersant, for example, Disperbyk-111 (BYK) and Solsperse 41000 (Lubrizol).

The first composition according to an example of the present application may further include a flame retardant or a flame retardant auxiliary agent. The first composition further containing a flame retardant or a flame retardant auxiliary agent can be cured to ensure flame retardancy. As the flame retardant, various known flame retardants may be applied without particular limitation, 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. If the amount of thermally conductive filler particles included in the first 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. Additionally, a silane coupling agent that can act as a flame retardant synergist may be added.

The first composition according to an example of the present application contains a flame retardant, a flame retardant auxiliary, or the sum of the flame retardant and a flame retardant auxiliary in an amount of at least 1 part by weight, at least 2 parts by weight, at least 3 parts by weight, and at least 4 parts by weight based on 100 parts by weight of the first resin component. or more than 5 parts by weight, or less than 20 parts by weight, less than 15 parts by weight, less than 10 parts by weight, less than 8 parts by weight, or less than 6 parts by weight, or the above-mentioned upper and lower limits may be included within an appropriately selected range. . Flame retardant properties can be secured by including the flame retardant within the above-mentioned content range.

The second composition according to an example of the present application may additionally include a flame retardant or a flame retardant auxiliary, if necessary. The first composition further containing a flame retardant or a flame retardant auxiliary agent may be cured to ensure flame retardancy. As the flame retardant, various known flame retardants may be applied without particular limitation, 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. If the amount of thermally conductive filler particles included in the first 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. Additionally, a silane coupling agent that can act as a flame retardant synergist may be added.

The first composition and the second composition according to an example of the present application may each independently additionally include a plasticizer as needed. The type of the 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 One or more of paraffin, chlorinated fatty acid esters, fatty acid compounds, compounds with a saturated aliphatic chain substituted with a sulfonic acid group to which a phenyl group is bonded (for example, mesamoll from LANXESS), and vegetable oil can be used. The phthalic acid compounds include dimethyl phthalate, diethyl phthalate, dibutyl phthalate, dihexyl phthalate, di-n-octyl phthalate, di-2-ethylhexyl phthalate, diisooctyl phthalate, dicapryl phthalate, dinonyl phthalate, and diisononyl. Phthalate, didecyl phthalate, diundecyl phthalate, dilauryl phthalate, ditridecyl phthalate, dibenzyl phthalate, dicyclohexyl phthalate, butyl benzyl phthalate, octyl decyl phthalate, butyl octyl phthalate, octyl benzyl phthalate, n-hexyl n- One or more of decyl phthalate, n-octyl phthalate, and n-decyl phthalate may be used. The phosphoric acid compound may be one or more of tricresyl phosphate, trioctyl phosphate, triphenyl phosphate, octyl diphenyl phosphate, cresyl diphenyl phosphate, and trichloroethyl phosphate. The adipic acid compound includes 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 be one or more of dibutyl sebacate, dioctyl sebacate, diisooctyl sebacate, and butyl benzyl. The citric acid compound may be one or more of triethyl citrate, acetyl triethyl citrate, tributyl citrate, acetyl tributyl citrate, and acetyl trioctyl citrate. The glycolic acid compound may be one or more of methyl phthalyl ethyl glycolate, ethyl phthalyl ethyl glycolate, and butyl phthalyl ethyl glycolate. The trimellitic acid compound may be one or more of trioctyl trimellitate and tri-n-octyl n-decyl trimellitate. The polyester compounds include butane diol, ethylene glycol, propane 1,2-diol, propane 1,3 diol, polyethylene glycol, glycerol, diacid (selected from adipic acid, succinic acid, succinic anhydride) and hydroxy acids (e.g. , hydroxystearic acid).

The first composition and the second composition according to an example of the present application each independently contain a viscosity modifier, for example, to increase or decrease the viscosity or to adjust the viscosity according to shear force, as needed. , a thixotropic agent, a diluent, or a coupling agent may be additionally included. The thixotropic agent can adjust the viscosity according to the shear force of each composition. Examples of thixotropic agents that can be used include fumed silica. Diluents are usually used to lower the viscosity of each composition, and various types known in the industry can be used without limitation as long as they can exhibit the above actions. In the case of coupling agents, for example, they can be used to improve the dispersibility of thermally conductive filler particles (for example, alumina, etc.), and various types known in the industry can be used as long as they can exhibit the above actions. It can be used without restrictions.

The laminate according to an example of the present application has a ratio (D ₁ /D ₂ ) of the thickness of the first layer (D ₁ ) and the thickness of the second layer (D ₂ ) of 10 or more, 20 or more, 50 or more, and 80 or more. , 100 or more, 120 or more, 150 or more, 180 or more, or 200 or less, or 1,000 or less, 900 or less, 800 or less, 700 or less, 600 or less, 500 or less, 400 or less, or 300 or less, or the upper and lower limits described above. It can be included within an appropriately selected range. By controlling the ratio of the respective thicknesses of the first layer and the second layer as described above, overall manufacturing efficiency can be secured through rapid curing while maintaining appropriate bearing capacity.

The method of manufacturing a laminate according to an example of the present application may include applying a second composition on the applied first composition and performing heat curing and active energy ray curing.

The method of manufacturing a laminate according to an example of the present application may include manufacturing a first composition by mixing an acrylic resin component and a filler component. Here, the filler component may include a spherical filler and a non-spherical filler. In this case, the non-spherical filler may be mixed first, and then the spherical filler may be additionally added and mixed. Through this, the first composition can further improve the dispersibility between the filler component and the acrylic resin component.

In the method of manufacturing a laminate according to an example of the present application, the first composition and the second composition have appropriately high viscosity as described above, so that the two layers do not mix directly, do not flow, and can exist while maintaining the laminated form. .

In the method of manufacturing a laminate according to an example of the present application, the method of applying the first composition may be a coating method used in the art, for example, bar coating, blade coating, spray coating, dip coating, and spin coating. etc. In addition, in the method of manufacturing a laminate according to an example of the present application, the method of applying the second composition may be a coating method used in the art as described above, but the second curable composition layer is applied to the first curable composition. Since it is thin compared to other materials, spray coating may be suitable.

In addition, the first composition and the second composition according to an example of the present application can be formed by mixing each of the components listed above, unless otherwise specified. Additionally, the mixing order of the second composition is not particularly limited as long as it can contain all necessary ingredients.

A device according to an example of the present application includes a heat generating element and a heat carrier in thermal contact with the heat generating element, and the heat carrier may include a laminate. Thermal contact, the term used in this application, refers to the fact that the laminate is in direct physical contact with the heat-generating element to dissipate heat generated from the heat-generating element, or even if the laminate is not in direct contact with the heat-generating element (i.e., lamination (a separate layer exists between the sieve and the heat-generating element) to dissipate the heat generated from the heat-generating element.

Devices according to an example of the present application include, for example, irons, washing machines, dryers, clothes care machines, electric razors, microwave ovens, electric ovens, rice cookers, refrigerators, dishwashers, air conditioners, fans, humidifiers, air purifiers, mobile phones, and walkie-talkies. , various electrical and electronic products such as televisions, radios, computers, and laptops, or batteries such as secondary batteries, and the laminate can dissipate heat generated from the devices. In particular, in electric vehicle batteries manufactured by gathering battery cells to form one battery assembly (or called a battery module) and multiple battery modules to form one battery pack, this application is used as a material for connecting battery modules. A laminate may be used. When the laminate of the present application is used as a material for connecting battery modules, it can serve to dissipate heat generated from battery cells and secure the battery cells from external shock and vibration. Specifically, the second layer of the laminate may be adhered to a battery cell.

In the device according to an example of the present application, heat generated from the heat generating element may be dissipated through a heat transfer material, and the heat may be transferred to a cooling area. The cooling portion may be in thermal contact with a heat carrier and may have a lower temperature than the heat generating element. The cooling area may refer to a area having a lower temperature than the temperature of the heating element due to a medium such as cooling water, or may mean an air area lower than the temperature of the heating element.

A device according to an example of the present application may be a battery assembly, and the battery assembly may include a battery cell and a laminate according to an example of the present application. Additionally, the battery cell may be adhered to the second layer of the laminate. The structure of the battery assembly may refer to the structure of the battery module in Patent Document 1 described above.

Additionally, a device according to an example of the present application may be a battery pack and may include the battery assembly described above.

The present application can provide a laminate that has excellent adhesion performance, excellent heat dissipation properties, no brittleness after curing, and appropriate surface hardness. Additionally, the present application can provide a battery assembly and a battery pack including the above laminate.

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

Manufacturing Example 1.

Monomer components 2-ethylhexyl acrylate (2-EHA, 2-ethylhexyl acrylate), isobonyl acrylate (IBoA), and 2-hydroxyethyl acrylate (2- HEA, 2-hydroxyethyl acrylate) was added at a weight ratio of 51.5:28.5:20 (2-EHA:IBoA:2-HEA). Afterwards, about 15 ppm of thermal initiator was additionally added based on the total weight of the monomer components. As the thermal initiator, a compound represented by the following chemical formula Ti was used. Afterwards, the mixture was stirred and reacted at about 80°C for 4 hours to obtain an acrylic resin component (A _s ) containing an acrylic polymer ( _AP ). The solid content of the acrylic resin component (A _s ) was about 33.27%, the viscosity measured at 25 ℃ and 20 rpm was about 1,100 cPs, and the glass transition temperature (T _g ) measured by DSC (Differential Scanning Calorimetry) is about -25℃. In addition, the acrylic polymer ( _AP ) had a weight average molecular weight of about 148,000 g/mol and a polydispersity index (PDI) of about 2.2.

[Chemical formula Ti]

Manufacturing example 2.

The acrylic resin component (A _s ), urethane crosslinking agent (U _H ), thermal initiator (Ti), flame retardant (FL) and dispersant ( D) was added at an amount ratio of 40:0.8:3.2:2:2 (A _s :U _H :Ti:FL:D) and stirred at about 6 rpm for about 10 minutes. Afterwards, about 400 parts by weight of non-spherical (plate-shaped) alumina with an average particle diameter of about 1 ㎛, based on 100 parts by weight of the added acrylic resin component ( _As ), was added to the mixer and then stirred at about 6 rpm for 10 minutes. It was stirred to some extent. Thereafter, 400 parts by weight compared to 100 parts by weight of the added acrylic resin component ( _As ) spherical alumina with an average particle diameter of about 80 ㎛ and 200 parts by weight compared to 100 parts by weight of the added acrylic resin component ( _As ). Spherical alumina with an average particle diameter of about 20 ㎛ was additionally added to the mixer and stirred at about 6 rpm for about 10 minutes. Afterwards, the first acrylic composition was prepared by defoaming and stirring under vacuum at about 2 rpm for 30 minutes.

In the above, PU-256 from Miwon was used as the urethane crosslinking agent (U _H ), and the thermal initiator (Ti) was the same as the thermal initiator used in Preparation Example 1. In addition, in the above, the flame retardant (FL) was used as a phosphorus-based flame retardant, FR-RDP from Campia, and the dispersant (D) was used as an anionic dispersant, Chemistat 3500 from Sanyo Chemical.

Manufacturing example 3.

The acrylic resin component (A _s ), urethane crosslinking agent (U _H ), thermal initiator (Ti), flame retardant (FL) and dispersant ( D) was added at an amount ratio of 40:1.6:3.2:2:2 (A _s :U _H :Ti:FL:D) and stirred at about 6 rpm for about 10 minutes. Afterwards, about 400 parts by weight of non-spherical (plate-shaped) alumina with an average particle diameter of about 1 ㎛ to 2 ㎛ based on 100 parts by weight of the added acrylic resin component ( _As ) was added to the mixer and then mixed at about 6 rpm. It was stirred for about 10 minutes. Afterwards, 400 parts by weight compared to 100 parts by weight of the added acrylic resin component ( _As ), spherical alumina with an average particle diameter of about 80 ㎛ and 200 parts by weight compared to 100 parts by weight of the added acrylic resin component ( _As ). Spherical alumina with an average particle diameter of about 20 ㎛ was additionally added to the mixer and stirred at about 6 rpm for about 10 minutes. Afterwards, the first acrylic composition was prepared by defoaming and stirring under vacuum at about 2 rpm for 30 minutes.

The urethane crosslinking agent (U _H ), thermal initiator (Ti), flame retardant (FL), and dispersant (D) were the same as those used in Preparation Example 2.

Manufacturing example 4.

The acrylic resin component (A _s ), urethane crosslinking agent (U _H ), and photoinitiator (Li) prepared in Preparation Example 1 were mixed in a planetary mixer maintained at about 15°C at a ratio of 40:0.8:1 (A A second acrylic composition was prepared by adding it at an amount ratio of _s :U _H :Li) and stirring it at about 6 rpm for about 10 minutes.

The urethane crosslinking agent (U _H ) was the same as that used in Preparation Example 2. In addition, the photoinitiator (Li) used was BASF's Irgacure-819 (I-819), a radical photoinitiator.

Manufacturing Example 5.

The acrylic resin component (A _s ), urethane crosslinking agent (U _H ), and photoinitiator (Li) prepared in Preparation Example 1 were mixed in a planetary mixer maintained at about 15°C at a ratio of 40:1.6:1 (A A second acrylic composition was prepared by adding it at an amount ratio of _s :U _H :Li) and stirring it at about 6 rpm for about 10 minutes.

The urethane crosslinking agent (U _H ) was the same as that used in Preparation Example 2. In addition, the photoinitiator (Li) was the same as that used in Preparation Example 4.

Example 1.

After placing a release film on a stainless steel plate, the first acrylic composition prepared according to Preparation Example 2 was applied on the release film to a thickness of about 2 mm, and the first acrylic composition according to Preparation Example 4 was applied on the first acrylic composition. A specimen was prepared by applying the second acrylic composition prepared accordingly to a thickness of about 10 ㎛. Thereafter, the specimen was placed on a hot plate maintained at 70° C., the stainless steel plate was removed, and the bottom of the first acrylic composition (i.e., the side opposite to the side on which the second acrylic composition was applied) was placed on the hot plate. The temperature was maintained in contact with the plate and curing was carried out for about 4 minutes to form the first layer. Thereafter, the specimen was separated from the hot plate, and the second acrylic composition of the specimen was placed so that it could be directly irradiated with ultraviolet rays generated from the ultraviolet curing machine. Afterwards, curing was performed by irradiating ultraviolet rays with an energy of about 1.5 J/cm ² for about 1 minute to form a second layer. The cured specimen was separated from the ultraviolet curing machine to prepare a laminate including a first layer and a second layer.

Example 2.

The first acrylic composition prepared according to Preparation Example 2 was applied to a thickness of about 2 mm, and the second acrylic composition prepared according to Preparation Example 5 was applied on the first acrylic composition to a thickness of about 10 ㎛. Except that the specimen was manufactured by coating, the curing reaction was performed in the same manner as in Example 1 to prepare a laminate including a first layer and a second layer.

Example 3.

The first acrylic composition prepared according to Preparation Example 3 was applied to a thickness of about 2 mm, and the second acrylic composition prepared according to Preparation Example 4 was applied on the first acrylic composition to a thickness of about 10 ㎛. Except that the specimen was manufactured by coating, the curing reaction was performed in the same manner as in Example 1 to prepare a laminate including a first layer and a second layer.

Example 4.

The first acrylic composition prepared according to Preparation Example 3 was applied to a thickness of about 2 mm, and the second acrylic composition prepared according to Preparation Example 5 was applied on the first acrylic composition to a thickness of about 10 ㎛. Except that the specimen was manufactured by coating, the curing reaction was performed in the same manner as in Example 1 to prepare a laminate including a first layer and a second layer.

Comparative Example 1.

After placing a release film on a stainless steel plate, the first acrylic composition prepared according to Preparation Example 2 was applied on the release film to a thickness of about 2 mm to prepare a specimen. Thereafter, the specimen was placed on a hot plate maintained at 70° C., the stainless steel plate and the release film were removed, and the bottom of the first acrylic composition (i.e., the opposite side of the side to which the second acrylic composition was applied) was placed on a hot plate maintained at 70° C. Curing was performed for about 4 minutes by maintaining the temperature while in contact with the hot plate to form a cured layer.

Comparative Example 2.

A cured layer was prepared by performing a curing reaction in the same manner as Comparative Example 1, except that the first acrylic composition prepared according to Preparation Example 3 was applied to a thickness of about 2 mm to prepare a specimen.

<Method for measuring physical properties>

1. Thermal conductivity

Thermal conductivity was measured using Hot Disk's TPS-2200, a thermal constant analyzer, according to ISO 22007-2 standards. Specifically, thermal conductivity was measured using samples of the laminate prepared in the above example and the cured layer prepared in the comparative example, aged at about 25° C. for about 24 hours. In the case of the laminate, the laminate is positioned so that the bottom of the first layer touches the sensor of the thermal analysis device and the second layer can be fixed with the fixing screw of the thermal analysis device, and then fixed with the fixing screw. Thermal conductivity was measured using an isotropic cross-sectional measurement method. In the case of the cured layer, the cured layer was placed on the sensor and fixed with a fixing screw, and then the thermal conductivity was measured using an isotropic cross-section measurement method. At this time, the type of sensor used is 5465.

2. Shore A hardness

Shore A hardness was measured according to ASTM D2240 standard. Specifically, the laminate prepared in the above example and the cured layer prepared in the comparative example were aged at about 25° C. for about 24 hours, and then the surfaces of the laminate and the cured layer in a flat state were The indenter capable of measuring Shore A type hardness was pierced with a hardness measuring instrument (manufacturer: TQC Sheen, product name: LD0550), and the hardness value displayed on the hardness measuring instrument was measured when the piercing force was maintained. At this time, the laminate was measured for the first layer.

3. Adhesion

Adhesion was achieved by attaching an aluminum pouch with a PET (poly(ethylene terephthalate)) interface of about 1 cm in width, 20 cm in length, and 150 μm in thickness to the laminate prepared in the above example and the cured layer prepared in the comparative example, It was aged at about 25°C for about 24 hours. The aluminum pouch can be used when manufacturing a battery cell, and was attached so that the PET interface contacts the laminate or cured layer. Afterwards, the aluminum pouch was peeled off at a peeling speed of about 0.3 mm/s and a peeling angle of 180 degrees using a physical property tester (manufacturer: Stable Micro Systems, Taxture analyzer) and the adhesive force was measured at 25°C. At this time, the laminate was measured for the second layer.

4. Viscosity

Viscosity was measured at 25°C using a viscosity meter (manufacturer: Brookfield, model name: Brookfield LV) and spindle LV-63. After performing zero point adjustment of the viscometer, a spindle, LV-63, was mounted on the spindle connection portion of the viscometer.

The measurement object was placed inside a 100 mL vial with a height longer than the length of the spindle LV-63. The inlet of the vial was located at the bottom of the spindle so that the spindle mounted on the viscometer could enter the inside of the vial. Thereafter, the vial was slowly raised until the spindle was located in the center of the measurement object inside the vial. Afterwards, a support jack was placed at the bottom of the vial to fix the position of the vial, and a shear rate of 20 rpm was applied to measure the viscosity.

5. Weight average molecular weight

Weight average molecular weight (M _w ) was measured using GPC (Gel permeation chromatography). Put the analysis target in a 20 mL vial and dilute it in THF (tetrahydrofuran) solvent to a concentration of about 20 mg/mL. Afterwards, the standard sample for calibration and the sample to be analyzed were filtered through a syringe filter (pore size: 0.2 ㎛) and then measured. The analysis program used was ChemStation from Agilent technologies, and the number average molecular weight (M _n ) and weight average molecular weight (M _w ) were obtained by comparing the elution time of the sample with the calibration curve. Here, the polydispersity index (PDI) was calculated by dividing the weight average molecular weight (M _w ) by the number average molecular weight (M _n ).

<GPC measurement conditions>

Instrument: 1200 series from Agilent technologies

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

Solvent: THF

Column temperature: 40℃

Sample concentration: 20 mg/mL, 10 μl injection

Use MP: 364000, 91450, 17970, 4910, 1300 as standard sample.

6. Glass transition temperature

The glass transition temperature was measured according to a conventional measurement method using DSC (Differential Scanning Calorimeter) equipment. As equipment, DSC-STAR3 equipment (Mettler Toledo) was used. Approximately 10 mg of the measurement object was sealed in a dedicated pen, and the endothermic and calorific values were confirmed according to temperature under a temperature increase condition of 10°C/min, and the glass transition temperature was measured.

The results of the test data measured in the examples and comparative examples are summarized in Table 1 below. In Table 1 below, the designation <a (a is an arbitrary number) means that the value of the measured physical property has a value less than a.

division Thermal conductivity (W/mK) Shore A hardness Adhesion (gf/10mm) Example 1 3.22 50 830 Example 2 3.25 80 797 Example 3 3.23 85 783 Example 4 3.22 85 755 Comparative Example 1 3.27 90 < 10 Comparative Example 2 3.29 95 < 10

Referring to Table 1, it can be seen that Examples 1 to 4 exhibit excellent thermal conductivity, Shower A hardness, and adhesion. However, the cured layers according to Comparative Examples 1 and 2 contained an excessive amount of filler component and exhibited excellent thermal conductivity and Shore A hardness. However, due to the excessive filler component, an appropriate initiation reaction was not performed in the resin component, and battery cells, etc. It showed low adhesion to a level where fixation was difficult.

Claims (20)

Comprising a first layer and a second layer,
The adhesion measured at 25°C to the surface of the second layer is 200 gf/10mm or more,
A laminate with a thermal conductivity of 1 W/mK or more. The method of claim 1, wherein the first layer includes a cured product of a first composition including a first resin component and a filler component, and the second layer includes a cured product of a second composition including a second resin component. Laminate. The laminate according to claim 1, wherein the Shore A hardness measured at 25° C. on the surface of the first layer is 60 or more. The laminate according to claim 1, wherein the first layer is formed by thermal curing. The laminate according to claim 1, wherein the second layer is formed by active energy ray curing. The laminate according to claim 2, wherein the first resin component includes a first acrylic polymer, and the second resin component includes a second acrylic polymer. The method of claim 6, wherein the first resin component includes a first acrylic polymer in the range of 10 to 50% by weight based on the total weight of the first resin component, and the second resin component includes a second acrylic polymer as the second resin. A laminate containing within the range of 10 to 50% by weight based on the total weight of the components. The method of claim 6, wherein the first acrylic polymer and the second acrylic polymer each independently comprise a (meth)acrylate unit containing an alkyl group (AA ₁ ) and a (meth)acrylate unit containing a hydroxy group (HA ₁ ). Contains,
A laminate wherein the weight ratio (AA ₁ /HA ₁ ) of the (meth)acrylate unit (AA ₁ ) containing the alkyl group and the (meth)acrylate unit (HA ₁ ) containing the hydroxy group is in the range of 1 to 10. The method of claim 8, wherein the first acrylic polymer and the second acrylic polymer are each independently a (meth)acrylate unit (AA 1 ) containing an alkyl group and a (meth)acrylate unit (AA ₁ ) containing a straight-chain or branched-chain alkyl group. _{1_1} ) and (meth)acrylate units containing a cyclic alkyl group (AA _{1_2} ),
The weight ratio (AA _{1_1} /AA _{1_2} ) of the (meth)acrylate unit (AA _{1_1} ) containing a straight-chain or branched alkyl group and the (meth)acrylate unit (AA _{1_2} ) containing a cyclic alkyl group is 0.1 to 5. Laminates within the scope of. The laminate according to claim 6, wherein the first acrylic polymer and the second acrylic polymer each independently have a weight average molecular weight in the range of 5,000 g/mol to 5,000,000 g/mol. 3. The method of claim 2, wherein the first resin component includes a first acrylic monomer component, and the second resin component includes a second acrylic monomer component,
The first acrylic monomer component and the second acrylic monomer component each independently include a (meth)acrylate containing an alkyl group and a (meth)acrylate containing a hydroxy group. The method of claim 11, wherein the first acrylic monomer component and the second acrylic monomer component are each independently a (meth)acrylate containing an alkyl group, and the (meth)acrylate containing a straight-chain or branched-chain alkyl group and a cyclic alkyl group. A laminate containing (meth)acrylate. The laminate according to claim 2, wherein the first composition includes a filler component in the range of 70% by weight to 98% by weight based on the total weight. The laminate according to claim 2, wherein the filler component is a thermally conductive filler component, and the thermally conductive filler component includes a spherical filler and a non-spherical filler. The laminate of claim 14, wherein the thermally conductive filler component has a weight ratio (OF/NF) of spherical filler (OF) and non-spherical filler (NF) in the range of 0.1 to 5. 3. The laminate of claim 2, wherein the second composition is substantially free of filler components. The laminate according to claim 1, wherein the ratio (D ₁ /D ₂ ) of the thickness (D ₁ ) of the first layer and the thickness (D ₂ ) of the second layer is in the range of 10 to 1,000. A battery assembly comprising a battery cell and the laminate of claim 1. 19. The battery assembly of claim 18, wherein the battery cells are bonded to the second layer of the laminate. A battery pack comprising the battery assembly of claim 18.