KR20220043792A - Manufacturing Method Of Resin Composition - Google Patents

Abstract

The present application provides a preparation method of a resin composition in which the surface treatment of a filler is performed in situ so that a process is simple, the cost is reduced, there is no environmental pollution problem, and the long-term storage stability of the resin composition is ensured due to the small change in physical properties over time.

Description

Method of manufacturing a resin composition {Manufacturing Method Of Resin Composition}

The present application relates to a method for producing a resin composition.

Heat dissipation materials are used in various fields. Taking a vehicle as an example, a heat-dissipating material can be used to treat heat generated from a battery module built in an electric vehicle capable of charging and discharging, an on-board charger (OBC) for charging the battery, etc. Heat dissipation material is applied to parts that consume high power and generate a lot of heat, such as modules, so that the lifespan of the LED module can be improved.

The silicone-based resin composition has excellent heat resistance and can be used as a heat dissipation material. A filler may be added to the silicone-based resin composition to realize excellent thermal conductivity.

For long-term storage stability of the silicone-based resin composition, it is required that physical properties (viscosity, hardness, etc.) of the resin composition do not change over time. For long-term storage stability, there is a method of surface-treating the filler and mixing the surface-treated filler with the silicone-based resin composition, but this method requires a lot of time and money, and requires a separate solvent removal process, thereby contaminating the environment. There is also the possibility that problems may arise.

In addition, a method of adding an additive without using a surface-treated filler may be considered, but this method has a problem in that storage stability is deteriorated because a change in physical properties of the resin composition occurs greatly.

An object of the present application is to provide a method for preparing a silicone-based resin composition having excellent storage stability without changes in physical properties such as viscosity or hardness during storage.

Another object of the present application is to provide a method for manufacturing a silicone-based resin composition in which the manufacturing process is simple, the cost is reduced, and does not cause environmental pollution problems.

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

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

In the present specification, the term "alkenyl group", unless otherwise specified, has 2 to 20 carbon atoms, 2 to 16 carbon atoms, 2 to 12 carbon atoms, 2 to 8 carbon atoms, or 2 to 4 carbon atoms straight chain, branched chain, or cyclic It may mean an alkenyl group. Representative alkenyl groups include a vinyl group or an allyl group.

In the present specification, the term "alkyl group" or "alkoxy group", unless otherwise specified, has 1 to 20 carbon atoms, 1 to 16 carbon atoms, 1 to 12 carbon atoms, 1 to 8 carbon atoms, or straight chain, branched chain having 1 to 4 carbon atoms. , or may mean a cyclic alkyl group or an alkoxy group.

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

The above-described alkenyl group, alkoxy group, alkyl group or aryl group may be optionally substituted with one or more substituents. In this case, the substituent includes a halogen such as chlorine or fluorine, an epoxy group such as a glycidyl group, an epoxyalkyl group, a glycidoxyalkyl group or an alicyclic epoxy group, an acryloyl group, a methacryloyl group, an isocyanate group, a thiol group, or a monovalent hydrocarbon Groups and the like may be exemplified, but are not limited thereto.

In the present specification, the term M unit usually refers to a so-called monofunctional siloxane unit that is sometimes expressed as (R ₃ SiO _{1 / 2} ), and the term D unit is usually expressed as (R ₂ SiO _{2 / 2} ). It means a so-called difunctional siloxane unit with, the term T unit means a so-called trifunctional siloxane unit, which is sometimes expressed as (RSiO _{3 / 2} ), and the term Q unit is usually expressed as (SiO _4/2 ) may mean so-called tetrafunctional siloxane units in some cases. In the formula of each siloxane unit, R is a functional group bonded to silicon (Si), and may be, for example, hydrogen, an alkyl group, an alkenyl group, an aryl group, an alkoxy group, or an epoxy group. and maintaining the mixture of the nyl group-containing polyorganosiloxane component, the alkylsilane compound, and the filler at a temperature within the range of 15°C to 200°C.

As used herein, the term polyorganosiloxane component may be a mixture of polyorganosiloxanes and/or a mixture of polyorganosiloxanes and siloxane monomers. In a more specific example, the polyorganosiloxane component may be a result of a polymerization reaction performed to obtain a specific target polyorganosiloxane. As the polyorganosiloxane component having an alkenyl group, a known polyorganosiloxane component may be used without any particular limitation. In one example, the polyorganosiloxane component may include a polyorganosiloxane component including a linear polyorganosiloxane.

The straight-chain polyorganosiloxane is a polyorganosiloxane having a structure in which both ends of a chain structure composed of D units are blocked by M units as is known.

In the above structure, various types of units may be used as the D unit. For example, as the D unit, a so-called dialkylsiloxane unit (a bifunctional siloxane unit in which R in the R ₂ SiO _{2 /2} structure is all alkyl groups), a diarylsiloxane unit (in the R ₂ SiO _{2 /2} structure, R is A bifunctional siloxane unit in which all are aryl groups), a dialkenylsiloxane unit (a bifunctional siloxane unit in which R is all alkenyl groups in the R ₂ SiO _{2 /2} structure), an alkylarylsiloxane unit (one R in the R ₂ SiO _{2 /2} structure) A difunctional siloxane unit in which this alkyl group and another R is an aryl group), an alkylalkenylsiloxane unit (a bifunctional siloxane unit in which one R is an alkyl group and the other R is an alkenyl group in the R ₂ SiO _{2 /2} structure) and arylal At least one unit selected from the group consisting of a kenyl siloxane unit (a bifunctional siloxane unit in which one R is an alkenyl group and the other R is an aryl group in the R ₂ SiO _{2 /2} structure) may be applied.

Suitable D units include, among others, a dialkylsiloxane unit (a bifunctional siloxane unit in which R is all alkyl groups in the R ₂ SiO _{2 /2} structure) and/or an alkylalkenylsiloxane unit (one of the R ₂ SiO _{2 /2} structures in the structure) a difunctional siloxane unit wherein R is an alkyl group and other R is an alkenyl group).

In the structure of the linear polyorganosiloxane, as M units at both ends of the chain structure consisting of D units, for example, an alkenyldialkylsiloxane unit (R ₃ SiO _{1/2 In} the structure, one of R is an alkenyl group, and the remaining monofunctional siloxane units in which two are alkyl groups) and/or trialkylsiloxane units (monofunctional siloxane units in which R is all alkyl groups in _the R ₃ SiO _1/2 structure) and the like may be exemplified. For example, in the case of a structure in which both ends are terminated with alkenyl groups, as the M unit, an alkenyldialkyl siloxane unit may be used.

In one example, as a polyorganosiloxane component having an alkenyl group, the D unit of the main chain structure of the straight-chain polyorganosiloxane is a dialkylsiloxane unit (in the R ₂ SiO _{2 /2} structure, R is a bifunctional siloxane unit in which all R is an alkyl group) and/or an alkylalkenylsiloxane unit (a bifunctional siloxane unit in which one R is an alkyl group and the other R is an alkenyl group in the R ₂ SiO _{2 /2} structure), and M units at both ends are an alkenyldialkylsiloxane unit (R ₃ In the SiO _1/2 structure _, one of R is an alkenyl group and the other two are monofunctional siloxane units having an alkyl group) may include a polyorganosiloxane component.

In the case where more than one type of D unit is used as the D unit of the main chain, the main chain may be in the form of a main chain of a random copolymer, a block copolymer, or a gradient copolymer.

Such a polyorganosiloxane component may include a polyorganosiloxane represented by Formula 1 below.

[Formula 1]

In Formula 1, R ₅ and R ₆ are each independently an alkenyl group, an alkyl group, or an aryl group, wherein at least one of R ₅ and R ₆ is an alkenyl group, and n is a number within the range of 5 to 100. In another example, n is 10 or more, 15 or more, 20 or more, 25 or more, or 30 or more, 95 or less, 90 or less, 85 or less, 80 or less, 75 or less, 70 or less, 65 or less, 60 or less, 55 or less, 50 or less. or less, 45 or less, 40 or less, or 35 or less.

Specific types of the alkenyl group, the alkyl group, or the aryl group in the definition of Formula 1 are the same as those described in the introduction of the means for solving the problems of the present specification.

The alkenyl group-containing polyorganosiloxane component having the above structure may include an alkenyl group in a ratio of 0.05 to 5 mmol/g. In another example, the alkenyl group-containing polyorganosiloxane component includes an alkenyl group of 0.1 mmol/g or more, 0.15 mmol/g or more, 0.2 mmol/g or more, 0.25 mmol/g or more, 0.3 mmol/g or more, 0.35 mmol/g or more, 0.4 mmol/g or more, 0.45 mmol/g or more, or 4 mmol/g or less, 3 mmol/g or less, 2 mmol/g or less, or 1 mmol/g or less.

In the polyorganosiloxane having the above structure, the ratio (Ak/Si) of the number of moles (Ak) of all alkenyl groups based on the number of moles (Si) of all silicon atoms in the polyorganosiloxane may be, for example, in the range of 0.01 to 1.5. In another example, the ratio (Ak/Si) is 0.05 or more, 0.1 or more, 0.15 or more, 0.2 or more, 0.25 or more, 0.3 or more, 0.35 or more, 0.4 or more, 0.45 or more, 0.5 or more, 0.55 or more, 0.6 or more, or 0.65 or more. , 1.4 or less, 1.3 or less, 1.2 or less, 1.1 or less, 1.0 or less, 0.9 or less, or 0.8 or less.

The polyorganosiloxane having an alkenyl group may have a viscosity in the range of 20 to 1000 cP at room temperature. Specifically, the polyorganosiloxane having an alkenyl group is about 25 cP or more, 30 cP or more, 35 cP or more, 40 cP or more, or 45 cP or more, or 900 cP or less, 800 cP or less, 700 cP or less, 600 cP or less, 500 cP or less, 400 cP or less , 300 cP or less, 200 cP or less, 100 cP or less, 80 cP or less, or 60 cP or less. The viscosity may be measured using, for example, a known brookfield viscometer or a rheometer (ARES), and may be a value measured at a shear rate of 0.1/s.

In one example, the polyorganosiloxane having an alkenyl group may have a number average molecular weight (Mn) within the range of 10 g/mol to 20,000 g/mol. Flowability and fairness can be secured within this range. The number average molecular weight (Mn) of the polyorganosiloxane having an alkenyl group is, in another example, 20 g/mol or more, 30 g/mol or more, 40 g/mol or more, 50 g/mol or more, 60 g/mol or more, 70 g/mol or more, 80 g/mol or more, 90 g/mol or more, 100 g/mol or more, 200 g/mol or more, 300 g/mol or more, 400 g/mol or more, 500 g/mol or more, 600 g /mol or more, 700 g/mol or more, 800 g/mol or more, 900 g/mol or more, 1,000 g/mol or more, 1,100 g/mol or more, 1,200 g/mol or more, 1,300 g/mol or more, 1,400 g/mol or more, 1,500 g/mol or more, 1,600 g/mol or more, 1,700 g/mol or more, 1,800 g/mol or more, or 1,900 g/mol or more, or 15,000 g/mol or more, 10,000 g/mol or less, 9,000 g/mol or less , 8,000 g/mol or less, 7,000 g/mol or less, 6,000 g/mol or less, 5,000 g/mol or less, 4,000 g/mol or less, 3,000 g/mol or less, or 2,500 g/mol or less.

A filler may be blended in order to secure heat dissipation or thermal conductivity properties of the resin composition. In this case, the filler may be surface-treated so that the resin composition may have an appropriate viscosity and ensure long-term storage stability. However, when the surface treatment of the filler is performed in an ex-situ method, it takes time and money, and a problem of environmental pollution may occur due to the use of a large amount of solvent. The method for preparing the resin composition of the present application has the advantage of reducing time and cost by performing the surface treatment of the filler in-situ, and providing a method of preparing a resin composition without environmental pollution problems.

In the present application, an alkylsilane compound may be blended for surface treatment of the filler. Specifically, unlike the prior art of surface-treating a filler with an alkylsilane compound by an ex situ method, the present invention is an in situ method in which an alkylsilane compound, a filler, and an alkenyl group-containing polyorganosiloxane component are mixed and left under certain conditions. It is characterized by a method for producing a resin composition by

As the filler in the present application, a thermally conductive filler may be applied. The term thermally conductive filler means a material having a thermal conductivity of about 1 W/mK or more, about 5 W/mK or more, about 10 W/mK or more, or about 15 W/mK or more. The thermal conductivity of the thermally conductive filler may be about 400 W/mK or less, about 350 W/mK or less, or about 300 W/mK or less. The type of the thermally conductive filler is not particularly limited, and ceramic particles such as alumina, aluminum nitride (AlN), boron nitride (BN), silicon nitride, SiC, ZnO or BeO, and carbon fillers such as graphite etc. may be applied.

In one example of the present application, the filler is aluminum hydroxide (Al(OH) ₃ ), magnesium hydroxide (Mg(OH) ₂ ), calcium hydroxide (Ca(OH) ₂ ) and hydromagnesite (Mg ₅ (CO ₃ ) ₄ (OH) ₂ ·4H ₂ O) may be at least one selected from the group consisting of. These fillers have excellent thermal conductivity, low specific gravity, which is advantageous for weight reduction, and includes -OH groups on the surface, so surface treatment with an alkylsilane compound is also easy.

The type of filler that can be applied is not particularly limited, and, for example, a spherical filler, a needle-shaped filler, a plate-shaped filler, or other amorphous fillers may be used.

In one example, the filler may have an average particle diameter in the range of 0.001 μm to 100 μm. The average particle diameter is the D50 particle diameter measured by the method described in Examples to be described later. The average particle diameter of the filler is 0.005 μm or more, 0.01 μm or more, 0.05 μm or more, 0.1 μm or more, 0.5 μm or more, 0.8 μm or more, 1 μm or more, 5 μm or more, 10 μm or more, 15 μm or more, 20 μm or more, 25 μm or more in another example. , 30 μm or more, 35 μm or more, 40 μm or more, or 45 μm or more, 95 μm or less, 90 μm or less, 85 μm or less, 80 μm or less, 75 μm or less, 70 μm or less, 65 μm or less, 60 μm or less, 55 μm or less, 50 μm or less, 45 μm or less, 40 μm or less, 35 μm or less, 30 μm or less, 25 μm or less, 20 μm or less, 15 μm or less, 10 μm or less, or 5 μm or less.

A mixture of two or more fillers having at least different average particle diameters may be used as the filler in order to secure appropriate filling properties and secure target properties. For example, as the filler, a first filler having an average particle diameter of 20 μm or more and a second filler having an average particle diameter of less than 20 μm within the aforementioned range may be used.

The average particle diameter of the first filler is, in another example, 25 μm or more, 30 μm or more, 35 μm or more, 40 μm or more, or 45 μm or more, or 100 μm or less, 95 μm or less, 90 μm or less, 85 μm or less, 80 μm or less, 75 μm or less, 70 μm or less, 65 μm or less, 60 μm or less, 55 μm or less.

In addition, the average particle diameter of the second filler is, in another example, 0.001 μm or more, 0.005 μm or more, 0.01 μm or more, 0.05 μm or more, 0.1 μm or more, 0.5 μm or more, or 0.8 μm or more, 18 μm or less, 15 μm or less, 10 μm It may be about 5 μm or less or 3 μm or less.

When the first and second fillers are simultaneously applied, the ratio (D1/D2) of the average particle diameter (D1) of the first filler to the average particle diameter (D2) of the second filler is 2 to 100 can be within the scope of tomorrow. The ratio (D1/D2) is 5 or more, 10 or more, 15 or more, 20 or more, 25 or more, 30 or more, 35 or more, 40 or more, or 45 or more, or 95 or less, 90 or less, 85 or less, 80 or less in another example. , 75 or less, 70 or less, 65 or less, 60 or less, or 55 or less.

When the first and second fillers are simultaneously applied, the ratio (W1/W2) of the used weight (W1) of the first filler based on the used weight (W2) of the second filler is 0.5 to 100 can be within the scope of tomorrow. In another example, the ratio (W1/W2) is 1 or more, 1.5 or more, or 2 or more, or 95 or less, 90 or less, 85 or less, 80 or less, 75 or less, 70 or less, 65 or less, 60 or less, 55 or less, 50 or less. , 45 or less, 40 or less, 35 or less, 30 or less, 25 or less, 20 or less, 15 or less, 10 or less, 5 or less, or 3 or less.

In order to obtain excellent heat dissipation performance, a high content of the filler may be blended. In one example, the filler surface-treated with the alkylsilane compound may be formulated in an amount of about 50% by volume or more based on the total volume of the resin composition. Specifically, the filler may be formulated in an amount of 55% by volume or more, 60% by volume or more, 65% by volume or more, or 70% by volume or more. In another example, the ratio may be formulated in 95 vol% or less, 92 vol% or less, 89 vol% or less, 86 vol% or less, 83 vol% or less, 80 vol% or less, 77 vol% or less, or 74 vol% or less. there is. The volume ratio may be obtained by considering the mass ratio and density of each component included in the resin composition, and components not included in the cured product of the final resin composition are not considered in the calculation.

In one example, the alkylsilane compound may be represented by Formula 2 below.

[Formula 2]

In Formula 2, R ₁ to R ₄ are each independently a hydrogen atom, an alkyl group having 6 to 15 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms, and at least one of R ₁ to R ₄ is an alkyl group having 6 to 15 carbon atoms.

When at least one of R ₁ to R ₄ in the alkylsilane compound represented by Formula 2 is an alkyl group having 6 to 15 carbon atoms, the viscosity of the resin composition can be controlled to be low, and the curing reaction (addition reaction) can be controlled to an appropriate level. Thus, it is advantageous to secure the desired hardness after sufficient curing.

In the mixture of the alkenyl group-containing polyorganosiloxane component, the alkylsilane compound, and the filler, the alkylsilane compound may be blended in an amount of 0.04 to 3 parts by weight based on 100 parts by weight of the polyorganosiloxane component. Specifically, based on 100 parts by weight of the polyorganosiloxane component, 0.05 parts by weight or more, 0.1 parts by weight or more, 0.2 parts by weight or more, 0.3 parts by weight or more, 0.4 parts by weight or more, 0.5 parts by weight or more, 0.6 parts by weight or more, 0.7 parts by weight or more, 0.8 parts by weight or more, 0.9 parts by weight or more, 1.0 parts by weight or more, or 1.1 parts by weight or more of the alkylsilane compound, or 2.5 parts by weight or less, 2 parts by weight or less, or 1.8 parts by weight or less. .

In addition, in the mixture of the alkenyl group-containing polyorganosiloxane component, the alkylsilane compound, and the filler, the alkylsilane compound may be blended in an amount of 0.8 to 2 parts by weight based on 100 parts by weight of the filler component. Specifically, based on 100 parts by weight of the filler component, 0.05 parts by weight or more, 0.06 parts by weight or more, 0.07 parts by weight or more, 0.08 parts by weight or more, 0.09 parts by weight or more, 0.1 parts by weight or more, 0.11 parts by weight or more, 0.12 parts by weight or more, 0.13 parts by weight or more It may be blended in an amount of at least 0.14 parts by weight, or at least 0.15 parts by weight, or in an amount of 1.5 parts by weight or less, 1 part by weight or less, 0.5 parts by weight or less, or 0.2 parts by weight or less. When the amount of the alkylsilane compound is less than 0.8 parts by weight relative to 100 parts by weight of the filler, the surface treatment effect is lowered and the degree of change over time of the physical properties (viscosity, hardness, etc.) of the resin composition increases, and there is a problem that the long-term storage stability of the resin composition is deteriorated, When the amount of the alkylsilane compound exceeds 2 parts by weight relative to 100 parts by weight of the filler, the hardness of the resin composition may decrease, and heat resistance may be deteriorated, which may cause a problem of volatilization at a high temperature (100° C. or higher).

According to the present invention, since the alkenyl group-containing polyorganosiloxane component, the alkylsilane compound, and the filler are mixed in-situ, the ex-situ filler surface that removes the solvent after mixing the filler, the surface treatment agent and the solvent Compared to the treatment method, no additional solvent removal process is required. Accordingly, there are advantages in that the process is simplified, the solvent removal cost is reduced, and environmental pollution problems caused by the use of the solvent can be prevented. At the same time, an advantageous effect of improving the long-term storage stability of the resin composition by reducing the degree of change over time of the physical properties of the resin composition including the surface-treated filler can be expected.

In one example of the present invention, after performing the first step of mixing the alkenyl group-containing polyorganosiloxane component and the alkylsilane compound, the second step of mixing the mixture and the filler in the first step may be performed. As described above, when the alkenyl group-containing polyorganosiloxane component corresponding to the silicone binder and the alkylsilane compound are first mixed, the alkylsilane compound may be more uniformly mixed in the binder.

The mixture may be maintained at a temperature range of 15° C. to 200° C. for 10 minutes to 20 hours. In one example, the mixture is maintained at a temperature of 20 °C or higher, 30 °C or higher, 40 °C or higher, 50 °C or higher, 60 °C or higher, or 70 °C or higher, or 180 °C or lower, 150 °C or lower, 120 °C or lower, 100 °C or higher. It can be maintained at a temperature below or below 90°C.

In one example, the mixture is maintained for about 20 minutes or more, about 30 minutes or more, about 40 minutes or more, about 50 minutes or more, about 60 minutes or more, or about 70 minutes or more, 15 hours or less, 10 minutes or more within the temperature range. hours or less, 5 hours or less, or 3 hours or less.

In one example, the present invention can maintain the mixture within the room temperature range. At this time, the room temperature is a natural temperature that is not heated or reduced, and may be, for example, any temperature within the range of 10°C to 30°C. Specifically, the mixture may be maintained at a temperature of about 15 °C, about 18 °C, about 21 °C, about 23 °C, or about 25 °C.

In another example, the present invention may include maintaining the mixture at a high temperature of 75° C. or higher and then cooling the mixture after the holding step. In the above step, the mixture is cooled at room temperature after maintaining the mixture at a high temperature of about 80°C or more, about 85°C or more, about 90°C or more, about 95°C or more, about 100°C or more, about 110°C or more, about 120°C or more. can When the mixture is maintained at a high temperature as described above and then cooled at room temperature, the degree of change over time of the physical properties (viscosity, hardness, etc.) of the resin composition is reduced, so that the long-term storage stability of the resin composition is improved.

The resin composition prepared according to the manufacturing method of the present application may be composed of a two-component type in which the silicone binder and the curing agent are physically separated so as not to contact before use, and may be composed of a one-component type in which the silicone binder and the curing agent are present together. may be

In one example, when the resin composition of the present application is a two-component resin composition, an addition reaction (hydrosilylation) that occurs between a polyorganosiloxane having an alkenyl group in the subject composition and a hydrogen polyorganosiloxane having a silicon atom-bonded hydrogen in the curable composition Curing may occur through the reaction product). In the curable composition of the present application, the silicone binder and the curing agent may be physically separated from each other until they are used.

In one example, the subject composition of the present invention may include an alkenyl group-containing polyorganosiloxane component and a surface-treated filler, and the curing agent composition comprises an alkenyl group-containing polyorganosiloxane component, and a polyorganosiloxane containing silicon-bonded hydrogen atoms. ingredients and surface-treated fillers. The description of the alkenyl group-containing polyorganosiloxane component included in the main composition and the curing agent composition and the description of the surface-treated filler are the same as described above.

In one example, the method for preparing the resin composition of the present invention may further perform the step of mixing the mixture maintained at a temperature within the range of 15° C. to 200° C. with the catalyst.

The catalyst may be involved in activating an addition reaction between a polyorganosiloxane having an alkenyl group and a hydrogen polyorganosiloxane to be described later. The type of catalyst is not particularly limited, but, for example, a platinum-based catalyst may be used, and a known or commercially available platinum-based catalyst may be used.

In one example, the catalyst may be included in an amount of 10 parts by weight or less based on 100 parts by weight of the polyorganosiloxane having an alkenyl group. Although not particularly limited, the lower limit of the content of the catalyst may be, for example, 0.01 parts by weight or more, 0.1 parts by weight or more, 0.5 parts by weight or more, or 1 part by weight or more, and the upper limit thereof is, for example, 5 parts by weight or less. , 3 parts by weight or less or 1 part by weight or less.

In one example, the catalyst may be in a form in which platinum or a platinum-containing compound is dispersed in a resin component. For example, the catalyst may be in a form in which a platinum-based compound is dispersed in a polysiloxane component. In this case, the metal content of platinum or the platinum-containing compound in the catalyst may be 0.001 to 1 wt%.

In one example, the method for preparing the resin composition of the present invention may further perform the step of mixing the mixture maintained at a temperature within the range of 15° C. to 200° C. with the hydrogen polyorganosiloxane component.

The hydrogen polyorganosiloxane contained in the curing agent composition is a polyorganosiloxane having silicon atom-bonded hydrogen, and a known material may be used without particular limitation. For example, as the hydrogen polyorganosiloxane, a linear polyorganosiloxane, that is, a polyorganosiloxane having a structure in which both ends of a chain structure consisting of D units are blocked by M units may be used.

In the above structure, various types of units may be used as the D unit. For example, as the D unit, a so-called dialkylsiloxane unit (a bifunctional siloxane unit in which R in the R ₂ SiO _{2 /2} structure is all alkyl groups), a diarylsiloxane unit (in the R ₂ SiO _{2 /2} structure, R is bifunctional siloxane unit in which all are aryl groups), dihydrogensiloxane unit (a bifunctional siloxane unit in which R is all hydrogen in R ₂ SiO _{2 /2} structure), alkylarylsiloxane unit (one R in R ₂ SiO _{2 /2} structure) This alkyl group and the other R is an aryl group), an alkylhydrogensiloxane unit (a bifunctional siloxane unit in which one R is an alkyl group and the other R is hydrogen in the R ₂ SiO _2/2 structure) and arylhydrogen At least one unit selected from the group consisting of a siloxane unit (a bifunctional siloxane unit in which one R is hydrogen and the other R is an aryl group in the R ₂ SiO _{2 /2} structure) may be applied.

Suitable D units include, among others, a dialkylsiloxane unit (a bifunctional siloxane unit in which R is all alkyl groups in the R ₂ SiO _{2 /2} structure) and/or an alkylhydrogensiloxane unit (one R in the R ₂ SiO _{2 /2} structure) A difunctional siloxane unit in which this alkyl group and other R is hydrogen) can be exemplified.

As M units at both ends of the chain structure consisting of D units in the structure of the straight-chain polyorganosiloxane, for example, a hydrogen dialkylsiloxane unit (R ₃ SiO _1/2 in _the structure, one of R is hydrogen, and the rest monofunctional siloxane units in which two are alkyl groups) and/or trialkylsiloxane units (monofunctional siloxane units in which R is all alkyl groups in _the R ₃ SiO _1/2 structure) and the like may be exemplified. For example, as the M unit in the case of a structure in which both ends are terminated with silicon atom-bonded hydrogen, a hydrogendialkyl siloxane unit may be used.

For example, the hydrogen polyorganosiloxane component may include at least one selected from the group consisting of a compound of Formula 3 and a compound of Formula 4 below. That is, as a curing agent, the compound of Formula 3 below, the compound of Formula 4 below, or a mixture of the compounds of Formulas 3 and 4 below may be applied.

[Formula 3]

In Formula 3, R ₄ is an alkyl group, p is a number within the range of 5 to 100, and q is a number within the range of 5 to 100. In another example, p and q are each independently 10 or more, 15 or more, 20 or more, 25 or more, 30 or more, or 35 or more, 95 or less, 90 or less, 85 or less, 80 or less, 75 or less, 70 or less, 65 or less , 60 or less, 55 or less, 50 or less, 45 or less, or 40 or less.

[Formula 4]

In Formula 4, R ₃ is an alkyl group, and m is a number within the range of 5 to 1500. In another example, m may be 10 or more, 15 or more, 20 or more, 25 or more, 30 or more, or 35 or more, or 1400 or less, 1300 or less, 1200 or less, 1100 or less, 1000 or less, or 900 or less.

The hydrogen polyorganosiloxane represented by Formula 3 is a hydrogen polyorganosiloxane having a silicon atom-bonded hydrogen in a side chain. In Formula 3, when the dialkylsiloxane unit (R ₃ R ₈ SiO _{2 /2} ) and the hydrogenalkylsiloxane unit (R ₄ HSiO _{2 / 2} ) are present at the same time, both units are present in the same form as the block copolymer. However, this is for convenience of description, and in actual polyorganosiloxane, the two units may exist in the form of a main chain of a random copolymer, a block copolymer or a gradient copolymer when present at the same time.

The hydrogen polyorganosiloxane represented by Formula 4 is a hydrogen polyorganosiloxane having silicon atom-bonded hydrogens at both ends. The compound of Formula 4 may function as a chain extender.

By using the curing agent as described above, the viscosity of the resin composition can be maintained at an appropriate level, and the curing reaction (addition reaction) is also controlled at an appropriate level, which is advantageous in securing the desired hardness after sufficient curing.

In the curing agent having the above structure, the hydrogen polyorganosiloxane component may include silicon atom-bonded hydrogen in an amount of 0.1 to 30 g/mol. In another example, the hydrogen polyorganosiloxane component contains silicon atom-bonded hydrogen of 0.2 g/mol or more, 0.3 g/mol or more, 0.4 g/mol or more, 0.5 g/mol or more, 0.6 g/mol or more, 0.7 g/mol or more. , 0.8 g/mol or more, 0.9 g/mol or more, or 1.0 g/mol or more, and may be included in 25 mol/g or less, 20 g/mol or less, 15 g/mol or less, or 10 g/mol or less.

In the hydrogen polyorganosiloxane, a ratio of the number of moles of hydrogen (H) based on the number of moles of all silicon atoms (Si) may be in the range of 0.01 to 3. The ratio (H / Si) is 0.05 or more, 0.1 or more, 0.15 or more, 0.2 or more, 0.25 or more, 0.3 or more, 0.35 or more, 0.4 or more, 0.45 or more, 0.5 or more, 0.55 or more, 0.6 or more, 0.7 or more, 0.8 or more, 0.9 or more, 1.0 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 2.8 or less, 2.6 or less, 2.4 or less, 2.2 or less, 2.0 or less, 1.8 It may be less than or about 1.6 or less. For example, each of the compounds of Formulas 3 and 4 may satisfy the H/Si ratio within the above range.

For example, when the hydrogen polyorganosiloxane component includes both the compound of Formula 3 and the compound of Formula 4, present in the compound of Formula 3 based on the number of moles (H4) of silicon-bonded hydrogen atoms present in Formula 4 The ratio of the number of moles (H3) of silicon-bonded hydrogen atoms (H3/H4) may be in the range of 1 to 10. In another example, the ratio (H3/H4) may be about 1.5 or more, 2 or more, 2.5 or more, 3 or more, or 3.5 or more, or 9 or less, 8 or less, 7 or less, 6 or less, 5 or less, or 4 or less.

The hydrogen polyorganosiloxane may be used in an amount of 10 to 300 parts by weight based on 100 parts by weight of the alkenyl group-containing polyorganosiloxane. In another example, the ratio is 20 parts by weight or more, 30 parts by weight or more, 40 parts by weight or more, 50 parts by weight or more, 60 parts by weight or more, 70 parts by weight or more, 80 parts by weight or more, or 90 parts by weight or more, or 290 parts by weight or more. or less, 280 parts by weight or less, 270 parts by weight or less, 260 parts by weight or less, 250 parts by weight or less, 240 parts by weight or less, 230 parts by weight or less, 220 parts by weight or less, 210 parts by weight or less, 200 parts by weight or less, 190 parts by weight or less The amount may be 180 parts by weight or less, 170 parts by weight or less, 160 parts by weight or less, 150 parts by weight or less, 140 parts by weight or less, 130 parts by weight or less, 120 parts by weight or less, or 110 parts by weight or less.

When the compound of Formula 3 and the compound of Formula 4 are simultaneously applied as a curing agent, a weight ratio between them (Formula 3/Formula 4) may be, for example, about 1 to 10. The ratio (Formula 3/Formula 4) is, in another example, 1.5 or more, 2 or more, 2.5 or more, 3 or more, or 3.5 or more, or about 9 or less, about 8 or less, about 7 or less, about 6 or less, about 5 or less, or It may be around 5.5 or less.

In one example, the resin composition prepared according to the manufacturing method of the present application may have a predetermined hardness at room temperature after curing. At this time, it is preferable that the cured layer of the resin composition exhibits appropriate hardness. For example, if the hardness of the hardened layer is too high, reliability may be adversely affected because the hardened layer has a brittle characteristic. Considering this point, it is possible to secure impact resistance and vibration resistance by adjusting the hardness of the hardened layer, and to ensure durability of the product. The hardened layer may have, for example, a hardness of 50 or more, 55 or more, 60 or more, 65 or more, or 70 or more, and 90 or less, 85 or less, 80 or less, or 75 or less in shore OO type. The hardness in the above range can be controlled by the content of the filler and curing agent in the resin composition.

The resin composition prepared according to the manufacturing method of the present application may be applied to various uses requiring a heat dissipation material, and the scope of the use is not particularly limited. For example, as a battery-related technology, the silicone resin composition may be applied as a heat dissipation material such as a battery module or a battery pack or a heat dissipation material of an On Board Charger (OBC) for a vehicle. Accordingly, the present application also relates to a battery module, battery pack, or on-board charger (OBC) including the resin composition or a cured product thereof as a heat dissipation material. In the battery module, battery pack, or on-board charger, the application location or application method of the resin composition or the cured product is not particularly limited, and a known method may be applied. In addition, the resin composition of the present application is not limited to the above use, and can be effectively applied to various uses requiring excellent heat dissipation properties, storage stability and adhesion.

In addition, the cured product of the resin composition prepared according to the manufacturing method of the present application may be used in electronic equipment or devices. The type of electronic equipment or device is not particularly limited, and for example, an AVN (audio video navigation) for a vehicle or an OBC (On Board Charger) module for an electric vehicle, an LED module, or an IC chip and a computer or mobile device including the same are exemplified. can

The cured product of the resin composition may dissipate heat within the equipment or device, and may provide durability and insulation against impact.

In the present application, the surface treatment of the filler is performed in-situ, so that the process is simple, the cost is reduced, there is no environmental pollution problem, and the long-term storage stability of the resin composition is ensured due to the small change in physical properties over time. can provide a manufacturing method.

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

1. Viscosity

The viscosity of the main agent, curing agent, or resin composition was measured using an Advanced Rheometic Expansion System (manufactured by Brookfield, DV3T Rheometer, CPA-52Z spindle). The temperature condition was set to room temperature (about 25° C.), and the gap was set to 5 mm. The viscosity was measured while changing the shear rate from 0.1/s to 10.0/s. Unless specifically stated otherwise, viscosities referred to herein are values at a shear rate of 1/s.

2. Hardness

The main and curing agent compositions prepared in Examples or Comparative Examples were mixed in a volume ratio of 1:1, and after curing in a film form having a thickness of about 5 mm, the hardness of the film surface was measured according to ASTM D 2240 standard. . The curing was performed by maintaining the mixture at room temperature for about 24 hours. For hardness measurement, an ASKER Durometer instrument was used. The initial hardness was measured by applying a load of about 1.5 kg to the surface of the sample in a flat state, and the hardness was evaluated by confirming the measured value as a stabilized value after 15 seconds. Shore OO hardness was measured.

Example One

The viscosity is about 50 cP, and 0.24 g of dodecyltrimethoxysilane was added to 19.8 g of a polyorganosiloxane component (manufacturer: AB specialty silicones, trade name: VS50) containing the polyorganosiloxane of Formula A, and mixed. . The dodecyltriethoxysilane was included in an amount of 1.2 parts by weight based on 100 parts by weight of the polyorganosiloxane component of Formula A.

Next, a filler mixture in which aluminum hydroxide (AH1) having a D50 particle diameter of about 50 μm and aluminum hydroxide (AH2) having a D50 particle diameter of about 1 μm is mixed in a weight ratio of 7:3 (AH1:AH2) is added to the mixture to prepare a mixture.

Viscosity is a value at a shear rate of 1/s measured according to the method for measuring viscosity of the composition described above.

The D50 particle size is the particle diameter (median diameter) at 50% cumulative by volume of the particle size distribution, and the particle size distribution is obtained based on the volume, and the particle at the point where the cumulative value becomes 50% in the cumulative curve with 100% of the total volume. is the diameter The D50 particle size was measured using a MASTERSIZER 3000 equipment manufactured by Marven in accordance with ISO-13320. Ethanol was used as a solvent for measurement.

At the time of mixing, the volume ratio (polyorganosiloxane component: filler) of the polyorganosiloxane component including the filler and the polyorganosiloxane of Formula A was about 27:73. In addition, the dodecyltriethoxysilane was added in a ratio of 0.17 parts by weight based on 100 parts by weight of the filler.

The mixture to which the filler was added was heat-treated in an oven at 80° C. for 1 hour and then cooled at room temperature for 30 minutes to prepare a primary composition.

Platinum catalyst (1,3-divinyl-1,1,3,3-tetramethyl-disiloxane-platinum(0)-complex) in the first composition was mixed in a weight ratio of 1:0.001 (first composition: catalyst) A subject composition was prepared.

In addition, 17.72 g of a polyorganosiloxane component containing the polyorganosiloxane of Formula A in the first composition, and 2.28 g of a polyorganosiloxane component containing a polyorganosiloxane of the following Formula B (trade name: FD5020, manufacturer: Yuchang FC) was added to prepare a curing agent composition. The mixing ratio of the curing agent composition was 7:77:1 (primary composition: polyorganosiloxane component containing polyorganosiloxane of formula A: polyorganosiloxane component containing polyorganosiloxane of formula B) was mixed in a weight ratio of .

As for the main agent and curing agent composition, each component is put into a paste mixer, and the heat generated after mixing and dispersing at 600 rpm and 500 rpm for rotation for 3 minutes is checked, It was prepared by defoaming for 4 minutes at 200 rpm rotation.

[Formula A]

In the formula (A), n is a number on the order of 34.

[Formula B]

In Formula B, p is a number of about 38, and q is a number of about 8.16.

Example 2

A main agent and a curing agent composition were prepared in the same manner as in Example 1, except that 0.8 parts by weight of dodecyltriethoxysilane was added relative to 100 parts by weight of the filler during the preparation of the primary composition.

Example 3

In the same manner as in Example 1, the main and A curing agent composition was prepared.

Example 4

In the same manner as in Example 2, the main and A curing agent composition was prepared.

comparative example One

First, a filler in which aluminum hydroxide (AH1) having a D50 particle diameter of about 50 μm and aluminum hydroxide (AH2) having a D50 particle diameter of about 1 μm in a weight ratio of 7:3 (AH1:AH2) is mixed with dodecyltriethoxy Surface-treated with silane to prepare a surface-treated filler.

The surface treatment is performed by mixing the dodecyltriethoxysilane and the filler in a weight ratio of 2:100 (dodecyltriethoxysilane:filler) in ethanol as a solvent, and then maintaining the temperature of the mixture at about 60°C, The reaction was carried out for 1 hour.

Then, 19.8 g of a polyorganosiloxane component comprising the polyorganosiloxane of Formula A of Example 1, 98 g of the surface-treated filler, and a platinum catalyst (1,3-divinyl-1,1,3,3-tetramethyl-disiloxane -platinum(0)-complex) 0.2g was added to prepare a main composition. In the above, the volume ratio of the filler to the polyorganosiloxane component (polyorganosiloxane component: filler) was about 27:73.

17.72 g of the polyorganosiloxane component comprising the polyorganosiloxane of formula A of Example 1 above, 2.28 g of the polyorganosiloxane component comprising the polyorganosiloxane of formula B above, and the same surface treatment as applied in the preparation of the subject composition The fillers were mixed to prepare a curing agent composition. In the above, the filler was such that the volume ratio (polyorganosiloxane component: filler) with the total polyorganosiloxane component in the curing agent composition was about 27:73.

The main agent and curing agent composition, each component is put in a paste mixer, and after mixing and dispersing for about 3 minutes at 600 rpm and 500 rpm in revolution, check the heat generated after dispersion, and revolution in a vacuum at 600 rpm, It was prepared by defoaming for 4 minutes at 200 rpm rotation.

comparative example 2

A main agent and a curing agent composition were prepared in the same manner as in Comparative Example 1 using a filler that was not surface-treated.

For the Examples and Comparative Examples, the viscosity immediately after preparation of the resin composition and the viscosity after maintaining the resin composition for 12 weeks were measured, and the hardness immediately after preparation of the resin composition and the hardness after maintaining the resin composition for 12 weeks were measured to determine the lapse of physical properties The degree of change was confirmed.

Viscosity
(Pa·s@1/s) Viscosity after 12 weeks
(Pa·s@1/s) Hardness
(shore OO) hardness after 12 weeks
(shore OO) Example 1 200 300 73 53 Example 2 200 200 73 73 Example 3 200 300 73 70 Example 4 200 190 73 72 Comparative Example 1 200 310 76 30 Comparative Example 2 200 310 73 57

Referring to Table 1, the resin composition of Examples did not show significant changes when comparing the viscosity and hardness immediately after preparation with the viscosity and hardness after 12 weeks, whereas the resin composition of Comparative Example was prepared after 12 weeks compared to the viscosity and hardness immediately after preparation. Viscosity and hardness were greatly changed.

In addition, among the resin compositions of Examples, the resin compositions of Examples 2 and 4, in which dodecyltriethoxysilane was added in an amount of 0.8 parts by weight compared to the filler, showed little change in physical properties over time, and after heat treatment in an oven at 80° C. for 20 hours, at room temperature The resin composition of Example 2, which was subjected to the cooling step, maintained the same viscosity and hardness. Through this, it was confirmed that dodecyltriethoxysilane is added in an amount of 0.8 parts by weight or more and heat treatment is performed after mixing the filler to ensure long-term storage stability of the composition.

In addition, although the resin compositions of Examples 1 and 3 have similar decreases in viscosity and hardness to those of Comparative Examples, the compositions can be prepared by a much simpler process compared to Comparative Examples, and there is no need to use a solvent. There is an advantage in that it is possible to reduce costs and solvent drying costs, and to prevent environmental pollution problems.

Claims (20)

A method for producing a resin composition comprising maintaining a mixture of an alkenyl group-containing polyorganosiloxane component, an alkylsilane compound, and a filler at a temperature within the range of 15°C to 200°C. The method of claim 1 , further comprising: a first step of mixing an alkenyl group-containing polyorganosiloxane component and an alkylsilane compound; and a second step of mixing the mixture and the filler of the first step. The method for producing a resin composition according to claim 1, wherein the alkenyl group-containing polyorganosiloxane component has a room temperature viscosity in the range of 20 to 1000 cP. The method according to claim 1, wherein the alkenyl group-containing polyorganosiloxane component comprises a polyorganosiloxane represented by the following formula (1):
[Formula 1]

In Formula 1, R ₅ and R ₆ are each independently an alkenyl group, an alkyl group, or an aryl group, wherein at least one of R ₅ and R ₆ is an alkenyl group, and n is a number within the range of 5 to 100. The method according to claim 1, wherein the alkenyl group-containing polyorganosiloxane component contains an alkenyl group in a ratio of 0.05 to 5 mmol/g. The method according to claim 1, wherein the alkylsilane compound is represented by the following formula (2):
[Formula 2]

In Formula 2, R ₁ to R ₄ are each independently a hydrogen atom, an alkyl group having 6 to 15 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms, and at least one of R ₁ to R ₄ is an alkyl group having 6 to 15 carbon atoms. The method of claim 1, wherein the filler comprises at least one selected from the group consisting of aluminum hydroxide, magnesium hydroxide, calcium hydroxide and hydromagnesite. The method of claim 1, wherein the filler includes a first filler having an average particle diameter of 20 μm or more and a second filler having an average particle diameter of less than 20 μm. The method according to claim 8, wherein the ratio (D1/D2) of the average particle diameter (D1) of the first filler to the average particle diameter (D2) of the second filler is in the range of 2 to 100. The method according to claim 8, wherein the ratio (W1/W2) of the used weight (W1) of the first filler to the used weight (W2) of the second filler is in the range of 0.5 to 100. The resin composition according to claim 1, wherein the mixture contains 0.04 to 3 parts by weight of the alkylsilane compound based on 100 parts by weight of the alkenyl group-containing polyorganosiloxane component, and 0.8 to 2 parts by weight based on 100 parts by weight of the filler component. manufacturing method. The method of claim 1, wherein the filler component is included in an amount of 50% by volume or more based on the total volume of the resin composition. The method for producing a resin composition according to claim 1, wherein the mixture is maintained at a temperature within the range of 15°C to 200°C for 10 minutes to 20 hours. The method for producing a resin composition according to claim 1, comprising maintaining the mixture at a temperature of 75° C. or higher and cooling the mixture after the holding step. The method of claim 1, further comprising the step of mixing the mixture maintained at a temperature within the range of 15°C to 200°C with the catalyst. The method of claim 1, further comprising mixing the mixture maintained at a temperature in the range of 15°C to 200°C with a hydrogen polyorganosiloxane component. The method according to claim 16, wherein the hydrogen polyorganosiloxane component comprises at least one selected from the group consisting of a compound of the following formula (3) and a compound of the following formula (4):
[Formula 3]

In Formula 3, R ₄ is an alkyl group, p is a number within the range of 5 to 100, and q is a number within the range of 5 to 100:
[Formula 4]

In Formula 4, R ₃ is an alkyl group, and m is a number within the range of 5 to 1500. The method for producing a resin composition according to claim 16, wherein the hydrogen polyorganosiloxane component contains silicon atom-bonded hydrogen atoms in a ratio of 0.1 to 30 mmol/g. 19. The compound of claim 18, wherein the hydrogen polyorganosiloxane component comprises a compound of Formula 3 and a compound of Formula 4, and the compound of Formula 3 based on the number of moles (H4) of silicon-bonded hydrogen atoms present in the compound of Formula 4 The ratio (H3/H4) of the number of moles (H3) of silicon-bonded hydrogen atoms present in the method for producing a resin composition is in the range of 1 to 10. The method according to claim 16, wherein the hydrogen polyorganosiloxane is blended in an amount of 5 to 300 parts by weight based on 100 parts by weight of the alkenyl group-containing polyorganosiloxane.