KR102437160B1 - Method for evaluating flowability of resin composition in equipment - Google Patents

Abstract

The present invention relates to a method for determining the flowability of a resin composition in equipment, the method comprising: discharging the resin composition using an injection equipment; acquiring at least one of a discharge volume, a discharge weight, and a solidification hardness of the resin composition discharged from the injection equipment for a unit time; and determining the flowability based on at least one of the discharge volume, the discharge weight, and the solidification hardness.

Description

Method for evaluating flowability of resin composition in equipment

The present invention relates to a method for determining the flowability of a resin composition (adhesive) in a filling/injecting equipment.

The heat dissipation adhesive is the main component that enters the pure electric vehicle and gives cooling/fixing performance. For example, a heat dissipation adhesive is a two-component type adhesive in which a polyol main agent (blue in Fig. 1) and an isocyanate curing agent (white in Fig. 1) meet and cure at room temperature. of fillers (such as alumina). Adhesives with more than 90% filler require high pressure (subject: 90 bar, hardener: 100 bar or more) when moving in the order of <adhesive can → pipe → mixer (cartridge) → injection module> in the filling/injecting equipment . The dispensing process under such high pipe pressure has a problem in that the inorganic filler solidifies (liquid phase/inorganic filler separation phenomenon) at the seam of the equipment.

In order for the adhesive to have high thermal conductivity, the filler must be highly filled, and in order for the adhesive applied to the module to have productivity, the dispensing processability must be excellent. .

Accordingly, it is an object of the present invention to provide a method for determining the flowability of an adhesive in a filling/injecting equipment with respect to the development of an excellent adhesive.

The present invention comprises the steps of discharging a resin composition using an injection device in order to achieve the above object; acquiring at least one of a discharge volume, a discharge weight, and a solidification hardness of the resin composition discharged from the injection equipment for a unit time; and determining the flowability based on at least one of the discharge volume, the discharge weight, and the solidification hardness.

In the present invention, the resin composition may be an adhesive composition.

In the present invention, the resin composition may be a heat dissipation adhesive composition comprising 50% by weight or more of a filler.

The method according to the present invention comprises the steps of injecting a resin composition into an injector prior to discharging; and mounting the injector to the holder and placing the container under the injector.

In the discharging step according to the present invention, the discharging pressure may be 1 to 20 bar, and the discharging time may be 1 to 50 seconds.

After measuring the weight and temperature of the resin composition discharged in the present invention, the discharge volume can be calculated.

In the present invention, in order to determine the flowability, after setting a specific discharge volume at a specific discharge pressure and a specific discharge time as a reference, if it is less than the reference discharge volume, it is determined that the flowability is bad, and if it exceeds the reference discharge volume, the flowability is good can be judged as

For flowability determination in the present invention, after setting a specific solidification hardness as a reference at a specific discharge pressure and a specific discharge time, if it is less than the reference solidification hardness, the flowability is judged to be good, and if the reference solidification hardness is exceeded, the flowability is bad can be judged as

The present invention is useful for screening adhesives with excellent flowability and equipment injectability by providing a tool for testing the flowability of the adhesive prior to testing the filling/injection equipment.

1 shows a flow test process for determining the flowability of a heat dissipation adhesive according to the present invention.

Hereinafter, the present invention will be described in detail.

The present invention relates to a tool for determining the flowability of an adhesive within a filling/injecting equipment. Using these tools, we want to develop an adhesive that 1) has excellent dispensing processability and 2) has excellent filling/injection even at low pipe pressure. Low pipe pressure is important because it can prevent liquid/inorganic filler separation (solidification) at the leakage present in the dispensing equipment.

As such, the present invention provides a test tool for determining the equipment flowability of the heat-dissipating adhesive prior to the filling/injecting equipment test, specifically, for example, 6 bar, By comparing the amount of adhesive discharged for 15 seconds, it is intended to screen adhesives with excellent flowability and equipment injection properties. Previously, there was no pressure-dependent injection fairness prediction tool.

resin composition

First, the resin composition to be determined (measured) for flowability is not particularly limited, and can be applied to any resin composition that can confirm flowability/rheology, and may preferably be an adhesive composition. Examples of the adhesive composition include a urethane-based resin composition, a silicone-based resin composition, an epoxy-based resin composition, and a gap filler composition. For example, the resin composition is a urethane-based resin composition, and may be a two-part type adhesive composition including a polyol main agent and an isocyanate curing agent. In particular, the resin composition may be a heat dissipation adhesive composition containing 50% by weight or more of the filler.

The resin composition may be, for example, a composition injected into a case of a battery module and used to contact one or more battery cells present in the battery module to fix the battery cells within the case of the module.

As the resin composition, a two-part urethane-based composition may be used. Two-component urethane refers to a polyurethane formed by mixing an isocyanate-based compound and a polyol-based compound, and is distinguished from a one-component polyurethane having a urethane group in a single composition.

In the case of a two-component polyurethane, a main agent including a polyol and the like and a curing agent including an isocyanate may be reacted at room temperature to be cured. That is, the resin composition may be a room temperature curing type. "Room temperature" is a state that is not particularly heated or reduced, and is any one temperature within the range of 10°C to 30°C, for example, 15°C or more, 18°C or more, 20°C or more, or 23°C or more, and 27°C or less. can mean the temperature of The curing reaction may be assisted by a catalyst such as, for example, dibutyltin dilaurate (DBTDL). Accordingly, the two-part urethane-based composition may include a physical mixture of the main component (polyol) and the curing agent component (isocyanate), and/or may include a reactant (cured product) of the main component and the curing agent component.

The two-part urethane-based composition may include a main composition (or a main part) containing at least a polyol resin, and a curing agent composition (or a curing agent part) including at least a polyisocyanate. Accordingly, the cured product of the resin composition may include both polyol-derived units and polyisocyanate-derived units. In this case, the polyol-derived unit may be a unit formed by the urethane reaction of the polyol with the polyisocyanate, and the polyisocyanate-derived unit may be a unit formed by the urethane reaction of the polyisocyanate with the polyol.

In addition, the resin composition may include a filler. For example, in order to secure thixotropic properties and/or to secure heat dissipation (thermal conductivity) within a battery module or battery pack, an excess of filler may be included in the resin composition as needed in the process.

The polyol resin and the isocyanate component included in the urethane-based composition may have a glass transition temperature (Tg) of less than 0° C. after curing. "Glass transition temperature after curing" refers to the NCO peak reference conversion rate in the vicinity of 2250 cm ^-1 confirmed by FT-IR analysis based on the 24-hour curing state at room temperature and 30 to 70% relative humidity conditions. It may be a glass transition temperature measured for a cured product of 80% or more.

If the glass transition temperature range is satisfied, brittle characteristics can be secured in a relatively short time even at a low temperature at which a battery module or battery pack can be used, and accordingly, impact resistance or vibration resistance can be guaranteed. can On the other hand, when the above-mentioned range is not satisfied, there is a possibility that the tacky of the cured product is too high or the thermal stability is lowered. The lower limit of the glass transition temperature of the urethane-based composition after curing may be -70°C or more, -60°C or more, -50°C or more, -40°C or more, or -30°C or more, and the upper limit is -5°C or less, -10°C or more. or less, -15°C or less, or -20°C or less.

As the polyol resin included in the main composition, an ester-based polyol resin may be used. When the ester-based polyol is used, it is advantageous to secure excellent adhesion and adhesion reliability in the battery module after curing the resin composition. As the ester-based polyol, for example, a carboxylic acid-based polyol or a caprolactone-based polyol may be used. The carboxylic acid-based polyol may be formed by reacting a component containing a carboxylic acid and a polyol (eg, a diol or a triol), and the caprolactone-based polyol may be formed by reacting a component containing caprolactone and a polyol. can In this case, the carboxylic acid may be a dicarboxylic acid.

The polyol may be, for example, a polyol represented by the following formula (1) or (2).

[Formula 1]

[Formula 2]

In Formulas 1 and 2, X is a unit derived from a carboxylic acid, and Y is a unit derived from a polyol. The unit derived from the polyol may be, for example, a triol unit or a diol unit. Also, n and m may be arbitrary numbers. The carboxylic acid-derived unit is a unit formed by reacting a carboxylic acid with a polyol, and the polyol-derived unit is a unit formed by a polyol reacting with a carboxylic acid or caprolactone. That is, when the hydroxy group of the polyol and the carboxyl group of the carboxylic acid react, an ester bond is formed as water (HO ₂ ) molecules are desorbed by the condensation reaction. After that, it means a portion excluding the ester bond portion. In addition, Y is a part excluding the ester bond after the polyol forms an ester bond by a condensation reaction. The ester bond is shown in formula (1).

In addition, Y in Formula 2 also represents a portion excluding the ester bond after the polyol forms an ester bond with caprolactone. The ester bond is shown in formula (2). On the other hand, when the polyol-derived unit of Y in the formula is a unit derived from a polyol including three or more hydroxyl groups, such as a triol unit, a branched structure may be implemented in the Y portion in the formula structure.

In Formula 1, the type of the carboxylic acid-derived unit of X is not particularly limited, but in order to secure desired physical properties, a phthalic acid unit, an isophthalic acid unit, a terephthalic acid unit, a trimellitic acid unit, a tetrahydrophthalic acid unit, and a hexahydrophthalic acid unit , tetrachlorophthalic acid unit, oxalic acid unit, adipic acid unit, azelaic acid unit, sebacic acid unit, succinic acid unit, malic acid unit, glataric acid unit, malonic acid unit, pimelic acid unit, suberic acid unit, 2,2- It may be at least one selected from the group consisting of dimethylsuccinic acid unit, 3,3-dimethylglutaric acid unit, 2,2-dimethylglutaric acid unit, maleic acid unit, fumaric acid unit, itaconic acid unit and fatty acid unit. In consideration of the glass transition temperature of the above-described low range, an aliphatic carboxylic acid-derived unit may be preferable rather than an aromatic carboxylic acid-derived unit.

In Formulas 1 and 2, the type of the polyol-derived unit of Y is not particularly limited, but in order to secure desired physical properties, an ethylene glycol unit, a diethylene glycol unit, a propylene glycol unit, a 1,2-butylene glycol unit, 2, 3-butylene glycol unit, 1,3-propanediol unit, 1,3-butanediol unit, 1,4-butanediol unit, 1,6-hexanediol unit, neopentyl glycol unit, 1,2-ethylhexyldiol unit , 1,5-pentanediol unit, 1,9-nonanediol unit, 1,10-decanediol unit, 1,3-cyclohexanedimethanol unit, 1,4-cyclohexanedimethanol unit, glycerin unit and trimethylol It may be any one or more selected from the group consisting of propane units.

In Formula 1, n is an arbitrary number, and the range may be selected in consideration of desired physical properties of the resin composition or a resin layer that is a cured product thereof. For example, n can be 2 to 10 or 2 to 5. In Formula 2, m is an arbitrary number, and the range may be selected in consideration of desired physical properties of the resin composition or a resin layer that is a cured product thereof. For example, m can be 1 to 10 or 1 to 5. When n and m in Chemical Formulas 1 and 2 are out of the above-described ranges, the crystallinity expression of the polyol may be strengthened, thereby adversely affecting the injection processability of the composition.

The molecular weight of the polyol may be adjusted in consideration of low-viscosity characteristics, durability, or adhesiveness, which will be described later, and, for example, may be in the range of 300 to 2,000. Unless otherwise specified, in the present specification, "molecular weight" may be a weight average molecular weight (Mw) measured using Gel Permeation Chromatograph (GPC). When out of the above range, the reliability of the resin layer after curing may be poor or problems related to volatile components may occur.

The polyisocyanate may mean a compound containing two or more isocyanate groups. The type of polyisocyanate included in the curing agent composition is not particularly limited, but a non-aromatic isocyanate compound that does not contain an aromatic group may be used to secure desired physical properties. That is, it may be advantageous to use an aliphatic or cycloaliphatic series. When the aromatic polyisocyanate is used, the reaction rate is too fast and the glass transition temperature of the cured product may be high, so it may be difficult to secure processability and physical properties suitable for the use of the composition of the present invention.

For example, an aliphatic or aliphatic cyclic polyisocyanate or a modified product thereof may be used. Specifically, aliphatic polyisocyanates such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate, norbornane diisocyanate methyl, ethylene diisocyanate, propylene diisocyanate or tetramethylene diisocyanate; aliphatic cyclic polyisocyanates such as transcyclohexane-1,4-diisocyanate, isophorone diisocyanate, bis(isocyanatemethyl)cyclohexane diisocyanate or dicyclohexylmethane diisocyanate; or any one or more of these; carbodiimide-modified polyisocyanate or isocyanurate-modified polyisocyanate; etc. may be used. Also, mixtures of two or more of the above-mentioned compounds may be used.

The ratio of the polyol-derived resin component and the polyisocyanate-derived resin component in the resin composition is not particularly limited, and may be appropriately adjusted to enable a urethane reaction between them. The mixing ratio of the main agent (or composition) and the curing agent (or composition) is 2:8 to 8:2 by weight or volume ratio, preferably 3:7 to 7:3, more preferably 4:6 to 6: 4, most preferably about 5:5 (ie about 1:1).

As described above, in order to secure heat dissipation (thermal conductivity) or to secure thixotropy as needed in the process, an excessive amount of filler may be included in the composition. fairness when injecting the composition into the case of Accordingly, it is necessary to have sufficient low-viscosity properties that do not interfere with processability while including an excess of filler. In addition, if only low viscosity is shown, proper thixotropy is required because it is also difficult to secure fairness, exhibits excellent adhesion while curing, and curing itself may be required to proceed at room temperature. In addition, although ester-based polyols are advantageous in securing adhesion after curing, they are highly crystalline at room temperature, so there is a high possibility of becoming a wax state at room temperature, and there is a disadvantage in securing proper injection processability due to an increase in viscosity. Even if the viscosity is lowered through melting, due to the crystallinity that occurs naturally during storage, the viscosity increase due to crystallization occurs in the injection or application process of the composition, which may be followed after mixing with the filler. and, as a result, fairness may be reduced.

In consideration of this point, the ester-based polyol used in the present invention may satisfy the following characteristics. The ester-based polyol may be amorphous or a polyol having sufficiently low crystallinity. "Amorphous" means a case in which the crystallization temperature (Tc) and the melting temperature (Tm) are not observed in differential scanning calorimetry (DSC) analysis. At this time, the DSC analysis can be performed within the range of -80 to 60 °C at a rate of 10 °C / min, for example, after raising the temperature from 25 °C to 50 °C at a rate of 10 °C / min, the temperature is reduced to -70 °C and raising the temperature to 50 °C again. In addition, "sufficiently low crystallinity" means that the melting point or melting temperature (Tm) observed in DSC analysis is less than 15 °C, and is 10 °C or less, 5 °C or less, 0 °C or less, -5 °C or less, -10 °C or less. or less, or about -20°C or less. At this time, the lower limit of the melting point is not particularly limited, but, for example, the melting point may be -80°C or more, -75°C or more, or -70°C or more. When the polyol is crystalline or does not satisfy the above-mentioned melting point range, if the crystallinity (at room temperature) is strong, the difference in viscosity according to the temperature tends to be large, so in the process of mixing the filler and the resin, the dispersion of the filler and the final mixture The viscosity may be adversely affected, and fairness may be deteriorated, and as a result, it may be difficult to satisfy the cold resistance, heat resistance and water resistance required in the adhesive composition for a battery module.

In addition, in order to secure the function required according to the use of the resin composition and its use, additives may be used. For example, the resin composition may include a predetermined filler in consideration of thermal conductivity, insulation, and heat resistance (TGA analysis) of the resin layer. The form or method in which a filler is contained in a resin composition is not restrict|limited in particular. For example, the filler may be used to form the urethane-based composition in a state previously included in the main composition and/or the curing agent composition. Alternatively, in the process of mixing the main composition and the curing agent composition, separately prepared fillers may be used in a manner in which they are mixed together.

The filler may be, for example, a thermally conductive filler. "Thermal conductive filler" may mean a material having a thermal conductivity of 1 W/mK or more, 5 W/mK or more, 10 W/mK or more, or 15 W/mK or more. Specifically, the thermal conductivity of the thermally conductive filler may be 400 W/mK or less, 350 W/mK or less, or 300 W/mK or less. The thermal conductivity of the filler may be measured according to a known method, and in this case, the thermal conductivity of the filler may be measured by melting the filler and then making a specimen.

The type of the filler is not particularly limited, but may be an inorganic filler or a ceramic filler when considering thermal conductivity and insulation together, for example, alumina, aluminum nitride (AlN), boron nitride (BN), silicon nitride, Ceramic particles such as SiC or BeO may be used.

The form or ratio of the filler is not particularly limited, and the viscosity of the urethane-based composition, the possibility of sedimentation in the cured resin layer of the composition, desired thermal resistance or thermal conductivity, insulation, filling effect or dispersibility, etc. can In general, as the size of the filler increases, the viscosity of the composition including the same increases, and the possibility that the filler settles in the resin layer increases. Also, the smaller the size, the higher the thermal resistance tends to be. Therefore, in consideration of this point, a filler of an appropriate type and size may be selected, and if necessary, two or more types of fillers may be used together. In addition, it is advantageous to use a spherical filler in consideration of the amount to be filled, but a filler having a needle shape or a plate shape may also be used in consideration of network formation or conductivity.

The average particle diameter of the filler may be 0.001 μm to 80 μm. The lower limit of the average particle diameter of the filler may be, for example, 0.01 µm or more, 0.1 µm or more, 0.5 µm or more, 1 µm or more, 2 µm or more, 3 µm or more, 4 µm or more, 5 µm or more, or 6 µm or more. The upper limit of the average particle diameter of the filler is, for example, 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. The average particle diameter may be measured using a particle size analysis (PSA) equipment. For example, the average particle diameter may mean D(50), which is the particle size of the 50th rank, when ranking from 1 to 100 for particles by size.

In order to obtain excellent heat dissipation performance, it may be considered that the thermally conductive filler is used in a high content (high content). For example, the filler may be used within the range of 50 to 2,000 parts by weight, based on 100 parts by weight of the total resin component, that is, the sum of the contents of the ester-based polyol resin and polyisocyanate. In addition, the content of the filler may be used in excess of the total resin component. Specifically, 100 parts by weight or more, 150 parts by weight or more, 200 parts by weight or more, 250 parts by weight or more, 300 parts by weight or more, 350 parts by weight or more, 400 Part by weight or more, 500 parts by weight or more, 550 parts by weight or more, 600 parts by weight or more, or 650 parts by weight or more of the filler may be used. The filler may be dispensed in equal amounts into the subject composition and the curing agent composition. Based on weight %, the content of the filler is at least 50% or more, preferably 60% or more, more preferably 70% or more, most preferably 80% or more, based on the total weight of the main composition and/or curing agent composition. can The upper limit of the content may be, for example, 99%, 98%, 97%, 96%, 95%, 94%, 93%, 92%, 91% or 90%.

As such, when the thermally conductive filler is used in a high content, the viscosity of the main composition including the filler, the curing agent composition, or the composition including the same may increase. As described above, when the viscosity of the resin composition is too high, the injection processability is not good, and accordingly, the physical properties required for the resin layer may not be sufficiently implemented in the entire resin layer. In consideration of this, it is preferable to use a liquid or low-viscosity component capable of having sufficient flow as the resin component.

In this regard, each of the ester-based polyol resin and the polyisocyanate component may have a viscosity of 10,000 cP or less. Specifically, the resin component may have a viscosity of 8,000 cP or less, 6,000 cP or less, 4,000 cP or less, 2,000 cP or 1,000 CP or less. Preferably, the upper limit of the viscosity may be 900 cP or less, 800 cP or less, 700 cP or less, 600 cP or less, 500 cP or less, or 400 cP or less. Although not particularly limited, the lower limit of the viscosity of the resin component may be 50 cP or more or 100 cP or more. If the viscosity is too low, fairness may be good, but as the molecular weight of the raw material is lowered, the possibility of volatilization increases, and heat resistance/cold resistance, flame retardancy, and adhesion may be deteriorated. Viscosity can be measured at room temperature using, for example, a Brookfield LV type viscometer.

In addition to those described above, various types of fillers may be used. For example, in order to secure the insulating properties of the resin layer in which the resin composition is cured, the use of a carbon-based filler such as graphite may be considered. Also, fillers such as, for example, fumed silica, clay or calcium carbonate may be used. The form or content ratio of these fillers is not particularly limited, and may be selected in consideration of the viscosity of the resin composition, the possibility of sedimentation in the resin layer, thixotropy, insulation, filling effect or dispersibility, and the like.

In addition, the resin composition may contain a viscosity modifier, for example, a thixotropic agent, a diluent, a dispersant, a surface treating agent, or a coupler, for controlling the required viscosity, for example, for increasing or decreasing the viscosity, or for controlling the viscosity according to a shear force. It may further include a ring agent and the like.

The thixotropy imparting agent may adjust the viscosity according to the shear force of the resin composition so that the manufacturing process of the battery module can be effectively performed. As a thixotropic agent that can be used, fumed silica and the like can be exemplified.

Diluents or dispersants are usually used to lower the viscosity of the resin composition, and as long as they can exhibit the above-described action, various types of known in the art may be used without limitation.

The surface treatment agent is for surface treatment of the filler introduced into the resin layer, and as long as it can exhibit the above-described action, various types of known in the art may be used without limitation.

In the case of the coupling agent, for example, it can be used to improve the dispersibility of the thermally conductive filler such as alumina, and as long as it can exhibit the above-described action, various types of known in the art can be used without limitation.

In addition, the resin composition may further include a flame retardant or a flame retardant auxiliary agent. In this case, a known flame retardant may be used without any particular limitation, for example, a flame retardant in the form of a solid filler or a liquid flame retardant may be applied. Examples of the flame retardant include organic flame retardants such as melamine cyanurate and inorganic flame retardants such as magnesium hydroxide. When the amount of filler filled in the resin layer is large, a liquid type flame retardant material, for example, TEP (Triethyl phosphate) TCPP (tris (1,3-chloro-2-propyl) phosphate) may be used. In addition, a silane coupling agent capable of acting as a flame retardant synergist may be added.

The resin composition may include the composition as described above, and may be a solvent-based composition, an aqueous composition, or a solvent-free composition, but in consideration of the convenience of the manufacturing process, the non-solvent type may be appropriate.

The thermal conductivity of the resin composition may be, for example, 1.5 W/mK or more, 2 W/mK or more, 2.5 W/mK or more, 3 W/mK or more, 3.5 W/mK or more, or 4 W/mK or more. The upper limit of thermal conductivity is, for example, 50 W/mK or less, 45 W/mk or less, 40 W/mk or less, 35 W/mk or less, 30 W/mk or less, 25 W/mk or less, 20 W/mk or less, 15 W/mk or less, 10 W/mK or less, 5 W/mK or less, or 4.5 W/mK or less. Thermal conductivity may be measured using a known hot disk (hot disk) equipment, for example, may be measured according to ASTM D5470 standard or ISO 22007-2 standard. The thermal conductivity of the resin composition can be secured by appropriately adjusting the filler included in the composition and the content ratio thereof.

The viscosity of the resin composition may be, for example, 100,000 kcP or more, 150,000 kcP or more, or 200,000 kcP or more. The upper limit of the viscosity may be, for example, 500,000 kcP or less, 450,000 kcP or less, 400,000 kcP or less, or 350,000 kcP or less. Viscosity can be measured at room temperature using a Brookfield LV type viscometer.

The above-described resin composition may effectively fix the battery cell in the module case, and improve heat dissipation and manufacturing processability of the battery module.

Flow determination method

The method for determining the flowability of the resin composition according to the present invention comprises: discharging the resin composition using an injection device; acquiring at least one of a discharge volume, a discharge weight, and a solidification hardness of the resin composition discharged from the injection equipment for a unit time; and determining the flowability based on at least one of the discharge volume, the discharge weight, and the solidification hardness.

The resin composition to be judged in the present invention is not particularly limited, but, for example, an adhesive composition, in particular, a heat dissipating adhesive composition containing 50% by weight or more of a filler may be used.

As illustrated in FIG. 1 , the method according to the present invention includes the steps of injecting a resin composition into an injector prior to discharging; and mounting the injector to the holder and placing the container under the injector. In the case of a two-component type adhesive composition, mixing the main agent and the curing agent is not appropriate because it hardens in the flow test. Therefore, a separate flow test can be performed on each of the main agent and the curing agent without mixing. The subject (or composition) and curing agent (or composition) may be introduced via piping from their respective storage/storage containers (cans or tanks) into the injector (injection module).

The injector may use a conventional syringe (syringe), etc., and the shape and size thereof are not particularly limited. The amount of the resin composition added to the injector may be 10 to 500 g, preferably 30 to 300 g, more preferably 60 to 200 g, most preferably 80 to 150 g. The container is for receiving the discharged resin composition, and the structure and type thereof are not particularly limited, and, for example, a cup-shaped container such as a paper cup may be used.

The injector may be connected to the dispenser body through a tube or the like, and air of a specific pressure is supplied from the dispenser body, so that the resin composition accommodated in the injector may be discharged to the outside. The dispenser used in the present invention may be composed of, for example, a pump, a valve, a tank, a nozzle, a needle, a syringe, a pipe, a cartridge, a barrel and/or a controller, and the like. The dispensing method of the dispenser may be, for example, an air pulse method. The control method of the dispenser may be, for example, a microcomputer controlled electric and/or pneumatic method. The dispensing mode of the dispenser may be, for example, a time mode and/or a manual mode. The discharge pressure of the dispenser may be, for example, 0.03 to 50 MPa, and the discharge time may be, for example, 0.001 to 9999 seconds. The vacuum pressure of the dispenser may be, for example, -0.02 to 0 MPa (gauge pressure), and the time may be, for example, 0.001 to 9999 seconds. The supply air pressure of the dispenser may be, for example, 100 to 2000 kPa (1 to 20 bar).

In the discharging step, the discharging pressure (air pressure) may be, for example, 1 to 20 bar, preferably 2 to 15 bar, more preferably 3 to 10 bar, and most preferably 4 to 8 bar. The discharge time may be, for example, 1 to 50 seconds, preferably 3 to 40 seconds, more preferably 5 to 30 seconds, and most preferably 10 to 20 seconds.

The criterion for determining the flowability may be a discharge volume, a discharge weight, and/or a solidification hardness (maximum solidification force) of the resin composition. It can be determined that the greater the discharge volume and the discharge weight, the better the flowability, and conversely, the smaller the solidification hardness, the better the flowability. It can be interpreted that the greater the maximum solidification force, the more likely solidification occurs in the equipment.

For example, in order to determine the flowability, after setting a specific discharge volume at a specific discharge pressure and a specific discharge time as a reference, if it is less than the reference discharge volume, the flowability is judged to be bad, and if it exceeds the reference discharge volume, the flowability is can be considered good. Specifically, for example, under the conditions of a discharge pressure of 6 bar and a discharge time of 15 seconds, after setting the discharge volume as 10 ml, 9 ml, 8 ml, 7 ml or 6 ml as a reference, if the discharge volume is less than the standard discharge volume, the flowability is bad. It can be determined, and when it exceeds the reference discharge volume, it can be determined that the flowability is good. Of course, if the discharging pressure and discharging time are changed, the discharging volume serving as a reference may also be changed.

The discharge volume may be indirectly calculated through the measured values after measuring the weight and temperature of the discharged resin composition. Specifically, from the weight value of the discharged resin composition, the discharge volume may be calculated using a previously known or previously measured density (density at the measurement temperature) of the resin composition. In addition, for example, it is also possible to directly measure the discharge volume by receiving the discharged resin composition in a container marked with a scale.

In addition, in order to determine the flowability, after setting a specific solidification hardness as a reference at a specific discharge pressure and a specific discharge time, if it is less than the reference solidification hardness, the flowability is judged to be good, and if the reference solidification hardness is exceeded, the flowability is bad can judge Specifically, for example, under the conditions of a discharge pressure of 6 bar and a discharge time of 15 seconds, after setting the solidification hardness as 300 gf, 250 gf, 200 gf, 150 gf, 100 gf, or 50 gf as a reference, the flow is less than or equal to the reference solidification hardness It can be judged that the property is good, and when it exceeds the standard solidification hardness, it can be judged that the flowability is bad.

The solidification hardness is also called the maximum solidification force (max force), and specifically, when pressing the solid material of the resin composition at a constant speed of 0.3 mm/s, 0.3 seconds to 0.7 seconds have elapsed from when the solid material is pressed. It can be defined as the force (unit gf) applied to the pressing means. The solid material of the resin composition may mean a specimen cut out of the solid material generated through the solidification generator. The solidification generating device may include a syringe, a filter positioned in the syringe discharging part, a pressurizing means capable of pressing the composition filled in the syringe, and the like.

Examples and Comparative Examples

Heat Dissipation Adhesive Manufacturing

The main composition and the curing agent composition were prepared differently for each Example and Comparative Example as follows.

Commonly, alumina was used as the filler, and the content thereof was 88.6% by weight and 88.4% by weight as shown in Table 1 in the main composition and the curing agent composition, respectively, and alumina was divided into the main composition and the curing agent composition in equal amounts. did.

Also, in common, a predetermined amount of dibutyltin dilaurate (DBTDL) was used as a catalyst.

(1) Example 1 and Comparative Example 1

A predetermined amount of the caprolactone-based polyol represented by Formula 2 was used in the main composition.

(2) Example 2 and Comparative Example 2

A mixture of hexamethylene diisocyanate (HDI) and HDI trimer was used for the curing agent composition.

(3) Example 3 and Comparative Example 3

The same subject composition as Example 1 and Comparative Example 1 was used except that the viscosity was different.

(4) Example 4 and Comparative Example 4

The same curing agent composition as in Example 2 and Comparative Example 2 was used except that the viscosity was different.

flow test

A flow test of the prepared heat-dissipating adhesive was performed. The flow test was set up in the laboratory using a dispenser equipment from Musashi, Japan, and the heat dissipation adhesive was discharged to compare and judge the flowability.

First, 100-105 g of heat-dissipating adhesive was put into the syringe, as shown in the first photo of FIG. 1 . Next, as shown in the 2nd photo of FIG. 1 , after inserting a syringe into the silver holder, a paper cup was placed underneath to set it. As shown in the 3rd picture of FIG. 1 , after the adhesive was discharged under the conditions of a discharge pressure (air pressure) of 6 bar and a discharge time of 15 sec, the weight of the discharged adhesive was measured. Next, as shown in the 4th photo of FIG. 1 , after measuring the temperature of the discharged adhesive, the discharged volume of the adhesive was calculated.

Table 1 compares the results of the flow test (Example) using the Musashi equipment in the laboratory and the flow test (Comparative Example) using the actual injection equipment. In Table 1, OH represents the polyol main composition and NCO represents the isocyanate curing agent composition.

Thermal conductivity was measured using a known hot disk equipment according to ISO 22007-2 standard.

Viscosity was measured at room temperature using a Brookfield LV type viscometer.

The discharge volume was calculated after measuring the weight and temperature of the discharged adhesive. The discharge volume was expressed as an average value of three times (measured at 25°C).

The solidification maximum force was measured as the solidification hardness. First, after inserting the GPC filter into the Musashi syringe (arbitrarily implementing a leak in the equipment), the liquid was arbitrarily removed by applying pressure, leaving only the alumina solid (solid). And the hardness (maximum solidification force) was measured by cutting the alumina solid that looked like chalk into a certain size. The hardness (H) of the solid material is measured when the solid specimen is pressed at a constant velocity of 0.3 mm/s, and the force applied to the pressing means is measured from the time the solid material is pressed. The force (gf) applied to the pressing means was taken as the hardness of the solid. As a pressurizing means, TA (Texture Analyzer) was used.

In the case of equipment inspection period, if the equipment inspection period due to the solidification problem was less than 2 weeks, it was marked as X, and if it was more than 2 weeks, it was marked as O. The equipment inspection cycle was indicated only for the actual injection equipment (comparative example).

Example (lab Musashi equipment) One 2 3 4 resin OH NCO OH NCO Filler content (wt%) 88.6 88.6 88.4 88.4 Thermal Conductivity (W/mK) 3.0-3.2 Viscosity (kcP) 290,000 21 million 350,000 160,000 Discharge volume (ml) 5.99 4.62 12.68 10.46 Solidification maximum force (gf) 323 458 50 43 Equipment maintenance cycle

Comparative example (actual injection equipment) One 2 3 4 resin OH NCO OH NCO Filler content (wt%) 88.6 88.6 88.4 88.4 Thermal Conductivity (W/mK) 3.0-3.2 Viscosity (kcP) 290,000 21 million 350,000 160,000 Discharge volume (ml) 5.93 4.76 11.89 10.40 Solidification maximum force (gf) 323 458 50 43 Equipment maintenance cycle X X O O

*Result 1: Since the conditions (6 bar, 15 seconds) using the Musashi equipment are similar to the actual injection equipment, it is possible to judge the flowability of the adhesive and the injectability of the equipment at the development stage. As can be seen in Table 1, the results of Examples and Comparative Examples were substantially the same, so the method according to the present invention can be equally applied to actual injection equipment. In addition, as in Examples 1-2 and Comparative Examples 1-2, the smaller the discharge volume, the greater the maximum solidification force, the shorter the equipment inspection cycle, so it can be determined that the flowability is poor. On the other hand, as in Examples 3-4 and Comparative Examples 3-4, the larger the discharge volume and the smaller the maximum solidification force, the longer the equipment inspection cycle, so it can be determined that the flowability is good.

*Result 2: As a result of the test in Table 1, it can be determined that the adhesive having excellent flowability has 1) less solidification in the pipeline, 2) less distortion of the mixing ratio, and 3) a long equipment inspection cycle.

Claims (8)

discharging the resin composition using injection equipment;
acquiring at least one of a discharge volume, a discharge weight, and a solidification hardness of the resin composition discharged from the injection equipment for a unit time; and
Determining flowability based on at least one of a discharge volume, a discharge weight, and a solidification hardness;
The resin composition contains a filler in the range of 50 to 99% by weight and has a thermal conductivity of 1.5 W / mK or more,
For determining the flow,
Under the conditions of a discharge pressure of 6 bar and a discharge time of 15 seconds, after setting a discharge volume of 10 ml as a reference, if the discharge volume is less than the reference discharge volume, the flowability is judged to be bad, and if the standard discharge volume is exceeded, the flowability is determined to be good,
Under the condition of a discharge pressure of 6 bar and a discharge time of 15 seconds, after setting a solidification hardness of 300 gf as a reference, if the solidification hardness is less than the reference solidification hardness, the flowability is judged to be good, and if the reference solidification hardness is exceeded, the flowability is judged to be bad A method for determining the flowability of a composition. The method of claim 1,
The resin composition is an adhesive composition, a method for determining the flowability of a resin composition. The method of claim 1,
The resin composition is a method for determining the flowability of a resin composition that is a heat dissipation adhesive composition. The method of claim 1,
Before discharging, injecting the resin composition into the injector; and mounting the injector to the holder and arranging the container under the injector. delete The method of claim 1,
After measuring the weight and temperature of the discharged resin composition, the flowability determination method of the resin composition to calculate the discharge volume. delete delete

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