KR20200130169A - Resin composition and uses of the same - Google Patents

Abstract

Provided is a resin composition. The resin composition comprises: (A) an epoxy resin; (B) a hardener; and (C) an inorganic filler. When (C) the inorganic filler is mixed with a liquid having the specific gravity in a range of 2.16 to 2.19, a part of (C) the inorganic filler is suspended in the liquid, and a weight ratio of the suspended part of (C) the inorganic filler to the total weight of (C) the inorganic filler is less than 0.6.

Description

Resin composition and uses of the same}

The present invention relates to a resin composition, particularly an epoxy resin-based resin composition containing an inorganic filler that satisfies certain conditions. The resin composition of the present invention can be used as a packaging material for semiconductor substrates, particularly as a packaging material for large-scale wafers.

In the semiconductor industry, a protective layer is often formed on a wafer by using a packaging material to protect the wafer. Wafer-level packaging refers to packaging the chips directly on the wafer instead of packaging the chips after cutting the wafer into small chips. In general, wafer level packaging can provide the following advantages: larger bandwidth, higher packaging speed, good reliability, and lower energy consumption. In recent years, taking into account the development of large-scale wafers (eg, wafers of 12 inches or larger), demands for mechanical strength and dimensional stability of packaging materials used for wafers have become more stringent. The addition of inorganic fillers to the resin composition can improve the dimensional stability of the packaging material provided therefrom, but packaging materials containing inorganic fillers generally cause defects during subsequent fan out wafer level packaging. It has a void.

In consideration of the above technical problem, the present invention relates to an epoxy resin-based resin composition and a packaging material formed by using the resin composition. By using an inorganic filler that satisfies specific conditions in the epoxy resin-based resin composition, the material obtained by curing the resin composition does not have voids after pulverization, and is thus suitable for packaging purposes, especially large-scale wafer packaging.

An object of the present invention is to provide a resin composition,

The resin composition has the following configuration:

(A) epoxy resin;

(B) a hardener; And

(C) an inorganic filler; Including,

When the inorganic filler (C) is mixed with a liquid having a specific gravity in the range of 2.16 to 2.19, a part of the inorganic filler (C) is suspended in the liquid, and the total weight of the inorganic filler (C) is The ratio of the weight of the suspended portion in the inorganic filler (C) is less than 0.6.

In some embodiments of the present invention, the ratio of the weight of the suspended portion of the inorganic filler (C) to the total weight of the inorganic filler (C) is greater than zero.

In some aspects of the invention, based on the total weight of the inorganic filler (C), the inorganic filler (C) comprises at least 90% by weight of silica.

In some embodiments of the present invention, the silica is fused silica.

In some embodiments of the present invention, the silica is spherical silica.

In some embodiments of the present invention, the inorganic filler (C) has the following particle size distribution-D90/D10 is 2 to 40, and D99 is 30 μm or less.

In some embodiments of the present invention, the resin composition is solvent-free, and the resin composition has a viscosity of 1000 Pa·s or less under standard temperature and pressure.

In some embodiments of the present invention, the epoxy resin (A) is a phenol epoxy resin, a cresol epoxy resin, a naphthalene epoxy resin, a bisphenol epoxy resin, It is selected from the group consisting of alicyclic epoxy resins, and combinations thereof.

In some embodiments of the present invention, the curing agent (B) is an anhydride, an imide compound, a sulfonium salt, an amino-containing compound, a hydroxyl-containing compound ( hydroxyl-containing compound), and combinations thereof.

In some embodiments of the present invention, based on the total weight of the (A) epoxy resin, (B) curing agent, and (C) inorganic filler, the total content of the (A) epoxy resin and (B) curing agent is 5% by weight. To 25% by weight, and the content of the inorganic filler (C) is 75 to 95% by weight.

Another object of the present invention is to provide a packaging material formed by curing the resin composition described above.

In order to achieve the above object, in order to make the technical features and advantages of the present invention more clear, the present invention will be described in detail with reference to some aspects below.

In the following, some aspects of the present invention will be described in detail. However, without departing from the spirit of the present invention, the present invention may be implemented in various aspects, and is not limited to the aspects described herein.

Unless otherwise stated, the expressions “a”, “the”, and the like mentioned in this specification and claims should include both singular and plural forms.

Unless otherwise stated, the expressions “first”, “second”, and the like mentioned in the specification and claims are used to simply distinguish the described elements or configurations without any special meaning.

The term "Dn" as used herein refers to the particle size when the cumulative percentage of the particle size distribution reaches n% by volume. That is, the term "D10" refers to the particle size when the cumulative percentage of the particle size distribution reaches 10% by volume. The term "D50" refers to the particle size when the cumulative percentage of the particle size distribution reaches 50% by volume. The term "D90" refers to the particle size when the cumulative percentage of the particle size distribution reaches 90% by volume. The term "D99" refers to the particle size when the cumulative percent of the particle size distribution reaches 99% by volume. The particle size distribution refers to a graph of the distribution of the particle size of a filler analyzed by using a laser particle size analyzer.

The term "normal temperature and pressure" as used herein refers to an environment where the temperature is 25°C and the pressure is 1 atm. The term "solvent-free" means that the content of the solvent, if present, is less than 0.5% by weight based on the total weight of the resin composition.

The term "suspended portion" of an inorganic filler as used herein includes an inorganic filler that is suspended in a liquid when the inorganic filler is mixed with a liquid, and is suspended on the surface of the liquid having a specific specific gravity. That is, the term "suspended part" refers to a part that does not settle in a liquid.

Compared to the prior art, the distinguishing feature of the present invention is that the resin composition of the present invention uses an epoxy resin, a curing agent, and an inorganic filler that satisfies certain conditions, and the material obtained by curing the resin composition has no voids in particular, so that the wafer It is suitable for packaging, especially large-scale wafer packaging. The components and production methods of the resin composition of the present invention are described in detail below.

1. Resin composition

The resin composition contains an epoxy resin (A), a curing agent (B), and an inorganic filler (C) as essential components, and other optional components that may be used as necessary.

1.1. Epoxy resin (A)

The type of epoxy resin (A) used in this specification is not particularly limited. Typical epoxy resins include phenolic epoxy resins and alicyclic epoxy resins. Examples of the phenolic epoxy resin include, but are not limited to, a phenol epoxy resin, a cresol epoxy resin, a naphthalene epoxy resin, and a bisphenol epoxy resin. An example of a cresol epoxy resin, ortho-cresol epoxy resin (epoxy resin ortho -cresol), meta-cresol epoxy resin, (meta -cresol epoxy resin), and para-cresol contained the epoxy resin (para -cresol epoxy resin), but this It is not limited, and an ortho-cresol epoxy resin is preferred. Examples of bisphenol epoxy resins include, but are not limited to, bisphenol A epoxy resins and bisphenol F epoxy resins. Each of the phenolic epoxy resins is preferably a novolac phenolic epoxy resin. Alicyclic epoxy resins are dicyclopentadiene epoxy resin, hydrogenated bisphenol A epoxy resin, and (3',4'-epoxycyclohexane) methyl 3,4-epoxycyclohexyl Carboxylate ((3',4'-epoxycyclohexane) methyl 3,4-epoxycyclohexyl carboxylate). The epoxy resin may be used alone or as a mixture of several of them or in combination with other epoxy resins.

In a preferred embodiment of the present invention, the epoxy resin (A) is a liquid epoxy resin under standard temperature and pressure. Specifically, the epoxy resin (A) is an epoxy resin having a viscosity of less than 1000 Pa·s under standard temperature and pressure. By using a liquid epoxy resin under standard temperature and pressure, the resin composition of the present invention may not need to add a solvent to disperse each of the components of the resin composition. That is, since the resin composition is solvent-free, the material obtained by curing the resin composition does not have defects such as bubbles, voids, etc. caused by evaporation of the solvent during heating and curing, which is disadvantageous in packaging applications.

In the resin composition of the present invention, the content of the epoxy resin (A) is not particularly limited. In general, based on the total weight of the epoxy resin (A), the curing agent (B) and the inorganic filler (C), the content of the epoxy resin (A) may be in the range of 4.5% by weight to 15% by weight. For example, the content of the epoxy resin (A) is 5 wt%, 5.5 wt%, 6 wt%, 6.5 wt%, 7 wt%, 7.5 wt%, 8 wt%, 8.5 wt%, 9 wt%, 9.5 wt% %, 10%, 10.5%, 11%, 11.5%, 12%, 12.5%, 13%, 13.5%, 14%, or 14.5%, or any described herein May be within a range between two values of.

1.2. Hardener (B)

The curing agent used herein refers to a component capable of initiating a ring-opening reaction of the epoxy functional group(s) and performing a crosslinking curing reaction with the epoxy resin. The type of the curing agent is not particularly limited as long as the curing agent can initiate the ring opening reaction of the epoxy functional group(s) and perform a crosslinking curing reaction with the epoxy resin. Examples of curing agents include, but are not limited to, anhydrides, imide compounds, sulfonium salts, amino-containing compounds, and hydroxyl-containing compounds. The curing agent may be used alone or as a mixture of several of them or in combination with other curing agents.

The anhydride includes, but is not limited to, monoanhydride, dianhydride, polyanhydride, and copolymers of the anhydrides and other copolymerizable monomers. Examples of monoanhydrides include acetic anhydride, maleic anhydride, succinic anhydride, 4-methylhexahydrophthalic anhydride, or hexahydrophthalic anhydride. anhydride), but is not limited thereto. Examples of the dianhydride include, but are not limited to, naphthalene tetracarboxylic dianhydride, or pyromellitic dianhydride. Examples of polyanhydrides include, but are not limited to, melitic trianhydride. Examples of copolymers of anhydrides and other copolymerizable monomers include, but are not limited to, a copolymer of styrene and maleic anhydride.

Imide compounds include, but are not limited to, bismaleimide compounds and imidazole compounds. Examples of the bismaleimide compound include 1,2-bismaleimidoethane, 1,6-bismaleimidohexane, 1,3-bismaleimidobenzene (1, 3-bismaleimidobenzene), 1,4-bismaleimidobenzene, 2,4-bismaleimidotoluene, 4,4-bismaleimidodiphenylmethane (4, 4'-bismaleimidodiphenylmethane), and the like. The bismaleimide compound may be used alone or as a mixture of several of them or in combination with other imidazole compounds.

Examples of sulfonium salts include, but are not limited to, products of model numbers SI-45L, SI-60L, SI-80L, SI-100L, SI-110L, SI-150, and SI-150L from Sanshin Chemical.

Examples of amino-containing compounds include diamino diphenylsulfone (DDS), diamino diphenylmethane (DDM), amino triazine novolac (ATN) resin, dicyandiamide , DICY), diethylenetriamine, triethylenetetramine, tetraethylenepentamine, diethylaminopropylamine, N-aminoethyl piperazine, Methanediamine, and isophorone diamine. The amino-containing compounds may be used alone or as a mixture of several of them or in combination with other amino-containing compounds.

Examples of hydroxyl-containing compounds include, but are not limited to, bisphenol A, tetrabromobisphenol A, bisphenol S, bisphenol F, and novolac resins. The hydroxyl-containing compounds may be used alone or in mixtures of several or in combination with other hydroxyl-containing compounds.

In a preferred embodiment of the present invention, the curing agent (B) is a liquid curing agent under standard temperature and pressure. Specifically, the curing agent (B) is a curing agent having a viscosity of less than 1000 Pa·s under standard temperature and pressure. In the accompanying examples, anhydride and sulfonium salts are used.

In the resin composition of the present invention, the content of the curing agent (B) is not particularly limited as long as it can provide the desired curing effect. In general, based on the total weight of the epoxy resin (A), the curing agent (B) and the inorganic filler (C), the content of the curing agent (B) may range from 0.1% to 15% by weight. For example, the content of the curing agent (B) is 0.2 wt%, 0.3 wt%, 0.4 wt%, 0.5 wt%, 0.6 wt%, 0.7 wt%, 0.8 wt%, 0.9 wt%, 1 wt%, 1.5 wt% , 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8 Wt%, 8.5 wt%, 9 wt%, 9.5 wt%, 10 wt%, 10.5 wt%, 11 wt%, 11.5 wt%, 12 wt%, 12.5 wt%, 13 wt%, 13.5 wt%, 14 wt% , Or 14.5% by weight, or in a range between any two values described herein.

In addition, in the resin composition of the present invention, based on the total weight of the epoxy resin (A), the curing agent (B) and the inorganic filler (C), the total content of the epoxy resin (A) and the curing agent (B) is from 5% by weight to It may be in the range of 25% by weight. For example, the total content of the epoxy resin (A) and the curing agent (B) is 6 wt%, 7 wt%, 8 wt%, 9 wt%, 10 wt%, 11 wt%, 12 wt%, 13 wt%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, or 24% by weight, or as described herein Can be within a range between any two values of.

1.3. Inorganic filler (C)

In the resin composition of the present invention, the inorganic filler (C) satisfies the following conditions: When the inorganic filler (C) is mixed with a liquid having a specific gravity of 2.16 to 2.19, such as a specific gravity of 2.16, 2.17, 2.18, or 2.19, Part of the inorganic filler (C) is suspended in the liquid, and the ratio of the weight of the suspended part of the inorganic filler (C) to the total weight of the inorganic filler (C) is less than 0.6, preferably less than 0.4. Preferably, when the inorganic filler (C) is mixed with a liquid having a specific gravity of 2.18, a part of the inorganic filler (C) is suspended in the liquid, and the amount of the inorganic filler (C) relative to the total weight of the inorganic filler (C) The weight ratio of the suspended portion is less than 0.6, preferably less than 0.4. It was found that when the inorganic filler (C) satisfies the above conditions, the cured product obtained by curing the resin composition of the present invention does not have void defects, which is advantageous in packaging applications. Here, the type of liquid is not particularly limited as long as it has the above specific gravity. For example, the liquid can be a solvent, a mixture of several solvents, or a solution containing solute(s) and solvent(s). In some embodiments of the invention, the liquid is a mixture of dibromomethane and ethanol.

In some embodiments of the present invention, the ratio of the weight of the suspended portion of the inorganic filler (C) to the total weight of the inorganic filler (C) is greater than 0, less than 0.6, preferably greater than 0 and less than 0.4. For example, the ratio of the weight of the suspended portion of the inorganic filler (C) to the weight of the inorganic filler (C) is 0.001, 0.002, 0.003, 0.004, 0.005, 0.006, 0.007, 0.008, 0.009, 0.01, 0.02, 0.03 , 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.1, 0.11, 0.12, 0.13, 0.14, 0.15, 0.16, 0.17, 0.18, 0.19, 0.2, 0.21, 0.22, 0.23, 0.24, 0.25, 0.26, 0.27, 0.28 , 0.29, 0.3, 0.31, 0.32, 0.33, 0.34, 0.35, 0.36, 0.37, 0.38, or 0.39, or within a range between any two values described herein.

On the premise that the inorganic filler (C) satisfies the above conditions, the type of the inorganic filler (C) is not particularly limited. Examples of inorganic fillers (C) include silica, alumina, calcium oxide, calcium carbonate, titanium dioxide, talc powder, mica powder, and boronite. Including, but not limited to, boron nitride. The fillers can be used alone or in mixtures of several or in combination with other fillers. In some aspects of the invention, the inorganic filler (C) comprises silica, alumina, or combinations thereof.

In a preferred embodiment of the present invention, the inorganic filler (C) comprises silica, and the content of silica is 90% by weight or more, based on the total weight of the inorganic filler (C). For example, the content of silica is 90.5 wt%, 91 wt%, 91.5 wt%, 92 wt%, 92.5 wt%, 93 wt%, 93.5 wt%, 94 wt%, 94.5 wt%, 95 wt%, 95.5 wt% %, 96%, 96.5%, 97%, 97.5%, 98%, 98.5%, 99%, 99.5%, or 100% by weight, or any two values described herein It can be within the range between. Without being bound by any theory, it is advantageous to improve the dimensional stability and mechanical properties of the packaging material when the inorganic filler (C) comprises at least 90% by weight of silica.

In a preferred embodiment of the present invention, the inorganic filler (C) includes fused silica. Fused silica refers to amorphous silica. In general, methods of determining whether silica is amorphous include Fourier transform infrared spectroscopy (FTIR), Ramen spectroscopy, x-ray diffraction (XRD), and transmission electron microscope (TEM). ), but is not limited thereto.

The form of the inorganic filler that can be used in the resin composition of the present invention is not particularly limited, and may be a sphere, a flake, a short-rod, a fiber, or a cube. . In a preferred embodiment of the present invention, spherical silica is used. Without being bound by any theory, it is believed that the spherical inorganic filler can be more evenly dispersed in the resin composition, which is advantageous for subsequent applications.

Further, in the resin composition of the present invention, the inorganic filler (C) preferably has a specific particle size distribution. Specifically, D90/D10 of the inorganic filler (C) is preferably in the range of 2 to 40. For example, D90/D10 of inorganic filler (C) is 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, or 39, or any two values described herein It can be within the range between. In addition, D99 of the inorganic filler (C) is preferably 30 µm or less. For example, D99 of the inorganic filler (C) is 29 µm, 28 µm, 27 µm, 26 µm, 25 µm, 24 µm, 23 µm, 22 µm, 21 µm, 20 µm, 19 µm, 18 µm, 17 µm , 16 ㎛, 15 ㎛, 14 ㎛, 13 ㎛, 12 ㎛, 11 ㎛, 10 ㎛, 9 ㎛, 8 ㎛, 7 ㎛, 6 ㎛, 5 ㎛, 4 ㎛, 3 ㎛, 2 ㎛, 1 ㎛, 0.9 Μm, 0.8 µm, 0.7 µm, 0.6 µm, 0.5 µm, 0.4 µm, 0.3 µm, 0.2 µm, or 0.1 µm, or in a range between any two values described herein. When the particle size distribution of the inorganic filler falls within the specified range, the resin composition can be provided with a lower viscosity, and the material obtained by curing the resin composition can be provided with more excellent Tg and mechanical strength. In a preferred embodiment of the present invention, the D50 of the inorganic filler (C) is in the range of 5 μm to 10 μm. For example, the D50 of the inorganic filler (C) is 5.5 µm, 6 µm, 6.5 µm, 7 µm, 7.5 µm, 8 µm, 8.5 µm, 9 µm, or 9.5 µm, or any two described herein. It can be within a range between values. When the D50 of the inorganic filler falls within the specified range, the resin composition may have improved packaging filling properties while still having a lower viscosity.

In addition, in order to increase the compatibility between the inorganic filler (C) and other components of the resin composition, and to improve the workability of the resin composition, the inorganic filler (C) is, for example, coupled before being added to the resin composition. It can be surface-modified with a ring agent. Examples of the coupling agent include a silane coupling agent, a titanate coupling agent, a zirconate coupling agent, and a poly-siloxane coupling agent. Including, but not limited to this, a silane coupling agent is preferred. The specific surface modification method is a general technique known to those skilled in the art, and it is not one of the main features of the present invention and will not be described in detail.

In the resin composition of the present invention, based on the total weight of the epoxy resin (A), the curing agent (B) and the inorganic filler (C), the content of the inorganic filler (C) may range from 75% to 95% by weight. . For example, the content of the inorganic filler (C) is 76 wt%, 77 wt%, 78 wt%, 79 wt%, 80 wt%, 81 wt%, 82 wt%, 83 wt%, 84 wt%, 85 wt% %, 86%, 87%, 88%, 89%, 90%, 91%, 92%, 93%, or 94% by weight, or any two values described herein It can be within the range between. When the content of the inorganic filler (C) is less than the specified range, the mechanical strength of the material obtained by curing the resin composition may be insufficient. On the other hand, when the content of the inorganic filler (C) exceeds the specified range, the viscosity of the resin composition may be too high for the next application.

1.4. Other optional ingredients

The resin composition of the present invention, if necessary, such as the catalyst described below and additives known in the art to appropriately improve the processability of the resin composition during manufacture or to improve the physicochemical properties of the material obtained by curing the resin composition. Other optional ingredients may be further included. Examples of additives known in the art are flame retardants, carbon black, coloring materials, defoaming agents, dispersing agents, viscosity modifiers, thixotropic agents ( thixotropic agents, leveling agents, coupling agents, mold-release agents, anti-mildew agents, stabilizers, anti-oxidants, and Includes, but is not limited to, anti-bacterial agents.

In some embodiments of the present invention, a catalyst is further added to the resin composition to accelerate the ring opening reaction of the epoxy functional group(s) and lower the curing reaction temperature of the resin composition. The type of catalyst is not particularly limited as long as the catalyst accelerates the ring opening reaction of the epoxy functional group(s) and lowers the curing reaction temperature of the resin composition. Suitable examples of catalysts include, but are not limited to, tertiary amines, imidazoles, organic phosphine compounds, amidines, and derivatives thereof. The catalyst can be used alone or in mixtures of several or in combination with other fillers. In the accompanying examples, an organic phosphine compound is used as a catalyst.

In general, based on the total weight of the resin composition, the content of the catalyst may be 0.05% by weight to 2% by weight. For example, the content of the catalyst is 0.06 wt%, 0.07 wt%, 0.08 wt%, 0.09 wt%, 0.1 wt%, 0.2 wt%, 0.3 wt%, 0.4 wt%, 0.5 wt%, 0.6 wt%, 0.7 wt% %, 0.8%, 0.9%, 1.0%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, or 1.9% , Or any two values described herein, but the invention is not limited thereto. The content of the catalyst can be adjusted according to the needs of a person skilled in the art.

1.5. Preparation of resin composition

The resin composition of the present invention can be prepared as a varnish for subsequent processing by uniformly mixing the components of the resin composition through a stirrer and dissolving or dispersing the obtained mixture in a solvent. The solvent may dissolve or disperse the components of the resin composition, but may be any inert solvent that does not react with the components of the resin composition. Examples of inert solvents are toluene, γ-butyrolactone, methyl ethyl ketone, cyclohexanone, butanone, acetone, xylene, isobutyl ketone, N,N-dimethylformamide (DMF), N,N-dimethylacet. Amide (DMAc), and N-methylpyrrolidone (NMP).

Further, as described above, the resin composition of the present invention is solvent-free, so that the material obtained by curing the resin composition will not have defects such as bubbles, voids, and the like caused by evaporation of the solvent during heating and curing. The solvent-free resin composition of the present invention is suitable for providing a packaging material, and can further comply with environmental requirements for low VOC (volatile organic compounds). For example, the solvent-free resin composition of the present invention can be prepared in the following manner. First, the respective components of the resin composition (including liquid epoxy resin (A), liquid curing agent (B) and inorganic filler (C), but excluding catalyst) were placed in a glass reaction kettle, sealed standard pressure and 25° C. Under and for 3 hours at a rotation speed of 1-2 rpm. Next, the catalyst was added to the reaction kettle and mixed under a sealed standard pressure and 25° C., and at a rotational speed of 1-2 rpm for 0.5 hours to obtain a pre-mixed resin composition. Thereafter, the pre-mixed resin composition was put into a three-roller mill and mixed at a first roller rotation speed of 0.5 to 1 rpm for three times to obtain a semi-cured (B-step) resin composition for subsequent processing. did.

2. Packaging material

Further, the present invention provides a packaging material provided by the resin composition, wherein the packaging material is formed by curing the resin composition. That is, the packaging material is a material obtained from a fully-cured (ie, C-stage) resin composition. The curing method of the resin composition is not particularly limited. In some aspects of the invention, the resin composition is cured by heating.

The packaging material of the present invention has high mechanical strength and weatherability, and is suitable for use in packaging of wafers or other semiconductor devices. Examples of semiconductor devices include, but are not limited to, solar cells and organic light emitting diode displays. However, the packaging material of the present invention is not limited to the above packaging applications, but may instead be used for packaging any other article requiring surface protection, such as the blades of a wind turbine generator.

3. Example

3.1. Test Methods

The invention will be further illustrated by the following aspects, the measuring instruments and methods, respectively:

[Test of the weight of the suspended part of the inorganic filler]

First, dibromomethane (purity> 99%, specific gravity is 2.497 g/cm ³ ) and ethanol (purity> 95%, specific gravity is 0.810 g/cm ³ ) are mixed under standard temperature and pressure to obtain a specific gravity of 2.18. 10 ml of the test solution was obtained. Then, 1 g of inorganic filler and 10 ml of test liquid were added to a test tube having an inner diameter in the range of 9 mm to 12 mm. The test tube was centrifuged at 25° C. at a rotation speed of 4200 rpm for 5 minutes, and then allowed to stand for 12 hours after centrifugation. After allowing to stand, the suspended portion of the inorganic filler was collected in a test tube, fired at 120° C. for 60 minutes, and then weighed. The weight obtained is the weight of the suspended portion of the inorganic filler. As mentioned above, the suspended portion of the inorganic filler comprises a portion of the inorganic filler suspended on the surface of the test liquid and inside the test liquid; That is, the suspended part refers to the part that does not precipitate in the test solution.

[Measurement of particle size distribution of filler]

The particle size distribution of the inorganic filler is analyzed by using a laser particle size analyzer (model: Mastersizer 2000, manufactured by Malvern). Automatic optical correction and background correction are performed prior to analysis such that the optical energy is less than 150, the laser intensity is greater than 65%, and the laser obscuration range is 1% to 5%. . The analysis conditions are as follows: the amount of steel balls on the screen is 40, the weight of the test sample is 5 g to 10 g, the mode is Airflow, the pressure is 2.0 bar, the feeding rate is 70%. , The number of measurements is 5 times. The refractive index of silica is 1.45, and the refractive index of alumina is 1.768.

[Flexural strength test]

First, after pouring the resin composition into a mold, it was heated and cured at 150° C. for 4 hours to obtain a test piece of 80 mm in length, 10 mm in width, and 4 mm in thickness. Thereafter, the test piece was placed in a tensioning device (model: HT-2402, manufactured by Hung Ta Instrument), the distance between the support points of the lever was 64 mm, and the test speed was 2 mm/min. The strength value at the time of failure of the test piece is recorded as the bending strength, and the unit of the bending strength is kgf/mm ² .

[Coefficient of thermal expansion test]

First, after putting the resin composition in a mold, it was heated and cured at 150° C. for 4 hours to obtain a test piece having a height of 2.8 mm, an upper limit width of 4 mm, a lower limit width of 5 mm, and a length of 3 mm. Then, the coefficient of thermal expansion of the test piece was measured using a thermomechanical analyzer (model: TMA-7, manufactured by Perkin-Elmer). The measurement conditions are as follows: heated to 250° C. at a heating rate of 5° C./min, and the loading amount is 10 g. The coefficient of thermal expansion obtained by calculating the coefficient of thermal expansion of a material under a temperature below Tg is referred to as α1-CTE. In this test, α1-CTE of the packaging material was calculated at a temperature in the range of 40°C to 90°C. The unit of the coefficient of thermal expansion is ppm/°C.

[Void detection]

First, the resin composition was poured into a mold having a length of 10 mm, a width of 10 mm, and a height of 4 mm. The resin composition was heated and cured at 150° C. for 4 hours to obtain a test piece. The test piece was cut into a 10 mm×10 mm×4 mm rectangular parallelepiped using a low-speed precision cutter (model: MINITOM, manufactured by STRUERS). Next, the test piece was placed between two transparent acrylic plates of 20 mm×20 mm×5 mm, and cold mounted with an instant adhesive. The center position of the test piece was aligned with a low-speed precision cutter, and the test piece and the acrylic plate were cut into two pieces at the center to obtain a sample having a cross section. After that, the cross-sections of the samples were respectively set to No. 1000 CarbiMet abrasive paper and No. It was ground for 5 minutes in turn using 2000 CarbiMet abrasive paper. Thereafter, the sample was placed on a flannel rotating disk of a polishing machine, and polished using a MasterPrep alumina final polishing suspension (alumina particle size: 0.05 µm). The polishing period is 5 minutes. The polished sample was observed using a 500X scanning electron microscope (SEM) to detect whether or not voids having a length×width greater than 2 μm×2 μm were present, and the observation range was 180 μm×240 μm. When the number of voids having a length x width greater than 2 mu m x 2 mu m was 0, the void detection result was passed, and "OK" was recorded. When the number of voids having a length x width greater than 2 mu m x 2 mu m was 1 or more, the result of void detection was not passed, and "NG" was recorded. In addition, some aspects were further detected to see whether the number of voids with length x width greater than 0.5 µm x 0.5 µm existed.

3.2 Example And In Comparative Example List of raw materials used

[Table 1] List of raw materials

3.3 Preparation of resin composition and measurement of properties

Resin compositions of Examples 1 to 9 and Comparative Examples 1 to 4 were prepared according to the ratios shown in Tables 2-1 to 2-3. First, the liquid epoxy resin (A), the liquid curing agent (B) and the inorganic filler (C) were put into a glass reaction kettle, and mixed under a sealed standard pressure and 25° C., and at a rotation speed of 1 rpm to 2 rpm for 3 hours. did. Next, the catalyst was added to the reaction kettle and mixed under sealed standard pressure and 25° C., and at a rotation speed of 1 rpm to 2 rpm for 0.5 hours to obtain a pre-mixed resin composition. Then, the pre-mixed resin composition was put into a three-roller mill (model: NR-84A, manufactured by NORITAKE), and mixed at the first roller rotation speed of 0.5 rpm to 1 rpm for 3 times, and each resin composition was Obtained (B-step).

The particle size distribution of the used filler and the suspended portion ratio of the resin compositions of Examples 1 to 9 and Comparative Examples 1 to 4 were measured according to the above test method, and the results are listed in Tables 2-1 to 2-3.

In addition, the properties of the cured product of the resin compositions of Examples 1 to 9 and Comparative Examples 1 to 4, including bending strength, α1-CTE, and void defects, were measured according to the test method, and the results are shown in Tables 3-1 to Listed in 3-2.

[Table 2-1] Composition and properties of resin compositions of Examples 1 to 4

[Table 2-2] Composition and properties of resin compositions of Examples 5 to 9

[Table 2-3] Composition and properties of resin compositions of Comparative Examples 1 to 4

[Table 3-1] Properties of cured products of the resin compositions of Examples 1 to 9 and Comparative Examples 1 to 4

[Table 3-2] Properties of the cured product of the resin compositions of Examples 3 and 7

As shown in Table 3-1, the cured product of the resin composition of the present invention has no void defects, and excellent dimensional stability (?1-CTE) and bending strength are provided. Specifically, Examples 1 to 9 show that when the inorganic filler contained in the resin composition satisfies the ratio of the specified suspended portion, the packaging material made of the resin composition does not have void defects. Examples 1 to 5 and 7 to 9 are the ratio of the suspended portion of the inorganic filler contained in the resin composition and the specified excellent particle size distribution (i.e., D90/D10 is preferably in the range of 2 to 40, and D99 is Preferably, it is 30 or less), the packaging material made of the resin composition can provide better mechanical strength and dimensional strength, and shows no void defects. In addition, Example 9, the inorganic filler may include a filler in addition to silica, the packaging material prepared from the resin composition has excellent mechanical strength and dimensional strength, as a whole, the proportion of the suspended portion and the particles in which the inorganic filler is designated It shows that as long as it has a size distribution, it does not have void defects. In addition, as shown in Table 3-2, when the ratio of the weight of the suspended portion of the inorganic filler (C) to the total weight of the inorganic filler (C) is less than 0.4, the packaging material obtained therefrom is strict void detection ( That is, no voids larger than 0.5 µm x 0.5 µm are present).

On the other hand, as shown in Table 3-1, a material obtained by curing a resin composition not according to the present invention has void defects. This shows that when the inorganic filler contained in the resin composition does not satisfy the specified condition of the ratio of the suspended portion, the packaging material made of the resin composition has void defects. In addition, Comparative Example 3 shows that when the inorganic filler does not have a desirable particle size distribution, the packaging material made of the above resin composition is provided with deteriorated mechanical strength and dimensional stability.

The above examples are used to explain the principles and efficacy of the present invention, and to show features of the present invention. Those skilled in the art can make various modifications and alternatives based on the disclosure and suggestions of the present invention as described without departing from the principles and spirit of the present invention. Accordingly, the scope of protection of the present invention is as defined in the appended claims.

Claims (12)

As a resin composition,
(A) epoxy resin;
(B) a hardener; And
(C) an inorganic filler; Including,
When the inorganic filler (C) is mixed with a liquid having a specific gravity in the range of 2.16 to 2.19, a part of the inorganic filler (C) is suspended in the liquid, and the total weight of the inorganic filler (C) is The ratio of the weight of the suspended portion in the inorganic filler (C) is less than 0.6, the resin composition.
The method of claim 1,
The resin composition, wherein the ratio of the weight of the suspended portion of the inorganic filler (C) to the total weight of the inorganic filler (C) is greater than zero.
The method of claim 1,
Based on the total weight of the inorganic filler (C), the inorganic filler (C) will contain at least 90% by weight of silica, the resin composition.
The method of claim 3,
The silica will be fused silica (fused silica), the resin composition.
The method of claim 3,
The silica will be spherical silica (spherical silica), the resin composition.
The method according to any one of claims 1 to 5,
The inorganic filler (C) has the following particle size distribution: D90/D10 is 2 to 40, and D99 is 30 μm or less;
The method according to any one of claims 1 to 5,
The resin composition is a solvent-free (solvent-free), the resin composition.
The method according to any one of claims 1 to 5,
The resin composition has a viscosity of 1000 Pa·s or less under normal temperature and pressure.
The method according to any one of claims 1 to 5,
The epoxy resin (A) is a phenol epoxy resin, a cresol epoxy resin, a naphthalene epoxy resin, a bisphenol epoxy resin, and an alicyclic epoxy resin. resin), and a resin composition selected from the group consisting of a combination thereof.
The method according to any one of claims 1 to 5,
The curing agent (B) is an anhydride, an imide compound, a sulfonium salt, an amino-containing compound, a hydroxyl-containing compound, and The resin composition that is selected from the group consisting of a combination thereof.
The method according to any one of claims 1 to 5,
Based on the total weight of the (A) epoxy resin, (B) curing agent, and (C) inorganic filler, the total content of the (A) epoxy resin and (B) curing agent is 5% to 25% by weight, the The content of the inorganic filler (C) is 75% to 95% by weight of the resin composition.
A packaging material formed by curing the resin composition according to any one of claims 1 to 5.