KR102179472B1 - Composition for epoxy molding, and epoxy molding film comprising the same - Google Patents

Abstract

The composition for epoxy molding according to the present invention is characterized in that flexibility can be given while maintaining high modulus, and also has excellent embedding properties, and thus can be usefully applied as EMF.

Description

Composition for epoxy molding, and epoxy molding film comprising the same

The present invention is to provide a composition for epoxy molding that can give flexibility while maintaining a high modulus, and also has excellent embedding properties.

A semiconductor encapsulant is a material that seals a semiconductor device to protect it from external conditions such as heat, moisture, impact, etc., and is generally referred to as EMC (Epoxy Molding Compound) or EMF (Epoxy Molding Film) manufactured therefrom. Use material. EMC is a mixture of various materials such as epoxy resin and has a very important effect on the function of the semiconductor because it plays a role of protecting semiconductor devices.

Conventionally, since the focus has been on the protection of such semiconductor devices, research has been conducted in the direction of implementing a high modulus. However, in recent years, with the development of electronic devices, foldable electronic devices and sensors are being developed, and according to this trend, limitations of the existing EMC or EMF are revealed.

For example, the existing EMC or EMF contains an excessive amount of silica, implements a high modulus, and has the advantage of lowering the warpage due to a low coefficient of thermal expansion (CTE). However, due to the excessive amount of silica, there is a brittle property, so there is a limit to apply to the package of foldable electronic devices. Therefore, development of EMC or EMF that can give flexibility while maintaining high modulus is required.

On the other hand, in order to manufacture the shape of a film like EMF, a material having a high molecular weight is required, and acrylic resin is usually used. Acrylic resin is advantageous in imparting flexibility, but if the melt viscosity is high, there is a problem that the embedding property decreases when packaged.

Accordingly, the inventors of the present invention confirmed that the above can be solved when using components as described below, as a result of intensive research on a composition for epoxy molding that can provide flexibility while maintaining a high modulus, and also has excellent embedding properties. Was completed.

The present invention is to provide an epoxy molding composition, which can provide flexibility while maintaining a high modulus, and also has excellent embedding properties, and an epoxy molding film prepared including the same.

In order to solve the above problems, the present invention provides a composition for epoxy molding comprising the following:

1) epoxy resin;

2) hardener;

3) a first acrylic resin having a molecular weight of 400,000 or more;

4) a second acrylic resin having a molecular weight of 300,000 or less; And

5) alumina,

Hereinafter, the present invention will be described in detail for each component.

Epoxy resin

The epoxy resin used in the present invention is not particularly limited as long as it is an epoxy resin used in a conventional EMC (Epoxy Molding Compound) or EMF (Epoxy Molding Film).

For example, the epoxy resin is a biphenyl-based epoxy resin, bisphenol A epoxy resin, bisphenol F epoxy resin, cresol novolac epoxy resin, phenol novolac epoxy resin, tetrafunctional epoxy resin, triphenolmethane type epoxy resin, alkyl At least one selected from the group consisting of a modified triphenolmethane type epoxy resin, a naphthalene type epoxy resin, a dicyclopentadiene type epoxy resin, and a dicyclopentadiene modified phenol type epoxy resin may be used. In addition, the epoxy resin may have an epoxy equivalent of 100 to 1000.

Hardener

The curing agent used in the present invention is not particularly limited as long as it is a curing agent used in conventional EMC or EMF. For example, the curing agent may be one or more selected from the group consisting of an amine-based curing agent, an acid anhydride-based curing agent, and a phenol novolak resin.

The curing agent is for crosslinking of the epoxy resin, and its content is not particularly limited, but is preferably used in a ratio of 0.7 to 1.1 equivalents to 1 equivalent of the epoxy resin. Specifically, the curing agent is used in an amount of 70 to 150 parts by weight, or 80 to 100 parts by weight based on 100 parts by weight of the epoxy resin.

Acrylic resin

In the present invention, two types of acrylic resins are used, and the two types of acrylic resins are classified by weight average molecular weight.

Like EMF, a material of high molecular weight is required to manufacture the shape of a film.However, as the molecular weight of high molecular weight material increases, the melt viscosity increases and the embedding property decreases when packaged. Conversely, as the molecular weight decreases, the embedding property improves. There is a problem that warpage occurs due to deterioration or affecting the properties of the molding film on the curing properties. Accordingly, in the present invention, by using two types of acrylic resins, these two characteristics are simultaneously improved.

Preferably, the weight average molecular weight of the first acrylic resin is 400,000 to 1,000,000, or 450,000 to 750,000. Also preferably, the weight average molecular weight of the second acrylic resin is 50,000 to 300,000, or 100,000 to 200,000.

Also, preferably, the first acrylic resin is used in an amount of 20 to 150 parts by weight, or 100 to 150 parts by weight based on 100 parts by weight of the epoxy resin. Also, preferably, the second acrylic resin is used in an amount of 20 to 150 parts by weight, or 100 to 150 parts by weight based on 100 parts by weight of the epoxy resin.

Also, preferably, the weight ratio of the first acrylic resin and the second acrylic resin is 1:9 to 9:1.

Preferably, the first acrylic resin and the second acrylic resin are each i) acrylic acid C _1-12 alkyl ester, and/or acrylic acid C _6-20 aryl ester, ii) acrylonitrile; iii) It is a copolymer of (meth)acrylate containing at least one functional group selected from glycidyl group, hydroxy group, and carboxyl group.

In the first acrylic resin and the second acrylic resin, preferably, the weight ratio of the i) monomer, ii) monomer, and iii) monomer is 60 to 80: 15 to 25: 5 to 20, respectively.

Examples of the acrylic acid C _1-12 alkyl ester include methyl acrylate, ethyl acrylate, propyl acrylate, and butyl acrylate, preferably butyl acrylate. As the acrylic acid C _6-20 aryl ester, benzyl acrylate may be used.

As the (meth)acrylate containing one or more functional groups selected from the glycidyl group, hydroxy group, and carboxyl group, glycidyl (meth)acrylate, hydroxy (meth)acrylate, hydroxyethyl (meth) Acrylate, carboxy (meth)acrylate, and the like, and glycidyl (meth)acrylate may be preferably used.

Alumina

In the present invention, alumina is used instead of the silica used in the conventional EMC or EMF.

Alumina is advantageous in realizing a high modulus due to its high density and high hardness of its own filler, which is about twice as high as silica, and can achieve similar effects when using silica while using a small amount.

It is preferable that the alumina has a hardness of 6 or more. In addition, as the alumina, particles having an average particle size of 100 nm to 100 µm may be used, and in consideration of embedding properties, it is preferable to use particles having an average particle size of 100 nm to 20 µm.

In addition, the alumina is preferably used in 5 to 1500 parts by weight, or 100 to 1000 parts by weight, or 500 to 1500 parts by weight based on 100 parts by weight of the epoxy resin.

Epoxy molding film

In addition, the present invention provides an epoxy molding film made of the above-described epoxy molding composition.

The epoxy molding film may have a thickness of 1 μm to 300 μm. In addition, the epoxy molding film may have a thickness of 1 µm or more, 3 µm or more, 5 µm or more, and 10 µm or more. In addition, the epoxy molding film may have a thickness of 300 μm or less, or 100 μm or less, or 90 μm or less, or 70 μm or less.

The epoxy molding film as described above can provide flexibility while maintaining a high modulus, and thus has an advantage that it can be applied to a package of a foldable electronic device. In addition, by using two types of (meth)acrylate-based resins having different molecular weights, there is an advantage in that the embedding property is excellent during package processing without deteriorating the modulus.

Therefore, it is possible to effectively protect the semiconductor of foldable electronic devices, and it can be usefully used as EMF because of its excellent processability.

The composition for epoxy molding according to the present invention described above has a feature that it can impart flexibility while maintaining a high modulus, and has excellent embedding properties, and thus can be usefully applied as an EMF.

Hereinafter, a preferred embodiment is presented to aid the understanding of the present invention. However, the following examples are provided for easier understanding of the present invention, and the content of the present invention is not limited thereby.

Example One

Phenol resin KA-1160 (DIC company, cresol novolac resin, hydroxyl equivalent 190 g/eq, softening point: 65°C) 6 g, epoxy resin EOCN-103S (Japanese powder company, cresol novolak type epoxy resin) , Epoxy equivalent 214 g/eq, softening point: 80° C.) 2 g, liquid epoxy resin RE-310S (Japanese Chemical Co., Bisphenol A epoxy resin, epoxy equivalent 180 g/eq) 5 g, and CB-P05 (alumina filler) ( Showa Denko Corporation, an alumina filler, an average particle diameter of 7 μm) 17 g, and DAW-05 (Denka Corporation, an alumina filler, an average particle diameter of 0.5 μm) 51 g were milled using a milling machine in a methyl ethyl ketone solvent.

To the mixture, a first acrylic resin (butyl acryl ethite: acrylonitrile: glycidyl methacrylate: benzyl methacrylate = 70:15: 5:10 acrylic resin synthesized in a composition ratio, weight average molecular weight of about 52 However, the glass transition temperature of 14°C) 7 g, the second acrylic resin (butyl acryl ethite: acrylonitrile: glycidyl methacrylate = an acrylic resin synthesized in a composition ratio of 65:20:15, a weight average molecular weight of about 10 However, glass transition temperature 14°C) 3 g, silane coupling agent A-187 (GE Toshiba Silicone, gamma-glycidoxypropyltrimethoxysilane) 0.1 g, curing accelerator DICY (Shikoku Chemical) 0.1 g, and 2MA- 0.1 g of OK (Shikoku Chemical) was added and further milled for 2 hours to obtain a solution of a resin composition for semiconductor bonding (solid content of 80% by weight). The milling solution was applied on the release-treated substrate and dried to obtain a film having a film thickness of 100 μm.

Example 2 and 3, Comparative example 1 and 2

A film was prepared in the same manner as in Example 1, except that the material used was changed as shown in Table 1 below.

Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Epoxy
Suzy RE-310S 5 g 4 g 5 g 5 g 5 g EOCN-103S 4 g 4 g 3 g 4 g 3 g Hardener KA-1160 7 g - 6 g 6 g 6 g KPH-3075 ¹⁾ - 7 g - - - acryl
Suzy First acrylic 7 g 13 g 6 g 7 g - 2nd acrylic 3 g 5 g 4 g 3 g - KG-3015P ²⁾ - - - - 18 g Alumina CB-P05 17 g 15 g 17 g - - DAW-05 51 g 45 g 51 g - - Silica Silica 1 ³⁾ - - - 17 g 15 g SC-2050 ⁴⁾ - - - 51 g 45 g 1) KPH-3075: Xylok novolac resin (DIC, softening point about 75°C, hydroxyl equivalent: 175 g/eq)
2) KG-3015P: acrylate resin (glycidyl methacrylate repeating unit 3% by weight, weight average molecular weight about 870,000, glass transition temperature: 10℃)
3) Silica 1: Denka silica FB-8S (average particle diameter about 6 ㎛)
4) SC-2050: spherical silica (Admatech, average particle diameter about 400 nm)

Experimental example

Using the films prepared in Examples and Comparative Examples, the following properties were evaluated.

1) Measurement of melt viscosity

The films obtained in the above Examples and Comparative Examples were laminated using a roll laminator at 60° C. until the thickness became 650 μm. Thereafter, each specimen was molded into a circular shape with a diameter of 10 mm, and then a heating rate of 20°C/min was applied at a shear rate of 1 Hz and 5 rads using TA's advanced rheometric expansion system (ARES). The melt viscosity was measured according to the temperature in the range of °C.

2) Stiffness measurement (flexibility)

A Texture Analyzer (Stable Micro System) was used to measure the stiffness characteristics of the films obtained in each of the Examples and Comparative Examples. Specifically, samples were prepared by cutting the films obtained in each of the Examples and Comparative Examples into a size of 15 mm in width and 100 mm in length, and a 5 cm portion of the double specimen was made into a ring. Then, the force measured when descending to 2 cm at a speed of 1 cm/min with a 5 g force was compared using a Texture Analyzer (Stable Micro System). At this time, the lower the force, the higher the ductility of the film.

3) Measurement of storage modulus (Storage Modulus)

The films obtained in the above Examples and Comparative Examples were laminated using a roll laminator at 60° C. until the thickness became 650 μm. Thereafter, each specimen was cured under conditions of 130°C, 1 hour, and 7 atmospheres, and then a 5.3 mm wide specimen was prepared. The storage modulus of the cured sample was measured.

4) Measurement of warpage after curing

The films obtained in each of the above Examples and Comparative Examples were laminated on a 4-inch wafer having a thickness of 200 μm at 60°C. After curing under the conditions of 130°C, 1 hour, and 7 atmospheres, the degree of warpage of the wafer was measured with an Ezi-Motion measuring instrument for warpage image and height. Higher height means more warpage.

5) Landfill evaluation

Attach the chips of 50 ㎛ × 5 mm × 5 mm to the 0.1T PCB at regular intervals using an adhesive. Separately, the 120 µm film prepared in Examples and Comparative Examples was attached to an 80 µm wafer and cut into a size of 12 mm × 9 mm to prepare a chip. The chips thus prepared were stacked and pasted so as to be in the center of the 50 µm × 5 mm × 5 mm chip prepared using a die bonder. After curing the prepared specimen under conditions of 130° C., 1 hour, and 7 atmospheres, an ultrasonic image analyzer (SAT) was used to observe whether it was embedded around a chip of 50 µm × 5 mm × 5 mm. The landfill tendency was evaluated by evaluating 20 specimens for each composition and counting the number of non-embedded specimens.

6) Measurement of permittivity

The films obtained in each of the Examples and Comparative Examples were cured at 175° C. for 2 hours to obtain a 15 cm×15 cm film. The film was placed between two electrodes (dielectric sensor) using Airgilent Technologies' E5071C Network Analyser, and a voltage of 1 GHz was applied to one electrode and the transmitted wavelength was measured at the other electrode. The dielectric constant of was measured.

The results are shown in Table 2 below.

Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Melt viscosity
(Pa·s) @100℃ 1800 2309 2200 5450 9700 @120℃ 1665 1908 1883 5220 9025 Stiffness (Force(g)) 53 45 63 230 120 Storage modulus
(MPa) @25℃ 8700 6062 9284 5572 4475 @250℃ 116 45 137 32 53 warpage Radius 586 1020 965 400 4330 Height 2.3 1.2 1.7 5 3.7 Landfill evaluation Unfilled number 0/20 0/20 0/20 3/20 8/20 permittivity
@1GHz permittivity 5.14 4.35 5.22 3.5 3.37 Df 0.03546 0.02760 0.02967 0.02127 0.02266

As shown in Table 2, the films prepared in Examples 1 to 3 using alumina have high filler hardness when using the same amount as compared to Comparative Examples 1 and 2 using silica, which is a general-purpose material. It was confirmed that the storage modulus was exhibited, and the volume occupied by the film was low due to its high density and thus excellent flexibility and excellent embedding property.

Because of this characteristic, warpage measurement has little warpage, so it can be expected that it is an excellent film to protect the package when applied to an actual flexible package or electronic device for fingerprint recognition.

Claims (12)

1) epoxy resin;
2) hardener;
3) a first acrylic resin having a molecular weight of 400,000 or more;
4) a second acrylic resin having a molecular weight of 300,000 or less; And
5) contains alumina,
The alumina is a particle having a diameter of 100 nm to 100 μm, and is contained in an amount of 500 to 1500 parts by weight based on 100 parts by weight of the epoxy resin,
Composition for epoxy molding.
The method of claim 1,
The epoxy resin is a biphenyl epoxy resin, bisphenol A epoxy resin, bisphenol F epoxy resin, cresol novolac epoxy resin, phenol novolac epoxy resin, tetrafunctional epoxy resin, triphenolmethane type epoxy resin, alkyl modified triphenol At least one selected from the group consisting of methane-type epoxy resin, naphthalene-type epoxy resin, dicyclopentadiene-type epoxy resin, and dicyclopentadiene-modified phenol-type epoxy resin,
Composition for epoxy molding.
The method of claim 1,
The epoxy resin has an epoxy equivalent of 100 to 1000,
Composition for epoxy molding.
The method of claim 1,
The curing agent is contained in 70 to 150 parts by weight based on 100 parts by weight of the epoxy resin,
Composition for epoxy molding.
The method of claim 1,
The molecular weight of the first acrylic resin is 400,000 to 1,000,000,
Composition for epoxy molding.
The method of claim 1,
The molecular weight of the second acrylic resin is 50,000 to 300,000,
Composition for epoxy molding.
The method of claim 1,
The first acrylic resin and the second acrylic resin are included in each of 20 to 150 parts by weight based on 100 parts by weight of the epoxy resin
Composition for epoxy molding.
The method of claim 1,
The weight ratio of the first acrylic resin and the second acrylic resin is 1:9 to 9:1,
Composition for epoxy molding.
The method of claim 1,
The first acrylic resin and the second acrylic resin may each include i) acrylic acid C _1-12 alkyl ester, and/or acrylic acid C _6-20 aryl ester, ii) acrylonitrile; iii) a copolymer of (meth)acrylate containing at least one functional group selected from glycidyl group, hydroxy group, and carboxyl group,
Composition for epoxy molding.
delete delete An epoxy molding film made of the epoxy molding composition according to any one of claims 1 to 9.