KR20220002080A - Insulation film for electronic device manufacturing - Google Patents

Abstract

The present invention relates to an insulation film for manufacturing an electronic device. The insulation film is a cured product of a composition including an epoxy-containing thermosetting resin, a thermoplastic resin, a curing agent and a filler having an average particle size (D_50) of 0.1-3 micrometers; can prevent generation of cracking, bending or distortion of a substrate during the lamination molding of an electronic part and an insulation film by defining a relationship between the thermal expansion coefficient before the glass transition temperature (Tg) and the thermal expansion coefficient after the glass transition temperature (Tg); shows excellent flexibility to allow application to a flexible substrate; and can be used as an interlayer adhesive film capable of thinning of a multilayer printed circuit board.

Description

Insulation film for electronic device manufacturing

The present invention relates to an insulating film for manufacturing an electronic device, and more particularly, by having characteristics of high heat resistance and low thermal expansion, it is possible to minimize the occurrence of warpage or distortion of the substrate of the electronic device, thereby reducing the defect rate of the substrate of the electronic device. It relates to an insulating film.

Recently, circuit boards such as printed circuit boards (PCBs) are manufactured by sequentially stacking and pressing various types of build-up insulating films for thinning and high integration.

However, the printed circuit board and the insulation film may be warped or distorted in the printed circuit board to which the insulation film is attached due to an imbalance in the physical properties and coefficient of thermal expansion between different materials. When bending or distortion occurs in the printed circuit board, subsequent operations such as circuit formation and laser processing are impossible, so that the manufactured printed circuit board must be discarded or manually performed. This problem is because the difference between the thermal expansion coefficient of the insulating film generated in the printed circuit board manufacturing process and the thermal expansion coefficient of the printed circuit board to which the insulating film is attached is not precisely controlled. In order to solve this problem, it is necessary to study the change in the coefficient of thermal expansion according to the temperature change of the insulating film.

In order to solve the above problems, the present invention limits the range of the average particle size of the filler included in the insulating film composition and the range of the coefficient of thermal expansion according to the temperature section of the insulating film, thereby preventing the bending or distortion of the substrate. Insulation for manufacturing electronic devices It aims to provide a film.

However, the technical problem to be achieved by the present invention is not limited to the above-mentioned problems, and other problems not mentioned will be clearly understood by those skilled in the art from the following description.

According to an embodiment of the present invention, the insulating film for manufacturing an electronic device according to the present invention is a composition comprising a thermosetting resin including an epoxy component, a thermoplastic resin, a curing agent, and a _{filler having an average particle size (D 50} ) of 0.1 μm to 3 μm. It is a cured product and satisfies the general formula (1).

[General formula 1]

0.5 < log (α2/α1) < 0.8

In Formula 1, α1 represents the coefficient of thermal expansion before the glass transition temperature (Tg) of the insulating film, and α2 is the coefficient of thermal expansion after the glass transition temperature (Tg) of the insulating film. Expansion).

The insulating film for manufacturing an electronic device according to the present invention has an average particle size range of the filler, a coefficient of thermal expansion before the glass transition temperature (Tg) and a coefficient of thermal expansion after the glass transition temperature (Tg). By limiting the range, it is possible to prevent a difference in the coefficient of thermal expansion between the components embedded in the electronic device and the insulating film surrounding the electronic components. As a result, it is possible to prevent the occurrence of cracks, warping or distortion in the substrate during the lamination molding process of the electronic component and the insulating film.

In addition, since the insulating film for manufacturing an electronic device according to the present invention exhibits excellent flexibility, it can be applied to a flexible substrate as well as used as an interlayer adhesive film capable of thinning a multilayer printed circuit board.

1 is a cross-sectional view showing an insulating film according to an embodiment of the present invention.
2 is a cross-sectional view of a printed circuit board on which an insulating film is laminated according to an embodiment of the present invention.

The objects, specific advantages and novel features of the present invention will become more apparent from the following detailed description taken in conjunction with the accompanying drawings and preferred embodiments. In the present specification, in adding reference numbers to the components of each drawing, it should be noted that only the same components are given the same number as possible even though they are indicated on different drawings. In addition, terms such as "first", "second", "one side", "the other side" are used to distinguish one component from other components, and it is not that the component is limited by the terms no. Hereinafter, in describing the present invention, detailed descriptions of related known technologies that may unnecessarily obscure the gist of the present invention will be omitted.

The insulating film for manufacturing an electronic device according to the present invention is a cured product of a composition including a thermosetting resin containing an epoxy component, a thermoplastic resin, a curing agent, and a _{filler having an average particle size (D 50} ) of 0.1 μm to 3 μm, Satisfies.

[General formula 1]

0.5 < log (α2/α1) < 0.8

In Formula 1, α1 represents the coefficient of thermal expansion before the glass transition temperature (Tg) of the insulating film, and α2 is the coefficient of thermal expansion after the glass transition temperature (Tg) of the insulating film. Expansion).

First, the composition of the insulating film for manufacturing an electronic device according to the present invention includes a thermosetting resin including an epoxy component.

The thermosetting resin including the epoxy component may impart heat resistance of an insulating film, bonding reliability between electronic device products, and an adhesive function. The thermosetting resin including the epoxy component is an insulating resin material, preferably a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a bisphenol S type epoxy resin, a bisphenol AF type epoxy resin, a dicyclopentadiene type epoxy resin, and a tris Phenolic epoxy resin, naphthol novolac epoxy resin, phenol novolak type epoxy resin, tert-butyl-catechol type epoxy resin, naphthalene type epoxy resin, glycidylamine type epoxy resin, glycidyl ester type epoxy resin, cresol novolac Epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin, alicyclic epoxy resin, heterocyclic epoxy resin, spiro ring-containing epoxy resin, cyclohexanedimethanol type epoxy resin, naphthylene ether type epoxy resin and trimethylol type epoxy resin and the like, and the epoxy resin may be used alone or in combination of two or more.

More specifically, the thermosetting resin may include a low-viscosity epoxy resin having a viscosity of 500 cps to 4,000 cps at room temperature (25° C.). Preferably, the thermosetting resin may include a low-viscosity epoxy resin having a viscosity of 1,000 cps to 3,500 cps at room temperature. More preferably, the thermosetting resin may include a low-viscosity epoxy resin having a viscosity of 1,500 cps to 3,500 cps at room temperature. When the thermosetting resin includes an epoxy resin having a viscosity of less than 500 cps, the insulating film deposited on the substrate overflows out of the substrate, thereby increasing the bleed area. The thermosetting resin according to the present invention contains a low-viscosity epoxy resin having a viscosity of 500 cps to 4,000 cps at room temperature, so that it can quickly penetrate into the gap between the electronic device product and the substrate due to excellent fluidity and flowability. can

In addition, the thermosetting resin may further include an epoxy resin having a solid state at room temperature (25° C.). When only a liquid epoxy resin is included as the thermosetting resin, the occurrence of voids between the substrate and the insulating film may increase as the tacky of the insulating film increases, and thus the bonding reliability between electronic device products may be reduced. have. In addition, there may be a problem that the curing rate of the insulating film composition is lowered. Therefore, as the epoxy resin among the thermosetting resins, it is preferable to include an epoxy resin having a solid state in an amount of 20 wt% to 80 wt%.

Next, the composition of the insulating film for manufacturing an electronic device according to the present invention includes a thermoplastic resin.

When the insulating film composition is formed in the form of a film, the thermoplastic resin may provide mechanical properties that are not easily torn, broken, or adhered. In addition, as it is uniformly dispersed in the insulating film, it is possible to impart resistance to cracking by evenly distributing and alleviating the stress generated inside the insulating film under the condition of repetitive flexing fatigue applied to the substrate. The thermoplastic resin is polyester resin, polyether resin, polyamide resin, polyamideimide resin, polyimide resin, polyvinyl butyral resin, polyvinyl formal resin, phenoxy resin, polyhydroxy polyether resin, polystyrene resins, butadiene resins, acrylonitrile-butadiene copolymers, acrylonitrile-butadiene styrene resins, styrene-butadiene copolymers, and the like, and the thermoplastic resins may be used alone or in combination of two or more. Preferably, the thermoplastic resin may include at least one of acrylonitrile butadiene rubber (NBR) and phenoxy resin, and thus may be more effective in realizing physical properties required for the insulating film.

Next, the composition of the insulating film for manufacturing an electronic device according to the present invention includes a curing agent.

The curing agent may improve the heat resistance of the insulating film. The curing agent is not particularly limited as long as it has a function of curing the thermosetting resin, but preferably at least one of an amine type hardener, a phenol type hardener, and an acid anhydride type hardener. can be used

Next, the composition of the insulating film for manufacturing an electronic device according to the present invention _{includes a filler having an average particle size (D 50} ) of 0.1 μm to 3 μm.

The filler may improve mechanical properties and reduce stress of the insulating film, and may reduce bleed caused by an increase in viscosity due to a specific surface area. In particular, the filler according to the present invention has an average particle size (D ₅₀ ) of 0.1 μm to 3 μm. Preferably, the filler may have an average particle size (D ₅₀ ) of 0.2 μm to 3 μm. More preferably, the filler may have an average particle size (D ₅₀ ) of 0.5 μm to 2 μm. The average particle size (D ₅₀ ) of the filler may be measured using, for example, a laser diffraction method. The laser diffraction method is generally capable of measuring particle sizes from a submicron region to several mm, and high reproducibility and high resolution results can be obtained. The filler having an average particle size (D ₅₀ ) of 0.1 μm to 3 μm according to the present invention can implement a low coefficient of thermal expansion of the insulating film, and lower the increase rate of the coefficient of thermal expansion of the insulating film at high temperature, so that the components embedded in the electronic device and the above It is possible to reduce the imbalance in the coefficient of thermal expansion between the insulating films surrounding the electronic components. As a result, it is possible to prevent the occurrence of cracks or warpage or distortion in the substrate during the lamination molding process of the electronic component and the insulating film.

Examples of the filler include silica, alumina, barium sulfate, talc, clay, mica powder, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum borate, barium titanate, strontium titanate, calcium titanate, titanate. and magnesium, bismuth titanate, titanium oxide, barium zirconate, and calcium zirconate, and the filler may be used alone or in combination of two or more. The filler is preferably silica such as amorphous silica, fused silica, crystalline silica, synthetic silica, hollow silica, and more preferably, the filler is spherical silica.

Next, the composition of the insulating film for manufacturing an electronic device according to the present invention, based on 100 parts by weight of the thermosetting resin, 10 to 60 parts by weight of the thermoplastic resin, 5 to 50 parts by weight of the curing agent, 50 to 400 parts by weight of the filler. can

When the amount of the thermoplastic resin is less than 10 parts by weight based on 100 parts by weight of the thermosetting resin, brittleness occurs in a state in which the insulating film is not completely cured, thereby causing a problem in which the contact surface between the insulating film and the substrate is broken. In addition, when the amount of the thermoplastic resin is more than 60 parts by weight based on 100 parts by weight of the thermosetting resin, there may be a problem in that the insulating film is separated from the substrate during manufacture or use of an electronic device.

When the curing agent is less than 5 parts by weight based on 100 parts by weight of the thermosetting resin, a problem of deterioration in heat resistance of the insulating film may occur. In addition, when the curing agent is more than 50 parts by weight based on 100 parts by weight of the thermosetting resin, there may be a problem in that the adhesive strength is lowered.

When the filler is less than 50 parts by weight based on 100 parts by weight of the thermosetting resin, the flame retardancy may be reduced or the coefficient of thermal expansion of the insulating film may be increased. Accordingly, a difference between the thermal expansion coefficient of the insulating film and the thermal expansion coefficient of the electronic device parts in contact with the insulating film may occur, which may cause cracks, warping, or distortion, and the insulating film peels off from the electronic device parts. may occur. In addition, when the filler is more than 400 parts by weight based on 100 parts by weight of the thermosetting resin, there may be a problem in that the interface is separated during the manufacturing of the substrate due to deterioration of the adhesiveness of the insulating film.

Next, the insulating film for manufacturing an electronic device according to the present invention may further include a carrier film covering one side of the insulating film and a cover film covering the other side of the insulating film.

1 illustrates a cross-sectional view of an insulating film to which a carrier film and a cover film are attached according to an embodiment of the present invention. 1 , one side of the insulating film 100 according to the present invention is covered with a carrier film 120 , and the other side of the insulating film 100 is covered with a cover film 110 . The carrier film 120 serves to protect the insulating film 100 from external environmental factors. Also, the carrier film 120 may be separated from the insulating film 100 when the insulating film 100 is deposited on the substrate 200 and the first circuit 210 . The type of the carrier film 120 is not particularly limited, but it is preferable to include oriented polypropylene (OPP) in consideration of the release force and economic feasibility with the insulating film 100 .

The cover film 110 protects the insulating film 100 from external environmental factors, and is separated from the cured insulating film 100 during the manufacturing of a printed circuit board to prevent damage to the insulating film 100 . have. The type of the cover film 110 is not particularly limited, but it is preferable to include polyethylene terephthalate (PET) in consideration of the release force and economic feasibility with the insulating film 100 after curing.

The cross-sectional thickness of the insulating film 100 is not particularly limited, but considering the use applied to the printed circuit board, when the cross-sectional thickness of the insulating film 100 is less than 25 μm, it is difficult to automate the process, and the insulating film 10 When the cross-sectional thickness of is more than 50 μm, economical efficiency is lowered, and the cross-sectional thickness of the insulating film 100 is preferably 25 μm to 50 μm.

In particular, the coefficient of thermal expansion before the glass transition temperature (Tg) and the coefficient of thermal expansion after the glass transition temperature (Tg) of the insulating film for manufacturing an electronic device according to the present invention are represented by the following general formula 1 is satisfied with

[General formula 1]

0.5 < log (α2/α1) < 0.8

In Formula 1, α1 represents the coefficient of thermal expansion before the glass transition temperature (Tg) of the insulating film, and α2 is the coefficient of thermal expansion after the glass transition temperature (Tg) of the insulating film. Expansion).

In general, the coefficient of thermal expansion (Coefficient of Thermal Expansion) of an insulating film is an important factor determining heat resistance, dimensional stability of a circuit pattern formed on the insulating film, and the like. The thermal expansion coefficient of the insulating film may be measured through a thermomechanical analysis (TMA) method.

A process for manufacturing an electronic device such as a printed circuit board includes sequentially laminating and compressing the insulating film, and in particular, the insulating film is adhered to the substrate and then subjected to a curing process. That is, the insulating film including the organic polymer material expands due to the movement of molecules in the polymer material by the curing process, which may change the thermal expansion characteristics of the insulating film.

For example, FIG. 2 shows a printed circuit board 10 on which insulating films 110a and 110b are stacked according to an embodiment of the present invention. As shown in FIG. 2 , it can be seen that the insulating film 110a is in contact with the stacked insulating film 110b , the substrate 200 , the first circuit 210 , and the second circuit 220 . In the manufacture of the printed circuit board 10, the insulating films 110a and 110b including the organic polymer material increase the coefficient of thermal expansion during the curing process at a high temperature, and accordingly, the solid substrate 200 and the first circuit 210 ) and an imbalance with the coefficient of thermal expansion with the second circuit 220 . That is, due to the imbalance in the coefficient of thermal expansion at the interface (not shown) where the insulating film 110a and the substrate 200, the first circuit 210, and the second circuit 220 are in contact with each other, the manufactured printed circuit A crack may be generated in the substrate 10 , or warpage or distortion may occur.

As such, the insulating films 110a and 110b necessarily undergo a high temperature curing process during the printed circuit board manufacturing process. , 110b) also affects the reliability of the product. For example, even if the disparity between the thermal expansion coefficient of the insulating film before curing and the thermal expansion coefficient of the substrate is not large, if the thermal expansion coefficient of the insulating film increases significantly during the high-temperature curing process, the imbalance between the thermal expansion coefficient of the insulating film and the thermal expansion coefficient of the substrate is can grow In addition, even if the thermal expansion coefficient of the insulating film before curing is slightly different, if the thermal expansion coefficient of the insulating film does not increase significantly during the high temperature curing process, the imbalance between the thermal expansion coefficient of the insulating film and the thermal expansion coefficient of the substrate may be reduced. have. That is, in the manufacturing process of an electronic device such as a printed circuit board, it can be seen that the thermal expansion coefficient of the insulating film before curing and the thermal expansion coefficient of the insulating film during the high temperature curing process are closely related to each other.

The present invention is by deriving an insulating film for manufacturing electronic devices in which the coefficient of thermal expansion before the glass transition temperature (Tg) and the coefficient of thermal expansion after the glass transition temperature (Tg) satisfy the following general formula (1). The film can prevent an increase in the imbalance of the coefficient of thermal expansion between the components embedded in the electronic device and the insulating film surrounding the electronic components, and cracks are generated on the substrate during the lamination molding process of the electronic component and the insulating film. There is an effect that can prevent bending or distortion from occurring.

[General formula 1]

0.5 < log (α2/α1) < 0.8

In Formula 1, α1 represents the coefficient of thermal expansion before the glass transition temperature (Tg) of the insulating film, and α2 is the coefficient of thermal expansion after the glass transition temperature (Tg) of the insulating film. Expansion).

The insulating film according to the present invention includes an organic polymer material such as a thermosetting resin and a thermoplastic resin including an epoxy component. As the temperature of the organic polymer material included in the insulating film increases, molecules begin to move with activity, and the point at which the molecules move with activity is referred to as the glass transition temperature (Tg). The glass transition temperature (Tg) may be measured through a thermomechanical analysis (TMA) method.

More specifically, in the general formula 1, the glass transition temperature (Tg) may be 100 ℃ to 190 ℃, in the general formula 1 α1 represents the coefficient of thermal expansion at 50 ℃ to 100 ℃, α2 is 190 ℃ 210 It can represent the coefficient of thermal expansion at ℃.

In Formula 1, the relationship between the coefficient of thermal expansion (α1) before the glass transition temperature (Tg) of the insulating film and the coefficient of thermal expansion (α2) after the glass transition temperature (Tg) of the insulating film is 0.5 < log (α2/α1) < 0.8, preferably 0.514 ≤ log (α2/α1) ≤ 0.744.

In Formula 1, when log (α2/α1) ≤ 0.5, the coefficient of thermal expansion before the glass transition temperature (Tg) is relatively high compared to the coefficient of thermal expansion after the glass transition temperature (Tg). and the heat resistance reliability may be reduced. In addition, in the case of 0.8 ≤ log (α2/α1) in Formula 1, the coefficient of thermal expansion after the glass transition temperature (Tg) significantly increases compared to the coefficient of thermal expansion before the glass transition temperature (Tg) of the insulating film. The imbalance in the coefficient of thermal expansion between the embedded components and the insulating film surrounding the electronic components is significantly increased, so that cracks or warpage or distortion may occur in the substrate during the lamination molding process of the electronic component and the insulation film.

For example, in Formula 1, α1 may have a thermal expansion coefficient of 45 ppm/°C or more, or α2 may have a thermal expansion coefficient of 250 ppm/°C or less. When the coefficient of thermal expansion of α1 is less than 45 ppm/℃ or the coefficient of thermal expansion of α2 is more than 250 ppm/℃, the peel strength between the insulating film and the substrate is lowered, so that the insulating film is separated from the substrate, or Thermal expansion may reduce thermal reliability.

The insulating film for manufacturing an electronic device according to the present invention is flexible, and in order to be applicable to thinning of a flexible substrate and a multilayer printed circuit board, the tensile modulus of elasticity at room temperature (25° C.) may be 0.5 GPa to 5 GPa. Preferably, the insulating film may have a tensile modulus of elasticity at room temperature (25° C.) of 0.5 GPa to 4.5 GPa. The tensile modulus of elasticity of the insulating film is a value measured while stretching at a rate of 10 mm/min under a condition of 50% RH. When the tensile modulus of elasticity at room temperature of the insulating film is less than 0.5 GPa, the rigidity of the insulating film is low and can be easily broken by an external impact. Although excellent, a problem in which sufficient flexibility cannot be secured may occur.

The insulating film for manufacturing an electronic device according to the present invention can be used for a printed circuit board that can be easily embedded even in a narrow space, and can also be used for a flexible printed circuit board having compactness and high density, and having repetitive flexibility.

In addition, the printed circuit board is a core component of electronic products, and includes mobile phones, cameras, notebook computers, and peripheral devices, wearable devices, video and audio devices, camcorders, printers, DVD players, TFT LCD displays, satellite devices, and military equipment. , and may be used in at least one of medical equipment, and preferably may be used in at least one of a mobile phone, a camera, a notebook computer, and a wearable device.

Hereinafter, preferred examples are presented to help the understanding of the present invention. However, the following examples are only provided for easier understanding of the present invention, and the contents of the present invention are not limited by the following examples.

<Example>

1. Example 1

(1) Preparation of insulating film composition

40 parts by weight of liquid epoxy resin having a viscosity of 2,500 cps to 2,800 cps (manufacturer: Kukdo Chemical, product name: KDS8161), 40 parts by weight of solid epoxy resin (manufacturer: NIPPON KAYAKU, product name: NC-3000), 20 parts by weight of phenoxy resin (Manufacturer: Gabriel, product name: PKHH), 4 parts by weight of acrylonitrile butadiene rubber (manufacturer: ZEON, product name: NIPOL 1072CGX) was stirred with 50 parts by weight of solvent naphtha and dissolved by heating. After cooling the mixture to room temperature, 40 parts by weight of a curing agent (manufacturer: DIC, product name: LA-7052), 0.1 parts by weight of an imidazole-based curing accelerator (manufacturer: SHIKOKU, product name: 2E4MZ), epoxy silane having an average particle size of 0.5 μm 120 parts by weight of surface-treated spherical silica (manufacturer: ADMATEC, product name: SC-2050MB) was mixed and uniformly dispersed with a mixer to prepare an insulating film composition.

(2) Manufacturing of insulating film

A polyethylene terephthalate film (manufacturer: Yulchon Chemical, product name: P38-S-3) was prepared as a cover film, and the insulating film composition was uniformly applied to the surface of the cover film with a die coater, and at 80 ° C to 110 ° C. After drying for 4 minutes, an insulating film was formed on the cover film. The cross-sectional thickness of the insulating film was 35 μm. Insulation with a cover film and a carrier film attached to the surface of the insulating film by laminating an oriented polypropylene film (manufacturer: Ojitokushu, product name: MA-411) as a carrier film at 70°C and atmospheric pressure A film was prepared.

(3) Attachment of insulating film to silicon wafer substrate

The first side (substrate and semiconductor device) of a silicon wafer substrate having bumps made of Sn/Ag (60 μm in height, 150 μm in pitch) on both surfaces of an insulating film having a cover film removed with a diameter of 8 inches and a thickness of 500 μm. surface to be connected), and then laminated using a vacuum laminator under the conditions of a lamination speed of 0.1 mm/min, a pressure of 0.3 Mpa, and a temperature of 200° C. to prepare a silicon wafer substrate with an insulating film attached thereto.

2. Example 2

In the process of preparing the composition of the insulating film of Example 1, instead of the spherical silica surface-treated with epoxy silane, spherical silica surface-treated with aminosilane having an average particle size of 0.5 μm (manufacturer: ADMATEC, product name: SC-2050MNS) was added by 120 weight An insulating film and a silicon wafer substrate to which the insulating film was attached were prepared in the same manner as in Example 1, except that it was used.

3. Example 3

In the same manner as in Example 1, the insulating film and A silicon wafer substrate to which the insulating film was attached was manufactured.

4. Example 4

In the process of preparing the composition of the insulating film of Example 1, the insulating film and the insulating film were attached in the same manner as in Example 1, except that 40 parts by weight of the curing agent (manufacturer: DIC, product name: KA-1165) was adjusted. A silicon wafer substrate was prepared.

5. Example 5

In the process of preparing the composition of the insulating film of Example 4, the insulating film and the insulating film were attached in the same manner as in Example 4 except that 20 parts by weight of the phenoxy resin (manufacturer: JER, product name: YX8100BH30) was adjusted. A silicon wafer substrate was prepared.

6. Example 6

An insulating film and a silicon wafer substrate to which the insulating film is attached were prepared in the same manner as in Example 1, except that the content of the phenoxy resin was adjusted to 40 parts by weight in the process of preparing the composition of the insulating film of Example 1 .

7. Example 7

In the same manner as in Example 1, except that the content of acrylonitrile-butadiene rubber was adjusted to 2 parts by weight in the process of preparing the composition of the insulating film of Example 1, the insulating film and the silicone to which the insulating film was attached A wafer substrate was prepared.

8. Example 8

In the process of preparing the composition of the insulating film of Example 1, 30 parts by weight of a liquid epoxy resin having a viscosity of 2,500 cps to 2,800 cps (Manufacturer: Kukdo Chemical, Product Name: KDS8161), 50 parts by weight of a solid epoxy resin (Manufacturer: NIPPON KAYAKU, Product name: NC-3000) was prepared in the same manner as in Example 1, except that an insulating film and a silicon wafer substrate to which the insulating film was attached were prepared.

9. Comparative Example 1

In the process of preparing the composition of the insulating film of Example 1, the insulating film and the insulating film were attached in the same manner as in Example 1, except that alumina having an average particle size of 3.2 μm was used instead of spherical silica having an average particle size of 0.5 μm. A silicon wafer substrate was prepared.

10. Comparative Example 2

In the process of preparing the composition of the insulating film of Example 1, the insulating film and the insulating film were attached in the same manner as in Example 1, except that spherical silica having an average particle size of 0.08 μm was used instead of spherical silica having an average particle size of 0.5 μm. A silicon wafer substrate was prepared.

11. Comparative Example 3

In the process of preparing the composition of the insulating film of Example 1, the insulating film and the insulating film were attached in the same manner as in Example 1, except that titanium oxide having an average particle size of 0.08 μm was used instead of spherical silica having an average particle size of 0.5 μm. A silicon wafer substrate was prepared.

12. Comparative Example 4

In the process of preparing the composition of the insulating film of Example 1, the insulating film and the insulating film were attached in the same manner as in Example 1, except that spherical silica having an average particle size of 3.15 μm was used instead of spherical silica having an average particle size of 0.5 μm. A silicon wafer substrate was prepared.

13. Comparative Example 5

In the process of preparing the composition of the insulating film of Example 1, the insulating film and the insulating film were attached in the same manner as in Example 1, except that titanium oxide having an average particle size of 3.2 μm was used instead of spherical silica having an average particle size of 0.5 μm. A silicon wafer substrate was prepared.

<Experimental Example 1> - Measurement of coefficients of thermal expansion (α1, α2) of insulating film

The insulating films prepared in Examples 1 to 8 and Comparative Examples 1 to 5 were prepared as test stripes for evaluation. First, each of the specimens was mounted on a holder to have a length of 10 mm, and a force was applied to both ends with 0.05N, and the length of the specimen was measured under the condition of a temperature increase rate of 10°C/min from 50°C to 250°C. The inflection point seen in the temperature increase section is specified as the glass transition temperature (Tg). Next, the coefficient of thermal expansion (CTE) required at the same time by measuring the glass transition temperature (Tg) was measured. The coefficient of thermal expansion α1 at a temperature lower than the glass transition temperature (Tg) was calculated as the slope of the specimen stretched from 50°C to 100°C, and the coefficient of thermal expansion α2 at a temperature higher than the glass transition temperature (Tg) was from 190°C to 210°C. It was calculated with the inclination of the stretched specimen.

<Experimental Example 2> - Measurement of tensile modulus of insulating film

The insulating films prepared in Examples 1 to 8 and Comparative Examples 1 to 5 were prepared as specimens having a width of 10 mm and a length of 100 mm. Each of the above specimens was mounted on a tensile strength measuring device, and the strength until fracture was measured while tensile at a rate of 10 mm/min under the conditions of 25 ° C and 50% H, and the tensile modulus of elasticity was measured by the following general formula 2.

[General formula 2]

Tensile modulus = (F/S) / (△L/L)

* F is the tensile strength, S is the cross-sectional area of the specimen, ΔL is the initial strain, and L is the sample standard distance of 20 mm.

<Experimental Example 3> - Measurement of warpage or distortion of the substrate

The maximum value of warpage or distortion of the silicon wafer substrates with the insulating films prepared in Examples 1 to 8 and Comparative Examples 1 to 5 was measured with a laser measuring device.

<Experimental Example 4> - Determination of cracks or peeling of the substrate

In Examples 1 to 8 and Comparative Examples 1 to 5, a total of 1,300 of each 100 silicon wafer substrates with an insulating film attached thereto were maintained at a temperature of -45° C. for 30 minutes, and the temperature was raised to 125° C. for 30 minutes. After 1000 cycles of thermal shock temperature cycle test by maintaining for a while, cracks or peeling of the substrate were visually confirmed.

When cracks and peeling were not observed on the substrate visually, it was judged to be suitable.

The evaluation results of Experimental Examples 1 to 4 are shown in Table 1 below.

α1 of the insulating film
Coefficient of thermal expansion (ppm/℃) α2 of the insulating film
Coefficient of thermal expansion (ppm/℃) Log(α2/α1)* Tensile modulus (GPa) warp or
Warp (㎛) crack and
Number of substrates for which no delamination was observed Example 1 51 210 0.61 4.4 67 99 Example 2 45.7 223 0.69 4.1 52 98 Example 3 46.3 221 0.68 3.8 63 99 Example 4 51.1 200 0.59 2.9 53 99 Example 5 51 190 0.57 3.2 53 98 Example 6 46.5 201.2 0.64 2.8 55 99 Example 7 47.7 202 0.63 3.1 54 99 Example 8 48.3 199 0.61 3.5 49 98 Comparative Example 1 32 280 0.94 5.3 316 32 Comparative Example 2 45 320 0.85 5.1 222 45 Comparative Example 3 48 320 0.82 3.5 221 54 Comparative Example 4 55 170 0.49 2.1 128 98 Comparative Example 5 54.7 166 0.48 2.2 158 97

* In the log(α2/α1), α1 is the coefficient of thermal expansion from 50°C to 100°C, and α2 is the coefficient of thermal expansion from 190°C to 210°C.

As can be seen in Table 1, Comparative Examples 1 to 5, which do not satisfy [General Formula 1] 0.5 < log (α2/α1) < 0.8, have warpage or distortion in the substrate due to the difference in the coefficient of thermal expansion between the insulating film and the substrate. It can be seen that a large In addition, in Comparative Examples 1 to 3, it can be confirmed that a number of cracks or peeling occurred on the substrate. [General Formula 1] In the insulating films of Examples 1 to 8 satisfying 0.5 < log (α2/α1) < 0.8, warpage or distortion hardly occurred in the substrate, and cracks and peeling were not observed in the majority of substrates. In addition, it can be confirmed that it can be used as an interlayer adhesive film capable of thinning a multilayer printed circuit board as well as being applicable to a flexible substrate due to its excellent elastic modulus.

Although the present invention has been described as described above, the present invention is not limited by the embodiments disclosed herein, and it is apparent that various modifications may be made by those skilled in the art within the scope of the technical idea of the present invention. In addition, even if the effect of the configuration of the present invention is not explicitly described and described while describing the embodiment of the present invention, it is natural that the effect predictable by the configuration should also be recognized.

Claims (18)

Thermosetting resin containing an epoxy component;
thermoplastic resin;
hardener; and
It is a cured product of a composition comprising; a filler having an average particle size (D _{50 ) of 0.1 μm to 3 μm,}
An insulating film for manufacturing an electronic device that satisfies the following general formula 1:
[General formula 1]
0.5 < log (α2/α1) < 0.8
In Formula 1, α1 represents the coefficient of thermal expansion before the glass transition temperature (Tg) of the insulating film, and α2 is the coefficient of thermal expansion after the glass transition temperature (Tg) of the insulating film. Expansion).
The method of claim 1,
The glass transition temperature (Tg) is characterized in that 100 ℃ to 190 ℃
Insulation film for manufacturing electronic devices.
The method of claim 1,
In the general formula 1, α1 represents the coefficient of thermal expansion at 50 °C to 100 °C, and α2 represents the coefficient of thermal expansion at 190 °C to 210 °C, characterized in that
Insulation film for manufacturing electronic devices.
According to claim 1,
α1 in the general formula 1 is characterized in that the thermal expansion coefficient is 45 ppm / ℃ or more
Insulation film for manufacturing electronic devices.
According to claim 1,
α2 in the general formula 1 is characterized in that the coefficient of thermal expansion is 250 ppm / ℃ or less
Insulation film for manufacturing electronic devices.
According to claim 1,
The insulating film has a tensile modulus of 0.5 GPa to 5 GPa at room temperature (25 ℃), characterized in that
Insulation film for manufacturing electronic devices.
According to claim 1,
The insulating film has a cross-sectional thickness of 25 μm to 50 μm.
Insulation film for manufacturing electronic devices.
According to claim 1,
The thermosetting resin is characterized in that it comprises a low-viscosity epoxy resin having a viscosity of 500 cps to 4,000 cps at room temperature (25° C.)
Insulation film for manufacturing electronic devices.
According to claim 1,
The epoxy component is characterized in that it comprises an epoxy component having a solid phase at room temperature (25° C.)
Insulation film for manufacturing electronic devices.
According to claim 1,
The thermoplastic resin, characterized in that it comprises at least one of acrylonitrile butadiene rubber (NBR) and phenoxy resin
Insulation film for manufacturing electronic devices.
According to claim 1,
The hardener comprises at least one of an amine type hardener, a phenol type hardener, and an anhydride type hardener.
Insulation film for manufacturing electronic devices.
According to claim 1,
The filler is characterized in that spherical silica
Insulation film for manufacturing electronic devices.
According to claim 1,
The composition is characterized in that it comprises 10 to 60 parts by weight of the thermoplastic resin, 5 to 50 parts by weight of the curing agent, and 50 to 400 parts by weight of the filler, based on 100 parts by weight of the thermosetting resin.
Insulation film for manufacturing electronic devices.
According to claim 1,
a carrier film covering one surface of the insulating film; and
A cover film covering the other surface of the insulating film; characterized in that it further comprises
Insulation film for manufacturing electronic devices.
15. The method of claim 14,
The carrier film is characterized in that it comprises an oriented polypropylene (OPP: Oriented polypropylene)
Insulation film for manufacturing electronic devices.
15. The method of claim 14,
The cover film is characterized in that it comprises polyethylene terephthalate (PET: Polyethylene terepthalate).
Insulation film for manufacturing electronic devices.
17. The method according to any one of claims 1 to 16,
The insulating film for manufacturing an electronic device is used for a printed circuit board,
Insulation film for manufacturing electronic devices.
18. The method of claim 17,
The printed circuit board is used in at least one of a mobile phone, a camera, a notebook computer, and a wearable device,
Insulation film for manufacturing electronic devices.

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