TWI792364B - Insulation film for electronic device manufacturing - Google Patents

Abstract

The present invention provides an insulating film for manufacturing an electronic device as follows: the insulating film is a cured product of a composition comprising: a thermosetting resin including an epoxy component; a thermoplastic resin; a curing agent; and a filler having an average particle diameter (D50 ) is 0.1 μm to 3 μm, which can prevent electronic accessories and Cracks or bending or warping occur on the substrate during lamination molding of the insulating film, and it exhibits excellent flexibility, so it can be used not only for flexible substrates but also as an interlayer adhesive film that can thin multilayer printed circuit boards .

Description

Insulating films used in the manufacture of electronic devices

The present invention relates to an insulating film for use in manufacturing electronic devices, and more particularly, to an insulating film that has high heat resistance and low thermal expansion, minimizes warping or warping of electronic device substrates, and can reduce defects in electronic device substrates Rate.

Recently, circuit boards such as printed circuit boards (PCBs) are manufactured by sequentially laminating and crimping various build-up insulating films for thinner boards and higher integration.

However, due to the imbalance in physical properties and coefficient of thermal expansion (Coefficient of Thermal Expansion) between the different materials between the printed circuit board and the insulating film, bending or warping may occur in the printed circuit board bonded with the insulating film. If the printed circuit board is bent or warped, subsequent operations such as circuit formation and laser processing cannot be performed, and problems may arise that require discarding the manufactured printed circuit board or performing manual work. These problems arise because the difference in the coefficient of thermal expansion of the insulating film and that of the printed circuit board to which the insulating film is attached, which occurs in the printed circuit board manufacturing process, is not accurately adjusted. In order to solve the above-mentioned problems, it is necessary to study the change of the thermal expansion coefficient according to the temperature of the insulating film.

The problem to be solved by the invention

In order to solve the above-mentioned problems, an object of the present invention is to provide an insulating film for manufacturing electronic devices that prevents the Bending or warping of the substrate.

However, the technical problems to be solved by the present invention are not limited to the above-mentioned problems, and those of ordinary skill in the technical field to which the present invention belongs can clearly understand other technical problems not mentioned through the following description.

technical means to solve problems

According to an embodiment of the present invention, the insulating film used for manufacturing electronic devices of the present invention is a cured product of a composition comprising: a thermosetting resin including an epoxy component; a thermoplastic resin; a curing agent; and a filler, the average particle size of which is The diameter (D50) is 0.1 μm to 3 μm, and the insulating film satisfies the general formula 1.

Formula 1

0.5<log(α2/α1)<0.8

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

Efficacy compared to prior art

The insulating film for manufacturing electronic devices of the present invention can prevent built-in A difference in coefficient of thermal expansion occurs between the component inside the electronic device and the insulating film surrounding the electronic component. As a result, it is possible to prevent the substrate from being cracked or warped or warped during lamination molding of the electronic component and the insulating film.

Also, the insulating film for manufacturing electronic devices of the present invention exhibits excellent flexibility, so that it can be applied not only to flexible substrates but also as an interlayer adhesive film that can thin multilayer printed circuit boards.

The purpose, specific advantages and novel features of the present invention can be more clearly understood through the following detailed description and preferred embodiments associated with the accompanying drawings. It should be noted that in assigning reference numerals to constituent elements in each drawing, even if they are shown in different drawings, the same constituent elements are assigned the same reference numerals as much as possible. Also, terms such as "first", "second", "one side", "another side" are only used to distinguish one structural element from other structural elements, and the structural elements are not limited by these terms. 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 electronic devices of the present invention is a cured product of a composition comprising: a thermosetting resin including an epoxy component; a thermoplastic resin; a curing agent; and a filler having an average particle diameter (D50) of 0.1 μm to 3 μm, the insulating film satisfies General Formula 1.

Formula 1

0.5<log(α2/α1)<0.8

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

First, the composition for manufacturing an insulating film of an electronic device of the present invention contains a thermosetting resin containing an epoxy component.

The thermosetting resin containing an epoxy component can impart heat resistance to an insulating film, bonding reliability between electronic device products, and adhesive functions. The thermosetting resin containing epoxy components is used as the insulating resin material, preferably, for example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, etc. Oxygen resin, dicyclopentadiene type epoxy resin, triphenol epoxy resin, naphthol novolac epoxy resin, novolak type epoxy resin, tert-butylcatechol type epoxy resin, naphthalene type epoxy resin, Glycidylamine epoxy resin, glycidyl ester epoxy resin, cresol novolak epoxy resin, biphenyl epoxy resin, linear aliphatic epoxy resin, cycloaliphatic epoxy resin, heterocyclic epoxy Resins, spiro-ring-containing epoxy resins, cyclohexanedimethanol-type epoxy resins, naphthyl ether-type epoxy resins, trimethylol-type epoxy resins, etc., these epoxy resins 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 4000 cps at normal temperature (25° C.). Preferably, the thermosetting resin may comprise a low-viscosity epoxy resin with a viscosity of 1000 cps to 3500 cps at normal temperature. More preferably, the thermosetting resin may comprise a low-viscosity epoxy resin with a viscosity of 1500cps to 3500cps at normal temperature. If the thermosetting resin contains epoxy resin with a viscosity less than 500 cps, the insulating film evaporated on the substrate will overflow to the outside of the substrate, and thus the problem of increased bleed area may occur. The thermosetting resin of the present invention includes a low-viscosity epoxy resin with a viscosity of 500cps to 4000cps at room temperature. Due to its excellent fluidity, it can quickly penetrate into the gap between the electronic device product and the substrate. Filling and fluidity .

In addition, the thermosetting resin may include an epoxy resin that is solid at normal temperature (25° C.). If the thermosetting resin only contains liquid epoxy resin, as the tackiness of the insulating film increases, the incidence of voids between the substrate and the insulating film may increase. Engagement reliability may decrease. Also, a problem that the curing speed of the insulating film composition decreases may also occur. Therefore, preferably, the thermosetting resin comprises 20% by weight to 80% by weight of epoxy resin in solid form.

Then, the composition for manufacturing an insulating film of an electronic device of the present invention contains a thermoplastic resin.

When the insulating film composition is formed into a film, the thermoplastic resin can impart mechanical properties that are not easily torn, broken or stuck. In addition, since it is uniformly dispersed in the insulating film, the stress generated inside the insulating film under the condition of repeated bending fatigue (flexing fatigue) applied to the substrate is uniformly dispersed and relieved, thereby imparting resistance to crack occurrence. Examples of the thermoplastic resin include polyester resins, polyether resins, polyamide resins, polyamideimide resins, polyimide resins, polyvinyl butyral resins, polyvinyl formal resins, Phenoxy resin, polyhydroxy polyether resin, polystyrene resin, butadiene resin, acrylonitrile butadiene copolymer, acrylonitrile butadiene styrene resin, styrene butadiene copolymer, etc., the thermoplastic resin can Use alone or in combination of two or more. Preferably, the thermoplastic resin can more effectively realize the required physical properties of the insulating film by including one of acrylonitrile butadiene rubber (NBR) and phenoxy resin.

Then, the composition for manufacturing an insulating film of an electronic device of the present invention contains a curing agent.

The curing agent can improve the heat resistance of the insulating film. The curing agent is not particularly limited as long as it has the function of curing thermosetting resins. Preferably, amine type hardeners (amine type hardeners), phenol type hardeners (phenol type hardeners) and acid anhydride type hardeners (Anhydride type hardeners) can be used. type hardener).

Then, the composition for manufacturing an insulating film of an electronic device of the present invention includes a filler having an average particle diameter (D50) of 0.1 μm to 3 μm.

The filler can improve the mechanical properties of the insulating film, reduce stress, and reduce bleed due to viscosity increase in non-surface areas. In particular, the average particle diameter (D50) of the filler of the present invention is 0.1 μm to 3 μm. Preferably, the filler has an average particle diameter (D50) of 0.2 μm to 3 μm. More preferably, the average particle diameter (D50) of the filler may be 0.5 μm to 2 μm. The average particle diameter (D50) of this filler can be measured using the laser diffraction method (laser diffraction method), for example. This laser diffraction method can usually measure particle diameters from the submicron region to several millimeters, and can obtain highly reproducible and highly resolvable results. The filler with an average particle size (D50) of 0.1 μm to 3 μm in the present invention can achieve a low thermal expansion coefficient of the insulating film, and can reduce the number of accessories and enclosures built into the electronic device by reducing the increase rate of the thermal expansion coefficient of the insulating film at high temperature The thermal expansion coefficient imbalance between insulating films of the electronic component. As a result, it is possible to prevent the substrate from being cracked or warped or warped during the layer-by-layer molding of the electronic component and the insulating film.

The type of filler can be, for example, silica, alumina, barium sulfate, talc, clay, mica powder, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum borate, titanic acid Barium, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, barium zirconate, calcium zirconate, and the like can be used alone or in combination of two or more. Preferably, the filler is amorphous silica, fused silica, crystalline silica, synthetic silica, hollow silica and other silica, especially more preferably, the filler can be spherical silica .

Then, relative to 100 parts by weight of the thermosetting resin, the composition for manufacturing an insulating film of an electronic device according to the present invention may include 10 parts by weight to 60 parts by weight of the thermoplastic resin, 5 parts by weight to 50 parts by weight of the cured resin. agent, 50 to 400 parts by weight of the filler.

If the thermoplastic resin is less than 10 parts by weight relative to 100 parts by weight of the thermosetting resin, the insulating film becomes brittle in an incompletely cured state, and the contact surface between the insulating film and the substrate is broken. In addition, if the thermoplastic resin is more than 60 parts by weight relative to 100 parts by weight of the thermosetting resin, there will be a problem that the insulating film is separated from the substrate during the manufacture or use of electronic equipment.

If the curing agent is less than 5 parts by weight with respect to 100 parts by weight of the thermosetting resin, there may be a problem that the heat resistance of the insulating film is lowered. Also, if the curing agent is more than 50 parts by weight relative to 100 parts by weight of the thermosetting resin, a problem of reduced adhesive force may occur.

If the filler is less than 50 parts by weight with respect to 100 parts by weight of the thermosetting resin, the flame retardancy may decrease or the thermal expansion coefficient of the insulating film may become high. Thereby, a difference occurs between the thermal expansion coefficient of the insulating film and the electronic equipment component in contact with the insulating film, so that cracks, warping or warping, and problems of peeling of the insulating film from the electronic equipment component may occur. Moreover, if the filler is more than 400 parts by weight relative to 100 parts by weight of the thermosetting resin, the problem of interface separation may occur during the manufacture of the substrate due to the decrease in the adhesiveness of the insulating film.

Then, the insulating film for manufacturing an electronic device of 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.

FIG. 1 shows a cross-sectional view of an insulating film with a carrier film and a cover film attached thereto according to an embodiment of the present invention. As shown in FIG. 1 , one side of the insulating film 100 of 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 functions to protect the insulating film 100 from external environmental factors. Furthermore, when the insulating film 100 is evaporated on the substrate 200 and the first circuit 210 , the carrier film 120 can be separated from the insulating film 100 . Although the type of the carrier film 120 is not limited, it is preferable to include oriented polypropylene (OPP: Oriented polypropylene) in consideration of release force with the insulating film 100 and economic efficiency.

The cover film 110 protects the insulating film 100 from external environmental factors, and may prevent damage of the insulating film 100 via separation from the cured insulating film 100 when manufacturing a printed circuit board. Although the type of the cover film 110 is not particularly limited, it preferably includes polyethylene terephthalate (PET: Polyethylene terepthalate) in consideration of release force with the insulating film 100 after curing and economic efficiency.

Although the cross-sectional thickness of the insulating film 100 is not particularly limited, considering the application of the printed circuit board, if the cross-sectional thickness of the insulating film 100 is less than 25 μm, it is difficult to apply to process automation. If the cross-sectional thickness of the insulating film 100 is greater than 50 μm , the economy will be reduced. Therefore, preferably, the cross-sectional thickness of the insulating film 100 is 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 of the present invention satisfy the following general formula 1.

Formula 1

0.5<log(α2/α1)<0.8

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

In general, the thermal expansion coefficient of an insulating film is an important factor for 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 can be measured by a thermomechanical analysis (TMA, thermomechanical analysis) method.

The manufacturing process of electronic devices such as printed circuit boards includes the steps of sequentially laminating and crimping the insulating films. In particular, the insulating films are subjected to a curing process after being attached to the substrate. That is, the insulating film including the organic polymer substance expands due to the movement of molecules in the polymer substance caused by the curing process, which may cause deformation of the thermal expansion characteristics of the insulating film.

As an example, FIG. 2 shows a printed circuit board 10 laminated with insulating films 110a and 110b according to an embodiment of the present invention. As shown in FIG. 2 , it was confirmed that the insulating film 110 a was in contact with all the stacked insulating films 110 b , the substrate 200 , the first circuit 210 , and the second circuit 220 . In the manufacture of the printed circuit board 10, the thermal expansion coefficient of the insulating films 110a, 110b including organic polymers increases during the high-temperature curing process, thereby causing thermal expansion with the solid substrate 200, the first circuit 210, and the second circuit 220. imbalance among coefficients. That is, due to the imbalance of thermal expansion coefficients in the interfaces (not shown) where the insulating film 110a is in contact with the substrate 200, the first circuit 210, and the second circuit 220, respectively, cracks may occur in the printed circuit board 10 manufactured or bending or warping may occur. song.

As mentioned above, since the insulating film, 110a, 110b must undergo a high-temperature curing process in the printed circuit board manufacturing process, in addition to the thermal expansion coefficient of the insulating film 110a, 110b before curing, the insulating film in the high-temperature curing process The coefficient of thermal expansion of 110a, 110b will also affect the reliability of the product. For example, even if the imbalance between the thermal expansion coefficient of the insulating film and the thermal expansion coefficient of the substrate before curing is not large, if the thermal expansion coefficient of the insulating film in the high-temperature curing process increases significantly, the imbalance between the thermal expansion coefficient of the insulating film and the thermal expansion coefficient of the substrate May get bigger. In addition, even if there is some difference in the unevenness of the thermal expansion coefficient of the insulating film before curing, if the thermal expansion coefficient of the insulating film does not increase significantly in the high-temperature curing process, the difference between the thermal expansion coefficient of the insulating film and the thermal expansion coefficient of the substrate can be reduced. unbalanced. That is, it is known in the manufacturing process of electronic devices such as printed circuit boards that the thermal expansion coefficient of the insulating film before curing and the thermal expansion coefficient of the insulating film during high-temperature curing have a close relationship with each other.

The present invention derives the thermal expansion coefficient before the glass transition temperature (Tg) and the thermal expansion coefficient after the glass transition temperature (Tg) satisfying the following general formula 1 for manufacturing an insulating film for electronic devices, so that the present invention is used for manufacturing The insulating film of the electronic device has the effect of preventing an uneven increase in the coefficient of thermal expansion between the component built in the electronic device and the insulating film surrounding the electronic component, and preventing the electronic component and the insulating film from being laminated during the lamination molding process. Cracks in the substrate or the effect of bending or warping.

Formula 1

0.5<log(α2/α1)<0.8

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

The insulating film of the present invention contains an organic polymer substance such as a thermosetting resin containing an epoxy component and a thermoplastic resin. The organic polymer substance contained in the insulating film becomes active and moves as the temperature rises, and the time point at which the molecules become active and starts to move is called the glass transition temperature (Tg). The glass transition temperature (Tg) can be measured by a thermomechanical analysis (TMA, thermomechanical analysis) method.

More specifically, in this general formula 1, the glass transition temperature (Tg) can be 100°C to 190°C, in this general formula 1, α1 can represent the thermal expansion coefficient at a temperature from 50°C to 100°C, and α2 can be Indicates the coefficient of thermal expansion at temperatures from 190°C to 210°C.

In this general formula 1, the relationship between the thermal expansion coefficient α1 before the glass transition temperature (Tg) of the insulating film and the thermal expansion coefficient α2 after the glass transition temperature (Tg) of the insulating film satisfies 0.5<log(α2/α1) <0.8, preferably, it can satisfy 0.514≤log(α2/α1)≤0.744.

In this general formula 1, if log(α2/α1)≤0.5, since the thermal expansion coefficient before the glass transition temperature (Tg) is relatively higher than that after the glass transition temperature (Tg), the physical properties of the insulating film may be change, and thermal reliability may decrease. And, in this general formula 1, if 0.8≤log(α2/α1), since the thermal expansion coefficient after the glass transition temperature (Tg) is significantly higher than the thermal expansion coefficient before the glass transition temperature (Tg), built-in The imbalance of thermal expansion coefficient between the components inside the electronic device and the insulating film surrounding the electronic component is significantly increased, so that the substrate may be cracked or warped or warped during lamination molding of the electronic component and the insulating film.

As an example, in General Formula 1, the thermal expansion coefficient represented by α1 may be 45 ppm/°C or higher, or the thermal expansion coefficient represented by α2 may be 250 ppm/°C or lower. If the coefficient of thermal expansion represented by α1 is less than 45ppm/°C, or the coefficient of thermal expansion represented by α2 is greater than 250ppm/°C, the peel strength between the insulating film and the substrate will be reduced, which may cause the insulating film to separate from the substrate, or the insulating film may be separated from the substrate. Thermal expansion due to temperature changes reduces thermal reliability.

In order to be flexible and applicable to the thinning of flexible substrates and multilayer printed circuit boards, the tensile elastic modulus of the insulating film used for manufacturing electronic devices of the present invention may be 0.5GPa to 5GPa at room temperature (25°C). Preferably, the tensile elastic modulus of the insulating film at normal temperature (25° C.) may be 0.5 GPa to 4.5 GPa. The tensile elastic modulus of the insulating film is a value measured when stretched at a speed of 10 mm/min under a humidity (RH) condition of 50%. If the tensile modulus of the insulating film at normal temperature is less than 0.5 GPa, the rigidity of the insulating film may be easily broken due to external impact. If the tensile modulus of the insulating film at normal temperature is greater than 5.0 GPa, although the rigidity of the insulating film is excellent, there may be a problem that sufficient flexibility cannot be ensured.

The insulating film for manufacturing electronic devices of the present invention can be used in printed circuit boards that are easy to incorporate in a small space, and can also be used in flexible printed circuit boards that can be miniaturized and high-density and have repeatability.

Moreover, as a core component of electronic products, the printed circuit board can be used in mobile phones, cameras, notebook computers, computers and peripheral equipment, wearable devices, video and audio equipment, camcorders, printers, high-density digital At least one of video disc (DVD) player, thin film field effect transistor (TFT)-liquid crystal display (LCD) device, satellite equipment, military equipment and medical equipment, preferably, can be used in mobile phones, cameras, notebooks At least one of small computers and wearable devices.

Hereinafter, preferred examples will be provided to help the understanding of the present invention. However, the following examples are provided only for easier understanding of the present invention, and the content of the present invention is not limited by the following examples.

Example

1. Example 1

(1) Preparation of insulating film composition

40 parts by weight of liquid epoxy resin with a viscosity of 2500cps to 2800cps (preparation company: KUKDO Chemical Company, product name: KDS8161), 40 parts by weight of solid epoxy resin 40 parts by weight (preparation company: NIPPON KAYAKU company, product name : NC-3000), 20 parts by weight of phenoxy resin (manufacturing company: Gabriel Company, product name: PKHH), 4 parts by weight of acrylonitrile-butadiene rubber (manufacturing company: ZEON Company, product name: NIPOL 1072CGX) After stirring with 50 parts by weight of solvent naphtha, it was dissolved by heating. After cooling the mixture at room temperature, 40 parts by weight of a curing agent (manufacturing company: DIC Corporation, product name: LA-7052), 0.1 part by weight of an imidazole-based curing accelerator (manufacturing company: SHIKOKU company, product name: 2E4MZ), 120 parts by weight of spherical silica (manufacturing company: ADMATEC, product name: SC-2050MB) treated with epoxysilane with an average particle size of 0.5 μm, and uniformly dispersed using a mixer to prepare an insulating film combination things.

(2) Preparation of insulating film

A polyethylene terephthalate film (manufacturing company: YOULCHON Chemical Co., Ltd., product name: P38-S-3) was prepared as a cover film, and the insulating film composition was uniformly applied to the cover film using a coater. After the surface of the film is dried, it is dried at a temperature of 80° C. to 110° C. for 4 minutes, thereby forming an insulating film on the cover film. The cross-sectional thickness of the insulating film was 35 μm. On the surface of the insulating film, an oriented polypropylene film (manufacturing company: Ojitokushu Co., Ltd, product name: MA-411) was used as a carrier film, and was prepared by lamination at 70°C and normal pressure. Insulating film with cover film and carrier film.

(3) Attach an insulating film on the silicon wafer substrate

Make the insulating film with the cover film removed and the first surface of the silicon wafer substrate (the surface where the substrate and the semiconductor device are connected) with a diameter of 8 inches, a thickness of 500 μm, and bumps (60 μm in height and 150 μm in height) made of Sn/Ag material on both sides. After the contact, the silicon wafer substrate with the insulating film adhered was prepared by bonding using a vacuum coater under the conditions of a coating speed of 0.1 mm/min (min), a pressure of 0.3 MPa, and a temperature of 200°C.

2. Example 2

In addition to using 120 parts by weight of spherical silica (manufacturing company: ADMATEC, product name: SC-2050MNS) with an average particle size of 0.5 μm that uses aminosilane to treat the surface instead of the composition of the insulating film in Example 1 In the preparation process, except for the spherical silicon dioxide on the surface treated with epoxy silane, an insulating film and a silicon wafer substrate attached with the insulating film were prepared in the same manner as in Example 1.

3. Example 3

In addition to adjusting the content of the curing agent during the preparation of the insulating film composition of Example 1 to 30 parts by weight, and adjusting the content of spherical silica with an average particle diameter of 0.5 μm to 110 parts by weight, with An insulating film and a silicon wafer substrate attached with the insulating film were prepared in the same manner as in Example 1.

4. Example 4

Except that the content of the curing agent (preparation company: DIC Corporation, product name: KA-1165) was adjusted to 40 parts by weight during the preparation of the composition of the insulating film of Example 1, the method was the same as that of Example 1. An insulating film and a silicon wafer substrate attached with the insulating film are prepared.

5. Example 5

Except for adjusting the content of phenoxy resin (manufacturing company: JER, product name: YX8100BH30) to 20 parts by weight during the preparation of the insulating film composition of Example 4, prepare insulating film and a silicon wafer substrate attached with the insulating film.

6. Example 6

Except that the content of the phenoxy resin in the preparation process of the insulating film composition of this Example 1 was adjusted to 40 parts by weight, the insulating film and the silicon wafer substrate with the insulating film attached were prepared in the same manner as in Example 1. .

7. Example 7

Except that the content of acrylonitrile-butadiene rubber in the preparation process of the insulating film composition of this Example 1 was adjusted to 2 parts by weight, the insulating film and the insulating film attached were prepared in the same manner as in Example 1. silicon wafer substrate.

8. Example 8

In addition to adjusting the content of liquid-phase epoxy resin (preparation company: KUKDO Chemical Company, product name: KDS8161) with a viscosity of 2500cps to 2800cps during the preparation of the insulating film composition of Example 1 to 30 parts by weight, solid Except that the content of epoxy resin (manufacturing company: NIPPON KAYAKU, product name: NC-3000) was adjusted to 50 parts by weight, an insulating film and a silicon wafer substrate with the insulating film attached were prepared in the same manner as in Example 1.

9. Comparative example 1

In the same manner as in Example 1, except that alumina with an average particle size of 3.2 μm was used instead of spherical silica with an average particle size of 0.5 μm used in the preparation of the insulating film composition of Example 1, An insulating film and a silicon wafer substrate attached with the insulating film are prepared.

10. Comparative example 2

Except that the spherical silica having an average particle diameter of 0.08 μm was used instead of the spherical silica having an average particle diameter of 0.5 μm used in the preparation process of the insulating film composition of Example 1, the method was the same as in Example 1. The insulating film and the silicon wafer substrate attached with the insulating film are prepared by the method.

11. Comparative example 3

In the same manner as in Example 1, except that titanium oxide with an average particle size of 0.08 μm was used instead of spherical silicon dioxide with an average particle size of 0.5 μm used in the preparation of the insulating film composition of Example 1, An insulating film and a silicon wafer substrate attached with the insulating film are prepared.

12. Comparative example 4

Except that the spherical silica having an average particle diameter of 3.15 μm is used instead of the spherical silica having an average particle diameter of 0.5 μm used in the preparation process of the insulating film composition of Example 1, the method is the same as in Example 1. The insulating film and the silicon wafer substrate attached with the insulating film are prepared by the method.

13. Comparative Example 5

In the same manner as in Example 1, except that titanium oxide with an average particle size of 3.2 μm was used instead of the spherical silicon dioxide with an average particle size of 0.5 μm used in the preparation of the insulating film composition of Example 1, An insulating film and a silicon wafer substrate attached with the insulating film are prepared.

Experimental example 1. Measurement of thermal expansion coefficient (α1, α2) of insulating film

The insulating films prepared in Example 1 to Example 8 and Comparative Example 1 to Comparative Example 5 were made into striped test pieces for evaluation. First, place the test pieces on the brackets so that their length reaches 10mm, apply a force of 0.05N at both ends, and measure the temperature of the test pieces under the condition that the temperature rise rate from 50°C to 250°C is 10°C/min. Stretch length. The inflection point seen in the temperature rise range is specified as the glass transition temperature (Tg). Then, the thermal expansion coefficient required at the same time is measured by measuring the glass transition temperature (Tg). The thermal expansion coefficient α1 at a temperature lower than the glass transition temperature (Tg) is calculated from the slope of a stretched test piece from 50°C to 100°C, and the thermal expansion coefficient at a temperature higher than the glass transition temperature (Tg) α2 is calculated from the slope of the test piece stretched from 190°C to 210°C.

Experimental example 2. Determination of tensile elastic modulus of insulating film

The insulating films prepared in Examples 1 to 8 and Comparative Examples 1 to 5 were made into test pieces with a width of 10 mm and a length of 100 mm. Each of the test pieces was installed in a tensile strength tester, stretched at a speed of 10mm/min under the conditions of 25°C and 50% humidity to measure the strength until fracture, and the tensile modulus was measured by the following general formula 2 quantity.

Formula 2

Tensile modulus of elasticity = (F/S)/(△L/L)

*The above-mentioned F represents the tensile strength, S represents the cross-sectional area of the test piece, △L represents the initial denaturation rate, and L represents the standard distance of the sample 20mm.

Experimental example 3. Bend or warpage measurement of substrates

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

Experimental example 4. Determination of cracks or peeling of substrates

Take 100 silicon wafer substrates attached with the insulating films prepared in Examples 1 to 8 and Comparative Examples 1 to 5, and take 1300 in total to keep it at a temperature of -45° C. for 30 minutes, and After raising the temperature to 125° C. and maintaining it for 30 minutes, a thermal shock temperature cycle test was performed. After the test was performed 1000 times in total, cracks or peeling of the substrate were confirmed with the naked eye.

When no crack or peeling of the substrate was observed with the naked eye, it was judged to be acceptable.

The evaluation results of the above-mentioned Experimental Examples 1 to 4 are shown in Table 1 below.

Table 1 α1 thermal expansion coefficient of insulating film (ppm/℃) α2 coefficient of thermal expansion of insulating film (ppm/℃) Log(α2/α1)* Tensile modulus of elasticity (GPa) Bending or warping (μm) Number of substrates where no cracks or peeling were 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 above log(α2/α1), α1 represents the thermal expansion coefficient from 50°C to 100°C, and α2 represents the thermal expansion coefficient from 190°C to 210°C.

From this Table 1, it can be confirmed that in the case of Comparative Examples 1 to 5 that do not satisfy the general formula 1 (0.5<log(α2/α1)<0.8), the difference in thermal expansion coefficient between the insulating film substrates caused the The substrate is significantly warped or warped. Furthermore, it was confirmed that many of the substrates of Comparative Examples 1 to 3 were cracked or peeled off. The insulating films of Examples 1 to 8 satisfying General Formula 1 (0.5<log(α2/α1)<0.8) hardly caused warpage or warpage on the substrate, and cracks and peeling were not observed in most substrates. In addition, it was confirmed that it can be used not only as a flexible substrate but also as an interlayer adhesive film that can reduce the thickness of a multilayer printed circuit board due to its excellent elastic modulus.

Although the present invention has been described in the above-mentioned manner, the present invention is not limited by the embodiments disclosed in the specification. It is obvious that those of ordinary skill in the technical field to which the present invention belongs can carry out Various variants. Furthermore, even if the effects brought about by the structures of the present invention are not clearly described in the foregoing description of the embodiments of the present invention, the predictable effects brought about by the related structures should be recognized.

10: Printed circuit board 100: insulating film 110: Cover film 110a: insulating film 110b: insulating film 120: carrier film 200: Substrate 210: The first circuit 220: second circuit

FIG. 1 is a cross-sectional view showing an insulating film according to an embodiment of the present invention.

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

100: insulating film

110: Cover film

120: carrier film

200: Substrate

210: The first circuit

Claims (12)

An insulating film for manufacturing electronic devices, which is a cured product of a composition, the composition comprising: 100 parts by weight of a thermosetting resin, including bisphenol A type epoxy resin, bisphenol F type epoxy resin, Bisphenol S type epoxy resin, bisphenol AF type epoxy resin, dicyclopentadiene type epoxy resin, triphenol epoxy resin, naphthol novolac epoxy resin, phenol novolak type epoxy resin, tert-butyl o Hydroquinone type epoxy resin, naphthalene type epoxy resin, glycidylamine type epoxy resin, glycidyl ester type epoxy resin, cresol novolak type epoxy resin, biphenyl type epoxy resin, linear aliphatic ring Oxygen resin, cycloaliphatic epoxy resin, heterocyclic epoxy resin, spiro ring-containing epoxy resin, cyclohexanedimethanol epoxy resin, naphthalene ether epoxy resin and trimethylol epoxy resin 10 to 60 parts by weight of a thermoplastic resin, including at least one of acrylonitrile-butadiene rubber and phenoxy resin; 5 to 50 parts by weight of a curing agent, including an amine curing agent , at least one of phenolic curing agent and acid anhydride curing agent; and 50 parts by weight to 400 parts by weight of a filler, including silicon dioxide, the average particle size (D50) of the filler is 0.1 μm to 3 μm, the insulating film Satisfy the following general formula 1, general formula 1: 0.5<log(α2/α1)<0.8; in the general formula 1, α1 represents a thermal expansion coefficient before a glass transition temperature (Tg) of the insulating film, α2 Represents a thermal expansion coefficient after the glass transition temperature (Tg) of the insulating film, the glass transition temperature (Tg) is 100°C to 190°C, the thermal expansion coefficient represented by α1 is above 45ppm/°C, and the thermal expansion coefficient represented by α2 The coefficient of thermal expansion is 250 ppm/°C or less. The insulating film for manufacturing electronic devices as claimed in claim 1, wherein, in the general formula 1, α1 represents a coefficient of thermal expansion at a temperature of 50°C to 100°C, and α2 represents a coefficient of thermal expansion at a temperature of 190°C to 210°C. Thermal expansion coefficient. The insulating film for manufacturing electronic devices according to claim 1, wherein a tensile elastic modulus of the insulating film at a normal temperature of 25° C. is 0.5 GPa to 5 GPa. The insulating film for manufacturing electronic devices according to claim 1, wherein a thickness of the section of the insulating film is 25 μm to 50 μm. The insulating film for manufacturing electronic devices according to claim 1, wherein the thermosetting resin comprises a low-viscosity epoxy resin with a viscosity of 500 cps to 4000 cps at a normal temperature of 25°C. The insulating film for manufacturing electronic devices according to claim 1, wherein the epoxy component includes an epoxy component that is solid at a normal temperature of 25°C. The insulating film for manufacturing electronic devices according to claim 1, wherein the filler is a spherical silicon dioxide. The insulating film for manufacturing electronic devices according to claim 1, further comprising: a carrier film covering one side of the insulating film; and a cover film covering the other side of the insulating film. The insulating film for manufacturing electronic devices as claimed in claim 8, wherein the carrier film comprises an oriented polypropylene. The insulating film for manufacturing electronic devices according to claim 8, wherein the cover film comprises polyethylene terephthalate. The insulating film for manufacturing an electronic device according to any one of claims 1 to 10, wherein the insulating film for manufacturing an electronic device is used for a printed circuit board. The insulating film for manufacturing an electronic device according to claim 11, wherein the printed circuit board is used for at least one of a mobile phone, a video camera, a notebook computer, and a wearable device.

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