TWI785514B - Bonding film, bonding film laminate comprising the same and metal clad laminate comprising the same - Google Patents

Abstract

The present invention provides an adhesive film, an adhesive film-attached laminate thereof, and a metal foil laminate thereof, wherein the adhesive film is formed from a composition for adhesive films comprising an adhesive resin, an epoxy resin, and a filler, wherein the adhesive resin contains a carboxylic acid modified Permanent styrene elastomers, carboxylic acid-modified olefin resins, and polyphenylene ether resins have a dielectric constant (Dk) of 2.5 or less measured under the conditions of 1GHz to 10GHz and 20°C to 80°C after the above-mentioned adhesive film is cured, The dielectric loss (Df) is 0.003 or less, and the moisture absorption rate is 0.1% or less after the above-mentioned adhesive film is cured.

Description

Adhesive film, its adhesive film-attached laminate, and metal foil laminate thereof

The present invention relates to an adhesive film, an adhesive film-attached laminate including the same, and a metal foil laminate including the same. More specifically, the present invention relates to an adhesive film, an adhesive film-attached laminate including the same, and a metal foil laminate including the same, which have low dielectric constant and dielectric loss and moisture absorption over a wide range of temperatures and frequencies. Low rate, excellent adhesion and heat resistance.

Recently, with the trend of integration, miniaturization, thinning, high density, and high bending of electronic products, the necessity of a printed circuit board (PCB) that can be easily embedded in a narrower space has increased. In particular, recently, a flexible printed circuit board (FPCB) having repeated bending properties has been developed. With the technological development of smartphones, portable mobile electronic devices, etc., the use of flexible printed circuit boards has increased dramatically, and the demand for them is also growing.

Generally, in a flexible wiring board, copper foil as a metal foil is laminated on a base film made of polyimide resin or the like as a base film. The base film and the metal foil are bonded to each other through the adhesive film. The existing adhesive film is formed by polyimide-based adhesives, acrylonitrile butadiene rubber-based adhesives, and the like. However, polyimide-based adhesives, acrylonitrile butadiene rubber-based adhesives, and the like are difficult to reduce the dielectric constant and moisture absorption rate.

The background art of the present invention is disclosed in Korean Laid-Open Patent No. 2016-0083204 and the like.

An object of the present invention is to provide an adhesive film with low dielectric constant, dielectric loss and moisture absorption.

Still another object of the present invention is to provide an adhesive film excellent in adhesive force and heat resistance.

Another object of the present invention is to provide an adhesive film with a low rate of change in dielectric constant and dielectric loss due to frequency changes and temperature changes.

Still another object of the present invention is to provide an adhesive film with a low minimum melt viscosity.

Yet another object of the present invention is to provide a low resistance, ion mobility that ensures a proper range of adhesion.

Still another object of the present invention is to provide an adhesive film-attached laminate and a metal foil laminate having the adhesive film of the present invention.

The adhesive film of the present invention is formed from a composition comprising an adhesive resin, an epoxy resin, and a filler. The adhesive resin includes a carboxylic acid-modified styrene elastomer, a carboxylic acid-modified olefin resin, and a polyphenylene ether resin. After the adhesive film is hardened, the dielectric constant (dielectric constant, Dk) measured under the conditions of 1GHz to 10GHz and 20°C to 80°C is 2.5 or less, and the dielectric loss (dielectric loss, Df) is 0.003 or less. After hardening, the moisture absorption rate is less than 0.1%.

In a specific embodiment, the above composition for conjunctiva does not contain a hardening agent.

In a specific embodiment, the glass transition temperature of the above-mentioned carboxylic acid-modified styrene elastomer may be lower than the glass transition temperature of the above-mentioned carboxylic acid-modified olefin resin and the above-mentioned polyphenylene ether resin.

In a specific embodiment, the above-mentioned carboxylic acid modified olefin resin may contain more than one of acrylic acid, methacrylic acid, maleic acid, itaconic acid, fumaric acid, maleic anhydride, itaconic anhydride, fumaric anhydride Modified olefin resins.

In a specific embodiment, the ratio of the total number of moles of carboxylic acid groups in the above-mentioned binder resin to the total number of moles of epoxy groups in the above-mentioned epoxy resin can be 1 to 2, that is, [in the binder resin The total number of moles of carboxylic acid groups]/[the total number of moles of epoxy groups in the epoxy resin] may be 1 to 2.

In a specific embodiment, the difference between the glass transition temperatures of the polyphenylene ether resin and the carboxylic acid-modified olefin resin may be 100°C to 250°C.

In a specific embodiment, the above-mentioned carboxylic acid-modified olefin resin may include carboxylic acid-modified linear polypropylene resin.

In a specific embodiment, in 100 parts by weight of the above-mentioned binder resin, 1 to 20 parts by weight of the above-mentioned carboxylic acid-modified styrene elastomer, 50 to 80 parts by weight of the above-mentioned carboxylic acid-modified permanent olefin resin and 5 to 30 parts by weight of the above-mentioned polyphenylene ether resin.

In a specific embodiment, the aforementioned filler may include a mixture of inorganic nano-silica and fluororesin filler.

In a specific embodiment, relative to 100 parts by weight of the above-mentioned binder resin, 2 to 18 parts by weight of the above-mentioned epoxy resin and 1 to 35 parts by weight of the above-mentioned filler may be included.

In a specific embodiment, at the same frequency, the ratio of the cured dielectric constant to the cured dielectric loss of the above-mentioned adhesive film can be more than 900, that is, the cured dielectric constant/hardened dielectric The electrical loss can be above 900.

In a specific embodiment, the glass transition temperature of the above-mentioned adhesive film after hardening may be 50°C to 80°C.

The adhesive film-adhered laminate of the present invention includes: a polyimide-based resin film; and the adhesive film of the present invention formed on at least one surface of the polyimide-based resin film.

The metal foil laminate of the present invention includes: a polyimide-based resin film; an adhesive film formed on at least one side of the polyimide-based resin film; and a metal foil formed on one side of the adhesive film formed on the adhesive film. Between the said polyimide resin film and the said metal foil, the said adhesive film is the adhesive film of this invention.

The invention provides an adhesive film with low dielectric constant, dielectric loss and moisture absorption.

The present invention provides an adhesive film excellent in adhesive force and heat resistance.

The present invention provides an adhesive film with a low rate of change in dielectric constant and dielectric loss due to frequency changes and temperature changes.

The present invention provides an adhesive film with a low minimum melt viscosity.

The present invention provides low electrical resistance, and ion mobility can ensure a proper range of adhesive membranes.

The present invention provides an adhesive film-adhered laminate and a metal foil laminate having the adhesive film of the present invention.

10: basement membrane

20: First mucosa

30:Second mucous membrane

40: First Metal Foil

50: Second metal foil

[ Fig. 1 ] is a cross-sectional view of an adhesive membrane-adhered laminate according to an embodiment of the present invention.

[ Fig. 2] Fig. 2 is a cross-sectional view of a metal foil laminate according to an embodiment of the present invention.

[ FIG. 3 ] shows the dielectric constant and dielectric loss of the adhesive films of Example 1, Comparative Example 1, and Comparative Example 2 due to frequency changes. In FIG. 3 , Δ is the result of Example 1, ◇ is the result of Comparative Example 1, and □ is the result of Comparative Example 2.

[ Fig. 4 ] shows the dielectric constant and dielectric loss caused by the temperature change of the adhesive film of Example 1 and Comparative Example 2. In FIG. 4 , ○ is the result of Example 1, and □ is the result of Comparative Example 2.

The present invention is described in detail through the following examples, so that those skilled in the art to which the present invention pertains can easily implement the present invention. The present invention can be embodied in various forms, and is not limited to the embodiments described here. In the drawings, in order to clarify the present invention, parts irrelevant to the description are omitted, and the same reference numerals are assigned to the same or similar components throughout the specification. In the drawings, the lengths, thicknesses, etc. of each component are used to illustrate the present invention, and the present invention is not limited to the lengths, thicknesses, etc. described in the drawings.

以及

Y)”。 In this specification, when describing a numerical range, "X to Y" means "above X and below Y (X

as well as

Y)".

In an adhesive film formed from an adhesive film composition containing an adhesive resin, an epoxy resin, and a filler, the inventors of the present invention included a carboxylic acid-modified styrene-based elastomer, a carboxylic acid-modified olefin-based Resin and polyphenylene ether-based resin, thereby confirming that the dielectric constant (Dk), dielectric loss (Df) and moisture absorption rate are remarkably low when the adhesive film is hardened, and completed the present invention.

In this specification, "dielectric constant" and "dielectric loss" are values measured at 1 GHz to 10 GHz and 20°C to 80°C. Preferably, the dielectric constant and dielectric loss are values measured at 10 GHz and 25°C.

Although it will be described below, the adhesive membrane of the present invention is in a semi-hardened state (grade B).

As long as there is no particular description in this specification, "hardening" in "after hardening" means hardening the conjunctiva at a temperature of 150° C. to 200° C. for 45 minutes to 90 minutes. That is, for example, "the dielectric constant after curing" means the dielectric constant measured after curing the adhesive film under the above conditions.

The adhesive film of the present invention has low dielectric constant and dielectric loss after curing over a wide range of frequencies and temperatures, and when the metal foil described below is laminated, reliability can be improved.

In a specific embodiment, the cured dielectric constant of the adhesive film may be less than 2.5, for example, may be 0.1 to 2.50. In the above range, movement of static electricity or electricity to the adhesive film-attached device can be minimized, whereby electric influence on the adhesive film can be minimized.

In a specific embodiment, the dielectric loss of the adhesive film after hardening may be less than 0.003, for example, may be 0.0001 to 0.003. In the above range, movement of static electricity or electricity to the adhesive film-attached device can be minimized, whereby electric influence on the adhesive film can be minimized.

The adhesive film of the present invention can ensure the above-mentioned dielectric constant and dielectric loss, and has a low rate of change in the dielectric constant and a rate of change in the dielectric loss due to frequency changes and temperature changes. As a result, uniform dielectric constant and dielectric loss can be secured over a wide range of frequencies, thereby improving practicability, and uniform dielectric constant and dielectric loss can be secured over a wide range of temperatures, thereby ensuring Reliability based on temperature changes of the adhesive membrane.

In a specific embodiment, in the adhesive film, the change rate of the dielectric constant based on the frequency change of the following formula 1 may be 0.6% or less, for example, may be 0% to 0.6%, based on the frequency change of the following formula 2 The change rate of the dielectric loss of the quantity may be 0.01% or less, for example, may be 0% to 0.01%. In the above-mentioned range, the above-mentioned practicability and reliability can be ensured.

[Formula 1] Change rate of dielectric constant =｜Dk(@10GHz)-Dk(@1GHz)｜/｜10-1｜×100

(In the above formula 1, Dk(@10GHz) is the dielectric constant at the frequency of 10GHz of the adhesive membrane after curing, and Dk(@1GHz) is the dielectric constant of the adhesive membrane at the frequency of 1GHz after curing.)

[Formula 2] Change rate of dielectric loss =｜Df(@10GHz)-Df(@1GHz)｜/｜10-1｜×100

(In the above formula 2, Df(@10GHz) is the dielectric loss at the frequency of 10 GHz of the adhesive membrane after hardening, and Df(@1GHz) is the dielectric loss at the frequency of 1 GHz of the adhesive membrane after curing)

Generally, the higher the measurement frequency, the lower the dielectric constant value of the adhesive membrane, and the higher the measurement frequency, the higher the dielectric loss value of the adhesive membrane. The adhesive film of the present invention can ensure the above-mentioned low dielectric constant and dielectric loss, and reduce the rate of change of the dielectric constant and the rate of change of the dielectric loss in the frequency change, thereby improving the performance of the laminated body described below. Availability and reliability.

In a specific embodiment, in the adhesive film, the change rate of the dielectric constant based on the temperature change of the following formula 3 may be 0.3% or less, for example, may be 0% to 0.3%, based on the temperature change of the following formula 4 The change rate of the dielectric loss of the quantity is 0.001% or less, for example, may be 0% to 0.001%. In the above range, the above-mentioned practicability and reliability can be ensured.

[Formula 3] Change rate of dielectric constant =｜Dk(@80℃)-Dk(@20℃)｜/｜80-20｜×100

(In Equation 3 above, Dk(@80°C) is the dielectric constant at 80°C of the adhesive membrane after hardening, and Dk(@20°C) is the dielectric constant at 20°C of the adhesive membrane after hardening. electric constant)

[Formula 4] Change rate of dielectric loss =｜Df(@80℃)-Df(@20℃)｜/｜80-20｜×100

(In Equation 4 above, Df(@80°C) is the dielectric loss at 80°C of the adhesive film after hardening, Df(@20°C) is the dielectric loss at 20°C of the adhesive film after hardening power loss)

Generally, the higher the measurement temperature, the higher the dielectric constant and dielectric loss value of the adhesive film. The adhesive film of the present invention can ensure the above-mentioned dielectric constant and dielectric loss, and can reduce the change rate of the dielectric constant and the change rate of the dielectric loss during temperature changes, thereby improving the practicability in the above-mentioned laminated body. and reliability.

In one embodiment, in the same frequency of the adhesive film, the ratio of the dielectric constant after hardening to the dielectric loss after hardening (dielectric constant after hardening/dielectric loss after hardening) can be more than 900, for example For example, it can be 900 to 1200. In the above range, when the adhesive film is applied to the laminated body described below, the bonding reliability can be improved, and the adhesiveness and electrical characteristics between the adherends can be improved.

In this specification, the "moisture absorption rate" refers to the value measured by immersion in water (immersion) for 24 hours under the temperature condition of 25 degreeC in accordance with IPC-TM-650 2.6.2.1 with respect to an adhesive film. Usually, moisture permeability is measured in an adhesive film bonding a base film and a metal foil. As is well known to those skilled in the technical field of the present invention, moisture permeability is to measure the degree of moisture passing through the conjunctiva after placing the conjunctiva under high temperature and high humidity conditions. In contrast, the adhesive film of the present invention significantly reduced the moisture absorption rate measured in a state in which the adhesive film was completely immersed in water.

In a specific embodiment, the cured moisture absorption rate of the adhesive film may be less than 0.1%, for example, may be 0% to 0.06%. In the above range, when mounting parts, it is possible to prevent problems with adhesion or electrical characteristics between the respective materials by reducing adverse effects caused by moisture flowing into the materials from the atmosphere.

The adhesive film can simultaneously satisfy the dielectric constant, dielectric loss and moisture absorption rate within the above range. Therefore, when the adhesive film is applied to the metal foil laminate described below, the adhesion reliability can be improved, and the adhesion and electrical characteristics between the adherends can be improved. For example, as in a metal foil laminate, an adhesive film may be used to bond the base film and the metal foil. This will be described in detail below.

The adhesive film of the present invention can ensure flexibility in addition to the above-mentioned electrical characteristics and battery characteristics, and thus, in the laminated body described below, it is used for bonding the base film and the metal plate, and in particular, the production of a flexible printed circuit board becomes easier. Simple.

The adhesive film of the present invention is suitable for the metal foil laminate described below, and has excellent peel strength (peel strength) with respect to the base film (for example, polyimide film) and metal foil (for example, copper plate), so that the bonding reliability is also high. excellent.

In a specific embodiment, the peel strength of the adhesive film after curing measured for a laminate in which the polyimide film, the adhesive film, and the polyimide film are sequentially laminated may be 1000 gf/cm or more. above In the above range, when the adhesive film is applied to the laminate described below, the adhesion reliability can be improved. For example, the above peel strength may be 2000 gf/cm to 3000 gf/cm.

In another specific embodiment, the peel strength of the adhesive film after curing measured for a laminate in which the polyimide film, the adhesive film, and the metal foil are sequentially laminated may be 1000 gf/cm or more. In the above range, when the adhesive film is applied to the laminate described below, the adhesion reliability can be improved. For example, the above peel strength may be 1000 gf/cm to 3000 gf/cm. In this specification, "peel strength" means the value measured based on IPC-TM-650 2.4.8C standard.

The temperature for minimizing the melt viscosity of the adhesive film after hardening may be 120°C to 150°C, for example, may be 125°C to 135°C, in which case the melt viscosity may be 30000Pa.s to 55000Pa.s, for example, 39000Pa .s to 46500Pa.s. In the above range, stable filling properties can be exhibited.

The cured glass transition temperature (Tg) of the adhesive film may be 50°C to 80°C, for example, 50°C to 70°C. In the above range, excellent bendability can be exhibited.

In the adhesive film, the temperature at which a mass loss ratio of 5% occurs based on the following Formula 5 may be 300°C to 500°C, for example, may be 330°C to 450°C. In the above range, the heat resistance of the adhesive film is excellent, and it can be applied to the laminated body demonstrated below.

[Formula 5] Mass loss ratio =｜The heated quality of the hardened conjunctiva-the initial quality of the hardened conjunctiva|/the initial quality of the hardened conjunctiva×100(%)

The temperature at which the above mass loss ratio of 5% occurs can be determined by thermogravimetric analysis (TGA, thermogravimetric analysis). Specifically, for an initial mass of 10 mg of the conjunctiva, it can be measured by heating at an initial temperature of 25° C. at a heating rate of 10° C./min.

The surface resistivity of the adhesive film after hardening may be 1×10 ⁶ MΩ to 10×10 ⁹ MΩ, for example, may be 2×10 ⁶ MΩ to 10×10 ⁹ MΩ. The volume resistivity of the adhesive film after hardening may be 1×10 ⁷ MΩ.cm to 10×10 ⁹ MΩ.cm, for example, may be 2×10 ⁷ MΩ.cm to 10×10 ⁹ MΩ.cm. In the above range, an optimal insulating effect may be obtained. In this specification, surface resistance and volume resistance can be measured by IPC-TM-650 2.5.17.1, respectively.

The thickness of the adhesive film may be 10 μm to 200 μm, for example, may be 20 μm to 100 μm. Within the above range, it can be used for the laminated body demonstrated below.

When a voltage of 50 V is applied to the adhesive membrane at 85° C. and a relative humidity of 85% for 500 hours, ion migration may be 1×10 ¹¹ Ω or more, for example, 1×10 ¹¹ Ω to 1×10 ^13Ω . In the above-mentioned range, it is possible to have an insulation resistance effect between circuits.

The adhesive membrane of the present invention can be embodied by the composition for adhesive membrane described below. Hereinafter, the composition for adhesive membranes of this invention is demonstrated.

The composition includes binder resin, epoxy resin and filler, and the binder resin includes carboxylic acid modified styrene elastomer, carboxylic acid modified olefin resin and polyphenylene ether resin. The composition needs to contain a carboxylic acid-modified styrene elastomer, a carboxylic acid-modified olefin resin, and a polyphenylene ether resin as a binder resin. The effects of the present invention cannot be normally exhibited unless one of the carboxylic acid-modified styrene elastomer, carboxylic acid-modified olefin resin, and polyphenylene ether resin is replaced by another type of resin described below.

In a specific embodiment, the binder resin may only be formed of three types of resins: carboxylic acid-modified styrene elastomer, carboxylic acid-modified olefin resin, and polyphenylene ether resin.

The composition for an adhesive film of the present invention can form an adhesive film by a reaction between a carboxylic acid-modified styrene elastomer, a carboxylic acid group contained in a carboxylic acid-modified olefin resin, and an epoxy resin. Therefore, the composition for adhesive membranes does not contain a curing agent.

The carboxylic acid-modified styrene elastomer is a component of the composition for the adhesive film, and imparts adhesiveness, flexibility and electrical properties to the adhesive film. Carboxylic acid-modified styrene elastomers modify random copolymers, block copolymers or alternating copolymers of conjugated diene compounds and aromatic vinyl compounds into different Saturated carboxylic acid.

The conjugated diene compound may be a conjugated diene compound of 4 carbon atoms to 10 carbon atoms. For example, the conjugated diene compound may be butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene, or the like. Preferably, the conjugated diene compound may be butadiene. The aromatic vinyl compound may be styrene, methylstyrene, divinylbenzene, diphenylstyrene, vinyltoluene, or the like. The unsaturated carboxylic acid may be acrylic acid, methacrylic acid, maleic acid, itaconic acid, fumaric acid, maleic anhydride, itaconic anhydride, fumaric anhydride, or the like.

In a specific embodiment, the carboxylic acid modified styrene elastomer may comprise styrene-ethylene-butylene-styrene copolymer, styrene-butadiene-styrene copolymer, styrene-ethylene-propylene copolymer more than one of them. Preferably, the carboxylic acid-modified styrene elastomer may be a carboxylic acid-modified styrene-ethylene-butylene-styrene copolymer, when included together with the carboxylic acid-modified olefin resin and polyphenylene ether resin described below , can better embody the effect of the present invention.

The acid value of the carboxylic acid-modified styrene elastomer may be 5.0 mgCH ₃ ONa/g to 15.0 mgCH ₃ ONa/g, for example, may be 5.0 mgCH ₃ ONa/g to 13.0 mgCH ₃ ONa/g. In the above range, good adhesiveness and heat resistance can be exhibited. The above "acid value" can be measured by the ASTM D 1613 method.

The glass transition temperature of the carboxylic acid-modified styrene elastomer may be lower than the glass transition temperature of the above-mentioned carboxylic acid-modified olefin resin and the above-mentioned polyphenylene ether resin. Thereby, the glass transition temperature of the above-mentioned adhesive film of the present invention can be achieved.

In a specific embodiment, the difference between the glass transition temperatures of the carboxylic acid-modified olefin resin and the carboxylic acid-modified styrene elastomer may be 50°C to 120°C, for example, may be 50°C to 100°C. The difference between the glass transition temperatures of the polyphenylene ether resin and the carboxylic acid-modified styrene elastomer may be 150°C to 300°C, for example, may be 150°C to 250°C.

The glass transition temperature of the carboxylic acid-modified styrene elastomer may be -80°C to -50°C, for example, may be -70°C to -50°C. In the above range, after the binder is prepared, it may have a flexibility effect.

In 100 parts by weight of the binder resin, 1 to 20 parts by weight of carboxylic acid-modified styrene elastomer can be included, preferably, 5 to 20 parts by weight can be included, more preferably, it can be included 5 parts by weight to 15 parts by weight. Within the above range, the dielectric constant and moisture absorption rate of the present invention can be achieved, and excellent bendability effects can be obtained.

The carboxylic acid-modified olefin resin is a component of the adhesive film composition, and imparts adhesive properties, flexibility, and electrical properties to the adhesive.

The carboxylic acid-modified olefin resin may include carboxylic acid-modified linear polyolefin resin. In this case, linear may include linear or branched polyolefin resins, preferably, may include linear polyolefin resins. In a specific embodiment, the olefin resin may contain more than one of polyethylene resin, polypropylene resin, and polybutene resin. Preferably, the olefin resin may contain polypropylene resin, and when contained together with the above-mentioned polyphenylene ether resin, the effect of the present invention can be easily exhibited.

The carboxylic acid-modified olefin resin may contain a prescribed deforming substance, for example, a polyolefin resin modified with an unsaturated carboxylic acid or an anhydride thereof. For example, the unsaturated carboxylic acid or its anhydride may contain one or more of acrylic acid, methacrylic acid, maleic acid, itaconic acid, fumaric acid, maleic anhydride, itaconic anhydride, and fumaric anhydride. Preferably, the above-mentioned modifying substance may be maleic anhydride.

The acid value of the carboxylic acid-modified olefin resin may be 0.5 mgCH ₃ ONa/g to 1.5 mgCH ₃ ONa/g, for example, may be 0.51 mgCH ₃ ONa/g to 1.5 mgCH ₃ ONa/g. In the above range, good adhesiveness and heat resistance can be exhibited. The above "acid value" can be measured by the ASTM D 1613 method.

The glass transition temperature of the carboxylic acid-modified olefin resin may be 5°C to 100°C, for example, may be 10°C to 50°C. In the above range, an excellent bendability effect can be obtained.

In 100 parts by weight of the binder resin, 50 to 80 parts by weight of carboxylic acid-modified olefin resin may be included, preferably, 60 to 80 parts by weight may be included. Within the above range, the dielectric constant and moisture absorption rate of the present invention can be achieved, and the cohesive force effect can be obtained.

The polyphenylene ether resin is a part of the above composition, which imparts adhesiveness, flexibility and electrical properties to the adhesive film.

The polyphenylene ether resin may contain one or more of unmodified polyphenylene ether and modified polyphenylene ether. Preferably, the polyphenylene ether resin may contain unmodified polyphenylene ether.

As the polyphenylene ether resin, one having a glass transition temperature higher than that of the carboxylic acid-modified olefin resin can be used. Thus, the effects of the present invention can be easily realized. The difference between the glass transition temperatures of the polyphenylene ether resin and the carboxylic acid-modified olefin resin may be 100°C to 250°C, for example, may be 100°C to 150°C. The glass transition temperature of the polyphenylene ether resin may be greater than 100°C and not more than 300°C, for example, may be 110°C to 200°C. Within the above range, a heat resistance effect may be exhibited.

In 100 parts by weight of the binder resin, 5 to 30 parts by weight of polyphenylene ether resin may be contained, preferably, 5 to 20 parts by weight, or 10 to 20 parts by weight. Within the above range, the dielectric constant and moisture absorption rate of the present invention can be achieved, and the effect of heat resistance can be obtained.

The epoxy resin can react with the above-mentioned binder resin, especially, the carboxylic acid group of the carboxylic acid-modified olefin resin to improve adhesiveness and heat resistance.

In 100 parts by weight of the binder resin, 2 parts by weight to 18 parts by weight of epoxy resin may be included, preferably, 2 parts by weight to 10 parts by weight may be included. In the above range, the dielectric constant and moisture absorption rate of the present invention can be achieved, and the cohesive force effect can be obtained.

The epoxy resin may include common epoxy resins well known to those skilled in the art to which the present invention pertains, having two or more epoxy groups. For example, the epoxy resin may include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AD type epoxy resin, rubber modified epoxy resin, fatty acid modified epoxy resin, Oxygen resin, polyurethane modified epoxy resin, low chlorine epoxy resin, silicon Alkane-modified epoxy resin, dicyclopentadiene epoxy resin, polyfunctional novolac epoxy resin, glycidyl ether epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin, bisphenol A novolak epoxy resin Epoxy resin, etc., but not limited thereto. Preferably, the epoxy resin may include cresol novolac epoxy resin.

The epoxy equivalent weight (EEW, epoxy equivalent weight) of the epoxy resin may be 100g/eq to 300g/eq. Within the above range, the effects of the present invention can be better exhibited.

On the other hand, the composition for adhesive membranes of this invention does not contain a hardener. The adhesive film of the present invention can be produced by reacting the epoxy group of the epoxy resin with the carboxylic acid in the above-mentioned adhesive resin, thereby eliminating the need to add an adhesive film.

For this purpose, the ratio of the total moles of carboxylic acid groups in the binder resin to the total moles of epoxy groups in the epoxy resin ([total moles of carboxylic acid groups in the binder resin]/[epoxy resin The total number of moles of end-point epoxy groups]) can be 1 to 2. Within the above range, the adhesive film of the present invention can be embodied without a hardening agent.

The filler may contain one or more of inorganic fillers and organic fillers. Preferably, the filler can be a mixture of inorganic fillers and organic fillers. Therefore, when combined with the above-mentioned binder resin and epoxy resin, the moisture absorption rate and dielectric constant of the present invention can be easily achieved.

The inorganic filler may include one or more of metals, nonmetals, metal oxides, and nonmetal oxides. For example, the inorganic filler may include one or more of silicon dioxide, titanium dioxide, aluminum oxide, zinc oxide, copper, and silver. Preferably, the inorganic filler may include silicon dioxide, for example, inorganic nano silicon dioxide. The average particle diameter (D50) of the inorganic filler may be 10 nm to 1000 nm, preferably, 10 nm to 500 nm. In the above-mentioned range, heat resistance and an effect of increasing cohesive force can be exhibited.

The organic filler may include a fluororesin filler. For example, the fluororesin filler may include polytetrafluoroethylene, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, tetrafluoroethylene-hexafluoropropylene copolymer, tetrafluoroethylene-ethylene copolymer, polychlorotrifluoroethylene more than one of them. Preferably, the organic filler may include tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer filler. The average particle size of the organic filler can be 1 μm to 100 μm, preferably 5 μm to 50 μm. In the above range, there may be a shrinkage stabilizing effect.

In the adhesive composition of the present invention, an inorganic filler and an organic filler may be included in a specific content ratio. For example, the organic filler may be included in 200 to 800 parts by weight, for example, 300 to 600 parts by weight, relative to 100 parts by weight of the inorganic filler. In the above range, an optimal volume reduction effect can be obtained.

The filler may be contained in an amount of 1 to 35 parts by weight, for example, 10 to 30 parts by weight, relative to 100 parts by weight of the binder resin. In the above range, the dielectric constant is likely to decrease.

If necessary, the composition for adhesive film of the present invention may further include one or more of additives such as plasticizers, leveling agents, ultraviolet absorbers and flame retardants, and thickeners, but is not limited thereto.

The composition of the present invention may also contain a solvent, thereby improving the coatability of the adhesive membrane. The above-mentioned solvent may include more than one of dimethylformamide, methyl ethyl ketone, and dimethylacetamide, but is not limited thereto.

Adhesive Film The above-mentioned composition for adhesive film is applied to a base film or a release film with a predetermined thickness, dried and heat-treated to form a semi-cured state. For example, the adhesive film can be made into a semi-hardened state by heat treatment at a temperature of 50° C. to 170° C. for 1 minute to 60 minutes.

Hereinafter, an adhesive film-adhered laminate according to an embodiment of the present invention will be described.

The adhesive membrane-adhered laminate of the present invention includes a base film and an adhesive film formed on at least one surface of the base film, and the adhesive film includes the adhesive film of the present invention. The adhesive membrane-adhered laminate of the present invention may include a cover film, but is not limited thereto.

Referring to FIG. 1 , the adhesive laminate may include: a base film 10; a first adhesive film 20 formed on one side of the base film 10; and a second adhesive film 30 formed on the other side of the base film 10, the first adhesive film 20. More than one of the second adhesive films 30 may include the adhesive films of the present invention.

The base film 10 includes a film formed of polyimide resin. Polyimide resin is a resin that provides high heat resistance, and can be used as a cover film for covering an adhesive film-attached laminate. The thickness of the base film 10 may be 5 μm to 100 μm, preferably, 5 μm to 50 μm. In the above range, it can be used as a base film of a cover film, and both flexibility and rigidity can be exhibited.

The first conjunctiva 20 and the second conjunctiva 30 can be the above-mentioned conjunctiva of the present invention, and only one of the first conjunctiva 20 and the second conjunctiva 30 can be the conjunctiva of the present invention. The first conjunctiva 20 and the second conjunctiva 30 may be in a semi-hardened state, that is, the conjunctiva in a B-grade state.

The thickness of the first adhesive film 20 and the second adhesive film 30 may be the same or different, for example, they may be within the thickness range of the above-mentioned adhesive film of the present invention.

Hereinafter, a metal foil laminate according to an embodiment of the present invention will be described.

The metal foil laminate of the present invention includes: a base film; an adhesive film formed on at least one side of the base film; and a metal foil formed on one side of the adhesive film including the adhesive film of the present invention. The metal foil laminate of the present invention may include a printed circuit board, for example, a flexible printed circuit board.

2, the metal foil laminate may include: a base film 10; a first adhesive film 20 formed on one side of the base film 10; a first metal foil 40 formed on one side of the first adhesive film 20; a second adhesive film 30 , formed on the other side of the base film 10 ; and the second metal foil 50 , formed on one side of the second adhesive film 30 .

The description of the basement membrane 10 , the first adhesive membrane 20 , and the second adhesive membrane 30 is as shown in FIG. 1 above. The first metal foil 40 and the second metal foil 50 may include more than one of copper foil, silver foil, aluminum foil, and stainless steel foil, preferably, may include copper foil. The first metal foil 40 and the second metal foil 50 may both be copper foil, or one may be copper foil and the other may be a metal foil other than copper foil. The thickness of the first metal foil 40 and the second metal foil 50 may be the same or different, for example, the thickness may be 5 μm to 200 μm, for example, the thickness may be 10 μm to 150 μm.

Hereinafter, the present invention will be described in more detail through examples, which are only used to illustrate the present invention, and the present invention is not limited thereto.

Example 1

Mix 8 parts by weight of carboxylic acid-modified styrene elastomer (SM300A, Toyobo, acid value: 10 mgCH ₃ ONa/g), 64 parts by weight of carboxylic acid-modified polypropylene resin (SM040A, acid value: 1.0 mgCH ₃ ONa/g g, Toyobo), 16 parts by weight of polyphenylene ether resin (PPO, -OH value: 800mg/KOH/g, Sabik), mixed with 2.5 parts by weight of cresol novolac epoxy resin (YDCN1P, EEW: 200g/eq , KUKDO chemical), 5 parts by weight of inorganic nano-silica (R972, average particle size (D50): 17hm, Evonik) as an inorganic filler, 20 parts by weight of a fluororesin filler (PFA , average particle diameter (D50): 10 μm, AGC), and 150 parts by weight of methyl ethyl ketone was added as a solvent to prepare a composition. In Table 1 below, "-" means that the corresponding component is not included.

The prepared composition was coated on a polyimide film with a predetermined thickness, dried and heat-treated at 130° C. for 3 minutes to prepare a semi-cured adhesive film (thickness: 25 μm).

Example 2 to Example 3

A semi-hardened conjunctiva was prepared by the same method as in Example 1, except that the content of each component in Example 1 was changed as shown in Table 1.

Comparative example 1

6 parts by weight of polyphenylene ether resin (PPO, -OH value: 800 mg/KOH/g, Sabik), 43 parts by weight of halogen-free epoxy p-Amino Phenol type (jER630, EEW: 100 g/eq, Mitsubishi Chemical) were mixed , 21 parts by weight of biphenyl epoxy resin (NC3000H, EEW: 290g/eq, Nippon Kayaku), 21 parts by weight of acrylonitrile butadiene rubber (Nipol1072, -COOH content: 8 weight percent, Nippon Zeon), 8 parts by weight of 4,4-diaminodiphenylphenone (DDS, EEW: 64 g/eq, Sigma-Aldrich) as a curing agent for epoxy resin, 0.2 parts by weight of 111 as a hardening accelerator Alkyl imidazole (C11Z, Hwaseong, Shikoku) was prepared by adding 130 parts by weight of methyl ethyl ketone as a solvent.

The prepared composition was coated on a polyimide film with a predetermined thickness, dried and heat-treated at 130° C. for 3 minutes to prepare a semi-cured adhesive film (thickness: 25 μm).

Comparative example 2

Mix 5 parts by weight of halogen-free epoxy p-Amino Phenol type (jER630, EEW: 100g/eq, Mitsubishi Chemical), 60 parts by weight of halogen-free modified polyoxymethylene amide (PIAD200, Arakawa), 25 parts by weight of Halogen-modified polyoxymethylene amide (PIAD150L, Arakawa), 10 parts by weight of ester-modified hardener (HPC-8150, DIC), 0.05 parts by weight of 2-ethyl 4-methylimidazole (2E4MZ , Shikoku Hwaseong), adding 130 parts by weight of methyl ethyl ketone as a solvent to prepare a composition.

The prepared composition was coated on a polyimide film with a predetermined thickness, dried and heat-treated at 130° C. for 3 minutes to prepare a semi-cured adhesive film (thickness: 25 μm).

Comparative example 3

Mix 7 parts by weight of carboxylic acid-modified styrene elastomer (SM300A, acid value: 10mgCH3ONa/g, Toyobo), 55 parts by weight of unmodified polypropylene resin (JSS-395N, acid value: _0mgCH3ONa /g, Hunan Petrochemical), 14 parts by weight of polyphenylene ether resin (PPO, -OH value: 800mg/KOH/g, Sabik), mixed with 2 parts by weight of cresol novolac epoxy resin (YDCN1P, EEW: 200g /eq, KUKDO chemical), 4 parts by weight of inorganic nano silicon dioxide (R972, average particle size (D50): 17nm, Evonik), 17 parts by weight of fluororesin filler (PFA, average particle size (D50): 10 μm, AGC), mixed with 1 part by weight of a hardener (DDS, Sigma-Aldrich), and added 120 parts by weight of methyl ethyl ketone as a solvent to prepare a composition.

The prepared composition was coated on a polyimide film with a predetermined thickness, dried and heat-treated at 130° C. for 3 minutes to prepare a semi-cured adhesive film (thickness: 25 μm).

Under the temperature condition of 160° C., the adhesive films of Examples and Comparative Examples were heat-treated for 60 minutes to produce hardened adhesive films. The physical properties of the hardened conjunctiva were evaluated as follows, and the results are shown in Table 2, Table 3, and Fig. 3 and Fig. 4 below.

(1) Peel strength (unit: gf/cm): Peel strength The peel strength was evaluated according to IPC-TM-650 2.4.8C. For polyimide (PI) film/adhesive membrane/polyimide (PI) film, polyimide (PI) film/adhesive film/copper foil (Cu), peel strength was evaluated under conditions of a temperature of 25° C., a peeling angle of 90 degrees, and a peeling speed of 50 mm/min.

(2) Welding resistance (unit: °C/second): Welding resistance Welding resistance was measured by IPC-TM-650 2.4.13F. Soldering resistance was measured for polyimide (PI) film/adhesive film/polyimide (PI) film, polyimide (PI) film/adhesive film/copper foil (Cu).

(3) Dielectric constant (unit: none) and dielectric loss (unit: none): Under the temperature condition of 25°C, at a frequency of 10GHz, the dielectric was evaluated using Network Analyzer (MS4642B 36585K, Anritsu Co.) constant and dielectric loss.

(4) Melt viscosity (unit: Pa.s, @130°C): For the adhesive film, after hardening, the melt viscosity was evaluated by ARES at a temperature of 130°C that minimizes the melt viscosity.

(5) Coefficient of thermal expansion (unit: ppm/°C): α1 and α2 were analyzed using a thermomechanical analyzer (TMA, thermomechanical analyzer) according to IPC-TM-650 2.4.41.3.

(6) Glass transition temperature (Tg, unit: °C): for the conjunctiva, a dynamic mechanical analyzer (DMA, dynamic mechanical analyzer) was used, and the temperature at which the tanδ modulus reached the maximum was taken as the glass transition temperature.

(7) 5% mass loss temperature (unit: °C): For the adhesive film, 5% mass loss was analyzed by thermogravimetric analysis.

(8) Surface resistance and volume resistance (unit: MΩ, MΩ.cm): For the adhesive film, the surface resistance and volume resistance were evaluated according to IPC-TM-650 2.5.17.

(9) Ion migration (ion-migration, unit: Ω): For the mucosa, the ion migration characteristics were evaluated at 85°C/85RH%/1000 hours, 50V, L/S=50μm/50μm.

(10) Moisture absorption rate (unit: %): The moisture absorption rate was measured in accordance with IPC-TM-650 2.6.2.1A for the mucous membrane.

(11) Dielectric constant and dielectric loss based on frequency change: Measure the dielectric constant and dielectric loss by the same method as (3), and change the frequency to 1GHz, 3GHz, 5GHz, 10GHz and measured the dielectric constant and dielectric loss.

(12) Dielectric constant and dielectric loss based on temperature change: The dielectric constant and dielectric loss are measured by the same method as (3). In 10GHz, the measurement temperature is changed to 20°C, 40°C, 60°C, 80°C and measure the dielectric constant and dielectric loss.

As shown in the above Table 2, the adhesive film of the present invention has low dielectric constant and low moisture absorption rate, both of which can reflect the above-mentioned effects of the present invention. Furthermore, as shown in Table 3, FIG. 3, and FIG. 4 above, the dielectric constant of the adhesive film is low, and the change rate of the dielectric constant due to frequency and temperature changes is also low.

In contrast, Comparative Example 1, which is an acrylonitrile butadiene-based adhesive film, Comparative Example 2, which is a polyimide-based adhesive film, and Comparative Example 3, which contains an unmodified carboxylic acid olefin resin and a hardener, cannot obtain the advantages of the present invention. Effect.

Simple modifications or alterations of the present invention can be easily implemented by those skilled in the art to which the present invention pertains, and such modifications or alterations all belong to the scope of the present invention.

10: basement membrane

20: First mucosa

30:Second mucous membrane

Claims (15)

An adhesive film formed from a composition comprising a binder resin, an epoxy resin and a filler, wherein the binder resin comprises a carboxylic acid-modified styrene elastomer, a carboxylic acid-modified olefin resin and a A polyphenylene ether resin, wherein in 100 parts by weight of the binder resin, 1 to 20 parts by weight of the carboxylic acid-modified styrene elastomer, 50 to 80 parts by weight of the carboxylic acid-modified olefin resin and 5 to 30 parts by weight of the polyphenylene ether resin, and after the adhesive film is hardened, the dielectric constant measured under the conditions of 1GHz to 10GHz and 20°C to 80°C is 2.5 or less, and the dielectric loss is 0.003 or less, after the conjunctiva hardens, the moisture absorption rate is 0.1% or less. The adhesive film according to claim 1, wherein the composition does not contain a hardening agent. The adhesive film according to claim 1, wherein the glass transition temperature of the carboxylic acid-modified styrene elastomer is lower than the glass transition temperatures of the carboxylic acid-modified olefin resin and the polyphenylene ether resin. The adhesive film as described in claim 1, wherein the carboxylic acid modified olefin resin contains acrylic acid, methacrylic acid, maleic acid, itaconic acid, fumaric acid, maleic anhydride, itaconic anhydride, fumaric anhydride More than one modified olefin resin. The adhesive film as described in claim 1, wherein the ratio of the total moles of carboxylic acid groups in the binder resin to the total moles of epoxy groups in the epoxy resin is 1 to 2, that is, (bonding agent The total number of moles of carboxylic acid groups in the resin)/(the total number of moles of epoxy groups in the epoxy resin) is 1 to 2. The adhesive film according to claim 1, wherein the difference between the glass transition temperatures of the polyphenylene ether resin and the carboxylic acid-modified olefin resin is 100°C to 250°C. The adhesive film according to claim 1, wherein the carboxylic acid-modified olefin resin comprises a carboxylic acid-modified linear polypropylene resin. The adhesive film according to claim 1, wherein the filler comprises a mixture of an inorganic nano-silicon dioxide and a fluororesin filler. The adhesive film according to claim 1, wherein relative to 100 parts by weight of the adhesive resin, 2 to 18 parts by weight of the epoxy resin and 1 to 35 parts by weight of the filler are included. The adhesive film according to claim 1, wherein at the same frequency, the ratio of the cured dielectric constant to the cured dielectric loss of the adhesive film is 900 or more, that is, the cured dielectric constant/hardened The final dielectric loss is above 900. The adhesive film according to claim 1, wherein the glass transition temperature of the adhesive film after hardening is 50°C to 80°C. An adhesive film-attached laminate, comprising: a polyimide resin film; and an adhesive film formed on at least one side of the polyimide resin film, the adhesive film comprising any one of claims 1 to 11 The described mucous membrane. A metal foil laminate comprising: a polyimide resin film; an adhesive film formed on at least one side of the polyimide resin film; and a metal foil formed on one side of the adhesive film, wherein the An adhesive film is formed between the polyimide resin film and the metal foil, and the adhesive film is the adhesive film described in any one of claims 1 to 11. The metal foil laminate as claimed in claim 13, wherein the metal foil comprises a copper foil. The metal foil laminate as claimed in claim 13, wherein the metal foil laminate is used as a flexible circuit board.

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