KR20180008373A - Laminate comprising low dielectric constant adhesive layer - Google Patents

Abstract

Provided is a laminate which has high adhesion with a low-polarity resin base material such as LCP or a metal base material as well as conventional polyimide and polyester films, can achieve high solder heat resistance, and is excellent in low dielectric properties. (Z) having a resin substrate and a metal substrate laminated via an adhesive layer containing a carboxyl group-containing polyolefin resin (A), wherein (1) the adhesive layer has a relative dielectric constant (? _C ) at a frequency of 1 MHz of not more than 3.0 (2) the dielectric loss tangent (tan?) Of the adhesive layer at a frequency of 1 MHz is 0.02 or less, (3) the peel strength between the resin substrate and the metal substrate is 0.5 N / mm or more, (4) (Z) characterized in that the heat resistance of the humidifying solder is 240 占 폚 or higher.

Description

LAMINATE COMPRISING LOW DIELECTRIC CONSTANT ADHESIVE LAYER [0002]

The present invention relates to a laminate containing an adhesive layer exhibiting low dielectric constant and low dielectric loss tangent. More particularly, the present invention relates to a laminate in which a resin substrate and a metal substrate are laminated via an adhesive layer exhibiting low dielectric constant and low dielectric loss tangent. To a laminate for a flexible printed wiring board (hereinafter abbreviated as FPC), and to a coverlay film, a laminate, a resin-attached copper foil and a bonding sheet containing the same.

2. Description of the Related Art In recent years, with the increase in the speed of a transmission signal in a printed wiring board, the frequency of a signal is increasing. As a result, the demand for low dielectric constant (low dielectric constant, low dielectric loss tangent) in the high frequency region is increasing for the FPC. As a substrate film used for the FPC, a liquid crystal polymer (LCP) having low dielectric properties, syndiotactic polystyrene (SPS), polyphenylene sulfide A base film such as a feed (PPS) film has been proposed.

However, due to the low polarity, the base film having low dielectric properties has a weak adhesive force when using conventional epoxy adhesive or acrylic adhesive, and it has been difficult to manufacture an FPC member such as a coverlay film or a laminate. Further, the epoxy adhesive or the acrylic adhesive does not have a low dielectric property and damages the dielectric property of the FPC.

On the other hand, polyolefin resins are known to have low dielectric properties. Therefore, an adhesive composition for an FPC using a polyolefin resin has been proposed. For example, Patent Document 1 proposes a heat-reactive adhesive composition using a polyolefin-based copolymer containing a carboxyl group, a block copolymer of an aromatic vinyl compound polymer block and a conjugated diene compound polymer block, and an epoxy resin. Further, in Patent Document 2, an adhesive composition using a carboxyl group-containing styrene elastomer and an epoxy resin has been proposed.

Patent Document 1: Japanese Patent No. 3621351 Patent Document 2: WO2014 / 147903A1

However, although Patent Document 1 describes the adhesiveness between the polyimide film and SUS and the solder heat resistance, the dielectric property is not mentioned, and it is difficult to obtain adhesion with a base film having low dielectric properties such as LCP. In Patent Document 2, the dielectric properties and the adhesiveness between the polyimide film and the copper foil have been described, but no mention has been made about the adhesion with a base film having low dielectric properties such as LCP. The solder heat resistance after drying has been described, but the solder heat resistance after humidification is not sufficient.

The present invention has been made in order to solve the problems described above. As a result of intensive studies, it has been found that the adhesive layer having specific physical properties is not only a conventional polyimide film but also a resin substrate having low dielectric properties such as LCP High solder heat resistance and low dielectric properties, and has completed the present invention.

In other words, it is an object of the present invention to provide a laminate which is laminated with an adhesive layer having good adhesiveness to various resin base materials such as polyimide and LCP, and also excellent in heat resistance and low dielectric property.

(Z) having a resin substrate and a metal substrate laminated via an adhesive layer containing a carboxyl group-containing polyolefin resin (A), wherein (1) the adhesive layer has a relative dielectric constant (? _C ) at a frequency of 1 MHz of not more than 3.0 (2) the dielectric loss tangent (tan?) Of the adhesive layer at a frequency of 1 MHz is 0.02 or less, (3) the peel strength between the resin substrate and the metal substrate is 0.5 N / mm or more, (4) (Z) characterized in that the heat resistance of the humidifying solder is 240 占 폚 or higher.

(1) a laminate (X) of the adhesive layer and the resin substrate used for the laminate (Z) in which a resin substrate and a metal substrate are laminated via an adhesive layer containing a carboxyl group-containing polyolefin resin (A) (2) the dielectric loss tangent (tan?) At a frequency of 1 MHz of the adhesive layer is 0.02 or less; and (3) the dielectric constant (? _C ) of the adhesive layer The peeling strength between the resin base material and the metal base material in the laminate when the metal base material is laminated is not less than 0.5 N / mm, (4) when the metal base material is laminated on the adhesive layer side of the laminate (X) Wherein the moisture resistance of the humidifying solder is 240 占 폚 or higher.

(1) a laminate (Y) of the adhesive layer and the metal substrate used for the laminate (Z) in which a resin substrate and a metal substrate are laminated via an adhesive layer containing a carboxyl group-containing polyolefin resin (A) (2) the dielectric loss tangent (tan?) At a frequency of 1 MHz of the adhesive layer is 0.02 or less; (3) the dielectric constant (? _C ) of the adhesive layer The peel strength between the resin base material and the metal base material in the laminate when the resin base material is laminated is not less than 0.5 N / mm, (4) the laminate material in which the resin base material is laminated on the adhesive layer side of the laminate (Y) Wherein the moisture-proof solder has a heat resistance of 240 占 폚 or higher.

(1) The adhesive layer used for the laminate (Z) in which the resin substrate and the metal substrate are laminated through the adhesive layer containing the carboxyl group-containing polyolefin resin (A) _c ) is not more than 3.0, (2) the dielectric loss tangent (tan?) of the adhesive layer at a frequency of 1 MHz is 0.02 or less, (3) a resin substrate is laminated on one side of the adhesive layer, (4) a resin substrate is laminated on one side of the adhesive layer, and a metal substrate is laminated on the other side of the laminate Wherein the laminate has a heat resistance of humidifying solder of 240 DEG C or more.

An adhesive sheet comprising the laminate (Z), the laminate (X), the laminate (Y) or an adhesive layer.

And the adhesive sheet as a component.

(1) the adhesive layer has a relative dielectric constant (epsilon _c ) at a frequency of 1 MHz of not more than 3.0, the adhesive layer having a dielectric constant (2) the dielectric tangent (tan?) At a frequency of 1 MHz of the adhesive layer is 0.02 or less, (3) the peel strength of the resin base material and the metal base is 0.5 N / mm or more, (4) It is possible to obtain high solder heat resistance as well as conventional polyimide and polyester films as well as high adhesion with low-polarity resin base materials and metal base materials such as LCP films which have not been assumed in the prior art And is also excellent in low dielectric properties.

Hereinafter, embodiments of the present invention will be described in detail. The layered product (Z) relating to the present invention is a laminate of a resin substrate and a metal substrate through an adhesive layer containing a carboxyl group-containing polyolefin resin (A).

≪ Carboxy group-containing polyolefin resin (A)

The carboxyl group-containing polyolefin resin (A) (hereinafter, simply referred to as component (A)) used in the present invention is not limited, but may be obtained by grafting at least one of an?,? - unsaturated carboxylic acid and an acid anhydride thereof to the polyolefin resin Is preferably obtained. The polyolefin resin is a polymer obtained by homopolymerization of an olefin monomer exemplified by ethylene, propylene, butene, butadiene, isoprene, etc., copolymerization with other monomers, and a polymer mainly composed of a hydrocarbon skeleton such as a hydride or a halide of the obtained polymer Point. That is, it is preferable that the carboxyl group-containing polyolefin is obtained by grafting at least one of an?,? - unsaturated carboxylic acid and an acid anhydride thereof to at least one of polyethylene, polypropylene and propylene -? - olefin copolymer.

The propylene-? -Olefin copolymer is obtained by copolymerizing propylene with an? -Olefin. As the? -olefin, for example, one or more kinds of ethylene, 1-butene, 1-heptene, 1-octene, 4-methyl-1-pentene and vinyl acetate can be used. Of these? -Olefins, ethylene and 1-butene are preferable. The ratio of the propylene component to the -olefin component in the propylene-? -Olefin copolymer is not limited, but is preferably 50 mol% or more, more preferably 70 mol% or more.

Examples of the at least one of the?,? - unsaturated carboxylic acid and its acid anhydride include maleic acid, itaconic acid, citraconic acid and their acid anhydrides. Of these, acid anhydrides are preferable, and maleic anhydride is more preferable. Specific examples thereof include a maleic anhydride-modified polypropylene, a maleic anhydride-modified propylene-ethylene copolymer, a maleic anhydride-modified propylene-butene copolymer and a maleic anhydride-modified propylene-ethylene-butene copolymer. One or more modified polyolefins may be used in combination.

The acid value of the carboxyl group-containing polyolefin resin (A) is preferably 100 equivalents / 10 ⁶ g or more, more preferably 200 equivalents / 10 ⁶ g or more, in view of heat resistance and adhesiveness to the resin base material or the metal base material , More preferably 250 equivalents / 10 ⁶ g. If it is less than the above-mentioned value, compatibility with the epoxy resin (D) and the carbodiimide resin (C) is low and the adhesive strength may not be exhibited. In addition, the crosslinking density is low and the heat resistance may be insufficient. The upper limit is preferably 1000 equivalents / 10 ⁶ g or less, more preferably 700 equivalents / 10 ⁶ g or less, and still more preferably 500 equivalents / 10 ⁶ g or less. If the value is exceeded, the adhesiveness may be lowered. In addition, the viscosity and stability of the solution deteriorate, and the pot life may be deteriorated. And the production efficiency is lowered.

The weight average molecular weight (Mw) of the carboxyl group-containing polyolefin resin (A) is preferably in the range of 10,000 to 180,000. More preferably in the range of 20,000 to 160,000, more preferably in the range of 30,000 to 150,000, particularly preferably in the range of 40,000 to 140,000, and most preferably in the range of 50,000 to 130,000. If it is less than the above-mentioned value, the cohesive force is weakened and the adhesive property may be deteriorated. On the other hand, when it exceeds the above-mentioned value, the fluidity is low and there is a problem in operability when bonding.

The method for producing the carboxyl group-containing polyolefin resin (A) is not particularly limited, and for example, a radical graft reaction (that is, a method in which a radical species is generated for a polymer as a main chain and an unsaturated carboxylic acid and / A reaction in which an acid anhydride is subjected to graft polymerization).

The radical generator is not particularly limited, but it is preferable to use an organic peroxide. Examples of the organic peroxide include, but are not limited to, di-tert-butyl peroxyphthalate, tert-butyl hydroperoxide, dicumyl peroxide, benzoyl peroxide, tert-butyl peroxybenzoate, Peroxides such as ethyl hexanoate, tert-butyl peroxypivalate, methyl ethyl ketone peroxide, di-tert-butyl peroxide, and lauroyl peroxide; And azonitriles such as azobisisobutylonitrile, azobisisopropionitrile, and the like.

<Adhesive Layer>

The adhesive layer in the present invention refers to a layer of an adhesive composition after the adhesive composition is applied to a substrate and dried. The thickness of the adhesive layer is not particularly limited, but is preferably 5 占 퐉 or more, more preferably 10 占 퐉 or more, and further preferably 15 占 퐉 or more. Further, it is preferably 200 占 퐉 or less, more preferably 100 占 퐉 or less, and further preferably 50 占 퐉 or less. When the thickness is excessively thin, the adhesion performance may not be sufficiently obtained. When the thickness is too large, the drying is insufficient and the residual solvent tends to become large, and bubbles are generated at the time of press production of the printed wiring board have.

The method of coating the adhesive composition on the substrate is not particularly limited, and examples thereof include a comma coater and a reverse roll coater. Alternatively, if necessary, the adhesive layer may be formed directly on the rolled copper foil or the polyimide film as the constituent material of the printed wiring board or by transferring. The drying conditions are not particularly limited, but the residual solvent ratio after drying is preferably 1% by mass or less. When the content exceeds 1% by mass, there is a problem that bubbles are formed due to foaming of the residual solvent at the time of pressing the printed wiring board.

&Lt; Resin substrate &

The resin base material in the present invention is not particularly limited as long as the adhesive composition of the present invention can be applied and dried to form an adhesive layer, but a resin base material such as a film-like resin (hereinafter also referred to as a base film layer) Do. Specific examples include polyester resins, polyamide resins, polyimide resins, polyamideimide resins, liquid crystal polymers (LCP), polyphenylene sulfide, syndiotactic polystyrene, polyolefin resins and fluorine resins. A commercially available product of the LCP film is, for example, Beckstar (registered trademark) manufactured by Kuraray Co., Ltd. As a commercially available product of the polyimide film, for example, Apicel (registered trademark) manufactured by Kaneka Corporation can be mentioned.

The thickness of the resin base material is not particularly limited, but is preferably 1 占 퐉 or more, more preferably 3 占 퐉 or more, and further preferably 10 占 퐉 or more. Further, it is preferably 50 占 퐉 or less, more preferably 30 占 퐉 or less, and further preferably 20 占 퐉 or less. When the thickness is excessively thin, it is difficult to obtain sufficient electrical performance of the circuit. On the other hand, when the thickness is too large, the processing efficiency and the like at the time of circuit production may be lowered. The relative dielectric constant (? _C ) of the resin substrate is preferably 5.0 or less, more preferably 4.0 or less, and further preferably 3.5 or less. The lower limit is not particularly limited, and there is no problem if it is 0.1 or more from an industrial point of view.

&Lt; Metal substrate &

As the metal substrate, any conventionally known conductive material usable for a circuit board can be used. Examples of the material include various metals such as SUS, copper, aluminum, iron, steel, zinc and nickel, and alloys, plated products and metals treated with other metals such as zinc and chromium compounds. It is preferably a metal foil, more preferably a copper foil. The thickness of the metal foil is not particularly limited, but is preferably 1 占 퐉 or more, more preferably 3 占 퐉 or more, and further preferably 10 占 퐉 or more. Further, it is preferably 50 占 퐉 or less, more preferably 30 占 퐉 or less, and further preferably 20 占 퐉 or less. When the thickness is too thin, it is difficult to obtain sufficient electrical performance of the circuit. On the other hand, when the thickness is excessively large, the processing efficiency at the time of circuit production may be lowered. The metal foil is usually provided in the form of a roll. The form of the metal foil used in producing the printed wiring board of the present invention is not particularly limited. When a metal foil in the form of a ribbon is used, its length is not particularly limited. The width is not particularly limited, but is preferably about 250 to 500 cm.

<Laminate>

The laminate (Z) of the present invention is a laminate of a resin base material and a metal base material through an adhesive layer (a three-layer laminate of resin base material / adhesive layer / metal base material) (Resin substrate / adhesive layer), and the layered product Y is a laminate of a metal substrate and an adhesive layer (metal substrate / adhesive layer). In the present invention, the layered product (X), the layered product (Y) and the layered product (Z) may be simply referred to as a laminate. The layered product (X) is obtained by applying the adhesive composition to a resin base material and drying it by a conventional method. Further, the layered product (Y) is obtained by applying the adhesive composition to a metal substrate and drying the same by a conventional method. The layered product (Z) can be obtained by laminating a metal substrate or a resin substrate on the layered product (X) or the layered product (Y), respectively. The releasing base material may be laminated on the surface of the adhesive layer of the layered product (X) or the layered product (Y). Further, an adhesive layer is further laminated (adhesive layer / resin substrate / adhesive layer / metal substrate, resin substrate / adhesive layer / metal substrate / adhesive layer, adhesive layer / resin substrate / resin substrate / Adhesive layer / metal substrate / adhesive layer).

The laminate of the present invention further satisfies the following requirements (1) to (4).

<Requirement (1)>

The requirement (1) will be described. In the layered product (Z) of the present invention, it is necessary that the adhesive layer has a relative dielectric constant (? _C ) at a frequency of 1 MHz of 3.0 or less. Specifically, the adhesive composition is applied to the release-type substrate so that the thickness after drying becomes 25 占 퐉 and dried at about 130 占 폚 for about 3 minutes. Then, it is cured by heat treatment at about 140 캜 for about 4 hours to peel the cured adhesive composition layer (adhesive layer) from the release film. The relative permittivity (? _C ) of the adhesive composition layer after peeling at a frequency of 1 MHz is measured. The relative dielectric constant (? _C ) is 3.0 or less, preferably 2.6 or less, and more preferably 2.3 or less. The lower limit is not particularly limited, but is practically 2.0. Further, it is preferable that the relative permittivity (? _C ) in the entire frequency range of 1 MHz to 10 GHz is 3.0 or less, more preferably 2.6 or less, and further preferably 2.3 or less.

The relative dielectric constant (? _C ) of the adhesive layer in the layered product (Z) can be measured as follows. That is, the metal substrate of the layered product (Z) is cleanly removed with an etching solution to obtain a laminate (X) of two layers of an adhesive layer and a resin substrate. The etching solution is not particularly limited, and an aqueous solution of ferric chloride, an aqueous solution of cupric chloride, a mixed aqueous solution of sulfuric acid and hydrogen peroxide, an alkali etchant, a nickel etchant, and the like can be used. Subsequently, the resin base material of the layered product (X) is cleanly peeled (removed), and a metal layer is formed on both surfaces of the remaining adhesive layer by a thin film method such as evaporation or sputtering or by applying a conductive paste, , And measuring the capacitance to calculate the relative permittivity (? _C ) from the thickness and the area. As another method, after a metal layer is formed on the resin base surface of the layered product (X) by a method as described above to measure a composite capacitance relative permittivity (? _C ) between the resin base material and the adhesive layer, The metal layer and the adhesive layer are cleanly peeled (removed) from the body X and the relative dielectric constant (epsilon _c ) of the remaining resin base material is made equal to that of the capacitor to measure the capacitance. Since the dielectric layer of the capacitor obtained from the layered product (X) can be regarded as a multilayer dielectric of the resin base material and the adhesive layer, the relative permittivity (? _C ) of the adhesive layer can be calculated from the difference between them.

<Requirement (2)>

The requirement (2) will be described. The layered product (Z) of the present invention needs to have a dielectric loss tangent (tan?) Of 0.02 or less at a frequency of 1 MHz for the adhesive layer. Specifically, the adhesive composition is applied to the release-type substrate so that the thickness after drying becomes 25 占 퐉 and dried at about 130 占 폚 for about 3 minutes. Then, it is cured by heat treatment at about 140 캜 for about 4 hours to peel the cured adhesive composition layer (adhesive layer) from the release film. The dielectric tangent (tan?) Of the adhesive composition after peeling at a frequency of 1 MHz is measured. The dielectric loss tangent (tan?) Is 0.02 or less, preferably 0.01 or less, and more preferably 0.005 or less. The lower limit is not particularly limited, but is practically 0.0001. The dielectric loss tangent (tan?) In the entire frequency range of 1 MHz to 10 GHz is preferably 0.02 or less, more preferably 0.01 or less, and even more preferably 0.005 or less.

The dielectric loss tangent (tan?) Of the adhesive layer in the layered product (Z) can also be measured by the same operation as the above dielectric constant.

<Requirement (3)>

The requirement (3) will be described. The layered product (Z) of the present invention is required to have a peel strength of 0.5 N / mm or more between the resin base material and the metal base material. Specifically, the adhesive composition is applied to the resin base material so that the thickness after drying becomes about 25 占 퐉, and is dried at about 130 占 폚 for about 3 minutes. Subsequently, a metal substrate is bonded to the surface of the adhesive composition layer (adhesive layer). The bonding is performed by vacuum pressing for about 30 seconds under a pressure of about 40 kgf / cm 2 at about 160 캜 so that the glossy surface of the metal base is in contact with the adhesive composition layer. And then cured by heat treatment at about 140 ° C for about 4 hours to prepare a three-layer laminate (Z) of a resin base material / adhesive layer / metal base material. At a room temperature (about 25 ° C), the resin base of the layered product (Z) is peeled at 90 ° at a tensile rate of 50 mm / min to measure the peel strength. The 90 占 peel strength is required to be 0.5 N / mm or more, preferably 0.8 N / mm or more, and more preferably 1.0 N / mm or more. Even if the layered product (Z) is produced by a method other than the above-mentioned method, it is included in the present invention if the 90 DEG peel strength is 0.5 N / mm or more.

The laminate (Z) of the present invention can be obtained from the laminate (X) by bonding a metal base material to the surface of the adhesive composition layer (adhesive layer) of the laminate (X). The bonding is performed by vacuum pressing for about 30 seconds under a pressure of about 40 kgf / cm 2 at about 160 캜 so that the glossy surface of the metal base is in contact with the adhesive composition layer. And then cured by heat treatment at about 140 ° C for about 4 hours to prepare a three-layer laminate (Z) of a resin base material / adhesive layer / metal base material. At a room temperature (about 25 ° C), the resin base of the layered product (Z) is peeled at 90 ° at a tensile rate of 50 mm / min to measure the peel strength. The 90 占 peel strength is required to be 0.5 N / mm or more, preferably 0.8 N / mm or more, and more preferably 1.0 N / mm or more.

The laminate (Z) of the present invention can be obtained from the laminate (Y) by bonding a resin substrate to the surface of the adhesive composition layer (adhesive layer) of the laminate (Y). The bonding is performed by vacuum pressing for about 30 seconds under a pressure of about 40 kgf / cm &lt; 2 &gt; at about 160 DEG C such that the resin substrate is in contact with the adhesive composition layer. Then, it is cured by heat treatment at about 140 占 폚 for about 4 hours to prepare a three-layer laminate (Z) of resin base material / adhesive layer / metal base material. At a room temperature (about 25 ° C), the resin base of the layered product (Z) is peeled at 90 ° at a tensile rate of 50 mm / min to measure the peel strength. The 90 占 peel strength is required to be 0.5 N / mm or more, preferably 0.8 N / mm or more, and more preferably 1.0 N / mm or more.

From the adhesive layer, the laminate (Z) of the present invention can be obtained by bonding a resin base material to one surface of an adhesive layer and bonding a glossy surface of a metal base to the other surface. The bonding is performed by roll lamination of the releasing substrate / adhesive layer and the resin substrate at about 100 ° C under a pressure of about 3 kgf / cm 2 at about 1 m / min to peel off the releasing base material, And vacuum-pressed at about 160 DEG C for about 30 seconds under a pressure of about 40 kgf / cm &lt; 2 &gt;. And then cured by heat treatment at about 140 ° C for about 4 hours to prepare a three-layer laminate (Z) of a resin base material / adhesive layer / metal base material. At a room temperature (about 25 ° C), the resin base of the layered product (Z) is peeled at 90 ° at a tensile rate of 50 mm / min to measure the peel strength. The 90 占 peel strength is required to be 0.5 N / mm or more, preferably 0.8 N / mm or more, and more preferably 1.0 N / mm or more.

<Requirement (4)>

The requirement (4) will be described. The layered product (Z) according to the present invention needs to have a heat resistance of humidifying solder of 240 DEG C or more. Specifically, the adhesive composition is applied to a resin substrate so that the thickness after drying becomes 25 占 퐉 and dried at about 130 占 폚 for about 3 minutes. Subsequently, a metal substrate is bonded to the surface of the adhesive composition layer (adhesive layer). The bonding is performed by vacuum pressing for about 30 seconds under a pressure of about 40 kgf / cm 2 at about 160 캜 so that the glossy surface of the metal base is in contact with the adhesive composition layer. And then cured by heat treatment at about 140 ° C for about 4 hours to prepare a three-layer laminate (Z) of a resin base material / adhesive layer / metal base material. The laminate (Z) was treated for about 72 hours under the conditions of about 40 캜 and about 80 RH%, and the solder bath was melted at each temperature for one minute to measure the temperature at which the appearance change such as swelling did not occur do. Humidifying solder heat resistance is required to be 240 占 폚 or higher, preferably 250 占 폚 or higher, and more preferably 260 占 폚 or higher. Even if the layered product (Z) is produced by a method other than the above-mentioned method, it is included in the present invention if the heat resistance of the humidifying solder is 240 캜 or higher.

The laminate (Z) of the present invention can be obtained from the laminate (X) by bonding a metal base material to the surface of the adhesive composition layer (adhesive layer) of the laminate (X). The bonding is performed by vacuum pressing for about 30 seconds under a pressure of about 40 kgf / cm 2 at about 160 캜 so that the glossy surface of the metal base is in contact with the adhesive composition layer. And then cured by heat treatment at about 140 ° C for about 4 hours to prepare a three-layer laminate (Z) of a resin base material / adhesive layer / metal base material. The laminate (Z) was treated for about 72 hours under the conditions of about 40 캜 and about 80 RH%, and the solder bath was melted at each temperature for one minute to measure the temperature at which the appearance change such as swelling did not occur do. Humidifying solder heat resistance is required to be 240 占 폚 or higher, preferably 250 占 폚 or higher, and more preferably 260 占 폚 or higher.

The laminate (Z) of the present invention can be obtained from the laminate (Y) by bonding a resin substrate to the surface of the adhesive composition layer (adhesive layer) of the laminate (Y). The bonding is performed by vacuum pressing for about 30 seconds under a pressure of about 40 kgf / cm &lt; 2 &gt; at about 160 DEG C such that the resin substrate is in contact with the adhesive composition layer. And then cured by heat treatment at about 140 ° C for about 4 hours to prepare a three-layer laminate (Z) of a resin base material / adhesive layer / metal base material. The laminate (Z) was treated for about 72 hours under the conditions of about 40 캜 and about 80 RH%, and the solder bath was melted at each temperature for one minute to measure the temperature at which the appearance change such as swelling did not occur do. Humidifying solder heat resistance is required to be 240 占 폚 or higher, preferably 250 占 폚 or higher, and more preferably 260 占 폚 or higher.

Further, the laminate (Z) of the present invention can be obtained from the adhesive layer by bonding a resin base material to one side of the adhesive layer and bonding a glossy surface of a metal base to the other side. After bonding the adhesive layer and the resin base material, the bonding is performed by vacuum pressing for about 30 seconds under a pressure of about 40 kgf / cm 2 at about 160 ° C so that the glossy surface of the metal base contacts the adhesive layer. And then cured by heat treatment at about 140 ° C for about 4 hours to prepare a three-layer laminate (Z) of a resin base material / adhesive layer / metal base material. The laminate (Z) was treated for about 72 hours under the conditions of about 40 캜 and about 80 RH%, and the solder bath was melted at each temperature for one minute to measure the temperature at which the appearance change such as swelling did not occur do. Humidifying solder heat resistance is required to be 240 占 폚 or higher, preferably 250 占 폚 or higher, and more preferably 260 占 폚 or higher.

&Lt; Adhesive composition >

The adhesive composition used in the present invention comprises at least a carboxyl group-containing polyolefin resin (A). By containing the carboxyl group-containing polyolefin resin (A), the laminate through the adhesive layer composed of the above adhesive composition can exhibit the above-mentioned excellent performances of (1) to (4).

The adhesive composition of the present invention may contain, in addition to the above component (A), a carboxyl group-containing styrene resin (B) (hereinafter, simply referred to as component (B)) or a carbodiimide resin (hereinafter also referred to simply as component (C) ) And / or an epoxy resin (D) (hereinafter, also simply referred to as component (D)). By containing the four types of resins (A) to (D), not only conventional polyimide and polyester films but also low-polarity resin base materials such as LCP films, which have not been assumed in the prior art, High adhesiveness, high solder heat resistance, and low dielectric property.

&Lt; Carboxyl group-containing styrene resin (B)

The carboxyl group-containing styrene resin (B) usable in the present invention is not limited, but may be a copolymer of aromatic vinyl compound alone or a block and / or random structure of an aromatic vinyl compound and a conjugated diene compound, , And those modified with an unsaturated carboxylic acid. Examples of the aromatic vinyl compound include, but are not limited to, styrene, t-butylstyrene,? -Methylstyrene, p-methylstyrene, divinylbenzene, 1,1-diphenylstyrene, N, Ethyl styrene, vinyl toluene, p-tert-butyl styrene, and the like. Examples of the conjugated diene compound include butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene and the like. Specific examples of the copolymer of the aromatic vinyl compound and the conjugated diene compound include styrene-ethylene-butylene-styrene block copolymer (SEBS), styrene-ethylene-propylene-styrene block copolymer (SEPS) Ethylene-propylene-styrene block copolymer (SEEPS), and the like.

Modification of the carboxyl group-containing styrene resin (B) can be performed, for example, by copolymerizing an unsaturated carboxylic acid at the time of polymerization of the styrene resin. It is also possible to heat and knead a styrene resin and an unsaturated carboxylic acid in the presence of an organic peroxide. The unsaturated carboxylic acid is not particularly limited and examples thereof include acrylic acid, methacrylic acid, maleic acid, itaconic acid, fumaric acid, maleic anhydride, itaconic anhydride, and fumaric anhydride.

The acid value of the carboxyl group-containing styrene resin (B) is preferably 10 equivalents / 10 ⁶ g or more, more preferably 100 equivalents / 10 ⁶ g or more, in view of heat resistance and adhesiveness with the resin base material or the metal base material , More preferably 150 equivalents / 10 ⁶ g.

If it is less than the above-mentioned value, compatibility with the epoxy resin (D) and the carbodiimide resin (C) is low and the adhesive strength may not be exhibited. In addition, the crosslinking density is low and the heat resistance may be insufficient. The upper limit is preferably 1000 equivalents / 10 ⁶ g or less, more preferably 700 equivalents / 10 ⁶ g or less, and still more preferably 500 equivalents / 10 ⁶ g or less. If it exceeds the above value, the adhesiveness and the low dielectric property may be lowered.

In the adhesive composition for use in the present invention, the content of the carboxyl group-containing styrene resin (B) is preferably in the range of 95 to 5 parts by mass based on the carboxyl group-containing styrene resin (B) relative to 5 to 95 parts by mass of the carboxyl group-containing polyolefin resin (A) , That is, the component (A) / the component (B) = 5 to 95/95 to 5 (mass ratio). More preferably, the component (A) / component (B) is 10 to 90/90 to 10 (mass ratio), and most preferably the component (A) / component (B) is 15 to 85/85 to 15 Range. If the amount of the component (A) is less than the above-mentioned range, the crosslinking density is lowered and the heat resistance of the humidifying solder may be lowered. If the amount of the component (A) exceeds the above-mentioned range, the wettability to the substrate decreases, and the adhesive strength may be lowered.

&Lt; Carbodiimide resin (C) >

The carbodiimide resin (C) is not particularly limited as long as it has a carbodiimide group in the molecule. And is preferably a polycarbodiimide having two or more carbodiimide groups in the molecule. By using the carbodiimide resin (C), the carboxyl group of the carboxyl group-containing polyolefin resin (A) or the carboxyl group-containing styrene resin (B) reacts with the carbodiimide to increase the interaction between the adhesive composition and the substrate, .

The content of the carbodiimide resin (C) in the adhesive composition used in the present invention is preferably in the range of 0.1 to 30 parts by mass per 100 parts by mass of the total amount of the carboxyl group-containing polyolefin resin (A) and the carboxyl group-containing styrene resin (B) . More preferably in the range of 1 to 25 parts by mass, and most preferably in the range of 2 to 20 parts by mass. If it is less than the above-mentioned value, there is a problem that the interaction with the substrate is not expressed and the adhesiveness is lowered. If the value is exceeded, there is a problem that the port life of the adhesive is lowered and the low dielectric property is lowered.

&Lt; Epoxy resin (D) >

The epoxy resin (D) is not particularly limited as long as it has a glycidyl group in the molecule, and preferably has two or more glycidyl groups in the molecule. Specific examples include, but are not limited to, biphenyl type epoxy resins, naphthalene type epoxy resins, bisphenol A type epoxy resins, bisphenol F type epoxy resins, novolak type epoxy resins, alicyclic epoxy resins, dicyclopentadiene type epoxy resins , Tetraglycidyldiaminodiphenylmethane, triglycidylparaaminophenol, tetraglycidylbisaminomethylcyclohexanone, and N, N, N ', N'-tetraglycidyl-m-xylylenediamine. At least one selected from the group can be used. Preferred are bisphenol A type epoxy resins, novolak type epoxy resins, or dicyclopentadiene type epoxy resins.

The content of the epoxy resin (D) in the adhesive composition used in the present invention is preferably in the range of 1 to 30 parts by mass based on 100 parts by mass of the total of the carboxyl group-containing polyolefin resin (A) and the carboxyl group-containing styrene resin (B) More preferably from 2 to 15 parts by mass, and most preferably from 3 to 10 parts by mass. When the amount is less than the above range, a sufficient curing effect can not be obtained and adhesiveness and heat resistance may be lowered. Above the above range, there is a problem that the port life of the adhesive is lowered and the low dielectric property is lowered.

The adhesive composition used in the present invention may further contain an organic solvent. The organic solvent used in the present invention is not particularly limited as long as it dissolves the carboxyl group-containing polyolefin resin (A), the carboxyl group-containing styrene resin (B), the carbodiimide resin (C) and the epoxy resin (D). Specific examples include aromatic hydrocarbons such as benzene, toluene and xylene, aliphatic hydrocarbons such as hexane, heptane, octane and decane, alicyclic hydrocarbons such as cyclohexane, cyclohexene, methylcyclohexane and ethylcyclohexane, Halogenated hydrocarbons such as ethylene, dichloroethylene, chlorobenzene and chloroform, alcohol solvents such as methanol, ethanol, isopropyl alcohol, butanol, pentanol, hexanol, propanediol and phenol, acetone, methyl isobutyl ketone, methyl ethyl ketone , Ketone solvents such as pentanone, hexanone, cyclohexanone, isophorone and acetophenone, cellosolves such as methyl cellosolve and ethyl cellosolve, methyl acetate, ethyl acetate, butyl acetate, methyl propionate, formic acid Butyl, etc .; ester solvents such as ethylene glycol mono n-butyl ether, ethylene glycol mono isobutyl ether, ethylene glycol mono tert-butyl ether, di Glycol ether type solvents such as ethylene glycol mono n-butyl ether, ethylene glycol mono n-butyl ether, diethylene glycol mono isobutyl ether, triethylene glycol mono n-butyl ether and tetraethylene glycol mono n-butyl ether. Two or more species can be used in combination.

The organic solvent is preferably in the range of 100 to 1000 parts by mass, more preferably 200 to 900 parts by mass, more preferably in the range of 200 to 900 parts by mass based on 100 parts by mass of the total of the carboxyl group-containing polyolefin resin (A) and the carboxyl group- And most preferably in the range of 300 to 800 parts by mass. If the amount is less than the above range, the liquid phase and the port life may be deteriorated. In addition, if it exceeds the above range, there is a problem in that it becomes disadvantageous in terms of manufacturing cost and transportation cost.

The adhesive composition used in the present invention may further contain other components as required. Specific examples of such components include flame retardants, tackifiers, fillers, and silane coupling agents.

<Flame Retardant>

A flame retardant may be added to the adhesive composition used in the present invention, if necessary. Examples of the flame retardant include bromine, phosphorus, nitrogen, and metal hydroxide compounds. Among them, phosphorus-based flame retardants are preferable, and phosphate-based flame retardants such as phosphates, such as phosphates, such as phosphates, such as trimethyl phosphate, triphenyl phosphate and tricresyl phosphate, can be used. These may be used alone or in combination of two or more. When the flame retardant is contained, the content of the flame retardant is preferably in the range of 1 to 200 parts by mass, more preferably 5 to 150 parts by mass, and still more preferably 5 to 150 parts by mass per 100 parts by mass of the total of the components (A) Most preferably 100 parts by mass. If it is less than the above range, flame retardancy may be low. Beyond the above range, there is a problem that adhesiveness, heat resistance, electric characteristics and the like are deteriorated.

&Lt; Adhesion imparting agent >

The adhesive composition used in the present invention may optionally contain a tackifier. Examples of the tackifier include polyterpene resin, rosin resin, aliphatic petroleum resin, alicyclic petroleum resin, copolymer petroleum resin, styrene resin and hydrogenated petroleum resin, and is used for the purpose of improving the bonding strength . These may be used alone or in combination of two or more.

<Filler>

The adhesive composition used in the present invention may optionally contain a filler such as silica. It is highly desirable that silica is blended to improve heat resistance. Hydrophilic silica and hydrophilic silica are generally known as silica, but hydrophobic silica treated with dimethyldichlorosilane, hexamethyldisilazane, octylsilane, or the like is preferable for imparting hygroscopicity to moisture. The amount of silica to be blended is preferably from 0.05 to 30 parts by mass per 100 parts by mass of the total of the components (A) to (D). If the amount is less than 0.05 part by mass, the effect of improving the heat resistance may not be exhibited. On the other hand, when the amount exceeds 30 parts by mass, dispersion failure of the silica may occur, or the solution viscosity may become excessively high, resulting in a problem in workability or deterioration of adhesion.

<Silane coupling agent>

The adhesive composition used in the present invention may optionally contain a silane coupling agent. The combination of the silane coupling agent is highly desirable because it improves the adhesion to metals and the heat resistance. The silane coupling agent is not particularly limited, and examples thereof include those having an unsaturated group, those having a glycidyl group, those having an amino group, and the like. Among them, from the viewpoint of heat resistance,? -Glycidoxypropyltrimethoxysilane or? - (3,4-epoxycyclohexyl) ethyltrimethoxysilane or? - (3,4-epoxycyclohexyl) ethyltriethoxysilane And a silane coupling agent having a glycidyl group. The blending amount of the silane coupling agent is preferably 0.5 to 20 parts by mass per 100 parts by mass of the total of the components (A) to (D). If the amount is less than 0.5 part by mass, heat resistance may be poor. On the other hand, if it exceeds 20 parts by mass, poor heat resistance and adhesion may be deteriorated.

&Lt; Adhesive sheet &

In the present invention, the adhesive sheet is obtained by laminating the laminate (Z) and the release substrate through an adhesive composition, or by laminating a release substrate on the adhesive layer side of the laminate (X) or the laminate (Y) And a releasing base material laminated on at least one side of the adhesive layer. Specific examples of the composition include a release type substrate / adhesive layer, release type substrate / adhesive layer / release type substrate, resin substrate / adhesive layer / release type substrate, metal substrate / adhesive layer / release type substrate, laminate / adhesive layer / release type substrate, Substrate / adhesive layer / laminate / adhesive layer / release substrate. And functions as a protective layer of the base material by laminating the releasing base material. Further, by using the releasing base material, the releasing base material can be released from the adhesive sheet, and the adhesive layer can be transferred to another base material.

The adhesive composition of the present invention can be obtained by applying the adhesive composition used in the present invention to various laminated bodies according to a conventional method and drying the same. Further, if the releasing base material is adhered to the adhesive layer after drying, it becomes possible to take up the composition without causing the composition to adhere to the rear surface of the base material, thereby improving workability and protecting the adhesive layer. Further, when the releasing base material is coated and dried, and if necessary another releasing base material is adhered, the adhesive layer itself can be transferred onto another base material.

<Release type substrate>

The release type substrate is not particularly limited. For example, a coated layer of a filler such as clay, polyethylene, or polypropylene is formed on both sides of a paper such as a top paper, a kraft paper, a roll paper or a gloss paper, Based, fluorine-based, and alkyd-based release agents. In addition, there may be mentioned those obtained by applying the releasing agent on various olefin films such as polyethylene, polypropylene, ethylene- alpha -olefin copolymer and propylene- alpha -olefin copolymer, and films such as polyethylene terephthalate. For example, a releasing force of the releasing base material and the adhesive layer, and an adverse effect on the electrical properties of silicon, etc., it is preferable to use a polypropylene peeling treatment on both sides of the upper surface tension paper and using an alkyd type releasing agent thereon or an alkyd releasing agent on polyethylene terephthalate Is preferably used.

<Printed wiring board>

The &quot; printed wiring board &quot; in the present invention includes a metal foil for forming a conductor circuit and a laminate formed of a resin substrate as constituent elements. The printed wiring board is produced by a conventionally known method such as a subtractive method using a metal clad laminate. A flexible circuit board (FPC), a flat cable, a circuit board for tape automated bonding (TAB), etc., which are partially or wholly covered with a cover film or screen printing ink or the like, It is collectively called.

The printed wiring board of the present invention can have any lamination structure that can be employed as a printed wiring board. For example, a printed wiring board composed of a base film layer, a metal foil layer, an adhesive layer, and a cover film layer can be formed. For example, a printed wiring board composed of five layers of a base film layer, an adhesive layer, a metal foil layer, an adhesive layer and a cover film layer can be used.

If necessary, two or more of the printed wiring boards may be laminated.

The adhesive composition used in the present invention can be suitably used for each adhesive layer of the printed wiring board. In particular, when the adhesive composition used in the present invention is used as an adhesive, it has high adhesion with a low-polarity resin base such as LCP, as well as conventional polyimide, polyester film, and copper foil constituting a printed wiring board, And the adhesive layer itself is excellent in low dielectric properties. Therefore, it is suitable as an adhesive composition used for a coverlay film, a laminated board, a resin-coated copper foil and a bonding sheet.

In the printed wiring board of the present invention, any resin film conventionally used as a base material of a printed wiring board can be used as the base film. As the resin of the base film, a polyester resin, a polyamide resin, a polyimide resin, a polyamideimide resin, a liquid crystal polymer, a polyphenylene sulfide, a syndiotactic polystyrene, a polyolefin resin and a fluorine resin can be exemplified. In particular, it has excellent adhesion to low polarity substrates such as liquid crystal polymers, polyphenylene sulfide, syndiotactic polystyrene, and polyolefin resins.

<Cover film>

As the cover film, any insulating film conventionally known as an insulating film for a printed wiring board can be used. For example, there can be mentioned polyimide, polyester, polyphenylene sulfide, polyether sulfone, polyether ether ketone, aramid, polycarbonate, polyarylate, polyimide, polyamideimide, liquid crystal polymer, polyphenylene sulfide, syndiotactic polystyrene , A polyolefin resin, and the like can be used. More preferably, it is a polyimide film or a liquid crystal polymer film.

The printed wiring board of the present invention can be manufactured by any conventionally known process except that the materials for the respective layers described above are used.

In a preferred embodiment, a semi-finished product (hereinafter referred to as a "semi-finished product on a cover film") in which an adhesive layer is laminated on a cover film layer is produced. On the other hand, an adhesive layer is laminated on a semi-finished product (hereinafter referred to as &quot; base material-side two-layer semi-finished product &quot;) or a base film layer in which a metal foil layer is laminated on a base film layer to form a desired circuit pattern, (Hereinafter referred to as &quot; base film side three-layer semi-finished product &quot;) (hereinafter, referred to as &quot; base film side semi-finished product &quot; ). By bonding the semi-finished product on the cover film side thus obtained and the semi-finished product on the base film side, a printed wiring board having four or five layers can be obtained.

(A) a step of applying a solution of a resin as a base film to the metal foil, and a step of initially drying the coating film; (B) a step of heat-treating and drying a laminate of the metal foil and the initial dried coating film obtained in (Hereinafter referred to as &quot; heat treatment / desolvating step &quot;).

The formation of the circuit in the metal foil layer can be performed by a conventionally known method. The active method may be used, or the subtractive method may be used. It is preferably a subtractive method.

The obtained base film side semi-finished product may be used for bonding with the semi-finished product on the cover film side as it is, or may be used for bonding with the semi-finished product on the side of the cover film after the releasing film is bonded and stored.

The semi-finished product on the cover film is produced, for example, by applying an adhesive to the cover film. If necessary, a crosslinking reaction in the applied adhesive can be performed. In a preferred embodiment, the adhesive layer is semi-cured.

The obtained semi-finished product on the cover film side may be used as it is for bonding with the semi-finished product on the base side, or may be used for bonding with the semi-finished product on the base film side after the releasing film is bonded and stored.

The semifinished product on the base film side and the semifinished product on the cover film side are each stored in the form of a roll, for example, and then joined to produce a printed wiring board. As the bonding method, any method can be used, and bonding can be performed using, for example, a press or a roll. Further, it is also possible to bond them together while heating is performed by a method such as a heating press or a heating roll apparatus.

The semi-finished product on the side of the reinforcing material is suitably produced by applying an adhesive to the reinforcing material in the case of a reinforcing material which can be gently wound, such as a polyimide film. Further, in the case of a reinforcing plate which is hard and can not be wound, such as a plate made of SUS, aluminum or the like, or a plate obtained by curing glass fiber with an epoxy resin, it is preferable that the reinforcing plate is produced by transfer-coating an adhesive applied to the mold- Further, the crosslinking reaction in the applied adhesive can be carried out, if necessary. In a preferred embodiment, the adhesive layer is semi-cured.

The obtained reinforcing-material-side semi-finished product may be used as it is for bonding with the back side of the printed wiring board as it is, or may be used for joining with the semi-finished product on the base film after bonding and storing the releasing film.

The semi-finished product on the base film side, the semi-finished product on the cover film side, and the semi-finished product on the side of the reinforcing agent are all the laminate for a printed wiring board in the present invention.

<Examples>

Hereinafter, the present invention will be described in more detail by way of examples. However, the present invention is not limited to the embodiments. In the examples and the comparative examples, simply referred to are parts by mass.

(Property evaluation method)

Acid value Component (A): a carboxyl group-containing polyolefin resin

Acid value (eq / 10 ⁶ g) according to the present invention, FT-IR (manufactured by Shimadzu produced Sosa manufacture, FT-IR8200PC) using, of maleic anhydride carbonyl stretching peak (the combination (C = O) 1780 cm ^- to using the factor (f) is obtained from the calibration curve created by a chloroform solution of ¹⁾ the absorbance (II) and production of maleic anhydride (Tokyo Kasei ^{a) to 1)} of the absorbance (I), isotactic-specific peak (840 cm The value calculated by the equation was expressed as equivalent (equivalent amount / 10 ⁶ g) in 1 ton of resin.

Acid value = [absorbance (I) / absorbance (II) x (f) / molecular weight of maleic anhydride x 2 x 10 ⁴ ]

Molecular weight of maleic anhydride: 98.06

Acid value Component (B): Carboxyl group-containing styrene resin

The acid value (equivalent weight / 10 ⁶ g) in the present invention was obtained by dissolving the carboxyl group-containing styrene resin in toluene and titrating phenolphthalein as an indicator with a methanol solution of sodium methoxide. (Equivalent amount / 10 ⁶ g) in 1 ton of resin.

Weight average molecular weight (Mw)

The weight average molecular weight in the present invention is a value measured by gel permeation chromatography (hereinafter referred to as GPC, standard material: polystyrene resin, mobile phase: tetrahydrofuran).

(1) Peel strength (adhesive property)

The adhesive composition to be described later was applied to a polyimide film having a thickness of 12.5 占 퐉 (Apikal manufactured by Kaneka Corporation) or an LCP film having a thickness of 25 占 퐉 (manufactured by Kuraray Co., Ltd., Beckstar) Lt; 0 &gt; C for 3 minutes. The adhesive film (B stage product) thus obtained was bonded to a rolled copper foil of 18 占 퐉. The bonding was carried out by press-bonding for 30 seconds under a pressure of 40 kgf / cm &lt; 2 &gt; at 160 DEG C such that the glossy surface of the rolled copper foil was in contact with the adhesive. And then heat-treated at 140 ° C for 4 hours to be cured to obtain a sample for peel strength evaluation. As for the peel strength, the film was pulled at 25 占 폚 to carry out a 90 占 peel test at a tensile speed of 50 mm / min to measure the peel strength. This test shows the bonding strength at room temperature.

<Evaluation Criteria>

?: 1.0 N / mm or more

?: 0.8 N / mm or more and less than 1.0 N / mm

?: 0.5 N / mm or more and less than 0.8 N / mm

X: less than 0.5 N / mm

(2) Dry solder heat resistance

A sample was prepared in the same manner as described above, and a sample piece of 2.0 cm x 2.0 cm was dried at 120 캜 for 30 minutes, flowed in a solder bath melted at each temperature for 1 minute to cause appearance change such as swelling Do not measure the temperature.

<Evaluation Criteria>

?: 310 占 폚 or more

○: 300 ° C or more and less than 310 ° C

DELTA: 290 DEG C or more and less than 300 DEG C

×: less than 290 ° C.

(3) Humidity soldering heat resistance

A sample was prepared in the same manner as described above, and a sample piece of 2.0 cm x 2.0 cm was treated at 40 캜 x 80 RH% x 72 hours. The solder bath melted at each temperature was flown for 1 minute, We measured the temperature that did not cause change.

<Evaluation Criteria>

?: 260 占 폚 or more

O: 250 deg. C or more and less than 260 deg.

DELTA: 240 DEG C or more and less than 250 DEG C

X: less than 240 占

(4) Relative dielectric constant (? _C ) and dielectric tangent (tan?)

The adhesive composition described later was applied to the glossy surface of an electrolytic copper foil having a thickness of 35 占 퐉 so as to have a thickness of 25 占 퐉 after drying and curing, followed by drying at 130 占 폚 for 3 minutes. Then, it was cured by heat treatment at 140 ° C for 4 hours to obtain a copper clad laminate for testing. On the cured adhesive composition surface of the obtained copper clad laminate for test, a conductive silver paste of a vapor-dry solid type was applied by screen printing to a circle having a diameter of 50 mm, dried and cured at 120 ° C for 30 minutes, A lead wire having a length of 30 mm was adhered with a conductive adhesive to obtain a parallel plate capacitor. The capacitance and the loss factor D (dielectric loss tangent) of the obtained parallel plate capacitor were measured using a PRECISION LCR meter HP-4284A under the conditions of 22 캜 and a frequency of 1 MHz, and the relative dielectric constant (ε _c ) was calculated from the following equation Respectively.

? _c = (Cap 占 d) / (S 占? ₀ )

Here Cap: Capacitance [F]

d: dielectric layer thickness = 25 x 10 ^-6 [m]

S: the measured dielectric area ^{= π × (25 × 10 -} 3) 2

ε ₀ : Permittivity of vacuum 8.854 × 10 ^-12

to be.

The obtained dielectric constant and dielectric loss tangent were evaluated as follows.

<Evaluation Criteria of Specific Permittivity>

⊚: not more than 2.3

O: not less than 2.3 and not more than 2.6

?: Not less than 2.6 but not more than 3.0

×: exceeding 3.0

&Lt; Criteria for evaluation of dielectric loss tangent &

?: 0.005 or less

?: Not less than 0.005 but not more than 0.01

?: More than 0.01 and not more than 0.02

×: exceeding 0.02

(Carboxyl group-containing polyolefin resin)

Manufacturing example  One

A 1 L autoclave was charged with 100 parts by mass of a propylene-butene copolymer (Tafmer (registered trademark) XM7080 manufactured by Mitsui Chemicals, Inc.), 150 parts by mass of toluene, 19 parts by mass of maleic anhydride, 6 parts by mass of di- After the temperature was raised to 140 캜, the mixture was further stirred for 3 hours. Thereafter, the obtained reaction solution was cooled and then poured into a container containing a large amount of methyl ethyl ketone to deposit a resin. Thereafter, the solution containing the resin was centrifuged to separate and purify an acid-modified propylene-butene copolymer obtained by graft-polymerizing maleic anhydride, (poly) maleic anhydride and a low molecular weight water. (CO-1, acid value: 410 equivalent / 10 ⁶ g, weight average molecular weight: 60,000, Tm of 80 ° C, ΔH of 35 J / g, weight average molecular weight of 60,000) by drying at 70 ° C. under reduced pressure for 5 hours ).

Manufacturing example  2

Modified maleic acid-modified propylene-butene copolymer (CO-2, acid value: 220 equivalent / 10 ⁶ g, weight average molecular weight: 65,000, Tm 78 (weight average molecular weight)) was obtained in the same manner as in Production Example 1 except that the amount of maleic anhydride was changed to 11 parts by mass.占 폚,? H 25 J / g).

Example  One

80 parts by mass of the maleic anhydride-modified propylene-butene copolymer (CO-1) obtained in Production Example 1 and 40 parts by mass of a carboxyl group-containing styrene resin (Turfec (registered trademark)) were placed in a 500 ml four-necked flask equipped with a reflux condenser and a stirrer. M1943) and 500 parts by weight of toluene were charged, and the mixture was heated to 80 DEG C with stirring, and the mixture was dissolved by stirring for 1 hour. 5 parts by mass of carbodiimide resin V-05 and 10 parts by mass of epoxy resin HP-7200 were mixed with the solution obtained by cooling to obtain an adhesive composition. Table 1 shows the blending amount, adhesive strength, solder heat resistance, and electric characteristics.

Example  2 to 10

The carboxyl group-containing polyolefin resin (A), the carboxyl group-containing styrene resin (B), the carbodiimide resin (C) and the epoxy resin (D) were changed to those shown in Table 1, Examples 2 to 14 were carried out in such a manner that the respective amounts were changed. Table 1 shows the adhesive strength, solder heat resistance and electric characteristics.

[Table 1]

Comparative Example  1 to 7

The carboxyl group-containing polyolefin resin (A), the carboxyl group-containing styrene resin (B), the carbodiimide resin (C) and the epoxy resin (D) were changed to those shown in Table 2, And the amounts were adjusted so as to be the respective blending amounts, and Comparative Examples 1 to 7 were carried out. The compounding amount, adhesive strength, solder heat resistance and electric characteristics are shown in Table 2.

[Table 2]

The polyolefin resin, the carboxyl group-containing styrene resin (B), the carbodiimide resin (C) and the epoxy resin (D) used in Tables 1 and 2 are as follows.

Carboxyl group-containing styrene resin: Tuftec (registered trademark) M1911 (manufactured by Asahi Kasei Chemical Co., Ltd.)

Carboxyl group-containing styrene resin: Tuftec (registered trademark) M1913 (manufactured by Asahi Kasei Chemical Co., Ltd.)

Carboxyl group-containing styrene resin: Tuftec (registered trademark) M1943 (manufactured by Asahi Kasei Chemical Co., Ltd.)

Polyolefin resin: TFMER (registered trademark) XM7080 (manufactured by Mitsui Chemicals)

Styrene resin: Tuftec (registered trademark) H1052 (manufactured by Asahi Kasei Chemical Co., Ltd.)

Carboxyl group-containing acrylonitrile butadiene rubber NBR (manufactured by JSR Corporation)

Carbodiimide resin: V-05 (manufactured by Nisshinbo Chemical Co., Ltd.)

Carbodiimide resin: V-03 (manufactured by Nisshinbo Chemical Co., Ltd.)

o-cresol novolak type epoxy resin: YDCN-700-10 (manufactured by Shin-Tetsu Sumikin Chemical Co., Ltd.)

Dicyclopentadiene type epoxy resin: HP-7200 (manufactured by DIC)

As is evident from Table 1, in Examples 1 to 14, both the liquid crystal polymer (LCP) and the copper foil have excellent adhesion and solder heat resistance, while having excellent adhesion and solder heat resistance to polyimide (PI) and copper foil. Further, the electric characteristics of the adhesive composition are both low and good in dielectric constant and dielectric tangent. On the other hand, as is apparent from Table 2, in Comparative Example 1, since the carboxyl group-containing styrene resin is not blended, the heat resistance of the humidifying solder and the adhesive strength are lowered. In Comparative Example 2, since the carboxyl group-containing polyolefin resin is not compounded, the cross-linking density is low and the heat resistance of the humidifying solder is low. In Comparative Example 3, since the polyolefin resin does not contain a carboxyl group, the cross-linking density is low and the heat resistance of the humidifying solder deteriorates. In Comparative Example 4, since the styrene resin does not contain a carboxyl group, the cross-linking density is low and the heat resistance of the humidifying solder drops. In Comparative Example 5, since no carbodiimide resin was blended, the interaction with the LCP interface was small and the bonding strength was low. In Comparative Example 6, since epoxy resin is not blended, the crosslinking density is low and solder heat resistance is poor. In Comparative Example 7, since the polyolefin resin and the styrene resin were not blended, the low dielectric property of the adhesive composition was deteriorated.

According to the present invention, not only a conventional polyimide and polyethylene terephthalate film but also a resin base material having low dielectric properties such as LCP and a metal base material such as a copper foil can be obtained and high solder heat resistance can be obtained, It is possible to provide a laminate excellent in dielectric characteristics. The above properties are useful for FPC applications requiring a low dielectric constant (low dielectric constant, low dielectric loss tangent) in a flexible printed wiring board application, particularly in a high frequency region.

Claims (6)

As a layered product (Z) in which a resin substrate and a metal substrate are laminated through an adhesive layer containing a carboxyl group-containing polyolefin resin (A)
(1) the adhesive layer has a relative dielectric constant (? _C ) at a frequency of 1 MHz of 3.0 or less,
(2) the dielectric loss tangent (tan?) Of the adhesive layer at a frequency of 1 MHz is 0.02 or less,
(3) the peel strength between the resin base material and the metal base is 0.5 N / mm or more,
(4) A laminate (Z) characterized in that the laminate (Z) has a heat resistance of humidifying solder of 240 DEG C or more. As a layered product (X) of the adhesive layer and the resin substrate used for the layered product (Z) in which a resin substrate and a metal substrate are laminated through an adhesive layer containing a carboxyl group-containing polyolefin resin (A)
(1) the adhesive layer has a relative dielectric constant (? _C ) at a frequency of 1 MHz of 3.0 or less,
(2) the dielectric loss tangent (tan?) Of the adhesive layer at a frequency of 1 MHz is 0.02 or less,
(3) When the metal substrate is laminated on the adhesive layer side of the laminate (X), the peel strength between the resin substrate and the metal substrate in this laminate is 0.5 N / mm or more,
(4) A laminated product (X), wherein the laminated product obtained by laminating a metal base material on the adhesive layer side of the laminated product (X) has a heat resistance of the humidifying solder of 240 캜 or more. As a layered product (Y) of the adhesive layer and the metal substrate used for the layered product (Z) in which a resin substrate and a metal substrate are laminated through an adhesive layer containing a carboxyl group-containing polyolefin resin (A)
(1) the adhesive layer has a relative dielectric constant (? _C ) at a frequency of 1 MHz of 3.0 or less,
(2) the dielectric loss tangent (tan?) Of the adhesive layer at a frequency of 1 MHz is 0.02 or less,
(3) When the resin base material is laminated on the adhesive layer side of the laminate (Y), the peeling strength between the resin base material and the metal base material in this laminate is 0.5 N / mm or more,
(4) A laminated product (Y), wherein the laminated product obtained by laminating the resin base material on the adhesive layer side of the laminated product (Y) has a heat resistance of the humidifying solder of 240 캜 or more. As the adhesive layer used for the layered product (Z) in which the resin base material and the metal base material are laminated through the adhesive layer containing the carboxyl group-containing polyolefin resin (A)
(1) the adhesive layer has a relative dielectric constant (? _C ) at a frequency of 1 MHz of 3.0 or less,
(2) the dielectric loss tangent (tan?) Of the adhesive layer at a frequency of 1 MHz is 0.02 or less,
(3) When the resin substrate is laminated on one side of the adhesive layer and the metal substrate is laminated on the other side, the peel strength between the resin substrate and the metal substrate in this laminate is 0.5 N / mm or more,
(4) An adhesive layer characterized in that the laminated product obtained by laminating the resin base material on one side of the adhesive layer and the metal base material on the other side has a heat resistance of the humidifying solder of 240 DEG C or more. An adhesive sheet containing the laminate (Z) according to claim 1, the laminate (X) according to claim 2, the laminate (Y) according to claim 3 or the adhesive layer according to claim 4. A printed wiring board comprising the adhesive sheet according to claim 5 as a component.