KR20180077099A - Low dielectric flame retardant adhesive composition - Google Patents

Abstract

The present invention relates to a laminate film having high adhesion to a low-polarity resin base material or a metal base such as LCP, as well as conventional polyimide and polyester films, capable of achieving high solder heat resistance, Provide sieve.
(Z) in which a resin substrate and a metal substrate are laminated through an adhesive layer containing a carboxyl group-containing polyolefin resin (A), wherein (1) the relative dielectric constant (? _C ) of the adhesive layer at a frequency of 1 MHz is 3.0 or less (2) the adhesive layer has a dielectric loss tangent (tan?) At a frequency of 1 MHz of 0.02 or less, (3) a peel strength between the resin substrate and the metal substrate is 0.5 N / mm or more, (4) (5) the layered product (X) of the adhesive layer and the resin substrate is VTM-0 in the UL-94 method.

Description

Low dielectric flame retardant adhesive composition

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

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 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, since the base film having low dielectric properties is low in polarity, when the conventional epoxy adhesive or acrylic adhesive is used, the adhesive force is weak and it is difficult to manufacture an FPC member such as a coverlay film or a laminated plate 1, 2). Further, the epoxy adhesive or the acrylic adhesive does not have a low dielectric property and damages the dielectric property of the FPC.

Further, since the adhesive composition used for the above purpose is often flammable, it is necessary to impart flame retardancy. The flame retardant has excellent flame retardancy by using a halogen-based organic compound. However, this method has a problem of emitting corrosive halogen gas at the time of combustion. Therefore, a halogen-free flame retardant that does not contain a halogen component is required. For example, phosphorus-based flame retardants. For example, Patent Document 3 discloses that organic phosphinic acid aluminum can be used as a flame retardant, and the range of the content of the flame retardant when the flame retardant is contained in the coverlay film described in this document is shown.

Patent Document 1: JP-A-2012-25917 Patent Document 2: WO2015 / 041085A1 publication Patent Document 3: Japanese Patent Application Laid-Open No. 2014-34668

However, although Patent Document 1 describes the adhesiveness between the polyimide and the rolled copper foil, the solder heat resistance, and the flame retardancy, it does not mention the low dielectric properties, and the adhesion to the base film having low dielectric properties such as LCP . Although Patent Document 2 describes the adhesiveness of the polyimide and the copper foil, the solder heat resistance, the insulation reliability, and the flame retardancy, it does not mention the dielectric properties, Adhesiveness is also not mentioned. Patent Document 3 describes the dielectric constant and the flame retardancy, but does not mention only the adhesiveness of the copper foil and the copper foil, and does not mention the adhesion property to the polyimide or the LCP substrate. Also, there is no mention of solder heat resistance required for FPC applications.

DISCLOSURE OF THE INVENTION The present invention has been made in order to solve the above-mentioned problems, and as a result, it has been found that the adhesive layer having specific physical properties is not limited to the conventional polyimide and polyethylene terephthalate film but also to a resin base material having low dielectric properties such as LCP, High adhesion, high solder heat resistance, and low dielectric characteristics with the base material, and completed the present invention with the flame retardancy of VTM-0 based on UL-94.

In other words, the object of the present invention is to provide a laminate excellent in heat resistance, low dielectric constant, and flame retardancy, having good adhesion to various resin base materials such as polyimide and LCP, and metal base material.

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 relative dielectric constant (? _C ) of the adhesive layer at a frequency of 1 MHz is 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) The humidifying soldering heat resistance of the layered product (Z) is 240 占 폚 or higher,

(5) A laminate (Z) characterized in that the laminate (X) obtained by removing the metal substrate from the laminate (Z) is VTM-0 in the UL-94 method.

As the layered product (X) of the adhesive layer and the resin substrate 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)

(1) the relative dielectric constant (? _C ) of the adhesive layer at a frequency of 1 MHz is 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 the laminate is 0.5 N / mm or more,

(4) The laminated product obtained by laminating the metal base material on the adhesive layer side of the laminate (X) has a heat resistance of the humidifying solder of 240 DEG C or more,

(5) The layered product (X) is VTM-0 in the UL-94 method.

A layered product (Y) of the adhesive layer and the metal substrate, which is used for a 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)

(1) the relative dielectric constant (? _C ) of the adhesive layer at a frequency of 1 MHz is 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 the adhesive layer side of the laminate (Y), the peel strength between the resin substrate and the metal substrate in the laminate is 0.5 N / mm or more,

(4) The laminated product obtained by laminating the resin base material on the adhesive layer side of the laminate (Y) has a heat resistance of the humidifying solder of 240 DEG C or more,

(5) A laminate (Z) is produced by laminating a resin substrate on the adhesive layer side of the laminate (Y), and then the laminate (X) after the metal substrate is removed is VTM-0 (Y).

As the adhesive layer 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 relative dielectric constant (? _C ) of the adhesive layer at a frequency of 1 MHz is 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 the laminate is 0.5 N / mm or more ,

(4) A laminate obtained by laminating a resin substrate on one surface of an adhesive layer and a metal substrate laminated on the other surface thereof has a heat resistance of the humidifying solder of 240 캜 or higher,

(5) An adhesive layer wherein the layered product (X) obtained by laminating the resin base material on one side of the adhesive layer is VTM-0 in the UL-94 method.

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

And the adhesive sheet as a component.

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) according to the present invention is characterized in that (1) the relative dielectric constant (? _C ) Is 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 substrate and the metal substrate is 0.5 N / mm or more, (4) (5) the layered product (X) of the adhesive layer and the resin substrate is VTM-0 in the UL-94 method. Has high adhesion with a low-polarity resin base material such as LCP or a metal base as well as conventional polyimide and polyester film, and can achieve high solder heat resistance, and is also excellent in low dielectric properties and flame retardancy.

Hereinafter, embodiments of the present invention will be described in detail. The laminate obtained by laminating the resin base material and the metal base material through the adhesive layer containing the carboxyl group-containing polyolefin according to the present invention satisfies the following (1) to (5).

≪ Carboxy group-containing polyolefin resin (A)

The carboxyl group-containing polyolefin resin (A) (hereinafter, also 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 . The polyolefin resin refers to a polymer composed mainly of a hydrocarbon skeleton such as a homopolymer of an olefin monomer exemplified by ethylene, propylene, butene, butadiene, isoprene, etc., or copolymerization with other monomers and a hydride or a halide of the obtained polymer . That is, the carboxyl group-containing polyolefin is preferably 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? -Olefin with propylene as a main component. As the? -olefin, for example, one kind or several 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 it exceeds the above-mentioned value, the adhesiveness may be lowered. Further, the viscosity and stability of the solution may be lowered, and the pot life may be deteriorated. In addition, the production efficiency is lowered, which is not preferable.

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 poor. 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 production method of 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 to be a main chain and an unsaturated carboxylic acid and / A reaction in which an acid anhydride is graft-polymerized), and the like.

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 hexanoate, tert-butyl peroxypivalate, methyl ethyl ketone peroxide, di-tert-butyl peroxide, and lauroyl peroxide; And azonitriles such as azobisisobutyronitrile and azobisisopropionitrile.

<Adhesive Layer>

In the present invention, the adhesive layer means a layer of the adhesive composition after the adhesive composition is applied to the 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 too 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, so that bubbles are generated at the time of pressing in the production of a printed wiring board .

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, an adhesive layer may be provided 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 is more than 1% by mass, the residual solvent is foamed at the time of pressing the printed wiring board to generate bubbles.

&Lt; Resin substrate &

The resin substrate in the present invention is not particularly limited as long as it is capable of forming an adhesive layer by applying and drying the adhesive composition of the present invention. However, a resin substrate such as a film type 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. As a commercially available product of the LCP film, for example, Beckstar (registered trademark) manufactured by Kabushiki Kaisha Kuraray Co., Ltd. can be mentioned. As a commercially available product of the polyimide film, for example, Apical (registered trademark) manufactured by Kaneka Corporation may 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 too thin, it is difficult to obtain a 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 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 value 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 in a circuit board can be used. Examples of the material include various metals such as stainless steel, 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 a 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 a resin base material / an adhesive layer / a 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 an adhesive composition to a resin substrate in accordance with a conventional method, followed by drying. Further, the layered product (Y) is obtained by applying the adhesive composition to a metal substrate and drying the adhesive composition according to a conventional method. The layered product (Z) can be obtained by laminating a metal base or a resin base 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, the 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 / Adhesive layer / metal substrate / adhesive layer).

The laminate of the present invention also satisfies the following requirements (1) to (5).

<Requirement (1)>

The requirement (1) will be described. The layered product (Z) according to the present invention is required to have a relative dielectric constant (? _C ) of 3.0 or less at a frequency of 1 MHz of the adhesive layer. Specifically, the adhesive composition is coated on 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. Subsequently, it is cured by heat treatment at about 140 캜 for about 4 hours, and the cured adhesive composition layer (adhesive layer) is peeled from the release film. The relative dielectric constant (? _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. The relative dielectric constant? _C in the entire region of the frequency of 1 MHz to 10 GHz is preferably 3.0 or less, more preferably 2.6 or less, and even more 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 base material of the layered product (Z) is cleanly removed with an etching solution to obtain a two-layered laminate (X) of an adhesive layer and a resin base material. 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 vapor deposition or sputtering or by application of a conductive paste, , And measuring the electrostatic capacity to calculate the relative dielectric constant ([epsilon] _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) according to the above-described method to prepare a capacitor, the composite capacitance relative permittivity (? _C ) of the resin base material and the adhesive layer is measured, 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 similarly converted into a 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 dielectric constant? _C of the adhesive layer can be calculated from the difference between them.

<Requirement (2)>

The requirement (2) will be described. In the layered product (Z) according to the present invention, it is necessary that the dielectric loss tangent (tan?) Of the adhesive layer at a frequency of 1 MHz is 0.02 or less. Specifically, the adhesive composition is coated on 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. Subsequently, it is cured by heat treatment at about 140 캜 for about 4 hours, and the cured adhesive composition layer (adhesive layer) is peeled 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 region of the frequency range of 1 MHz to 10 GHz is preferably 0.02 or less, more preferably 0.01 or less, and still 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) according to 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 a resin substrate so that the thickness after drying is about 25 占 퐉, and dried at about 130 占 폚 for about 3 minutes. Subsequently, the metal substrate is bonded to the surface of the adhesive composition layer (adhesive layer). The bonding is performed by vacuum pressing at a temperature of about 160 占 폚 under a pressure of about 40 kgf / cm2 for about 30 seconds so that the glossy surface of the metal base contacts the adhesive composition layer. Subsequently, heat treatment is performed at about 140 占 폚 for about 4 hours to cure the resin layer / adhesive layer / metal-based three-layer laminate (Z). At a room temperature (about 25 ° C), the resin base of the layered product (Z) is peeled at 90 ° at a tensile speed 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. Further, even in the layered product (Z) produced by a method other than the above method, if the 90 DEG peel strength is 0.5 N / mm or more, it is included in the present invention.

From the laminate (X), the laminate (Z) of the present invention can be obtained by bonding a metal base material to the surface of the adhesive composition layer (adhesive layer) of the layered product (X). The bonding is performed by vacuum pressing at a temperature of about 160 占 폚 under a pressure of about 40 kgf / cm2 for about 30 seconds so that the glossy surface of the metal base contacts the adhesive composition layer. Subsequently, heat treatment is performed at about 140 占 폚 for about 4 hours to cure the resin layer / adhesive layer / metal-based three-layer laminate (Z). At a room temperature (about 25 ° C), the resin base of the layered product (Z) is peeled at 90 ° at a tensile speed 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 laminate (Y), the laminate (Z) of the present invention can be obtained 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 the resin substrate in contact with the adhesive composition layer at about 160 캜 for about 30 seconds under a pressure of about 40 kgf / cm 2. Subsequently, heat treatment is performed at about 140 占 폚 for about 4 hours to cure the resin layer / adhesive layer / metal-based three-layer laminate (Z). At a room temperature (about 25 ° C), the resin base of the layered product (Z) is peeled at 90 ° at a tensile speed 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 DEG C under a pressure of about 3 kgf / cm &lt; 2 &gt; and then peeling 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;. Subsequently, heat treatment is performed at about 140 占 폚 for about 4 hours to cure the resin layer / adhesive layer / metal-based three-layer laminate (Z). At a room temperature (about 25 ° C), the resin base of the layered product (Z) is peeled at 90 ° at a tensile speed 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 is required to have a humidifying solder heat resistance of 240 캜 or higher. 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, the metal substrate is bonded to the surface of the adhesive composition layer (adhesive layer). The bonding is performed by vacuum pressing at a temperature of about 160 占 폚 under a pressure of about 40 kgf / cm2 for about 30 seconds so that the glossy surface of the metal base contacts the adhesive composition layer. Subsequently, heat treatment is performed at about 140 占 폚 for about 4 hours to cure the resin layer / adhesive layer / metal-based three-layer laminate (Z). The laminate (Z) is treated for about 72 hours under the conditions of about 40 DEG C and about 80% RH, and the solder bath is melted at each temperature for one minute to measure a temperature at which no change in appearance such as expansion occurs . 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) produced by a method other than the above method is also included in the present invention if the heat resistance of the humidifying solder is 240 캜 or higher.

From the laminate (X), the laminate (Z) of the present invention can be obtained by bonding a metal base material to the surface of the adhesive composition layer (adhesive layer) of the layered product (X). The bonding is performed by vacuum pressing at a temperature of about 160 占 폚 under a pressure of about 40 kgf / cm2 for about 30 seconds so that the glossy surface of the metal base contacts the adhesive composition layer. Subsequently, heat treatment is performed at about 140 占 폚 for about 4 hours to cure the resin layer / adhesive layer / metal-based three-layer laminate (Z). The laminate (Z) is treated for about 72 hours under the conditions of about 40 DEG C and about 80% RH, and the solder bath is melted at each temperature for one minute to measure a temperature at which no change in appearance such as expansion occurs . 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.

From the laminate (Y), the laminate (Z) of the present invention can be obtained 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 the resin substrate in contact with the adhesive composition layer at about 160 캜 for about 30 seconds under a pressure of about 40 kgf / cm 2. Subsequently, heat treatment is performed at about 140 占 폚 for about 4 hours to cure the resin layer / adhesive layer / metal-based three-layer laminate (Z). The laminate (Z) is treated for about 72 hours under the conditions of about 40 DEG C and about 80% RH, and the solder bath is melted at each temperature for one minute to measure a temperature at which no change in appearance such as expansion occurs . 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.

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 bonding the adhesive layer and the resin substrate together and then vacuum-pressing the resin substrate at a temperature of about 160 캜 under a pressure of about 40 kgf / cm 2 for about 30 seconds so that the glossy surface of the metal substrate is in contact with the adhesive layer. Subsequently, heat treatment is performed at about 140 占 폚 for about 4 hours to cure the resin layer / adhesive layer / metal-based three-layer laminate (Z). The laminate (Z) is treated for about 72 hours under the conditions of about 40 DEG C and about 80% RH, and the solder bath is melted at each temperature for one minute to measure a temperature at which no change in appearance such as expansion occurs . 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.

<Requirement (5)>

The requirement (5) will be described. The layered product (Z) according to the present invention needs to have VTM-0 when the layered product (X) constituting the layered product (Z) is evaluated by a flame retardancy evaluation test based on UL-94. Specifically, the adhesive composition of the present invention is coated on 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 test piece (50 ± 0.5 mm × 200 ± 0.5 mm) was cut from the layered product (X) obtained by curing by heat treatment at about 140 ° C. for about 4 hours, and the thickness was measured. The specimen is to be rounded in the shape of a cylinder having a length of 200 mm and a diameter of about 10 mm and fixed on a stand. The flame of the gas burner is adjusted to about 20 mm in height, and the bottom of the test piece is polished for 3 seconds, and the burning time is measured. Repeat 2 times for 1 sample. It is judged that the respective combustion times are 10 sec or less and the two total combustion times are 30 sec or less. Tests were conducted with N = 5 for each, and all passes were equivalent to VTM-0.

From the layered product (Z), the metal base material 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.

From the laminate Y, a resin substrate is bonded to the surface of the adhesive composition layer (adhesive layer) of the laminate Y to obtain a laminate Z, and then the metal substrate of the laminate Z is etched The layered product (X) can be obtained.

&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 (5).

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) ), An epoxy resin (hereinafter, simply referred to as component (D)) and / or a flame-retardant filler (hereinafter also referred to simply as component (E)). By containing the five types of resins (A) to (E), not only conventional polyimide and polyester films but also low-polarity resin bases such as LCP films which are not assumed in the prior art, High adhesiveness, and excellent solder heat resistance, electrical characteristics (low dielectric properties) and flame retardancy.

&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 are preferable. 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), styrene- 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) / the component (B) is 10 to 90/90 to 10 (mass ratio), and most preferably the component (A) / the component (B) . 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. When the amount of the component (A) exceeds the above-mentioned range, the wettability to the substrate decreases, and the adhesive strength may decrease.

&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 the amount 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, 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. In addition, if it exceeds the above range, there is a problem that the port life of the adhesive is lowered and the low dielectric property is lowered.

<Flame Retardant Filler (E)>

The flame-retardant filler (E) is not particularly limited, but it is preferable that the flame-retardant filler (E) does not dissolve in an organic solvent, and examples thereof include an inorganic flame retardant filler and an organic flame retardant filler. Examples of the inorganic flame retardant filler include metal hydroxide compounds such as aluminum hydroxide, magnesium hydroxide, zirconium hydroxide, calcium hydroxide, and barium hydroxide; Metal carbonate compounds such as basic magnesium carbonate, zinc carbonate, magnesium carbonate-calcium, calcium carbonate and barium carbonate; Metal oxides such as magnesium oxide, molybdenum oxide, zirconium oxide, tin oxide, hydrate of tin oxide, and antimony oxide; Metal borate compounds such as zinc borate, zinc metaborate and barium metaborate; Inorganic metal compounds such as dolomite, hydrotalcite and borax; And the like. Examples of the organic flame retardant filler include inorganic fillers such as melamine phosphate, melamine polyphosphate, guanidine phosphate, guanidine polyphosphate, ammonium phosphate, ammonium polyphosphate, ammonium phosphate amide, ammonium polyphosphate, phosphoric acid carbamate, polyphosphoric acid carbamate, Aluminum ethylphosphinate, aluminum trismethylethylphosphinate, aluminum trisdiphenylphosphinate, zinc bis diethylphosphinate, zinc bismethylethylphosphinate, zinc bisdiphenylphosphinate, bisdiethylphosphinantitanyl, tetrakis Phosphorus-based flame retardants such as titanium diethylphosphinate, bismethylethylphosphinostatitanyl, titanium tetrakis methylethylphosphinate, bisdiphenylphosphinostatitanyl, and tetrakis diphenylphosphinic acid titanium; Melamine, melamine and melamine cyanurate; nitrogen-based flame retardants such as a cyanuric acid compound, an isocyanuric acid compound, a triazole-based compound, a tetrazole compound, a diazo compound and urea; Silicon-based flame retardants such as silicone compounds and silane compounds, and the like. As the flame retardant filler, a metal hydroxide compound or a phosphorus compound is preferable. Among them, a phosphorus compound is more preferable, and a known phosphorus flame retardant filler such as aluminum phosphinate can be used. In addition, the phosphorus flame retardant includes a type (phosphorus-based flame retardant filler) which is insoluble in organic solvents and a type (phosphorus-based flame retardant non-filler) which is soluble in an organic solvent. In the present invention, desirable. The flame-retardant filler may be used alone, or two or more flame-retardant fillers may be used in combination.

In the adhesive composition used in the present invention, the content of the flame-retardant filler is preferably in the range of 20 to 100 parts by mass, more preferably in the range of 30 to 90 parts by mass per 100 parts by mass of the total of the components (A) to (D) And more preferably 40 to 90 parts by mass. Below the above range, it may be difficult to obtain flame retardancy. Beyond the above range, adhesiveness, heat resistance, electric characteristics, and the like may be deteriorated.

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, alcoholic solvents such as methanol, ethanol, isopropyl alcohol, butanol, pentanol, hexanol, propanediol and phenol, acetone, methyl isobutyl ketone, methyl ethyl Ketone solvents such as acetone, methyl ethyl ketone, pentanone, hexanone, cyclohexanone, isophorone and acetophenone, cellosolves such as methyl cellosolve and ethyl cellosolve, methyl acetate, ethyl acetate, butyl acetate, Ester solvents such as butyl formate, ethylene glycol mono n-butyl ether, ethylene glycol mono isobutyl ether, ethylene glycol mono tert-butyl ether, diethylene glycol Glycol ether solvents such as mono n-butyl ether, diethylene glycol mono iso-butyl ether, triethylene glycol mono-n-butyl ether and tetraethylene glycol mono-n-butyl ether. Or more 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, and most preferably 300 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- To 800 parts by mass. Below the above range, the liquid form and the port life property 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 a tackifier, a filler different from the component (E), and a silane coupling agent.

&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 adhesive strength. These may be used alone or in combination of two or more.

<Filler different from (E) component>

In the adhesive composition used in the present invention, a filler different from the above-mentioned component (E) such as silica may be blended if necessary. 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 blending amount of silica 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 problems in workability or adherence.

<Silane coupling agent>

The adhesive composition used in the present invention may optionally contain a silane coupling agent. It is very preferable because the adhesiveness to metal and the property of heat resistance are improved by blending a silane coupling agent. 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) Or a releasing base material laminated on at least one surface 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, / 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 and drying the adhesive composition used in the present invention to various laminated bodies according to a conventional method. Further, if the releasing base material is applied to the adhesive layer after drying, the film can be wound without causing backing on the base material, so that workability is excellent and the adhesive layer is protected. Further, when the releasing base material is coated and dried, and then another releasing base material is stuck if necessary, the adhesive layer itself can be transferred onto another base material.

<Release type substrate>

The releasing base material is not particularly limited. For example, it is possible to provide a coating layer of a frosting agent such as clay, polyethylene or polypropylene on both sides of paper such as a top paper, a kraft paper, a roll paper or a gloss paper, Fluorine-based or alkyd-based release agent is further coated on the layer. Further, it is also possible to use a film of olefinic film alone such as polyethylene, polypropylene, ethylene- alpha -olefin copolymer, propylene- alpha -olefin copolymer or the like and a film of polyethylene terephthalate coated with the above releasing agent. For example, a releasing force of the releasing base material and the adhesive layer, and an adverse influence on the electrical characteristics of silicon, etc., it is preferable to use a polypropylene base fabric on both sides of the topsheet and to use an alkyd type releasing agent thereon, Based release agent is preferably used.

<Printed wiring board>

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

The printed wiring board of the present invention may 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 three or more 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 copper foil having a resin, and a bonding sheet.

In the printed wiring board of the present invention, any resin film conventionally used as a substrate 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. Particularly, it also 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 conventionally known insulating film can be used as an insulating film for a printed wiring board. For example, polyimide, polyester, polyphenylene sulfide, polyether sulfone, polyether ether ketone, aramid, polycarbonate, polyarylate, polyimide, polyamideimide, liquid crystal polymer, syndiotactic polystyrene, A film made of various polymers of the same type 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 thus obtained semi-finished product on the cover film side and the semi-finished product on the base film side, a printed wiring board having four or five layers can be obtained.

The semi-finished product on the base film side can be obtained by, for example, (A) applying a solution of a resin to be a base film to the metal foil and drying the coating film in advance, (B) heating 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 conventionally known methods. The additive 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, or may be used for joining 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 a cover film. 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 semi-finished product on the cover film may be used for bonding with the semi-finished product on the base film 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 bonded to each other 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. In addition, they may be bonded 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 smooth and windable reinforcing material such as a polyimide film. Further, in the case of a reinforced plate which is hard and can not be wound, such as a plate made of, for example, SUS, aluminum or the like, or a plate obtained by curing glass fiber with an epoxy resin, it is preferable that the reinforced plate is manufactured by transfer coating an adhesive applied to the mold- Further, the crosslinking reaction in the applied adhesive can be performed, 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 surface 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 material 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 comparative examples, simply referred to as "part" represents "part by mass".

(Property evaluation method)

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

The acid value (equivalent weight / 10 ⁶ g) of the carboxyl group-containing polyolefin resin (A) used in the present invention was measured using FT-IR (FT-IR8200PC manufactured by Shimadzu Seisakusho Co., Ltd.) ) stretching peak (1780 ㎝ of ^bond-1) absorbance (I), isotactic-specific peak (840 ㎝) absorbance (II) and maleic anhydride (Tokyo Kasei factor obtained from the calibration curve created by the chloroform solution of the production) of the (f), the value calculated according to the following formula is 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 / 10 ⁶ g) of the carboxyl group-containing styrene resin (B) in the present invention was determined by dissolving the carboxyl group-containing styrene resin in toluene and titrating phenolphthalein as a indicator with a methanol solution of sodium methoxide. (Equivalents / 10 ⁶ g) in 1 ton of resin.

Weight average molecular weight (Mw)

The weight average molecular weight in the present invention is measured by gel permeation chromatography (hereinafter referred to as GPC, reference material: polystyrene resin, mobile phase: tetrahydrofuran, column: Shodex KF-802 manufactured by Shimadzu Seisakusho Co., + KF-804L + KF-806L, column temperature: 30 占 폚, flow rate: 1.0 ml / min, detector: RI detector).

(1) Peel strength (adhesive property)

The adhesive composition described below was laminated on a polyimide film (Apicel (registered trademark) manufactured by Kaneka Corporation) having a thickness of 12.5 占 퐉 or an LCP film having a thickness of 25 占 퐉 (manufactured by Kabushiki Kaisha Kuraray Co., ) To a thickness of 25 mu m after drying, and dried at 130 DEG 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 pressing the laminated sheet with the glossy surface of the rolled copper foil in contact with the adhesive at 160 캜 under a pressure of 40 kgf / cm 2 for 30 seconds. Subsequently, the resultant was heat-treated at 140 占 폚 for 4 hours and cured to obtain a sample for peel strength evaluation. The peel strength was measured at 25 deg. C by 90 degree peel test at a pulling rate of film and a tensile rate 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, The temperature was measured.

<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 80 RH% for 72 hours. The solder bath melted at each temperature was flown for 1 minute to change the appearance Was measured.

<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 below 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 the drying and curing, followed by drying at 130 占 폚 for 3 minutes. Subsequently, heat treatment was performed at 140 占 폚 for 4 hours to cure the copper clad laminate. The conductive silver paste of the evaporation dry solid type was coated in a circular form having a diameter of 50 mm by screen printing on the cured adhesive composition surface of the resultant copper clad laminate and 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 (Cap) 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, The electromotive force (? _C ) was calculated.

? _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.

&Lt; Criteria for evaluation of relative dielectric constant &

⊚: 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

(5) Flame retardancy

The adhesive composition to be described later was applied to a polyimide film having a thickness of 25 占 퐉 (Apicel 占 manufactured by Kaneka Corporation) so that the thickness after drying became 25 占 퐉 and dried at 130 占 폚 for 3 minutes. Subsequently, the resultant was heat-treated at 140 占 폚 for 4 hours and cured to obtain a laminate. A sample piece was prepared on the basis of UL-94 using a laminate, and a combustion test was conducted based on the VTM method.

<Evaluation Criteria>

○: Satisfies VTM-0 condition

×: VTM-1 or more, and VTM-0 condition is not satisfied

(Carboxyl group-containing polyolefin resin)

Manufacturing example  One

A 1 L autoclave was charged with 100 parts by mass of a propylene-butene copolymer ("TFMER (registered trademark) XM7080" manufactured by Mitsui Chemicals, Inc.), 150 parts by mass of toluene, 19 parts by mass of maleic anhydride, And the mixture was heated to 140 캜, followed by further stirring 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 precipitate 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. (CO-1, acid value: 410 equivalents / 10 ⁶ g, weight average molecular weight: 60,000, Tm 80 ° C, ΔH 35 J / g (weight average molecular weight)) 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: 224 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 content 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 (manufactured by Tuftec (registered trademark)) were added to a 500 ml four-necked flask equipped with a stirrer, ) M1943), 450 parts by mass of methylcyclohexane and 50 parts by mass of methyl ethyl ketone were charged, and the temperature was raised to 80 ° C while stirring, and the stirring was continued for 1 hour to dissolve. To the solution obtained by cooling, 5 parts by mass of carbodiimide resin V-09GB and 10 parts by mass of epoxy resin HP-7200 were mixed to obtain a mixed solution. 60 parts by mass of a flame-retardant filler OP-935 was added to the obtained mixed solution to obtain an adhesive composition. Table 1 shows the blending amount, adhesive strength, solder heat resistance, electrical characteristics and flame retardancy.

Example  2 to 10

The carboxyl group-containing polyolefin resin, the carboxyl group-containing styrene resin, the carbodiimide resin, the epoxy resin and the flame-retardant filler were changed to those shown in Table 1 and the amounts shown in Table 1 were changed in the same manner as in Example 1, 2 to 10 were performed. Table 1 shows the adhesive strength, solder heat resistance, electrical characteristics and flame retardancy.

Comparative Example  1-4

The carboxyl group-containing polyolefin resin, the carboxyl group-containing styrene resin, the carbodiimide resin, the epoxy resin and the flame-retardant filler were changed to those shown in Table 2 and the amounts shown in Table 2 were changed in the same manner as in Example 1, 1 to 4 were performed. Table 2 shows the adhesive strength, solder heat resistance, electrical characteristics and flame retardancy.

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

A carboxyl group-containing styrene resin: Tuftec (registered trademark) M1913 (manufactured by Asahi Kasei Chemical Co., Ltd.), an acid value of 185 equivalent / 10 ⁶ g

A carboxyl group-containing styrene resin: Tuftec (registered trademark) M1943 (manufactured by Asahi Kasei Chemical Co., Ltd.), an acid value of 185 equivalent / 10 ⁶ g

Carbodiimide resin: V-09 GB (manufactured by Nisshinbo Chemical Co., Ltd.)

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

Flame retardant filler: EXOLIT (registered trademark) OP-935 (Clariant)

Metal hydrate flame retardant filler: MGZ-3 (manufactured by Sakai Kagaku Kogyo Co., Ltd.)

Intermecent flame retardant filler: FP-2100JC (manufactured by ADEKA)

Flame-retardant non-filler: PX-200 (manufactured by Daihatsu Chemical Co., Ltd.)

As is clear from Table 1, in Examples 1 to 10, the liquid crystal polymer (LCP) and the copper foil have excellent adhesiveness and solder heat resistance while having good adhesion between the polyimide (PI) and the copper foil and solder heat resistance. In addition, the electrical characteristics of the adhesive composition are both low and good in dielectric constant and dielectric tangent. It also achieves VTM-0 and is excellent in flame retardancy. On the other hand, as is clear from Table 2, in Comparative Example 1, the amount of the flame-retardant filler was small and the flame retardancy was poor. In Comparative Example 2, the amount of the flame-retardant filler was large, and adhesiveness and humidifying solder heat resistance were poor. In Comparative Example 3, an organophosphorus flame retardant is blended, and adhesiveness and humidifying solder heat resistance are inferior because it is excessively compatible with an adhesive. In Comparative Example 4, since it is only a carboxyl-containing styrene group, the crosslinking density is low and the heat resistance of the humidifying solder is poor.

According to the present invention, not only the conventional polyimide and polyethylene terephthalate film but also a resin substrate having low dielectric properties such as LCP and a metal substrate such as a copper foil can be obtained with high adhesiveness and high solder heat resistance , Low dielectric constant, and flame retardancy can be provided. 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, particularly in a high frequency range.

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 relative dielectric constant (? _C ) of the adhesive layer at a frequency of 1 MHz is 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) The humidifying soldering heat resistance of the layered product (Z) is 240 占 폚 or higher,
(5) A laminate (Z) characterized in that the laminate (X) obtained by removing the metal substrate from the laminate (Z) is VTM-0 in the UL-94 method. As the layered product (X) of the adhesive layer and the resin substrate 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)
(1) the relative dielectric constant (? _C ) of the adhesive layer at a frequency of 1 MHz is 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 the laminate is 0.5 N / mm or more,
(4) The laminated product obtained by laminating the metal base material on the adhesive layer side of the laminate (X) has a heat resistance of the humidifying solder of 240 DEG C or more,
(5) The layered product (X) is VTM-0 in the UL-94 method. A layered product (Y) of the adhesive layer and the metal substrate, which is used for a 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)
(1) the relative dielectric constant (? _C ) of the adhesive layer at a frequency of 1 MHz is 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 the adhesive layer side of the laminate (Y), the peel strength between the resin substrate and the metal substrate in the laminate is 0.5 N / mm or more,
(4) The laminated product obtained by laminating the resin base material on the adhesive layer side of the laminate (Y) has a heat resistance of the humidifying solder of 240 DEG C or more,
(5) A laminate (Z) is produced by laminating a resin substrate on the adhesive layer side of the laminate (Y), and then the laminate (X) after the metal substrate is removed is VTM-0 (Y). As the adhesive layer 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 relative dielectric constant (? _C ) of the adhesive layer at a frequency of 1 MHz is 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 material in the laminate when the resin base material is laminated on one surface of the adhesive layer and the metal base material is laminated on the other surface is 0.5 N /
(4) A laminate obtained by laminating a resin substrate on one surface of an adhesive layer and a metal substrate laminated on the other surface thereof has a heat resistance of the humidifying solder of 240 캜 or higher,
(5) An adhesive layer wherein the layered product (X) obtained by laminating the resin base material on one side of the adhesive layer is VTM-0 in the UL-94 method. 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.