JP2018177949A - Thermosetting composition, cured product, electromagnetic wave shielding film and method of manufacturing the same, and printed wiring board with electromagnetic wave shielding film and method of manufacturing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermosetting composition and a cured product thereof capable of forming an insulating resin layer and an adhesive layer having excellent adhesiveness, quickly curing, and improved flame retardancy, the thermosetting composition or the cured product. Provided are an electromagnetic wave shielding film provided with a layer containing, and a method for producing the same, and a printed wiring board with an electromagnetic wave shielding film and a method for producing the same. An electromagnetic wave shielding film 1 having an insulating resin layer 10, a metal thin film layer 22 adjacent to the insulating resin layer 10, and an adhesive layer 24 adjacent to the side opposite to the insulating resin layer 10 of the metal thin film layer 22. The electromagnetic shielding film 1 is such that at least one of the insulating resin layer 10 and the adhesive layer 24 is a thermosetting composition containing a specific compound or a cured product thereof. [Selection diagram] Fig. 1

Description

  The present invention relates to a thermosetting composition, a cured product, an electromagnetic wave shielding film and a method of manufacturing the same, a printed wiring board with an electromagnetic wave shielding film, and a method of manufacturing the same.

  In order to shield electromagnetic wave noise generated from a flexible printed wiring board and electromagnetic wave noise from the outside, an electromagnetic shielding film comprising an insulating resin layer, a metal thin film layer adjacent to the insulating resin layer, and an adhesive layer It may provide on the surface of a flexible printed wiring board via a coverlay film (for example, refer to patent documents 1).

  The electromagnetic wave shielding film is formed, for example, by applying a coating liquid containing a thermosetting resin, a curing agent and a solvent on one side of a first release film which is a carrier film, and drying to form an insulating resin layer. It manufactures by providing a metal thin film layer and an adhesive bond layer (for example, conductive adhesive bond layer) on the surface of an insulating resin layer.

  In the first release film, an electromagnetic wave shielding film is attached to the surface of an insulating film provided on the surface of a flexible printed wiring board (FPC) so that the conductive adhesive layer is in contact with the insulating film, and then insulating It peels from the resin layer.

JP, 2016-086120, A

  The improvement of the flame retardance is calculated | required by the electromagnetic wave shielding film affixed on FPC etc. Also, conventionally, in the production of an electromagnetic wave shielding film, lamination processing of bonding an insulating resin layer or an adhesive layer to a metal thin film layer may be repeated a plurality of times, and reduction of the number is also required. Furthermore, conventionally, when the electromagnetic wave shielding film is attached to the FPC by heat press, the adhesive component of the electromagnetic wave shielding film may be eluted, and it is also required to suppress this elution.

  The present invention is a thermosetting composition capable of forming an insulating resin layer and an adhesive layer having excellent adhesion, curing rapidly, and improved flame retardancy, a cured product thereof, the thermosetting composition, or the cured composition. Provided are an electromagnetic wave shielding film provided with a layer including an object, a method of manufacturing the same, a printed wiring board with the electromagnetic wave shielding film, and a method of manufacturing the same.

[1] One or more types of epoxy group-containing compounds and two or more types selected from the group of compounds (1) represented by the following formula (1), wherein at least one of the two or more types is 25 A thermosetting composition which is solid at 1 atm and which is liquid at 25 ° C and 1 atm.
[2] The thermosetting composition according to [1], wherein the compound (1) which is a solid is a compound represented by the following formula (1a).
[3] The thermosetting composition according to [1], wherein the liquid compound (1) is a compound represented by the following formula (1b).
[4] The thermosetting composition according to [1], wherein the compound (1) which is a solid is a compound represented by the following formula (1a-1).
[5] The thermosetting composition according to [1], wherein the liquid compound (1) is a compound represented by the following formula (1b-1).
[6] The thermosetting composition according to any one of [1] to [5], further comprising a black colorant.
[7] The thermosetting composition according to any one of [1] to [5], further comprising conductive particles.
[8] The thermosetting composition according to any one of [1] to [7], further including one or more selected from the group of compounds represented by the following formula (2).
[9] The thermosetting composition according to any one of [1] to [8], further comprising a solvent.
[10] A cured product of the thermosetting composition according to any one of [1] to [9].
[11] An electromagnetic shielding film comprising: an insulating resin layer; a metal thin film layer adjacent to the insulating resin layer; and an adhesive layer adjacent to the metal thin film layer opposite to the insulating resin layer, An electromagnetic shielding film, wherein at least one of the insulating resin layer and the adhesive layer is a thermosetting composition according to any one of [1] to [9] or a cured product according to [10].
[12] The electromagnetic wave shielding film according to [11], wherein the adhesive layer is an anisotropic conductive adhesive layer.
[13] A printed wiring board provided with a printed circuit on at least one side of a substrate, an insulating film adjacent to the surface of the printed wiring board on which the printed circuit is provided, and the adhesive layer A printed wiring board with an electromagnetic wave shielding film, comprising: the electromagnetic wave shielding film according to [11] or [12] provided adjacently.
[14] The method for producing an electromagnetic wave shielding film according to [11], wherein the coating obtained by applying the thermosetting composition to a substrate film is cured to an arbitrary degree by heating. A method for producing an electromagnetic wave shielding film, comprising the step of forming at least one of the insulating resin layer and the adhesive layer.
[15] A manufacturing method of the electromagnetic wave shield film according to [11], wherein the insulating resin layer, the metal thin film layer, and the adhesive layer are laminated in this order, and heating and pressure are applied. The manufacturing method of the electromagnetic wave shield film which has the process of performing at least one adhesion | attachment among adhesion | attachment of the said insulation resin layer and the said metal thin film layer, and adhesion | attachment of the said metal thin film layer and the said adhesive bond layer by applying.
[16] The method for producing a printed wiring board with an electromagnetic wave shielding film according to [13], wherein the adhesive layer of the electromagnetic wave shielding film is in contact with the surface of the insulating film of the printed wiring board And a pressure-bonding step of bonding the adhesive layer to the surface of the insulating film by pressure-bonding these.
[17] The manufacturing method according to [16], wherein the insulating resin layer and the adhesive layer are pressed while being heated when pressure bonding is performed in the pressure bonding step.
[18] The method according to [16] or [17], comprising a curing step of curing the thermosetting composition by further heating the insulating resin layer and the adhesive layer after the pressure bonding step. Production method.

In the above formula (1), R ₁ , R ₂ and R ₃ are each independently a hydrogen atom or an optional substituent, and R ₁ and R ₂ may combine with each other to form a ring.
In Formula (1a), R ₂ is a hydrogen atom or an optional substituent, and R ₂ may be bonded to a phenyl group bonded to a phosphorus atom to form a ring.
In the above formula (1b), R ₂ may be a hydrogen atom or any substituent, and R ₂ may be bonded to a phenyl group bonded to a phosphorus atom to form a ring; R ₃ is a hydroxyl group and a carboxyl group Or any substituent having one or more of at least one of the following.

  In the formula (2), L1 and L2 each independently represent a single bond or a divalent linking group having 1 to 8 carbon atoms, m and n each independently represent an integer of 1 to 5, and m + n is 2 to 2 6 and any one or more hydrogen atoms of the hydrogen atoms bonded to the benzene ring are substituted by a (HO-L1-) group, and any other one or more hydrogen atoms are (-L2 Any one or more hydrogen atoms which are substituted by -COOH) group and which are not substituted by (HO-L1-) group and (-L2-COOH) group may be substituted by any substituent .

According to the thermosetting composition and the cured product thereof of the present invention, it is possible to form an insulating resin layer and an adhesive layer which cure rapidly and have improved flame retardancy and adhesiveness.
The electromagnetic wave shielding film and the printed wiring board with the electromagnetic wave shielding film of the present invention have improved flame retardancy.
According to the manufacturing method of the electromagnetic wave shielding film of the present invention, the number of times of the laminating process of bonding the insulating resin layer or the adhesive layer to the metal thin film layer can be reduced.
According to the method of producing a flexible printed wiring board with an electromagnetic wave shielding film of the present invention, the thermosetting composition according to the present invention is also cured quickly during heat pressing, so when sticking the electromagnetic wave shielding film to FPC by heat pressing In addition, elution of the components of the thermosetting composition can be suppressed. This makes it easier to control the adhesion and thickness of the insulating resin layer and the adhesive layer to be formed.

It is a sectional view showing one embodiment of an electromagnetic wave shield film of the present invention. It is sectional drawing which shows other embodiment of the electromagnetic wave shielding film of this invention. It is sectional drawing which shows the manufacturing process of the electromagnetic wave shielding film of FIG. It is sectional drawing which shows the manufacturing process of the electromagnetic wave shielding film of FIG. BRIEF DESCRIPTION OF THE DRAWINGS It is sectional drawing which shows one Embodiment of the printed wiring board with an electromagnetic wave shielding film of this invention. It is sectional drawing which shows the manufacturing process of the printed wiring board with an electromagnetic wave shielding film of FIG.

The following definitions of terms apply throughout the specification and claims.
"Epoxy" is a radical name for -O- groups attached to two carbon atoms linked by a carbon chain.
The "(meth) acryloyl group" is a generic term for acryloyl group and methacryloyl group.
The "isotropically conductive adhesive layer" means a conductive adhesive layer having conductivity in the thickness direction and in the surface direction.
The "anisotropically conductive adhesive layer" means a conductive adhesive layer having conductivity in the thickness direction but not in the surface direction.
The “conductive adhesive layer having no conductivity in the surface direction” means a conductive adhesive layer having a surface resistance of 1 × 10 ⁴ Ω or more.
Regarding the average particle size of particles, 30 particles are randomly selected from microscopic images of the particles, and the minimum diameter and the maximum diameter are measured for each particle, and the median value of the minimum diameter and the maximum diameter is one particle The value is obtained by arithmetically averaging the particle diameters of the 30 particles measured as the diameter. The same applies to the average particle size of the conductive particles.
The thickness of the film (mold release film, insulation film, etc.), coating film (insulation resin layer, conductive adhesive layer, etc.), metal thin film layer, etc. is 5 points of observation of the cross section of the object to be measured using a microscope. The thickness is measured and averaged.
The storage elastic modulus is calculated from the stress applied to the object to be measured and the detected strain, and is measured as one of the visco-elastic characteristics using a dynamic visco-elasticity measuring device that outputs as a function of temperature or time.
For surface resistance, two thin film metal electrodes (10 mm in length, 5 mm in width, 10 mm in inter-electrode distance) formed by vapor deposition of gold on quartz glass are placed on the electrodes to be measured. From the object, a 10 mm × 20 mm area of the object to be measured is pressed with a load of 0.049 N, which is the resistance between the electrodes measured at a measurement current of 1 mA or less.

<< Thermosetting composition >>
The first aspect of the present invention includes one or more types of epoxy group-containing compounds and two or more types selected from the group of compounds (1) represented by the following formula (1), and among the two or more types, A thermosetting composition in which at least one is solid at 25 ° C. and 1 atm, and at least one is liquid at 25 ° C. and 1 atm.

［式（１）中、Ｒ_１、Ｒ_２及びＲ_３はそれぞれ独立に水素原子又は任意の置換基であり、Ｒ_１及びＲ_２が互いに結合して環を形成してもよい。］

[In formula (1), R ₁ , R ₂ and R ₃ are each independently a hydrogen atom or an optional substituent, and R ₁ and R ₂ may combine with each other to form a ring. ]

The optional substituents of R ₁ , R ₂ and R _{3 in} the compound (1) may be monovalent substituents or may be linked to each other by divalent substituents to form a ring .
The monovalent substituent of R ₁ , R ₂ and R ₃ of the compound (1) is, for example, an aromatic group, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, or 1 carbon atom To 10 alkoxy groups, halogen and the like. -O-, -C (= O)-, -C (= O) O-, -O-C (=, except that one or more of the methylene groups of the alkyl group are bonded to each other by an oxygen atom. It may be substituted by O)-, -NH-, or -S-.
As said aromatic group, a phenyl group, a naphthyl group, an anthracenyl group etc. are mentioned, for example. The aromatic group may be bonded to a phosphorus atom or an oxygen atom via a C1-C3 linking group.

  The compound (1) which is the solid is preferably a compound (1a) represented by the following formula (1a) from the viewpoint of further enhancing the function of the compound (1) which is the solid as a flame retardant and a curing agent. .

［式（１ａ）中、Ｒ_２は水素原子又は任意の置換基であり、リン原子に結合したフェニル基にＲ_２が結合して環を形成していてもよい。］

[In formula (1a), R ₂ is a hydrogen atom or an optional substituent, and R ₂ may be bonded to a phenyl group bonded to a phosphorus atom to form a ring. ]

The optional substituent of R ₂ of the compound (1a) may be a monovalent substituent or may be a divalent substituent and substitute an optional hydrogen atom of a phenyl group bonded to a phosphorus atom. It may be combined to form a ring.
Examples of the monovalent substituent in R ₂ of the compound (1a), may be exemplified the same substituents as R ₂ of the compound described above (1).
The compound (1a) having the above-mentioned suitable substituent tends to be solid at 25 ° C. and 1 atm, rapidly cures the thermosetting composition, and suppresses the outflow of part of the components upon curing, as designed The insulating resin layer and the adhesive layer having a thickness of can be easily formed.

  As a preferable specific example of the compound (1a), a phosphorus compound (HCA) represented by the following formula (1a-1) (chemical name: 9,10-dihydro-9-oxa-10-phosphophenanthrene-10-oxide) Can be mentioned.

  The compound (1) which is the solid is preferably a compound (1b) represented by the following formula (1b) from the viewpoint of enhancing the function of the compound (1) which is the solid as a flame retardant and a curing agent. .

［式（１ｂ）中、Ｒ_２は水素原子又は任意の置換基であり、リン原子に結合したフェニル基にＲ_２が結合して環を形成していてもよく；Ｒ_３は水酸基及びカルボキシル基のうち少なくとも一方を１つ以上有する任意の置換基である。］

[In formula (1b), R ₂ may be a hydrogen atom or any substituent, and R ₂ may be bonded to a phenyl group bonded to a phosphorus atom to form a ring; R ₃ is a hydroxyl group and a carboxyl group Or any substituent having one or more of at least one of the following. ]

The optional substituent of R ₂ of the compound (1 b) may be a monovalent substituent or may be a divalent substituent and substitute an optional hydrogen atom of a phenyl group bonded to a phosphorus atom. It may be combined to form a ring.
Examples of the monovalent substituent in R ₂ of the compound (1b), can be exemplified the same substituents as R ₂ of the compound described above (1).

R _{3 in the} compound (1b) is a substituent having one or more hydroxyl groups, a substituent having one or more carboxyl groups, or a substituent having one or more hydroxyl groups and one or more carboxyl groups. Is preferred.

As a substituent represented by R ₃ of the compound (1b), at least one hydrogen atom of the linear, branched or cyclic alkyl group having 1 to 20 carbon atoms is substituted by a hydroxyl group or a carboxyl group Preferred substituents. Especially, it is more preferable that it is a C1-C20 branched alkyl group and it is a substituent which has one or more hydroxyl groups or carboxyl groups in each branched chain. In addition, one or more of the methylene groups of the above alkyl group is -O-, -C (= O)-, -C (= O) O- or -O-C, except that oxygen atoms are bonded to each other. It is preferably substituted by (= O) —, more preferably by —C (= O) O— or —O—C (= O) —.
The compound (1b) having the above-mentioned suitable substituent tends to be a highly fluid liquid at 25 ° C. and 1 atm, is excellent in dispersibility in the thermosetting composition, and is inhibited from causing a decrease in the degree of curing Thus, the insulating resin layer and the adhesive layer can be easily formed by the adhesion.

  The phosphorus compound represented by following formula (1 b-1) as a suitable specific example of a compound (1 b) is mentioned. It is preferable that this phosphorus compound is liquid at 25 ° C. and 1 atm, and a glycol solvent such as ethylene glycol and propylene glycol is used as the dilution solvent.

Content ratio represented by A / B of the content A of the compound (1) which is solid at 25 ° C. and 1 atmosphere and the content B of the compound (1) which is liquid contained in the thermosetting composition Is preferably 1/10 to 10/1, more preferably 1/5 to 5/1, and still more preferably 1/35 to 3.5 / 1 on a mass basis.
It can harden more rapidly also at the time of a heat press as it is more than the lower limit of the said range, and it can suppress more that it flows out out of the hardened | cured material which a part of component of the said thermosetting composition forms.
Adhesiveness improves more that it is below the upper limit of the said range, and sufficient adhesiveness can be more easily obtained by comparatively mild lamination process.

(Epoxy group-containing compound)
The epoxy group-containing compound contained in the thermosetting composition is preferably a compound having two or more epoxy groups, and more preferably a resin having two or more epoxy groups (epoxy resin), More preferably, it is an epoxy resin having an epoxy group at least at both ends of the resin.
When the above-mentioned suitable epoxy group-containing compound is used, the adhesive composition can be easily formed with less curing shrinkage of the thermosetting composition, increased adhesion, and excellent adhesion to metal.
The epoxy group-containing compound contained in the thermosetting composition may be one type or two or more types.

In the present specification, an epoxy group is a monovalent group having one arbitrary hydrogen atom removed from an epoxy. Examples of the epoxy include epoxy ethane (alias: ethylene oxide), 1,3′-epoxypropane (alias: trimethylene oxide, oxetane) and the like.
The epoxy group-containing compound is preferably a glycidyl group-containing compound having a glycidyl group in which a methylene group is bonded to a monovalent bond of the epoxy group.

An epoxy resin known as the epoxy resin can be applied, and can be appropriately selected according to the application of the thermosetting composition. The epoxy resin contained in the thermosetting composition may be one kind or two or more kinds.
Specific examples of the epoxy resin include epoxy resins obtained by condensation reaction of bisphenol having two hydroxyphenyl groups with epichlorohydrin, and examples thereof include bisphenol A epoxy resin and bisphenol F epoxy resin. In addition, mention may be made of, for example, polyfunctional epoxy resins such as dicyclopentadiene type epoxy resin, cresol novolac type epoxy resin, phenol novolac type epoxy resin, naphthalene type epoxy resin, biphenyl type epoxy resin, triphenylmethane type epoxy resin, etc. it can.

The total content ratio of the epoxy group-containing compound and the compound (1) in the thermosetting composition is preferably a content ratio sufficient for the compound (1) to cure the epoxy group-containing compound. Specifically, it is preferable that the number-of-moles of the active hydrogen group in a compound (1) is a content ratio of 0.01 mol or more and 1.5 mol or less per 1 mol of epoxy groups of an epoxy-group containing compound. Here, the active hydrogen group refers to hydrogen, a hydroxyl group and a carboxyl group bonded to the phosphorus atom of the compound (1).
The amount of the compound (1) reacting with the epoxy group-containing compound is increased to be at least the above lower limit, and the thermosetting composition is rapidly cured to further enhance the flame retardancy, hardness and adhesion of the cured product. Can.
The hardening speed of a thermosetting composition becomes moderate as it is below the said upper limit, the hardness of hardened | cured material becomes it easy to become uniform, and it can suppress that hardness becomes high excessively or it becomes low excessively.
When the thermosetting composition contains a curing agent other than the compound (1), the content ratio of the compound (1) to the epoxy group-containing compound may be outside the above range.

In the thermosetting composition, the total content of the compound (1) relative to a total of 100 parts by mass of the epoxy group-containing compound is preferably 10 parts by mass or more and 1000 parts by mass or less, and 50 parts by mass or more and 500 parts by mass or less More preferably, 100 parts by mass or more and 300 parts by mass or less are more preferable.
The amount of the compound (1) reacting with the epoxy group-containing compound is increased to be at least the above lower limit, and the thermosetting composition is rapidly cured to further enhance the flame retardancy, hardness and adhesion of the cured product. Can.
The hardening speed of a thermosetting composition becomes moderate as it is below the said upper limit, the hardness of hardened | cured material becomes it easy to become uniform, and it can suppress that hardness becomes high excessively or it becomes low excessively.

(Additive)
The thermosetting composition may contain, as an optional component, one or more kinds of additives other than the epoxy group-containing compound and the compound (1) as long as the thermosetting composition does not prevent the curing.
As an additive, a conductive material, a coloring agent, a filler, a solvent, a hardening agent, a hardening accelerator, a stress reducing agent etc. are mentioned, for example.

The thermosetting composition preferably contains a compound (2) represented by the following formula (2).
In the compound (2) in the thermosetting composition, the epoxy group of the epoxy group-containing compound and the active hydrogen group of the hydroxyl group or carboxyl group possessed by the compound (2) react with heat to function as a curing agent. Moreover, the adhesiveness with respect to the metal of the hardened | cured material of the said thermosetting composition can be improved by containing a compound (2).

  As a particularly suitable compound (2), for example, 4-hydroxybenzoic acid represented by the following formula (2a) and gallic acid (gallic acid) represented by the following formula (2b) can be mentioned.

In the formula (2), L1 and L2 each independently represent a single bond or a divalent linking group having 1 to 8 carbon atoms, m and n each independently represent an integer of 1 to 5, and m + n is 2 to 2 6 and any one or more hydrogen atoms of the hydrogen atoms bonded to the benzene ring are substituted by a (HO-L1-) group, and any other one or more hydrogen atoms are (-L2 Any one or more hydrogen atoms which are substituted by -COOH) group and which are not substituted by (HO-L1-) group and (-L2-COOH) group may be substituted by any substituent .
In the above formulas (2a) and (2b), one or more hydrogen atoms bonded to the benzene ring may be substituted by any substituent.

In said Formula (2), 1-3 are preferable, and, as for n, 1-3 are preferable.
In the above formula (2), except in the case of m = 1 and n = 1, the hydrogen atom of the carboxyl group of the (-L2-COOH) group is linear, branched or cyclic having 1 to 10 carbon atoms May be substituted by an alkyl group of to form a carboxylic acid ester.

It is preferable that a C1-C8 bivalent coupling group represented by L1 and L2 in said Formula (2) is a C1-C8 alkylene group and a C2-C8 alkenylene group. The alkylene group and one or more methylene groups constituting the alkenylene group are —O—, —C (= O) —, —C (= O) O—, except when oxygen atoms are bonded to each other. It may be substituted by -O-C (= O)-, -NH- or -S-.
When m is 2 or more, the plurality of L1 may be the same as or different from each other.
When n is 2 or more, the plurality of L2 may be the same as or different from each other.

  Examples of the optional substituent which may substitute the hydrogen atom of the benzene ring include, for example, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, and an alkoxy group having 1 to 10 carbon atoms. And halogens. One or more methylene groups of the alkyl group, except when oxygen atoms are bonded to each other, are -O-, -C (= O)-, -C (= O) O-, -O-C (= It may be substituted by O)-, -NH-, or -S-.

As specific examples of the compound (2), for example, mono compounds such as 4-hydroxybenzoic acid, 3-hydroxybenzoic acid, 2-hydroxybenzoic acid (salicylic acid), 2- (hydroxymethyl) benzoic acid, vanillic acid, silicic acid and the like Hydroxybenzoic acid and its derivatives;
2,3-Dihydroxybenzoic acid (2-pyrocatechic acid), 2,4-dihydroxybenzoic acid (β-resorcylic acid), 2,5-dihydroxybenzoic acid (gentisic acid), 2,6-dihydroxybenzoic acid (γ- Resorcynic acid), 3,4-dihydroxybenzoic acid (protocatechuic acid), 3,5-dihydroxybenzoic acid (α-resorcynic acid), 3,6-dihydroxybenzoic acid, dihydroxybenzoic acid such as orsilenic acid and derivatives thereof;
Trihydroxybenzoic acid and derivatives thereof such as 3,4,5-trihydroxybenzoic acid (gallic acid), 2,4,6-trihydroxybenzoic acid (phloroglucinol carboxylic acid);
Hydroxycinnamic acid and its derivatives such as melilotonic acid, phlorettic acid, umbellic acid, caffeic acid, ferulic acid, sinapinic acid;
Aromatic dicarboxylic acids having one or more hydroxy groups such as 5-hydroxyisophthalic acid, 2-hydroxyterephthalic acid, 2,5-dihydroxyterephthalic acid and derivatives thereof; and the like can be mentioned.
The compound (2) contained in the thermosetting composition may be one type or two or more types.

The content ratio of the epoxy group-containing compound to the compound (2) in the thermosetting composition may be a content ratio sufficient for the compound (2) to cure the epoxy group-containing compound. Specifically, it is preferable that the molar ratio of the active hydrogen group in the compound (2) is 0.5 mol or more and 1.5 mol or less per 1 mol of the epoxy group of the epoxy group-containing compound. Here, an active hydrogen group means both a hydroxyl group and a carboxyl group which the compound (2) has.
The quantity of the compound (2) which reacts with an epoxy-group containing compound as it is more than the said lower limit increases, and the hardness of the hardened | cured material of a thermosetting composition and adhesiveness can be raised more.
The hardening speed of a thermosetting composition becomes moderate as it is below the said upper limit, the hardness of hardened | cured material becomes it easy to become uniform, and it can suppress that hardness becomes high excessively or it becomes low excessively.

The total content of the compound (2) relative to a total of 100 parts by mass of the epoxy group-containing compound in the thermosetting composition is preferably 1 part by mass or more and 100 parts by mass or less, and 5 parts by mass or more and 50 parts by mass or less More preferably, 10 parts by mass or more and 30 parts by mass or less are more preferable.
The quantity of the compound (2) which reacts with an epoxy-group containing compound as it is more than the said lower limit increases, and the hardness of the hardened | cured material of a thermosetting composition and adhesiveness can be raised more.
The hardening speed of a thermosetting composition becomes moderate as it is below the said upper limit, the hardness of hardened | cured material becomes it easy to become uniform, and it can suppress that hardness becomes high excessively or it becomes low excessively.

  When applying the said thermosetting composition to the adhesive bond layer of the electromagnetic wave shielding film mentioned later, a conductive adhesive layer can be formed by adding a electrically conductive material to the said thermosetting composition. As the conductive material, conductive particles are preferable.

Examples of the conductive particles include metal particles such as silver, platinum, gold, copper, nickel, palladium, aluminum and solder, graphite powder, fired carbon particles, and fired carbon particles plated.
The suitable average particle diameter of the conductive particles may be, for example, about 0.1 μm or more and 50 μm or less, as described later.
As content of the electroconductive particle with respect to the total mass of solid content except the solvent of the said thermosetting composition, 1 mass% or more and 50 mass% or less are mentioned, for example, 10 mass% or more and 30 mass% or less are preferable . The conductive adhesive layer mentioned later can be easily formed as it is this range.

Examples of the stress reducing agent (stress relaxation agent) include vinyl acetate resin and silicone compound.
The content of the stress reducing agent relative to the total mass of the solid content excluding the solvent of the thermosetting composition may be, for example, 10% by mass to 80% by mass, although it depends on the type, 30% % Or more and 70% by mass or less is preferable. Within this range, a cured product with good flexibility can be easily formed.

Examples of the colorant include carbon black, azo dyes, metal complexes and the like. Among these, black colorants are preferred.
The content of the colorant relative to the total mass of the solid content excluding the solvent of the thermosetting composition is, for example, 1% or more and 30% or less, depending on the type thereof, and is 5% or more and 20% or less Is preferred.
Since it can fully be colored as it is said range, the insulating resin layer which can be distinguished from a mold release film can be formed easily.

  Examples of the filler include powders such as quartz glass, talc, fused silica, crystalline silica, and alumina.

  The solvent is preferably capable of dissolving or dispersing the epoxy group-containing compound and the compound (1), and for example, esters (butyl acetate, ethyl acetate, methyl acetate, isopropyl acetate, ethylene glycol monoacetate, etc.), ketones (methyl ethyl ketone) And methyl isobutyl ketone, acetone, methyl isobutyl ketone, cyclohexanone and the like, alcohols (methanol, ethanol, isopropanol, butanol, propylene glycol monomethyl ether, propylene glycol and the like) and the like.

  Examples of the curing agent include dicyclopentadiene type phenol resin, phenol novolac resin, cresol novolac resin, phenol aralkyl resin, biphenyl type phenol resin and the like, and polyfunctional phenol resin such as triphenylmethane type phenol resin and the like.

  Examples of the curing accelerator include organic phosphorus compounds such as tetraphenylphosphonium tetraphenylborate and triphenylphosphine, imidazole compounds such as 2-ethyl-4-methylimidazole, 2-methylimidazole and phenylimidazole, and 1,8- Examples include tertiary amine compounds such as diazabicyclo (5.4.0) undecen-7 (DBU), 1,5-diazabicyclo (4.3.0) nonene-5 (DBN), N-aminoethyl piperazine and the like.

  As said additive, you may also contain other components other than the said component. Examples of the other components include a mold release agent, a flame retardant other than the compound (1), a pigment, an ion trap agent, a coupling agent, a heat resisting agent and the like.

  The content of each of the curing agent, the curing accelerator, the filler, and the other components relative to the total mass of the thermosetting composition is not particularly limited, and, for example, the total content is 0.1 It can prepare in the range of mass% or more and 30 mass% or less.

(Method for producing thermosetting composition)
The thermosetting composition according to the first aspect of the present invention may be prepared, for example, by appropriately blending a solvent, the epoxy group-containing compound, the two or more compounds (1), additives, etc. It can be prepared by mixing according to the method.

<Function effect>
The compound (1) contained in the thermosetting composition of the present invention functions as a flame retardant at the burning temperature of the cured product. Although the details of this chemical mechanism have not been elucidated, the mechanism similar to that of conventional triphenyl phosphate causes compound (1) to form a flame-retardant char during combustion and suppresses the combustion of the cured product. It is thought that.
Among the two or more compounds (1) contained in the thermosetting composition of the present invention, the compound (1), which is solid at 25 ° C. and 1 atm, has flame retardancy and a thermosetting composition. Functions as a curing agent at the time of curing and contributes to quick curing. Although the details of this chemical mechanism have not been elucidated, the active hydrogen bonded to the phosphorus of the compound (1) reacts with the epoxy group by heat, and the compound (1) is added to the epoxy group-containing compound, It is believed to increase the degree of cure.
Among the two or more compounds (1) contained in the thermosetting composition of the present invention, the compound (1) which is liquid at 25 ° C. and 1 atm has a flame retardancy and a thermosetting composition. It is excellent in the dispersibility in the inside, the distribution in the hardened | cured material also becomes uniform, and it is hard to reduce the hardness of the hardened | cured material or a coating film. Furthermore, since it is a liquid, the adhesion to the substrate is improved, and the layer containing the cured product can be sufficiently adhered to a substrate such as a metal thin film layer by a relatively gentle laminating process.

<< Cured product >>
The second aspect of the present invention is a cured product of the thermosetting composition of the first aspect. The degree of curing of the cured product may be in the near uncured state as in the B-stage, in the B-staged (semi-cured) state, or in the completely cured state.
As an example of embodiment of hardened | cured material, the coating film formed by hardening the thermosetting composition apply | coated on the surface of a base material is mentioned, for example.
The adhesion of the coating to the substrate is excellent, so the coating is useful as an adhesive layer. Moreover, when the said base material is metal, and the said coating film contains the said compound (2), the adhesiveness with respect to the metal surface is more excellent. For this reason, the said coating film exhibits the adhesiveness outstanding as an insulating resin layer and an adhesive bond layer which are laminated | stacked on the metal thin film layer of the electromagnetic wave shielding film mentioned later.
The film thickness of the coating film is not particularly limited, and examples thereof include 1 μm to 100 μm.

The method for obtaining the cured product is not particularly limited as long as it is a method which can supply heat for curing the epoxy group-containing compound and the compound (1) to be cured, and for example, it is injected into a container or a mold and heated. And a method of applying and heating on the surface of a substrate.
The temperature of heating at the time of obtaining the cured product may be at least the temperature at which the reaction occurs, and is preferably room temperature or more, and from the viewpoint of facilitating reaction control, 50 to 200 ° C., 1 minute to 24 hours It is preferable to cure under the heating conditions of
The curing reaction may be completely cured in one heating, or may be cured stepwise via B-stage in a plurality of heatings.

<Function effect>
The cured product of the second aspect of the present invention, which contains the epoxy group-containing compound and the two or more compounds (1), exhibits excellent adhesion to a substrate in contact during curing. Moreover, since the compound (1) is contained, the flame retardancy is also excellent.

"Electromagnetic wave shield film"
The third aspect of the present invention is an electromagnetic wave shielding film having an insulating resin layer, a metal thin film layer adjacent to the insulating resin layer, and an adhesive layer adjacent to the metal thin film layer opposite to the insulating resin layer. In the electromagnetic shielding film, at least one of the insulating resin layer and the adhesive layer is a cured product of the second aspect.
Hereinafter, although it demonstrates with reference to drawings, the dimension ratio in a drawing may differ from an actual thing for convenience of explanation.

FIG. 1 is a cross-sectional view showing the electromagnetic wave shielding film 1 of the first embodiment, and FIG. 2 is a cross-sectional view showing the electromagnetic wave shielding film 1 of the second embodiment.
The electromagnetic wave shielding film 1 comprises: an insulating resin layer 10; a metal thin film layer 22 adjacent to the insulating resin layer 10; an adhesive layer 24 adjacent to the metal resin layer 10 opposite to the insulating resin layer 10; A first release film 30 adjacent to the metal thin film layer 22 on the opposite side and a second release film 40 adjacent to the metal thin film layer 22 on the adhesive layer 24 on the opposite side.

The electromagnetic wave shielding film 1 according to the first embodiment is an example in which the adhesive layer 24 is an anisotropic conductive adhesive layer 24.
The electromagnetic wave shielding film 1 of the second embodiment is an example in which the adhesive layer 26 is an isotropic conductive adhesive layer 26.

(Insulating resin layer)
The insulating resin layer 10 adheres the electromagnetic wave shielding film 1 to the surface of the insulating film provided on the surface of the flexible printed wiring board, and after peeling off the first release film 30, the protective layer of the metal thin film layer 22 is formed. It becomes.

  As the insulating resin layer 10, a coating formed by applying a coating containing a thermosetting resin and a curing agent, and semi-curing or curing the coating; a coating formed by applying a coating containing a thermoplastic resin; The layer etc. which consist of the film which melt-molded the composition containing a thermoplastic resin are mentioned. From the viewpoint of heat resistance at the time of soldering or the like, a coating film containing a thermosetting resin and a curing agent is applied, and a coating film formed by semi-curing or curing is preferable.

As a thermosetting resin, an amide resin, an epoxy resin, a phenol resin, an amino resin, an alkyd resin, a urethane resin, a synthetic rubber, an ultraviolet curing acrylate resin, etc. are mentioned. As a thermosetting resin, an amide resin and an epoxy resin are preferable from the point which is excellent in heat resistance.
As a hardening agent, the well-known hardening agent according to the kind of thermosetting resin is mentioned.

The insulating resin layer 10 is either a coloring agent (pigment, dye, etc.) and / or a filler in order to conceal the printed circuit of the printed wiring board or to impart design to the printed wiring board with an electromagnetic wave shielding film. Both may be included.
From the viewpoint of weatherability, heat resistance and hiding ability, a pigment or a filler is preferable as one or both of a coloring agent and a filler, and from the viewpoint of hiding ability of printed circuit and design, a black pigment or a black pigment More preferred is a combination with other pigments or fillers.

The insulating resin layer 10 may contain a flame retardant other than the compound (1).
The insulating resin layer 10 may contain other components as needed as long as the effects of the present invention are not impaired.

The surface resistance of the insulating resin layer 10 is preferably 1 × 10 ⁶ Ω or more from the viewpoint of electrical insulation. The surface resistance of the insulating resin layer 10 is preferably 1 × 10 ¹⁹ Ω or less in terms of practical use.
The thickness of the insulating resin layer 10 is preferably 0.1 μm to 30 μm, and more preferably 0.5 μm to 20 μm. If the thickness of the insulating resin layer 10 is equal to or more than the lower limit value of the above range, the insulating resin layer 10 can sufficiently exhibit the function as a protective layer. If the thickness of the insulating resin layer 10 is equal to or less than the upper limit of the above range, the electromagnetic wave shielding film 1 can be made thinner.

(Conductive layer)
As the conductive layer 20, a metal thin film layer 22 adjacent to the insulating resin layer 10, and a conductive adhesive layer (anisotropic conductive adhesive layer 24 to be the outermost layer on the opposite side to the insulating resin layer 10 in the conductive layer 20). Or a conductive layer (I) having an isotropic conductive adhesive layer 26); or a conductive layer (II) consisting only of the isotropic conductive adhesive layer 26. As the conductive layer 20, a conductive layer (I) is preferable in that it can sufficiently function as an electromagnetic wave shielding layer.

(Metal thin film layer)
The metal thin film layer 22 is a layer made of a metal thin film. Since the metal thin film layer 22 is formed so as to spread in the surface direction, it has conductivity in the surface direction and functions as an electromagnetic wave shield layer or the like.

  Examples of the metal thin film layer 22 include a deposition film formed by physical vapor deposition (vacuum deposition, sputtering, ion beam deposition, electron beam deposition, etc.) or CVD, a plating film formed by plating, a metal foil, and the like. From the viewpoint of excellent conductivity in the surface direction, a vapor deposition film or a plating film is preferable, and the thickness can be small, and even if the thickness is thin, the conductivity in the surface direction is excellent, and it can be easily formed by a dry process. The vapor deposition film is more preferable, and the vapor deposition film by physical vapor deposition is more preferable.

  As a metal which comprises the metal thin film layer 22, aluminum, silver, copper, gold | metal | money, electroconductive ceramics etc. are mentioned. Copper is preferred from the viewpoint of electrical conductivity, and conductive ceramics is preferred from the viewpoint of chemical stability.

  0.001 ohm or more and 1 ohm or less are preferable, and, as for the surface resistance of the metal thin film layer 22, 0.001 ohm or more and 0.5 ohm or less are more preferable. If the surface resistance of the metal thin film layer 22 is equal to or more than the lower limit value of the above range, the metal thin film layer 22 can be made sufficiently thin. If the surface resistance of the metal thin film layer 22 is equal to or less than the upper limit value of the above range, it can sufficiently function as an electromagnetic wave shielding layer.

  0.01 micrometer or more and 1 micrometer or less are preferable, and, as for the thickness of the metal thin film layer 22, 0.05 micrometer or more and 1 micrometer or less are more preferable. When the thickness of the metal thin film layer 22 is 0.01 μm or more, the conductivity in the surface direction is further improved. When the thickness of the metal thin film layer 22 is 0.05 μm or more, the shielding effect of electromagnetic wave noise is further improved. If the thickness of the metal thin film layer 22 is equal to or less than the upper limit value of the above range, the electromagnetic shielding film 1 can be made thinner. In addition, the productivity and flexibility of the electromagnetic wave shielding film 1 are improved.

(Conductive adhesive layer)
The conductive adhesive layer is conductive at least in the thickness direction and has adhesiveness.
As the conductive adhesive layer, an anisotropic conductive adhesive layer 24 having conductivity in the thickness direction and not having conductivity in the surface direction, or having conductivity in the thickness direction and the surface direction, etc. Conductive adhesive layer 26 may be mentioned. As the conductive adhesive layer in the conductive layer (I), the conductive adhesive layer can be made thin and the amount of conductive particles becomes small. As a result, the electromagnetic wave shielding film 1 can be made thin, and the electromagnetic wave shielding film 1 can be flexible The anisotropic conductive adhesive layer 24 is preferable from the viewpoint of improving the properties. As the conductive adhesive layer in the conductive layer (I), an isotropic conductive adhesive layer 26 is preferable in that it can function sufficiently as an electromagnetic wave shielding layer.

As the conductive adhesive layer in the present embodiment, a coating film made of the thermosetting composition of the first aspect of the present invention or the cured product of the second aspect is used. Since the said coating film is thermosetting, it is excellent in heat resistance. Moreover, since the said 2 or more types of compounds (1) are contained, it can adhere easily by comparatively mild lamination process. Moreover, since it hardens | cures rapidly also at the time of heat press, while outflow of the component in a composition at the time of heat press is suppressed, it is excellent also in the hardness after hardening, and a flame retardance. Furthermore, when it contains the said epoxy group containing compound and a compound (2), the adhesiveness with respect to the metal thin film layer 22 is especially excellent.
The degree of curing of the thermosetting composition constituting the conductive adhesive layer is not particularly limited, and may be in an uncured state, a B-staged state, or a completely cured state.
The cured product constituting the conductive adhesive layer may be in an uncured state, in a B-staged state, or in a completely cured state as compared to the B-stage.

The thermosetting anisotropically conductive adhesive layer 24 is made of, for example, a thermosetting composition 24a containing conductive particles 24b.
The thermosetting isotropic conductive adhesive layer 26 is made of, for example, a thermosetting composition 26a containing conductive particles 26b.

The thermosetting composition may contain a rubber component (carboxy-modified nitrile rubber, acrylic rubber, etc.) for imparting flexibility, a tackifier, and the like.
The thermosetting composition may optionally contain a flame retardant other than the compound (1).
The thermosetting composition may contain a cellulose resin or microfibrils (glass fiber or the like) in order to enhance the strength of the conductive adhesive layer and improve the punching characteristics.
The said thermosetting composition may contain the other component as needed in the range which does not impair the effect of this invention.

  Examples of the conductive particles include particles of metals (silver, platinum, gold, copper, nickel, palladium, aluminum, solder, etc.), graphite powder, fired carbon particles, plated fired carbon particles, and the like. As the conductive particles, metal particles are preferable from the viewpoint that the conductive adhesive layer comes to have an appropriate hardness and the pressure loss in the conductive adhesive layer at the time of hot pressing can be reduced, and copper particles are preferable. More preferable.

  2 micrometers or more and 26 micrometers or less are preferable, and, as for the average particle diameter of the electroconductive particle 24b in the anisotropically conductive adhesive layer 24, 4 micrometers or more and 16 micrometers or less are more preferable. If the average particle diameter of the conductive particles 24 b is at least the lower limit value of the above range, the thickness of the anisotropic conductive adhesive layer 24 can be secured, and sufficient adhesive strength can be obtained. If the average particle diameter of the conductive particles 24 b is equal to or less than the upper limit value of the above range, the flowability (followability to the shape of the through hole of the insulating film) of the anisotropic conductive adhesive layer 24 can be secured. The inside of the through hole can be sufficiently filled with the conductive adhesive.

  0.1 micrometer or more and 10 micrometers or less are preferable, and, as for the average particle diameter of the electroconductive particle 26b in the isotropic conductive adhesive layer 26, 0.2 micrometer or more and 1 micrometer or less are more preferable. When the average particle diameter of the conductive particles 26 b is equal to or more than the lower limit value of the above range, the number of contact points of the conductive particles 26 b is increased, and the conductivity in the three-dimensional direction can be stably enhanced. If the average particle diameter of the conductive particles 26 b is equal to or less than the upper limit value of the above range, the flowability (followability to the shape of the through hole of the insulating film) of the isotropic conductive adhesive layer 26 can be secured. The inside of the through hole can be sufficiently filled with the conductive adhesive.

  The proportion of the conductive particles 24b in the anisotropically conductive adhesive layer 24 is preferably 1% by volume or more and 30% by volume or less of 100% by volume of the anisotropically conductive adhesive layer 24, and is 2% by volume or more and 15% by volume The following are more preferable. If the proportion of the conductive particles 24 b is at least the lower limit value of the above range, the conductivity of the anisotropic conductive adhesive layer 24 becomes good. If the ratio of the conductive particles 24 b is equal to or less than the upper limit value of the above range, the adhesiveness of the anisotropic conductive adhesive layer 24 and the flowability (followability to the shape of the through holes of the insulating film) become good. Also, the flexibility of the electromagnetic wave shielding film 1 is improved.

  The proportion of the conductive particles 26b in the isotropic conductive adhesive layer 26 is preferably 50% by volume to 80% by volume in 100% by volume of the isotropic conductive adhesive layer 26, and is 60% by volume to 70% by volume. The following are more preferable. If the proportion of the conductive particles 26 b is at least the lower limit value of the above range, the conductivity of the isotropic conductive adhesive layer 26 becomes good. If the ratio of the conductive particles 26 b is equal to or less than the upper limit value of the above range, the adhesiveness and flowability (followability to the shape of the through hole of the insulating film) of the isotropic conductive adhesive layer 26 become good. Also, the flexibility of the electromagnetic wave shielding film 1 is improved.

The storage elastic modulus at 180 ° C. of the conductive adhesive layer is preferably 1 × 10 ³ Pa or more and 5 × 10 ⁷ Pa or less, and more preferably 5 × 10 ³ Pa or more and 1 × 10 ⁷ Pa or less. If the storage elastic modulus at 180 ° C. of the conductive adhesive layer is equal to or more than the lower limit value of the above range, the conductive adhesive layer has a further appropriate hardness, and the conductive adhesive layer at the time of hot pressing Pressure loss in the As a result, the conductive adhesive layer and the printed circuit of the printed wiring board are sufficiently adhered, and the conductive adhesive layer is electrically connected by the printed circuit of the printed wiring board through the through holes of the insulating film. Ru. If the storage elastic modulus at 180 ° C. of the conductive adhesive layer is not more than the upper limit value of the above range, the flexibility of the electromagnetic wave shielding film 1 is improved. As a result, the electromagnetic wave shielding film 1 easily sinks into the through hole of the insulating film, and the conductive adhesive layer is electrically connected reliably by the printed circuit of the printed wiring board through the through hole of the insulating film.

The surface resistance of the anisotropic conductive adhesive layer 24 is preferably 1 × 10 ⁴ Ω or more and 1 × 10 ¹⁶ Ω or less, and more preferably 1 × 10 ⁶ Ω or more and 1 × 10 ¹⁴ Ω or less. If the surface resistance of the anisotropic conductive adhesive layer 24 is equal to or more than the lower limit value of the above range, the content of the conductive particles 24 b can be suppressed low. If the surface resistance of the anisotropic conductive adhesive layer 24 is equal to or less than the upper limit value of the above range, there is practically no problem with anisotropy.

  The surface resistance of the isotropic conductive adhesive layer 26 is preferably 0.05 Ω or more and 2.0 Ω or less, and more preferably 0.1 Ω or more and 1.0 Ω or less. If the surface resistance of the isotropic conductive adhesive layer 26 is at least the lower limit value of the above range, the content of the conductive particles 26 b is suppressed low, the viscosity of the conductive adhesive does not become too high, and the coatability is further increased. It becomes good. Moreover, the fluidity (followability to the shape of the through hole of the insulating film) of the isotropic conductive adhesive layer 26 can be further secured. When the surface resistance of the isotropic conductive adhesive layer 26 is not more than the upper limit value of the above range, the entire surface of the isotropic conductive adhesive layer 26 has uniform conductivity.

  3 micrometers or more and 25 micrometers or less are preferable, and, as for the thickness of the anisotropic conductive adhesive layer 24, 5 micrometers or more and 15 micrometers or less are more preferable. If the thickness of the anisotropically conductive adhesive layer 24 is equal to or more than the lower limit value of the above range, the fluidity (followability to the shape of the through hole of the insulating film) of the anisotropically conductive adhesive layer 24 can be secured. The inside of the through hole of the insulating film can be sufficiently filled with the conductive adhesive. If the thickness of the anisotropically conductive adhesive layer 24 is not more than the upper limit value of the above range, the electromagnetic wave shielding film 1 can be made thinner. Also, the flexibility of the electromagnetic wave shielding film 1 is improved.

  5 micrometers or more and 20 micrometers or less are preferable, and, as for the thickness of the isotropic conductive adhesive layer 26, 7 micrometers or more and 17 micrometers or less are more preferable. If the thickness of the isotropic conductive adhesive layer 26 is equal to or more than the lower limit value of the above range, the conductivity of the isotropic conductive adhesive layer 26 becomes good, and can sufficiently function as an electromagnetic shielding layer. In addition, the flowability (followability to the shape of the through hole of the insulating film) of the isotropic conductive adhesive layer 26 can be secured, and the through hole of the insulating film can be sufficiently filled with the conductive adhesive. The foldability is also ensured, and the isotropic conductive adhesive layer 26 is not broken even if it is repeatedly bent. If the thickness of the isotropic conductive adhesive layer 26 is not more than the upper limit value of the above range, the electromagnetic wave shielding film 1 can be made thinner. Also, the flexibility of the electromagnetic wave shielding film 1 is improved.

(First release film)
The first release film 30 is to be a carrier film of the insulating resin layer 10 and the conductive layer 20, and makes the handling property of the electromagnetic wave shielding film 1 good. The first release film 30 is peeled off from the insulating resin layer 10 after the electromagnetic wave shielding film 1 is attached to a printed wiring board or the like.

  The first release film 30 has a release film main body 32 and an adhesive layer 34 provided on the surface of the release film main body 32 on the insulating resin layer 10 side.

  The resin material of the release film body 32 is polyethylene terephthalate (hereinafter referred to as PET), polyethylene naphthalate, polyethylene isophthalate, polybutylene terephthalate, polyolefin, polyacetate, polycarbonate, polyphenylene sulfide, polyamide, ethylene-vinyl acetate Copolymers, polyvinyl chloride, polyvinylidene chloride, synthetic rubbers, liquid crystal polymers and the like can be mentioned. As a resin material, PET is preferable in terms of heat resistance (dimensional stability) at the time of producing the electromagnetic wave shielding film 1 and cost.

The release film body 32 may contain one or both of a colorant (pigment, dye, etc.) and a filler.
It differs from the insulating resin layer 10 in that it can be clearly distinguished from the insulating resin layer 10 as either one or both of the coloring agent and the filler, and it is easy to notice the peeling off of the first release film 30 after hot pressing. Colors are preferred, and white pigments, fillers, or combinations of white pigments with other pigments or fillers are more preferred.

The storage elastic modulus at 180 ° C. of the release film main body 32 is preferably 8 × 10 ⁷ Pa or more and 5 × 10 ⁹ Pa, and more preferably 1 × 10 ⁸ Pa or more and 8 × 10 ⁸ Pa. If the storage elastic modulus at 180 ° C. of the release film main body 32 is equal to or more than the lower limit value of the above range, the first release film 30 comes to have an appropriate hardness, and the first release at the time of hot pressing. The pressure loss in the mold film 30 can be reduced. If the storage elastic modulus at 180 ° C. of the release film main body 32 is not more than the upper limit value of the above range, the flexibility of the first release film 30 becomes good.

  3 micrometers or more and 75 micrometers or less are preferable, and, as for the thickness of the release film main body 32, 12 micrometers or more and 50 micrometers or less are more preferable. When the thickness of the release film main body 32 is equal to or more than the lower limit value of the above range, the handling property of the electromagnetic wave shielding film 1 becomes good. If the thickness of the release film main body 32 is not more than the upper limit value of the above range, heat is easily transmitted to the conductive adhesive layer when the conductive adhesive layer of the electromagnetic wave shielding film 1 is heat pressed on the surface of the insulating film .

  The pressure-sensitive adhesive layer 34 is formed, for example, by applying a pressure-sensitive adhesive composition containing a pressure-sensitive adhesive to the surface of the release film main body 32. When the first release film 30 has the adhesive layer 34, the second release film 40 is peeled off from the conductive adhesive layer, or the electromagnetic wave shield film 1 is attached to a printed wiring board or the like by heat press At this time, peeling of the first release film 30 from the insulating resin layer 10 can be suppressed, and the first release film 30 can sufficiently play a role as a protective film.

The pressure-sensitive adhesive does not easily peel off the first release film 30 from the insulating resin layer 10 before the heat pressing, and after the heat pressing, the first release film 30 can be peeled off from the insulating resin layer 10 It is preferable to impart appropriate adhesiveness to the pressure-sensitive adhesive layer 34.
Examples of the pressure-sensitive adhesive include acrylic pressure-sensitive adhesives, urethane-based pressure-sensitive adhesives, and rubber-based pressure-sensitive adhesives.
-100-60 degreeC is preferable and, as for the glass transition temperature of an adhesive, -60-40 degreeC is more preferable.

  25 micrometers or more and 125 micrometers or less are preferable, and, as for the thickness of the 1st release film 30, 38 micrometers or more and 100 micrometers or less are more preferable. If the thickness of the first release film 30 is equal to or more than the lower limit value of the above range, the handling property of the electromagnetic wave shielding film 1 becomes good. If the thickness of the first release film 30 is equal to or less than the upper limit of the above range, heat is applied to the conductive adhesive layer when the conductive adhesive layer of the electromagnetic wave shielding film 1 is heat pressed on the surface of the insulating film. It is easy to transmit.

(Second release film)
The second release film 40 protects the conductive adhesive layer and improves the handling of the electromagnetic wave shielding film 1. The second release film 40 is peeled from the conductive adhesive layer before the electromagnetic wave shield film 1 is attached to a printed wiring board or the like.

  The second release film 40 has, for example, a release film main body 42 and a release agent layer 44 provided on the surface of the release film main body 42 on the side of the conductive adhesive layer.

As a resin material of the release film main body 42, the thing similar to the resin material of the release film main body 32 is mentioned.
The release film main body 42 may contain a coloring agent, a filler and the like.
The thickness of the release film main body 42 is preferably 5 μm to 500 μm, more preferably 10 μm to 150 μm, and still more preferably 25 μm to 100 μm.

The release agent layer 44 is formed by treating the surface of the release film main body 42 with a release agent. When the second release film 40 has the release agent layer 44, the second release film 40 can be easily peeled off when the second release film 40 is peeled off from the conductive adhesive layer, and the conductive film is electrically conductive. Adhesive layer is less likely to break.
As the release agent, a known release agent may be used.

  The thickness of the release agent layer 44 is preferably 0.05 μm to 30 μm, and more preferably 0.1 μm to 20 μm. If the thickness of the release agent layer 44 is within the above range, the second release film 40 is more easily peeled off.

(Thickness of electromagnetic wave shielding film)
5 micrometers or more and 50 micrometers or less are preferable, and, as for the thickness (except a mold release film) of the electromagnetic wave shielding film 1, 8 micrometers or more and 30 micrometers or less are more preferable. When the thickness of the electromagnetic wave shielding film 1 not including the release film is equal to or more than the lower limit value of the above range, the first release film 30 is hardly broken when it is peeled off. If the thickness of the electromagnetic wave shielding film 1 which does not contain a release film is below the upper limit of the said range, the printed wiring board with an electromagnetic wave shielding film can be made thin.

<< Production method of electromagnetic wave shield film >>
A fourth aspect of the present invention is a method for producing an electromagnetic wave shielding film of the third aspect.
In the first embodiment of the present aspect, the insulating resin layer and the above are obtained by curing a coating obtained by applying the thermosetting composition of the first aspect to a substrate film to an arbitrary degree by heating the coating. It is a manufacturing method of the above-mentioned electromagnetic wave shield film which has a process of forming at least one side among adhesive agent layers.

  The form of the base film is not particularly limited, and examples thereof include a carrier film, a first release film, and a second release film. A metal thin film layer may be formed beforehand on the application side of the thermosetting composition of these base films. Specifically, for example, the base film may be a laminated film of a carrier film and a metal thin film layer.

  The temperature and time for heating the coating film are not particularly limited as long as the thermosetting composition cures to a desired degree, for example, 50 ° C. to 200 ° C., 10 seconds to 10 minutes. Can be mentioned.

  In the second embodiment of the fourth aspect, the insulating resin layer, the metal thin film layer, and the adhesive layer are laminated in this order, and the insulating resin layer is subjected to a laminating process of heating and pressing. It is a manufacturing method of the electromagnetic wave shield film which has a process of performing adhesion of at least one side among adhesion of the metal thin film layer, and adhesion of the metal thin film layer and the adhesive agent layer.

As a method of laminating each layer in the above order, for example, the insulating resin layer and the metal thin film layer are formed in this order on the first release film, and the adhesive layer is formed on the second release film. The method of mounting the said 2nd release film in the said 1st release film so that the said adhesive bond layer may be affixed on the said metal thin film layer is mentioned.
Instead of the above method, the insulating resin layer is formed on the first release film, the adhesive layer and the metal thin film layer are formed on the second release film in this order, and the metal thin film layer is formed The method of mounting the said 1st release film on the said 2nd release film so that the said insulating resin layer may be stuck can also be illustrated.
The conditions for the heating temperature and pressure of the laminating process are preferably the conditions in the step (c3) described in detail later.

<Function effect>
In the method for producing an electromagnetic wave shielding film of the present invention, since the two or more compounds (1) are contained in at least one of the insulating resin layer and the adhesive layer, the two or more compounds (1 The adhesive property of the insulating resin layer containing 1) and the adhesive layer to the substrate film is excellent, and can be easily adhered by a relatively gentle laminating process. As a result, the manufacturing efficiency of the electromagnetic wave shielding film can be improved.
Hereinafter, in more detail, the manufacturing method of the electromagnetic wave shielding film concerning this invention is illustrated.

  The electromagnetic wave shielding film of the present invention is produced, for example, by the following method (α), the following method (β) or the like. As a method for producing the electromagnetic wave shielding film of the present invention, the method (α) is preferable from the viewpoint that the adhesion between the insulating resin layer and the metal thin film layer becomes good.

The method (α) is a method comprising the following steps (a) to (c).
Process (a): The process of providing a metal thin film layer on the surface of a carrier film as needed.
Process (b): A process of providing an insulating resin layer on the surface of the metal thin film layer provided on the surface of the carrier film.
Step (c): a step of peeling the carrier film from the metal thin film layer and providing an adhesive layer on the surface of the metal thin film layer opposite to the insulating resin layer.

Method (β) is a method comprising the following steps (x) to (z).
Step (x): a step of providing an insulating resin layer on the surface of the first release film.
Step (y): a step of providing a metal thin film layer on the surface of the insulating resin layer.
Step (z): providing an adhesive layer on the surface of the metal thin film layer.

The method (α) will be described in detail below.
(Step (a))
As a carrier film, what has a base material layer and the adhesive layer provided in the surface of the base material layer is mentioned.
As a resin material of a base material layer, the thing similar to the resin material of the base material layer 32 of the 1st release film 30 is mentioned.
A known pressure-sensitive adhesive may be used as the pressure-sensitive adhesive of the pressure-sensitive adhesive layer.

  The metal thin film layer may be formed by physical vapor deposition, a method of forming a deposition film by CVD, a method of forming a plating film by plating, a method of attaching a metal foil, or the like. From the viewpoint of being able to form a metal thin film layer excellent in conductivity in the plane direction, a method of forming a deposition film by physical vapor deposition, CVD or a method of forming a plating film by plating is preferable, and the thickness of the metal thin film layer can be reduced And, even if the thickness is thin, a metal thin film layer excellent in conductivity in the surface direction can be formed, and a method of forming a vapor deposition film by physical vapor deposition or CVD is more preferable because a metal thin film layer can be easily formed by a dry process. The method of forming a vapor deposition film by physical vapor deposition is more preferable.

  Step (a) may be omitted by obtaining a commercially available laminate having a metal thin film layer provided on the surface of the carrier film.

(Step (b))
As a method of providing the insulating resin layer on the surface of the metal thin film layer, for example, a photocurable composition is applied to the surface of the metal thin film layer, and if it contains a solvent, it is dried and then irradiated with light (such as ultraviolet light) And semi-curing or curing.

In the step (b), a first release film may be provided on the surface of the insulating resin layer.
As a method of providing the first release film on the surface of the insulating resin layer, the first release film having the base material layer and the pressure-sensitive adhesive layer on the surface of the insulating resin layer, the insulating resin layer and the pressure-sensitive adhesive layer Affixing so as to be in contact with the surface; after providing an adhesive layer on the surface of the insulating resin layer, affixing the base material layer of the first release film to the surface of the adhesive layer, the surface of the insulating resin layer And a method of providing the first release film.

(Step (c))
In the step (c), a second release film with an adhesive layer provided with an adhesive layer on the surface of the second release film is formed on the surface of the metal thin film layer opposite to the insulating resin layer, The adhesion may be made so that the thin film layer and the adhesive layer are in contact with each other; the adhesive layer may be provided directly on the surface of the metal thin film layer. Moreover, after providing an adhesive bond layer on the surface of a metal thin film layer, you may affix a 2nd release film on the surface of an adhesive bond layer.

  As a method of providing an adhesive layer on the surface of the second release film or metal thin film layer, an adhesive, a solvent, and, if necessary, conductive particles are formed on the surface of the second release film or metal thin film layer. The method of apply | coating and drying the coating liquid containing is mentioned.

(One embodiment of a method of manufacturing an electromagnetic wave shielding film)
Hereinafter, a method of manufacturing the electromagnetic wave shielding film 1 of the first embodiment shown in FIG. 1 will be described with reference to FIGS. 3 and 4.

Process (a):
As shown in FIG. 3, a metal thin film layer 22 is provided by vapor-depositing metal on the surface on the release agent layer 104 side of the carrier film 100 having the base material layer 102 and the release agent layer 104.

Process (b1):
As shown in FIG. 3, a coating liquid for forming an insulating resin layer (a thermosetting composition according to the first aspect of the present invention) containing a black colorant (not shown) is applied to the surface of the metal thin film layer 22; The insulating resin layer 10 is provided by drying while heating.

Process (b2):
As shown in FIG. 3, the first release film 30 having the base material layer 32 and the pressure-sensitive adhesive layer 34 on the surface of the insulating resin layer 10 is in contact with the insulating resin layer 10 and the pressure-sensitive adhesive layer 34. paste.

Process (c1):
As shown in FIG. 4, the adhesive 24 a, the conductive particles 24 b, and the solvent are formed on the surface of the second release film 40 having the base layer 42 and the release agent layer 44 on the release agent layer 44 side. A coating liquid for forming an adhesive layer (a thermosetting composition according to the first aspect of the present invention) is applied and dried while heating to form an anisotropic conductive adhesive layer 24 (adhesive layer 24). . In this way, a second release film with an adhesive layer is obtained.

Process (c2):
As shown in FIG. 4, in the laminate obtained in the step (b2), the carrier film 100 is peeled off from the metal thin film layer 22. Thus, a first release film with an insulating resin layer and a metal thin film layer is obtained.

Process (c3):
As shown in FIG. 4, a first release film with an insulating resin layer and a metal thin film layer, and a second release film with an adhesive layer, a metal thin film layer 22 and an anisotropic conductive adhesive layer 24. Are bonded so as to be in contact with each other, and are heated as needed to cure the insulating resin layer and the adhesive layer, to obtain the electromagnetic wave shielding film 1.

When laminating the metal thin film layer 22 and the anisotropic conductive adhesive layer 24 in the step (c3), it is preferable to carry out a lamination process (a process of bonding in a laminated state) under milder conditions than a hot press. .
As a heating temperature in the said lamination process, 50-100 degreeC is preferable, for example.
The pressure in the laminating process is, for example, preferably 100 kPa (0.1 MPa) or less, more preferably 0.1 kPa to 20 kPa, and still more preferably 1 kPa to 10 kPa.
The heating and pressurizing time in the laminating process is preferably, for example, 10 seconds to 30 minutes, and more preferably 30 seconds to 10 minutes.
The metal thin film layer 22 and the anisotropic conductive adhesive layer 24 can be easily bonded with sufficient adhesive force by laminating at the above suitable heating temperature, pressure and treatment time.

<Function effect>
In the electromagnetic wave shielding film 1 according to the present invention, at least one of the insulating resin layer 10 and the anisotropic conductive adhesive layer 24 is formed of the thermosetting composition according to the first embodiment, so Excellent. In addition, at the time of production, sufficient adhesion of the insulating resin layer 10 and the anisotropic conductive adhesive layer 24 to the metal thin film layer 22 can be easily obtained by lamination under relatively mild conditions.
Further, if the thermosetting composition contains the compound (2), the adhesion of the insulating resin layer 10 to the metal thin film layer 22 and the anisotropic conductive adhesive layer 24 is further enhanced, and the release film is obtained. At the time of peeling, peeling of the metal thin film layer 22 and the insulating resin layer 10 or the anisotropic conductive adhesive layer 24 is prevented.

The electromagnetic wave shielding film according to the present invention is not limited to the illustrated embodiment, as long as at least one of the insulating resin layer and the conductive adhesive layer contains the epoxy group-containing compound and the compound (1). .
For example, the second release film may have a pressure-sensitive adhesive layer instead of the release agent layer if the tackiness of the surface of the conductive adhesive layer is low. Alternatively, the second release film may be omitted.
When the release property of the release film main body is high, the second release film may not have a release agent layer and may consist of only the release film main body.
The insulating resin layer may have two or more layers. In the case of having two or more insulating resin layers, it is preferable that any one or more insulating resin layers be formed of the thermosetting composition of the first aspect of the present invention.

<Printed wiring board with electromagnetic wave shield film>
FIG. 5 is a cross-sectional view showing an embodiment of a printed wiring board with an electromagnetic wave shielding film of the present invention.
The electromagnetic wave shielding film-included flexible printed wiring board 2 includes a flexible printed wiring board 50, an insulating film 60, and the electromagnetic wave shielding film 1 of the first embodiment.
The flexible printed wiring board 50 has a printed circuit 54 provided on at least one side of the base film 52.
The insulating film 60 is provided on the surface of the flexible printed wiring board 50 on which the printed circuit 54 is provided.
The anisotropic conductive adhesive layer 24 of the electromagnetic wave shielding film 1 is adhered to the surface of the insulating film 60 and is cured. Also, the anisotropic conductive adhesive layer 24 is electrically connected to the printed circuit 54 through a through hole (not shown) formed in the insulating film 60.
In the flexible printed wiring board 2 with the electromagnetic wave shielding film, the second release film 40 is peeled from the anisotropic conductive adhesive layer 24.

  When the first release film 30 becomes unnecessary in the flexible printed wiring board 2 with the electromagnetic wave shielding film, the first release film 30 is peeled off from the insulating resin layer 10.

In the vicinity of the printed circuit 54 (signal circuit, ground circuit, ground layer, etc.) except for the part having the through holes, the metal thin film layer 22 of the electromagnetic wave shield film 1 comprises the insulating film 60 and the anisotropic conductive adhesive layer 24. It is spaced apart and arranged opposite to each other.
The separation distance between the printed circuit 54 and the metal thin film layer 22 excluding the portion having the through holes is approximately equal to the sum of the thickness of the insulating film 60 and the thickness of the anisotropic conductive adhesive layer 24. 30 micrometers or more and 200 micrometers or less are preferable, and 60 micrometers or more and 200 micrometers or less of a separation distance are more preferable. If the separation distance is less than 30 μm, the impedance of the signal circuit will be low, and in order to have a characteristic impedance such as 100 Ω, the line width of the signal circuit must be reduced. As a result, the reflected resonance noise due to the impedance mismatch can easily get on the electrical signal. When the separation distance is larger than 200 μm, the flexible printed wiring board 2 with the electromagnetic wave shielding film becomes thick, and the flexibility is insufficient.

(Flexible printed wiring board)
The flexible printed wiring board 50 is a printed circuit (a power supply circuit, a ground circuit, a ground layer, etc.) by processing the copper foil of a copper-clad laminate into a desired pattern by a known etching method.
As a copper-clad laminate, a copper foil attached to one side or both sides of a base film 52 via an adhesive layer (not shown); a resin solution or the like for forming the base film 52 was cast on the surface of the copper foil And the like.
Examples of the material of the adhesive layer include epoxy resin, polyester, polyimide, polyamide imide, polyamide, phenol resin, urethane resin, acrylic resin, melamine resin and the like.
The thickness of the adhesive layer is preferably 0.5 μm to 30 μm.

(Base film)
As the base film 52, a film having heat resistance is preferable, a polyimide film and a liquid crystal polymer film are more preferable, and a polyimide film is more preferable.
The surface resistance of the base film 52 is preferably 1 × 10 ⁶ Ω or more in terms of electrical insulation. The surface resistance of the base film 52 is preferably 1 × 10 ¹⁹ Ω or less in terms of practical use.
The thickness of the base film 52 is preferably 5 μm or more and 200 μm or less, more preferably 6 μm or more and 25 μm or less, and more preferably 10 μm or more and 25 μm or less from the viewpoint of flexibility.

(Printed circuit)
Examples of the copper foil constituting the printed circuit 54 (signal circuit, ground circuit, ground layer, etc.) include rolled copper foil, electrolytic copper foil and the like, and in view of flexibility, rolled copper foil is preferable.
1 micrometer or more and 50 micrometers or less are preferable, and, as for the thickness of copper foil, 18 micrometers or more and 35 micrometers or less are more preferable.
The end (terminal) in the longitudinal direction of the printed circuit 54 is not covered with the insulating film 60 or the electromagnetic wave shielding film 1 for solder connection, connector connection, component mounting, and the like.

(Insulation film)
The insulating film 60 (coverlay film) is obtained by forming an adhesive layer (not shown) on one side of an insulating film main body (not shown) by applying an adhesive, sticking an adhesive sheet, or the like.
The surface resistance of the insulating film body is preferably 1 × 10 ⁶ Ω or more from the viewpoint of electrical insulation. The surface resistance of the insulating film body is preferably 1 × 10 ¹⁹ Ω or less in terms of practical use.
As the insulating film main body, a film having heat resistance is preferable, a polyimide film and a liquid crystal polymer film are more preferable, and a polyimide film is more preferable.
The thickness of the insulating film body is preferably 1 μm or more and 100 μm or less, and more preferably 3 μm or more and 25 μm or less from the viewpoint of flexibility.
Examples of the material of the adhesive layer include epoxy resin, polyester, polyimide, polyamide imide, polyamide, phenol resin, urethane resin, acrylic resin, melamine resin, polystyrene, polyolefin and the like. The epoxy resin may contain a rubber component (carboxy-modified nitrile rubber etc.) for imparting flexibility.
1 micrometer or more and 100 micrometers or less are preferable, and, as for the thickness of an adhesive bond layer, 1.5 micrometers or more and 60 micrometers or less are more preferable.

  The shape of the opening of the through hole is not particularly limited. Examples of the shape of the opening of the through hole 62 include a circle, an ellipse, and a square.

(Manufacturing method of printed wiring board with electromagnetic wave shielding film)
The printed wiring board with the electromagnetic wave shielding film of the present invention can be produced, for example, by a method having the following steps (d) to (g).
Step (d): providing an insulating film having through holes at positions corresponding to the printed circuit on the surface of the printed wiring board on which the printed circuit is provided, to obtain a printed wiring board with an insulating film.
Step (e): After the step (d), the conductive adhesive layer contacts the surface of the insulating film with the printed wiring board with the insulating film and the electromagnetic shielding film of the present invention in which the second release film is peeled off. To bond the conductive adhesive layer to the surface of the insulating film and electrically connect the conductive adhesive layer to the printed circuit through the through holes, Process of obtaining a printed wiring board with a shield film.
Step (f): The step of peeling off the first release film when the first release film becomes unnecessary after the step (e).
Step (g): A step of main curing the anisotropic conductive adhesive layer between step (e) and step (f) or after step (f), as required.

  Hereinafter, a method of manufacturing a flexible printed wiring board with an electromagnetic wave shielding film will be described with reference to FIG.

(Step (d))
As shown in FIG. 6, the insulating film 60 having the through holes 62 formed at the positions corresponding to the printed circuit 54 is superimposed on the flexible printed wiring board 50, and the adhesive layer of the insulating film 60 is formed on the surface of the flexible printed wiring board 50. By bonding (not shown) and curing the adhesive layer, a flexible printed wiring board 3 with an insulating film is obtained. The adhesive layer of the insulating film 60 may be temporarily adhered to the surface of the flexible printed wiring board 50, and the adhesive layer may be fully cured in the step (g).
The bonding and curing of the adhesive layer are performed by, for example, heat pressing using a press (not shown) or the like.

(Step (e))
As shown in FIG. 6, the electromagnetic wave shielding film 1 in which the second release film 40 is peeled off is superimposed on the flexible printed wiring board 3 with the insulating film, and is thermally pressed to make the surface of the insulating film 60 anisotropically conductive. The adhesive layer 24 is adhered, and the anisotropic conductive adhesive layer 24 is electrically connected to the printed circuit 54 through the through holes 62 to obtain a flexible printed wiring board 2 with an electromagnetic shielding film.

Bonding and curing of the anisotropically conductive adhesive layer 24 are performed by, for example, heat press using a press (not shown) or the like.
20 seconds or more and 60 minutes or less are preferable, and, as for the time of heat press, 30 seconds or more and 30 minutes or less are more preferable. If the time of heat pressing is equal to or more than the lower limit value of the above range, the anisotropic conductive adhesive layer 24 is easily adhered to the surface of the insulating film 60. If the time of the heat press is equal to or less than the upper limit value of the above range, the manufacturing time of the flexible printed wiring board 2 with the electromagnetic wave shielding film can be shortened.

  140 degreeC or more and 190 degrees C or less are preferable, and, as for the temperature (temperature of the hot platen of a press), 150 degrees C or more and 175 degrees C or less of the heat press are more preferable. If the temperature of the heat press is equal to or higher than the lower limit value of the above range, the anisotropic conductive adhesive layer 24 is easily adhered to the surface of the insulating film 60. In addition, the time of heat pressing can be shortened. If the temperature of the heat press is equal to or lower than the upper limit value of the above range, deterioration of the electromagnetic wave shielding film 1, the flexible printed wiring board 50 and the like can be easily suppressed.

  The pressure of the hot press is preferably 0.5 MPa or more and 20 MPa or less, and more preferably 1 MPa or more and 16 MPa or less. If the pressure of the heat press is equal to or higher than the lower limit value of the above range, the anisotropic conductive adhesive layer 24 is adhered to the surface of the insulating film 60. In addition, the time of heat pressing can be shortened. If the pressure of the heat press is equal to or less than the upper limit value of the above range, damage or the like of the electromagnetic wave shielding film 1, the flexible printed wiring board 50 and the like can be suppressed.

(Step (f))
As shown in FIG. 6, when the first release film becomes unnecessary, the first release film 30 is peeled off from the insulating resin layer 10.

(Step (g))
When the time of the heat press in step (e) is a short time of 20 seconds or more and 10 minutes or less, an anisotropic conductive adhesive layer between step (e) and step (f) or after step (f) It is preferable to perform 24 main curing.
The main curing of the anisotropically conductive adhesive layer 24 is performed using, for example, a heating device such as an oven.
The heating time is 15 minutes or more and 120 minutes or less, and more preferably 30 minutes or more and 60 minutes or less. If the heating time is equal to or more than the lower limit value of the above range, the anisotropically conductive adhesive layer 24 can be sufficiently cured. If the heating time is equal to or less than the upper limit value of the above range, the manufacturing time of the flexible printed wiring board 2 with the electromagnetic wave shielding film can be shortened.
120 degreeC or more and 180 degrees C or less are preferable, and 120 degreeC or more and 150 degrees C or less of a heating temperature (ambient temperature in an oven) are more preferable. If heating temperature is more than the lower limit of the said range, heating time can be shortened. When the heating temperature is equal to or lower than the upper limit value of the above range, deterioration of the electromagnetic wave shielding film 1, the flexible printed wiring board 50, and the like can be suppressed.

<Function effect>
In the method of manufacturing the flexible printed wiring board 2 with the electromagnetic wave shielding film described above, since the electromagnetic wave shielding film 1 is used, the insulating resin layer 10 and the anisotropic conductive adhesive layer are used in the bonding by the heat press. It is suppressed that a part of components flow out from 24 and it is excellent also in the flame retardance after hardening.
Moreover, in the flexible printed wiring board 2 with an electromagnetic wave shielding film after manufacture, since the electromagnetic wave shielding film 1 is provided, it is excellent in a flame retardance. Furthermore, if the thermosetting composition contains the compound (2), the adhesion of the insulating resin layer 10 and the anisotropic conductive adhesive layer 24 to the metal thin film layer 22 is further enhanced, and the first separation is performed. When the mold film 30 is peeled off, the peeling of the metal thin film layer 22 and the insulating resin layer 10 or the anisotropic conductive adhesive layer 24 is prevented.

(Other embodiments)
In the printed wiring board with an electromagnetic wave shielding film of the present invention, the printed wiring board, the insulating film adjacent to the surface of the printed wiring board on which the printed circuit is provided, the conductive layer adjacent to the insulating film, and the conductive layer The present invention is not limited to the illustrated embodiment as long as it has the electromagnetic wave shielding film of the present invention electrically connected to the printed circuit through the through holes formed in the insulating film.
For example, the flexible printed wiring board may have a ground layer on the back side. Moreover, a flexible printed wiring board may have a printed circuit on both surfaces, and the insulating film and the electromagnetic wave shielding film may be stuck on both surfaces.
A flexible printed circuit may be used instead of the flexible printed wiring board.
Instead of the electromagnetic wave shielding film 1 of the first embodiment, the electromagnetic wave shielding film 1 or the like of the second embodiment may be used.

Example 1
A solution of a compound having a (meth) acryloyl group (EXCELATE RUA-054, an acrylic polymer acrylate, solid content: 73% by mass, a solvent, as a coating liquid (photocurable composition) for forming an insulating resin layer : 1.71 g of photo radical polymerization initiator (manufactured by BASF, IRGACURE (registered trademark) 184), 100 g of butyl acetate, methyl isobutyl ketone, black dye (manufactured by Orient Chemical Industries, Ltd., ORIPACS (registered trademark) B-) 20, prepared by adding an azo compound (chromium complex).

  As a coating liquid (thermosetting composition) for forming an adhesive layer, vinyl acetate resin solution (manufactured by Showa Denko, Binirole (registered trademark) K-2S, solid content: 15 mass, solvent: methyl isobutyl ketone, methyl ethyl ketone, 100 g of methanol, and 4.1 g of copper powder (average particle size: 8 μm) to 4.1 g of an epoxy resin (Mitsubishi Chemical Corporation, jER (registered trademark) 1031 S, solid content: 60 mass, solvent: methyl ethyl ketone) And 2.9 g of the solid phosphorus compound (manufactured by Sanko Co., Ltd., HCA) represented by the above-mentioned formula (1a-1), and the liquid phosphorus compound (manufactured by Sanko Co., Ltd., M-Ester) represented by the above-mentioned formula A mixture of 2.9 g of a concentration of 80% by mass, 2.9 g of a solvent: ethylene glycol, and 0.5 g of the gallic acid represented by the formula (2b) was prepared. Thus, the total of the phosphorus compounds was about 0.84 mol and the active hydrogen group of gallic acid was about 0.6 mol per 1 mol of epoxy groups of the epoxy resin.

Process (b1):
As shown in FIG. 3, a laminate having a metal thin film layer provided on the surface of a carrier film (Cape Seduce (registered trademark), manufactured by Toray KP Film Co., Ltd., copper foil with release layer, thickness of copper foil: 0. The coating liquid for insulating resin layer formation was apply | coated using the bar coater of # 4 on the surface of the metal thin film layer of 5 micrometers, copper foil surface resistance: 0.015 ohm, and PET thickness: 50 micrometers. The coated film was dried at 100 ° C. for 1 minute, and then irradiated with ultraviolet light of 400 mJ to provide an insulating resin layer (thickness: 10 μm, surface resistance: 1.0E + 12 Ω or more) on the surface of the metal thin film layer.

Process (b2):
On the surface of the insulating resin layer, a first release film (Panak Co., Ltd., Pana Protect (registered trademark) GN, adhesive film, adhesive force: 0.49 N / cm, PET thickness: 75 μm) is used as the insulating resin layer It stuck so that the adhesive layer might contact | connect, and it obtained the laminated body.

Process (c1):
On the surface of the second release film (Panak Co., Ltd., PanaPeel (registered trademark) SM-1, release film, PET thickness: 50 μm) on the side of the release agent layer, a coating liquid for forming an adhesive layer is added as a comma The coating was applied at a thickness of 25 μm using a coater. The coated film is dried at 100 ° C. for 1 minute to provide an anisotropic conductive adhesive layer (thickness: 10 μm, surface resistance: 1.0 E + 12 Ω or more), and a second release film with an adhesive layer is formed. Obtained.

Process (c2):
In the laminate obtained in the step (b2), the carrier film was peeled from the metal thin film layer to obtain an insulating resin layer and a first release film with a metal thin film layer.

Process (c3):
The first release film with an insulating resin layer and metal thin film layer and the second release film with an adhesive layer are placed at 95 ° C. and 5 kPa so that the metal thin film layer and the anisotropic conductive adhesive layer are in contact with each other. It laminated by pressure and obtained the electromagnetic wave shielding film. In the case of adhesion by this lamination, when adhesion was insufficient, the lamination process was performed again, and the number of times of lamination until sufficient adhesion was measured. The results are shown in Table 1.

Process (d):
An insulating adhesive composition is applied to the surface of a 25 μm thick polyimide film (insulating film main body) so that the dry film thickness is 25 μm, an adhesive layer is formed, and an insulating film (thickness: 50 μm) is formed. Obtained. Through holes (hole diameter: 150 μm) were formed at positions corresponding to the grounds of the printed circuit.

A flexible printed wiring board having a printed circuit formed on the surface of a polyimide film (base film) with a thickness of 12 μm was prepared.
An insulating film was attached to a flexible printed wiring board by heat pressing to obtain a flexible printed wiring board with an insulating film.

Process (e):
The electromagnetic wave shield film from which the second release film has been peeled off is superimposed on the flexible printed wiring board with insulating film, and using a hot press (G-12 manufactured by Orihara Mfg. Co., Ltd.), heating plate temperature: 180 ° C., load: 3 MPa The resultant was hot pressed for 1 minute to bond the anisotropic conductive adhesive layer to the surface of the insulating film. At this time, the periphery of the adhesive surface of the insulating film was observed, and it was confirmed whether the component (adhesive component) of the anisotropically conductive adhesive layer of the electromagnetic wave shielding film had flowed out. The results are shown in Table 1.

Process (f):
The first release film was peeled off from the insulating resin layer to obtain a flexible printed wiring board with an electromagnetic wave shielding film. The obtained flexible printed wiring board with an electromagnetic wave shielding film was dried at 150 ° C. for 1 hour to cure the insulating resin layer and the anisotropic conductive adhesive layer.

<Evaluation>
About the produced flexible printed wiring board with an electromagnetic wave shielding film, the combustion test was implemented by the following method. The results are shown in Table 1.
(Combustion test)
A flame of a gas burner was applied to the lower end of the vertically held sample for 10 seconds, and the time for which the flexible printed wiring board with the electromagnetic wave shielding film continued to burn was measured. The shorter the time, the higher the flame retardancy.

(Example 2)
Example 1 except that the composition of the solid phosphorus compound (HCA, manufactured by Sanko Co., Ltd.) was changed to 1.45 g and the composition of the liquid phosphorus compound (M-Ester, manufactured by Sanko Co., Ltd.) was changed to 4.35 g Similarly to the above, a flexible printed wiring board with an electromagnetic wave shielding film was obtained. The results of measuring the number of times of lamination, the results of observing the presence or absence of elution of the adhesive component at the time of hot pressing, and the results of the combustion test are shown in Table 1.

(Example 3)
Example 1 except that the composition of the solid phosphorus compound (HCA, manufactured by Sanko) was changed to 4.35 g, and the composition of the liquid phosphorus compound (M-Ester, manufactured by Sanko) was changed to 1.35 g Similarly to the above, a flexible printed wiring board with an electromagnetic wave shielding film was obtained. The results of measuring the number of times of lamination, the results of observing the presence or absence of elution of the adhesive component at the time of hot pressing, and the results of the combustion test are shown in Table 1.

(Comparative example 1)
An electromagnetic wave was prepared in the same manner as in Example 1, except that the solid phosphorus compound (HCA, manufactured by Sanko) was not added, and the composition of the liquid phosphorus compound (M-Ester, manufactured by Sanko) was changed to 5.8 g. The flexible printed wiring board with a shield film was obtained. The results of measuring the number of times of lamination, the results of observing the presence or absence of elution of the adhesive component at the time of hot pressing, and the results of the combustion test are shown in Table 1.

(Comparative example 2)
The same procedure as in Example 1 was carried out except that the composition of the solid phosphorus compound (HCA, manufactured by Sanko) was changed to 5.8 g and the liquid phosphorus compound (M-Ester, manufactured by Sanko) was not added. A flexible printed wiring board with an electromagnetic wave shielding film was obtained. The results of measuring the number of times of lamination, the results of observing the presence or absence of elution of the adhesive component at the time of hot pressing, and the results of the combustion test are shown in Table 1.

(Comparative example 3)
A flexible printed wiring board with an electromagnetic wave shielding film as in Example 1, except that the solid phosphorus compound (HCA, manufactured by Sanko) and the liquid phosphorus compound (M-Ester, manufactured by Sanko) were not added. I got The results of measuring the number of times of lamination, the results of observing the presence or absence of elution of the adhesive component at the time of hot pressing, and the results of the combustion test are shown in Table 1.

The electromagnetic wave shielding film and the electromagnetic wave shielding film-equipped FPC of Examples 1 to 3 contain both the solid compound (1) and the liquid compound (1) in the anisotropic conductive adhesive layer, and therefore, they are laminated at the time of manufacture There were few times, there was no outflow of the adhesive component by heat press, and it was excellent in manufacture efficiency and manufacture yield. In addition, the flame retardancy was also improved. Furthermore, since the anisotropic conductive adhesive layer contains the compound (2), there was no peeling between the metal thin film layer and the anisotropic conductive adhesive layer when the release sheet was removed .
The electromagnetic wave shielding film of Comparative Example 1 contained no solid compound (1), so the adhesive component flowed out at the time of heat pressing.
The electromagnetic wave shielding film of Comparative Example 2 did not contain the liquid compound (1), so the number of times of lamination processing was sufficient until sufficient adhesion was obtained by lamination processing.
Since the electromagnetic wave shielding film of Comparative Example 3 does not contain any compound (1), the number of times of lamination processing is sufficient until sufficient adhesion is obtained by lamination processing, and the adhesive component flows out during heat pressing The flame retardancy was also low.
The above results show that excellent flame retardancy, production efficiency and production yield can be obtained by using the solid compound (1) and the liquid compound (1) in combination.

  The electromagnetic wave shielding film of the present invention is useful as a member for shielding electromagnetic waves in a flexible printed wiring board for electronic devices such as smart phones, mobile phones, optical modules, digital cameras, game machines, notebook computers, and medical instruments.

1 electromagnetic shielding film,
2 Flexible printed wiring board with electromagnetic wave shielding film,
3 Flexible printed wiring board with insulating film,
10 insulating resin layer,
22 metal thin film layer,
20 conductive layers,
24 anisotropic conductive adhesive layer,
24a thermosetting composition (adhesive),
24b conductive particles,
26 isotropic conductive adhesive layer,
26a thermosetting composition (adhesive),
26b conductive particles,
30 first release film,
32 base layer,
34 adhesive layer,
40 second release film,
42 base layers,
44 release agent layer,
50 flexible printed wiring boards,
52 base film,
54 printed circuits,
60 insulating film,
62 through holes,
100 carrier films,
102 base layer,
104 Release agent layer.

Claims (18)

At least one epoxy group-containing compound,
And two or more selected from the group of compounds (1) represented by the following formula (1):
A thermosetting composition, wherein at least one of the two or more species is solid at 25 ° C. and 1 atm, and at least one is liquid at 25 ° C. and 1 atm.

[In formula (1), R ₁ , R ₂ and R ₃ are each independently a hydrogen atom or an optional substituent, and R ₁ and R ₂ may combine with each other to form a ring. ] The thermosetting composition according to claim 1, wherein the compound (1) which is a solid is a compound represented by the following formula (1a).

[In formula (1a), R ₂ is a hydrogen atom or an optional substituent, and R ₂ may be bonded to a phenyl group bonded to a phosphorus atom to form a ring. ] The thermosetting composition according to claim 1, wherein the liquid compound (1) is a compound represented by the following formula (1b).

[In formula (1b), R ₂ may be a hydrogen atom or any substituent, and R ₂ may be bonded to a phenyl group bonded to a phosphorus atom to form a ring; R ₃ is a hydroxyl group and a carboxyl group Or any substituent having one or more of at least one of the following. ] The thermosetting composition according to claim 1, wherein the compound (1) which is a solid is a compound represented by the following formula (1a-1).

The thermosetting composition according to claim 1, wherein the liquid compound (1) is a compound represented by the following formula (1b-1).

  The thermosetting composition according to any one of claims 1 to 5, further comprising a black colorant.   The thermosetting composition according to any one of claims 1 to 5, further comprising conductive particles. The thermosetting composition as described in any one of Claims 1-7 which further contain 1 or more types chosen from the group of the compound represented by following formula (2).

[Wherein, L 1 and L 2 each independently represent a single bond or a divalent linking group having 1 to 8 carbon atoms, m and n each independently represent an integer of 1 to 5, and m + n is 2 to 6 And one or more hydrogen atoms of the hydrogen atoms bonded to the benzene ring are substituted by a (HO-L1-) group, and any other one or more hydrogen atoms are (-L2-COOH) Any one or more hydrogen atoms which are substituted by groups and which are not substituted by (HO-L1-) group and (-L2-COOH) group may be substituted by any substituent. ]   The thermosetting composition according to any one of claims 1 to 8, further comprising a solvent.   A cured product of the thermosetting composition according to any one of claims 1 to 9. An insulating resin layer,
A metal thin film layer adjacent to the insulating resin layer;
And an adhesive layer adjacent to the metal thin film layer on the opposite side to the insulating resin layer.
An electromagnetic shielding film, wherein at least one of the insulating resin layer and the adhesive layer is the thermosetting composition according to any one of claims 1 to 9 or the cured product according to claim 10.   The electromagnetic wave shielding film according to claim 11, wherein the adhesive layer is an anisotropic conductive adhesive layer. A printed wiring board provided with a printed circuit on at least one side of the substrate;
An insulating film adjacent to the surface of the printed wiring board on which the printed circuit is provided;
The electromagnetic wave shielding film according to claim 11 or 12, wherein the adhesive layer is provided adjacent to the insulating film;
Printed circuit board with electromagnetic wave shielding film. It is a manufacturing method of the electromagnetic wave shielding film of Claim 11, Comprising:
A process of forming at least one of the insulating resin layer and the adhesive layer by curing the coating obtained by applying the thermosetting composition to a base film to an arbitrary degree by heating the coating to an arbitrary degree The manufacturing method of an electromagnetic wave shielding film to have. It is a manufacturing method of the electromagnetic wave shielding film of Claim 11, Comprising:
The insulating resin layer, the metal thin film layer, and the adhesive layer are laminated in this order and subjected to a laminating process of heating and pressing to bond the insulating resin layer to the metal thin film layer, and the metal The manufacturing method of the electromagnetic wave shielding film which has the process of performing at least one adhesion | attachment among adhesion | attachment of a thin film layer and the said adhesive bond layer. A method of manufacturing a printed wiring board with an electromagnetic wave shielding film according to claim 13, wherein
A pressure bonding step of bonding the adhesive layer to the surface of the insulating film by overlapping the adhesive layer of the electromagnetic wave shielding film so as to be in contact with the surface of the insulating film of the printed wiring board Having a manufacturing method.   The manufacturing method according to claim 16, wherein the insulating resin layer and the adhesive layer are pressed while being heated when the pressure bonding is performed in the pressure bonding step.   The manufacturing method according to claim 16 or 17, further comprising a curing step of curing the thermosetting composition by further heating the insulating resin layer and the adhesive layer after the pressure bonding step.

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