JP6365712B1 - Dry resist film, printed wiring board with electromagnetic wave shielding sheet, and manufacturing method thereof - Google Patents

Abstract

An object of the present invention is to have a high patterning property capable of forming a fine opening, which is required in recent years, while also having a high light-shielding property by a black colorant, and to satisfy heat-resistant pressure-bonding property, migration resistance and flexibility. Provided is a dry resist film capable of forming a cover coat layer. Moreover, it provides a printed wiring board with an electromagnetic wave shielding sheet that is excellent in visibility, flexibility, and long-term insulation reliability, and can be used for miniaturization due to high density of circuits.
An active energy ray curable resin, an active energy ray polymerization initiator, and a resin layer formed from an active energy ray curable resin composition containing a black colorant,
The cured product of the resin layer is solved by using a dry resist film having a storage elastic modulus at 85 ° C. of 1.0E + 07 to 1.0E + 10 Pa.
[Selection] Figure 1

Description

  INDUSTRIAL APPLICATION This invention is used for the printed wiring board with an electromagnetic wave shield sheet which comprises the cover coat layer formed from the dry resist film mainly used in order to protect a copper circuit of a flexible printed circuit board, and an electromagnetic wave shield sheet. The present invention relates to a dry resist film.

  In recent years, flexible and flexible flexible printed boards (hereinafter referred to as FPCs) have become indispensable in electronic devices such as mobile phones, video cameras, and notebook personal computers that are rapidly becoming smaller and thinner. Furthermore, as the performance of electronic devices increases, the signal wiring built-in is becoming narrower and higher in frequency, and countermeasures against electromagnetic noise are becoming increasingly important. For this reason, an FPC is generally incorporated with an electromagnetic shielding material that shields or absorbs electromagnetic noise generated from signal wiring.

  The FPC is composed of a copper clad laminate (CCL) formed by etching and a cover coat layer. The cover coat layer is generally selected from a cover lay film, photosensitive ink (solder resist), or photosensitive film (dry resist film), and is easy to handle, durable, and insulation reliability. Because of this height, coverlay films are often used.

  The cover lay film is a material in which a thermosetting adhesive is applied to an insulating base material. As a form of use using such a cover lay film, Patent Document 1 discloses that a conductive material is formed on a cover coat layer of an FPC. An electromagnetic wave in which a metal thin film layer is electrically connected by bonding a conductive adhesive layer to a ground wiring through an opening of an FPC cover coat layer while bonding a shield layer having a conductive adhesive layer, a metal thin film layer, etc. An FPC having a shielding function is disclosed.

  Further, with the increase in density of FPC accompanying the reduction in the thickness of electronic devices, a cover coat layer having a fine opening pattern has been required. Patent Document 2 discloses an alkali-developable resin, an epoxy resin, optical A resin composition and a dry film excellent in resolution and crack resistance have been proposed by a reaction initiator, a photopolymerization monomer, and a surface-treated inorganic filler.

  The cover coat layer is also required to have high jet blackness from the viewpoint of information protection and visibility. Patent Document 3 discloses compounds having a carboxyl group and an ethylenically unsaturated group, urethane (meth) acrylate, Other than the above, a black photosensitive composition and a dry film excellent in shielding properties and storage stability have been proposed by using a polymerizable compound having an ethylenically unsaturated group, a photopolymerization initiator, and carbon black.

JP 2007-294996 A JP, 2006-177174, A JP 2012-141605 A

  However, the cover coat layer using a resist film often has a single layer structure that does not have an insulating base material compared to the cover lay film. When the electromagnetic wave shield sheet is laminated, the cover coat layer is covered by the heat and pressure at the time of bonding. The coating layer may flow, the thickness may decrease (heat-resistant pressure-bonding property), and the migration resistance may be extremely deteriorated.

In addition, the black colorant used to provide light-shielding properties is not only hard to cure with active energy rays, making it difficult to form fine openings, but also migration resistance when electromagnetic wave shield sheets are laminated. It is also a problem that it gets worse.
Further, if the crosslink density is increased in order to improve the migration resistance and the hardness of the film is increased, there is a problem that cracks occur at the time of bending (flexibility), and it is difficult to achieve both migration resistance and flexibility. .

  Thus, while having a high light-shielding property by the black colorant, it has excellent patternability that can be formed in recent years and can form fine openings, and even when an electromagnetic wave shield sheet is laminated, At present, no dry resist film capable of forming a cover coat layer satisfying migration resistance and flexibility is obtained.

  In order to solve the above-mentioned problems, the present inventors have intensively studied, and as a result, an active energy ray-curable resin composition containing an active energy ray-curable resin, an active energy ray polymerization initiator, and a black colorant. It was found that the above-mentioned problems can be solved by controlling the storage elastic modulus at 85 ° C. of the cured product of the resin layer, which has a resin layer formed of

  That is, the present invention is a dry resist film for a printed wiring board comprising an electromagnetic wave shielding sheet, a cover coat layer formed from a dry resist film, and a substrate having a signal wiring and an insulating base material, It has a resin layer formed from an active energy ray curable resin composition containing an energy ray curable resin, an active energy ray polymerization initiator, and a black colorant, and the cured product of the resin layer is: It is related with the dry resist film characterized by the storage elastic modulus in 85 degreeC being 1.0E + 07-1.0E + 10Pa.

  According to the present invention, the black colorant has an excellent patterning property capable of forming a fine opening, which has been required in recent years, while having a high light-shielding property, and also satisfies heat-resistant pressure-bonding property, migration resistance, and flexibility. It is possible to provide a dry resist film capable of forming a cover coat layer that can be used. Thereby, it is possible to provide a printed wiring board with an electromagnetic wave shielding sheet that is excellent in visibility, bendability, and long-term insulation reliability, and can cope with miniaturization due to high density of circuits.

It is the conceptual diagram explaining the migration test.

  Hereinafter, an example of an embodiment to which the present invention is applied will be described. In addition, the size and ratio of each member in the following drawings are for convenience of explanation, and are not limited to this. In the present specification, the description “any number A to any number B” includes the number A as a lower limit and the number B as an upper limit in the range. The “sheet” in this specification includes not only “sheet” defined in JIS but also “film”. Moreover, the numerical value specified in this specification is a value calculated | required by the method disclosed by embodiment or an Example.

  The dry resist film of the present invention is a dry resist film for a printed wiring board comprising an electromagnetic wave shielding sheet, a cover coat layer formed from the dry resist film, and a substrate having a signal wiring and an insulating substrate. A resin layer formed from an active energy ray-curable resin composition containing an active energy ray-curable resin, an active energy ray polymerization initiator, and a black colorant, and curing the resin layer The product is characterized in that the storage elastic modulus at 85 ° C. is 1.0E + 07 to 1.0E + 10 Pa.

《Dry resist film》
The dry resist film of the present invention has a resin layer formed from an active energy ray curable resin composition containing an active energy ray curable resin, an active energy ray polymerization initiator, and a black colorant. The cured product of the resin layer has a storage elastic modulus at 85 ° C. of 1.0E + 07 to 1.0E + 10 Pa.
Thereby, it can be set as the cover coat layer which has high light-shielding property, the outstanding patterning property which can form a fine opening part, and can satisfy heat-resistant crimping | compression-bonding property, migration resistance, and flexibility.

<Storage elastic modulus at 85 ° C>
In the dry resist film of the present invention, the cured product of the resin layer has a storage elastic modulus at 85 ° C. of 1.0E + 07 to 1.0E + 10 Pa. Moreover, 4.0E + 07-5.0E + 9Pa is preferable and 5.0E + 07-1.0E + 9Pa is more preferable. By setting the storage elastic modulus at 85 ° C. to 1.0E + 07 to 1.0E + 10 Pa, migration resistance and flexibility can be imparted.
Note that 1.0E + 07 to 1.0E + 10 Pa is the same as 1.0 × 10 ^{7 to} 1.0 × 10 ¹⁰ Pa and 0.01 to ¹⁰ GPa.

  The cured product of the resin layer is obtained by applying an active energy ray-curable resin composition to one surface of a transparent substrate and drying the resin layer obtained by irradiating an active energy ray, followed by heating. Obtained by curing. That is, the storage elastic modulus at 85 ° C. is a value obtained using a cured product obtained by further heat-curing the resin layer after irradiation of the active energy ray.

As a condition for making such a cured product obtained by curing the resin layer of the dry resist film, for example, for a dry resist film having a resin layer formed by applying an active energy ray-curable resin composition, After irradiating active energy rays from the transparent substrate side so as to obtain an integrated light amount of 200 to 1000 mJ / cm ² , the peelable sheet is peeled off, and the exposed resin layer surface is covered with a 1% aqueous sodium carbonate solution at a liquid temperature of 30 ° C. for 60 seconds. Resin obtained by developing and drying and removing moisture in the film using a drying oven at 80 to 100 ° C., followed by heat curing in a box oven at 140 to 180 ° C., and finally peeling off the transparent substrate The storage modulus can be measured for the cured product of the layer.

In addition, when it is difficult to measure the storage elastic modulus at 85 ° C. because the thickness of the cured product of the resin layer is thin or the resin layer is flexible, a cured product is obtained by laminating the resin layer, Moreover, the storage elastic modulus can be calculated | required by irradiating not only one side of a laminated body but active energy ray from both surfaces, and setting it as the fully hardened resin layer.
Specifically, for example, two samples from which a peelable sheet of a dry resist film with a substrate is peeled are prepared, and the exposed resin layer surfaces are vacuum laminated (heating temperature 60 ° C., vacuum time 60 seconds, vacuum ultimate pressure 2 hPa). , Pressure 0.4 MPa, pressurization time 60 seconds), and after irradiating active energy rays on the both sides from the transparent substrate side so as to obtain an integrated light amount of 200 to 1000 mJ / cm ² , one transparent substrate The surface of the exposed resin layer was developed with a 1% sodium carbonate aqueous solution having a liquid temperature of 30 ° C. for 60 seconds, and moisture in the film was removed by drying using a drying oven at 80 to 100 ° C. The storage elastic modulus can be measured for the cured product of the resin layer obtained by heat-curing in a box oven and finally peeling off the other transparent substrate.
The storage elastic modulus can be appropriately adjusted depending on the type and molecular weight of the resin, the type and content ratio of the curing agent, the type and content of the black colorant, and the like.

<Light transmittance>
In the dry resist film of the present invention, the light transmittance at a wavelength of 450 nm to 700 nm is preferably 10% or less, and the light transmittance at a wavelength of 300 to 450 nm is preferably 5% or more. The light transmittance of 450 nm to 700 nm is preferably 10% or less on average, but is more preferably 10% or less and even more preferably 5% or less in the entire wavelength region of wavelengths 450 nm to 700 nm. The light transmittance at a wavelength of 300 to 450 nm is preferably 5% or more on average, but more preferably 5% or more, and even more preferably 6% or more in the entire wavelength region of a wavelength of 300 to 450 nm. By being the said light transmittance, it can be made to harden | cure to the bottom part of the film | membrane which has active energy ray curable resin, and migration tolerance and heat-resistant crimping | compression-bonding property improve.
For the light transmittance in the present invention, a dry resist film with a substrate having a resin layer obtained by coating and drying the active energy ray-curable resin composition on one surface of the transparent substrate, It can be obtained by measuring the light incident from the transparent substrate side.

  Measurement can be performed using a spectrophotometer U-4100 (manufactured by Hitachi High-Technologies Corporation), and the light transmittance at a wavelength of 300 to 700 nm can be obtained.

<Active energy ray-curable resin composition>
The dry resist film of the present invention has a resin layer formed from an active energy ray-curable resin composition, and the active energy ray-curable resin composition includes an active energy ray-curable resin and active energy ray polymerization initiation. And a black colorant.

[resin]
Conventionally known thermoplastic resins, thermosetting resins, and the like can be used as the resin, and at least an active energy ray curable resin is included. The active energy ray-curable resin is a resin having curability by irradiation with active energy rays, and is preferably a compound having an ethylenically unsaturated double bond. Moreover, in order to provide developability, it is preferable that it is alkali-soluble.

  The weight average molecular weight (Mw) of the resin is preferably 2000 to 40000, more preferably 3000 to 30000. By setting the Mw of the resin to 2000 to 40000, the alkali solubility can be improved and the patterning property can be improved.

  The active energy ray-curable resin can be used alone, but it is preferable to use a thermosetting resin in combination from the viewpoint of further improving the patterning property. When the thermosetting resin is used in combination, the mixing ratio of the active energy ray-curable resin and the thermosetting resin is preferably 30:70 to 70:30, and 40:60 to 60: in terms of the solid content ratio of the resin. 40 is more preferable. Patterning property improves by making the compounding ratio of active energy ray-curable resin and thermosetting resin into the said range.

(Active energy ray curable resin)
As the active energy ray curable resin, an alkali-soluble acrylic resin obtained by copolymerizing an acidic group-containing ethylenically unsaturated monomer is preferably used. In order to further improve the active energy ray sensitivity and the like, an active energy ray-curable resin having an ethylenically unsaturated double bond can also be used.
The acid value of the active energy ray-curable resin is preferably 50 to 120 mgKOH / g, more preferably 60 to 110 mgKOH / g. Patternability and migration resistance are improved by setting the acid value of the active energy ray-curable resin to 50 to 120 mgKOH / g.

  Examples of the acrylic alkali-soluble resin copolymerized with an acidic group-containing ethylenically unsaturated monomer include resins having an acidic group such as a carboxyl group or a sulfone group. Specific examples of the alkali-soluble resin include an acrylic resin having an acidic group, an α-olefin / (anhydrous) maleic acid copolymer, a styrene / styrene sulfonic acid copolymer, an ethylene / (meth) acrylic acid copolymer, or Examples include isobutylene / (anhydrous) maleic acid copolymer. Among these, at least one resin selected from an acrylic resin having an acidic group and a styrene / styrene sulfonic acid copolymer, particularly an acrylic resin having an acidic group, is preferably used because of high migration resistance.

  Examples of the resin having an ethylenically unsaturated double bond include resins into which an ethylenically unsaturated double bond has been introduced by the methods (i) and (ii) shown below.

・ Method (i)
As the method (i), for example, a side chain epoxy group of a copolymer obtained by copolymerizing an ethylenically unsaturated monomer having an epoxy group and one or more other monomers is used. Addition reaction of a carboxyl group of an unsaturated monobasic acid having an ethylenically unsaturated double bond, and further reacting a polybasic acid anhydride with the generated hydroxyl group to convert an ethylenically unsaturated double bond and a carboxyl group. There is a way to introduce.

  Examples of the ethylenically unsaturated monomer having an epoxy group include glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate, 2-glycidoxyethyl (meth) acrylate, and 3,4-epoxybutyl (meth) acrylate. And 3,4-epoxycyclohexyl (meth) acrylate, which may be used alone or in combination of two or more. From the viewpoint of reactivity with the unsaturated monobasic acid in the next step, glycidyl (meth) acrylate is preferred.

  Examples of unsaturated monobasic acids include (meth) acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, α-haloalkyl of (meth) acrylic acid, alkoxyl, halogen, nitro, cyano substituted products, etc. Monocarboxylic acid etc. are mentioned, These may be used independently or may use 2 or more types together.

  Examples of polybasic acid anhydrides include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, maleic anhydride, etc., and these may be used alone or in combination of two or more. It doesn't matter. If necessary, use a tricarboxylic anhydride such as trimellitic anhydride or a tetracarboxylic dianhydride such as pyromellitic dianhydride to increase the number of carboxyl groups. The group can be hydrolyzed. Further, when tetrahydrophthalic anhydride or maleic anhydride having an ethylenically unsaturated double bond is used as the polybasic acid anhydride, the ethylenically unsaturated double bonds can be further increased.

  As a method similar to the method (i), for example, a side chain of a copolymer obtained by copolymerizing an ethylenically unsaturated monomer having a carboxyl group and one or more other monomers. There is a method in which an ethylenically unsaturated monomer having an epoxy group is added to a part of a carboxyl group to introduce an ethylenically unsaturated double bond and a carboxyl group.

・ Method (ii)
As the method (ii), an ethylenically unsaturated monomer having a hydroxyl group is used, and a monomer of an unsaturated monobasic acid having another carboxyl group or another monomer is copolymerized. There is a method of reacting an isocyanate group of an ethylenically unsaturated monomer having an isocyanate group with the side chain hydroxyl group of the obtained copolymer.

  Examples of the ethylenically unsaturated monomer having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2- or 3-hydroxypropyl (meth) acrylate, 2- or 3- or 4-hydroxybutyl (meth) acrylate, and glycerol. Examples thereof include hydroxyalkyl (meth) acrylates such as (meth) acrylate or cyclohexanedimethanol mono (meth) acrylate, and these may be used alone or in combination of two or more. Further, polyether mono (meth) acrylate obtained by addition polymerization of ethylene oxide, propylene oxide, and / or butylene oxide to the above hydroxyalkyl (meth) acrylate, (poly) γ-valerolactone, (poly) ε-caprolactone And / or (poly) 12-hydroxystearic acid added (poly) ester mono (meth) acrylate can also be used.

  Examples of the ethylenically unsaturated monomer having an isocyanate group include 2- (meth) acryloyloxyethyl isocyanate, 1,1-bis [(meth) acryloyloxy] ethyl isocyanate, and the like. In addition, two or more types can be used in combination.

  It is also preferable to use a photosensitive resin (A) as the active energy ray-curable resin. Hereinafter, the photosensitive resin (A) will be described.

  As shown below, the photosensitive resin (A) of the present invention is a hydroxyl group-containing photosensitive resin (A-1) or a carboxyl group-containing photosensitive resin (A-2). The hydroxyl group-containing photosensitive resin (A-1) of the present invention comprises, as a first step, an epoxy compound (a) having at least two epoxy groups in one molecule and at least two phenolic compounds in one molecule. A side chain hydroxyl group-containing resin (c) is prepared by reacting with a phenol compound (b) having a hydroxyl group. Next, as a second step, the side chain hydroxyl group-containing resin (c) and the polybasic acid anhydride (d) are reacted to produce a carboxyl group-containing resin (e). Furthermore, as a third step, the carboxyl group-containing resin (e) is obtained by reacting the epoxy group or oxetane group in the compound (f) having an epoxy group or oxetane group and an ethylenically unsaturated group. be able to. Furthermore, the carboxyl group-containing photosensitive resin (A-2) of the present invention comprises, as the fourth step, an acid anhydride in the hydroxyl group polybasic acid anhydride (d) in the hydroxyl group-containing resin (A-1). It can be obtained by the group. Hereinafter, the manufacturing method of photosensitive resin (A) is demonstrated in detail.

  First, the side chain hydroxyl group-containing resin (c) obtained in the first step of the present invention will be described. The side chain hydroxyl group-containing resin (c) reacts an epoxy compound (a) having at least two epoxy groups in one molecule with a phenol compound (b) having at least two phenolic hydroxyl groups in one molecule. In the epoxy compound (a) having at least two epoxy groups in one molecule and in the phenol compound (b) having at least two phenolic hydroxyl groups in one molecule. It is preferable to prepare a phenolic hydroxyl group by reacting with a molar ratio of epoxy group / phenolic hydroxyl group = 1/1 to 1 / 2.5. If the phenolic hydroxyl group is less than the above molar ratio range, the remaining excess epoxy group may react and gel in the subsequent synthesis step. Moreover, when there are more phenolic hydroxyl groups than the range of the said molar ratio, the molecular weight of the photosensitive resin (A) finally obtained becomes low, and it becomes difficult to obtain desired coating-film resistance and film formability. Furthermore, the phenol compound (b) having at least two phenolic hydroxyl groups in one excess molecule may adversely affect physical properties such as solder heat resistance and electrical insulation.

  In addition, the molar ratio as used in the field of this invention is a molar ratio with which functional groups actually react, and various starting materials use the quantity which enables reaction by the said molar ratio. Therefore, for example, in the reaction of “epoxy compound (a) having at least two epoxy groups in one molecule” and “phenol compound (b) having at least two phenolic hydroxyl groups in one molecule”, When the starting material is charged, “having at least two phenolic hydroxyl groups in one molecule” with respect to 1.0 mol of epoxy groups in “epoxy compound (a) having at least two epoxy groups in one molecule”. The phenolic hydroxyl group in the “phenolic compound (b)” may be charged in an amount exceeding 2.5 mol (preferably charged at an upper limit of 2.7 mol).

  The epoxy compound (a) having at least two epoxy groups in one molecule used in the present invention is not particularly limited as long as it is preferably a compound containing two epoxy groups in the molecule. Specifically, for example, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, tetramethylene glycol diglycidyl ether, polytetramethylene glycol diglycidyl ether, 1,6- Hexanediol diglycidyl ether, bisphenol A / epichlorohydrin type epoxy resin, bisphenol F / epichlorohydrin type epoxy resin, biphenol / epichlorohydrin type epoxy resin, polyglycidyl ether of glycerin / epichlorohydrin adduct , Resorcinol diglycidyl ether, polybutadiene diglycidyl ether, hydroquinone diglycidyl ether, dibromoneope Tyl glycol diglycidyl ether, neopentyl glycol diglycidyl ether, hexahydrophthalic acid diglycidyl ester, hydrogenated bisphenol A type diglycidyl ether, dihydroxyanthracene type epoxy resin, polypropylene glycol diglycidyl ether, diphenylsulfone diglycidyl ether, dihydroxybenzophenone Diglycidyl ether, biphenol diglycidyl ether, diphenylmethane diglycidyl ether, bisphenol fluorenediglycidyl ether, biscresol fluorenediglycidyl ether, bisphenoxyethanol fluorenediglycidyl ether, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane N, N-diglycidylaniline, N, N-dig Ricidyl toluidine, an epoxy compound having excellent flexibility disclosed in JP-A No. 2004-156024, JP-A No. 2004-315595, and JP-A No. 2004-323777, and the following formulas (1) to (3) An epoxy compound having a structure represented by:

Formula (1)

Formula (2)

Formula (3)

  Among them, polyethylene glycol diglycidyl ether is preferable in the case where the finally obtained hydroxyl group-containing photosensitive resin (A-1) is provided with flexibility and solubility in an alkaline developer, and is preferably a bisphenol A / epichlorohydrin type. The epoxy resin is preferable in the case where heat resistance is imparted to the finally obtained carboxyl group-containing modified ester resin (A). Thus, in the present invention, the epoxy compound (d) having at least two epoxy groups in one molecule can be selected according to the purpose, and these may be used alone or in combination. Use in combination is also preferred.

The phenol compound (b) having at least two phenolic hydroxyl groups in one molecule used in the present invention is not particularly limited as long as it is a compound containing two phenolic hydroxyl groups in the molecule. For example, 2,2-bis (4-hydroxyphenyl) propane (also known as bisphenol A) is a representative example, and other examples include bis (4-hydroxyphenol) methane, 1,1-bis (4-hydroxyphenyl). ) Ethane, 1,1-bis (4-hydroxyphenyl) -n-propane, 1,1-bis (4-hydroxyphenyl) -n-butane, 1,1-bis (4-hydroxyphenyl) -n-pentane 1,1-bis (4-hydroxyphenyl) -n-hexane, 1,1-bis (4-hydroxyphenyl) -n-heptane, 1,1-bis (4-hydroxyphenyl) -n-octane, , 1-bis (4-hydroxyphenyl) -n-nonane, 1,1-bis (4-hydroxyphenyl) -n-decane, bis (4-hydroxyphenyl) phenylmethane, bi (4-hydroxyphenyl) naphthylmethane, bis (4-hydroxyphenyl) toluylmethane, bis (4-hydroxyphenyl)-(4-ethylphenyl) methane, bis (4-hydroxyphenyl)-(4-n-propylphenyl) ) Methane, bis (4-hydroxyphenyl)-(4-isopropylphenyl) methane, bis (4-hydroxyphenyl)-(4-n-butylphenyl) methane, bis (4-hydroxyphenyl)-(4-pentylphenyl) ) Methane, bis (4-hydroxyphenyl)-(4-hexylphenyl) methane, bis (4-hydroxyphenyl)-(4-fluorophenyl) methane, bis (4-hydroxyphenyl)-(4-chlorophenyl) methane, Bis (4-hydroxyphenyl)-(2-fluorophenyl) me Bis (4-hydroxyphenyl)-(2-chlorophenyl) methane, bis (4-hydroxyphenyl) tetrafluorophenylmethane, bis (4-hydroxyphenyl) tetrachlorophenylmethane, bis (3-methyl-4-hydroxyphenyl) ) Methane, bis (3,5-dimethyl-4-hydroxyphenyl) methane, bis (3-ethyl-4-hydroxyphenyl) methane, bis (3-isobutyl-4-hydroxyphenyl) methane, bis (3-t- Butyl-4-hydroxyphenyl) -1-phenylmethane, bis (3-phenyl-4-hydroxyphenyl) -1-phenylmethane, bis (3-fluoro-4-hydroxyphenyl) methane, bis (3,5-difluoro -4-hydroxyphenyl) methane, bis (3-chloro-4-hydro) Xylphenyl) methane, bis (3,5-dichloro-4-hydroxyphenyl) methane, 1,1-bis (3-methyl-4-hydroxyphenyl) ethane, 1,1-bis (3,5-dimethyl-4-) Hydroxyphenyl) ethane, 1,1-bis (3-ethyl-4-hydroxyphenyl) ethane, 1,1-bis (3-isobutyl-4-hydroxyphenyl) ethane, 1,1-bis (3-fluoro-4) -Hydroxyphenyl) ethane, 1,1-bis (3,5-difluoro-4-hydroxyphenyl) ethane, 1,1-bis (3-chloro-4-hydroxyphenyl) ethane, 1,1-bis (3 Bisphenols in which a hydrogen atom is bonded to a central carbon such as 5-dichloro-4-hydroxyphenyl) ethane;
2,2-bis (4-hydroxyphenyl) -n-butane, 2,2-bis (4-hydroxyphenyl) -n-pentane, 2,2-bis (4-hydroxyphenyl) -n-hexane, 2, 2-bis (4-hydroxyphenyl) -n-heptane, 2,2-bis (4-hydroxyphenyl) -n-octane, 2,2-bis (4-hydroxyphenyl) -n-nonane, 2,2- Bis (4-hydroxyphenyl) -n-decane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane (commonly called bisphenol P), 1,1-bis (4-hydroxyphenyl) -1-naphthylethane 1,1-bis (4-hydroxyphenyl) -1-toluylethane, 1,1-bis (4-hydroxyphenyl) -1- (4-ethylphenyl) ethane, 1,1-bis (4 Hydroxyphenyl) -1- (4-n-propylphenyl) ethane, 1,1-bis (4-hydroxyphenyl) -1- (4-isopropylphenyl) ethane, 1,1-bis (4-hydroxyphenyl)- 1- (4-n-butylphenyl) ethane, 1,1-bis (4-hydroxyphenyl) -1- (4-pentylphenyl) ethane, 1,1-bis (4-hydroxyphenyl) -1- (4 -Hexylphenyl) ethane, 1,1-bis (3-tert-butyl-4-hydroxyphenyl) -1-phenylethane, 1,1-bis (3-phenyl-4-hydroxyphenyl) -1-phenylethane, 1,1-bis (4-hydroxyphenyl) -1- (4-fluorophenyl) ethane, 1,1-bis (4-hydroxyphenyl) -1- (4-chlorophenyl) 1,1-bis (4-hydroxyphenyl) -1- (2-fluorophenyl) ethane, 1,1-bis (4-hydroxyphenyl) -1- (2-chlorophenyl) ethane, 1,1-bis Bisphenols in which one methyl group is bonded to the central carbon such as (4-hydroxyphenyl) -1-tetrafluorophenylethane, 1,1-bis (4-hydroxyphenyl) -1-tetrachlorophenylethane;
2,2-bis (3-methyl-4-hydroxyphenyl) propane (commonly called bisphenol C), 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane, 2,2-bis (3-ethyl) -4-hydroxyphenyl) propane, 2,2-bis (3-isobutyl-4-hydroxyphenyl) propane, 2,2-bis (3-fluoro-4-hydroxyphenyl) propane, 2,2-bis (3 Central carbon such as 5-difluoro-4-hydroxyphenyl) propane, 2,2-bis (3-chloro-4-hydroxyphenyl) propane, 2,2-bis (3,5-dichloro-4-hydroxyphenyl) propane Bisphenols having two methyl groups bonded to each other;
Bis (4-hydroxyphenyl) -1,1-diphenylmethane, bis (3-methyl-4-hydroxyphenyl) -1,1-diphenylmethane, bis (3-t-butyl-4-hydroxyphenyl) -1,1- Bisphenols which are diphenylmethane derivatives such as diphenylmethane, bis (3-phenyl-4-hydroxyphenyl) -1,1-diphenylmethane, bis (3-chloro-4-hydroxyphenyl) -1,1-diphenylmethane;
1,1-bis (4-hydroxyphenyl) cyclohexane (commonly called bisphenol Z), 1,1-bis (3-methyl-4-hydroxyphenyl) cyclohexane, 1,1-bis (3,5-dimethyl-4-hydroxy) Phenyl) cyclohexane, 1,1-bis (3-ethyl-4-hydroxyphenyl) cyclohexane, 1,1-bis (3-isobutyl-4-hydroxyphenyl) cyclohexane, 1,1-bis (3-fluoro-4-) Hydroxyphenyl) cyclohexane, 1,1-bis (3,5-difluoro-4-hydroxyphenyl) cyclohexane, 1,1-bis (3-chloro-4-hydroxyphenyl) cyclohexane, 1,1-bis (3,5 Bisph is a cyclohexane derivative such as -dichloro-4-hydroxyphenyl) cyclohexane Nord like;
1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 1,1-bis (3-methyl-4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 1,1- Bis (3,5-dimethyl-4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 1,1-bis (3-ethyl-4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 1, 1-bis (3-isobutyl-4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 1,1-bis (3-fluoro-4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 1, -3,3,5-trimethylsilane such as 1-bis (3,5-difluoro-4-hydroxyphenyl) -3,3,5-trimethylcyclohexane Bisphenols is Rohekisan derivatives;
9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (3-methyl-4-hydroxyphenyl) fluorene, 1,1-bis (3,5-dimethyl-4-hydroxyphenyl) fluorene, 9 , 9-bis (3-ethyl-4-hydroxyphenyl) fluorene, 9,9-bis (3-isobutyl-4-hydroxyphenyl) fluorene, 1,1-bis (3-fluoro-4-hydroxyphenyl) fluorene, Bisphenols which are fluorene derivatives such as 9,9-bis (3,5-difluoro-4-hydroxyphenyl) fluorene;
1,1-bis (4-hydroxyphenyl) -cyclopentane, 1,1-bis (4-hydroxyphenyl) cyclopentane, 1,1-bis (4-hydroxyphenyl) cyclooctane, 1,1-bis (4 Bisphenols which are cycloalkane derivatives such as -hydroxyphenyl) cyclononane, 1,1-bis (4-hydroxyphenyl) cyclodecane;
Biphenols directly linked with aromatic rings such as 4,4′-biphenol;
Bis (4-hydroxyphenyl) sulfone, bis (3-methyl-4-hydroxyphenyl) sulfone, bis (3,5-dimethyl-4-hydroxyphenyl) sulfone, bis (3-ethyl-4-hydroxyphenyl) sulfone, Bisphenols which are sulfone derivatives such as bis (3-isobutyl-4-hydroxyphenyl) sulfone, bis (3-fluoro-4-hydroxyphenyl) sulfone, bis (3,5-difluoro-4-hydroxyphenyl) sulfone;
Bis (4-hydroxyphenyl) ether, bis (3-methyl-4-hydroxyphenyl) ether, bis (3,5-dimethyl-4-hydroxyphenyl) ether, bis (3-ethyl-4-hydroxyphenyl) ether, Bisphenols having an ether bond such as bis (3-isobutyl-4-hydroxyphenyl) ether, bis (3-fluoro-4-hydroxyphenyl) ether, bis (3,5-difluoro-4-hydroxyphenyl) ether;
Bis (4-hydroxyphenyl) sulfide, bis (3-methyl-4-hydroxyphenyl) sulfide, bis (3,5-dimethyl-4-hydroxyphenyl) sulfide, bis (3-ethyl-4-hydroxyphenyl) sulfide, Bisphenols having a sulfide bond such as bis (3-isobutyl-4-hydroxyphenyl) sulfide, bis (3-fluoro-4-hydroxyphenyl) sulfide, bis (3,5-difluoro-4-hydroxyphenyl) sulfide;
Bis (4-hydroxyphenyl) sulfoxide, bis (3-methyl-4-hydroxyphenyl) sulfoxide, bis (3,5-dimethyl-4-hydroxyphenyl) sulfoxide, bis (3-ethyl-4-hydroxyphenyl) sulfoxide, Bisphenols which are sulfoxide derivatives such as bis (3-isobutyl-4-hydroxyphenyl) sulfoxide, bis (3-fluoro-4-hydroxyphenyl) sulfoxide, bis (3,5-difluoro-4-hydroxyphenyl) sulfoxide;
Bisphenols having a heteroatom-containing aliphatic ring such as phenolphthalein;
Bis (2,3,5,6-tetrafluoro-4-hydroxyphenyl) difluoromethane, 1,1-bis (2,3,5,6-tetrafluoro-4-hydroxyphenyl) perfluoroethane, 2,2 Examples thereof include bisphenols having no carbon-hydrogen bond such as -bis (2,3,5,6-tetrafluoro-4-hydroxyphenyl) perfluoropropane.

And dihydroxybenzenes such as hydroquinone, resorcinol, catechol, methylhydroquinone;
Examples thereof include dihydroxynaphthalenes such as 1,5-dihydroxynaphthalene and 2,6-dihydroxynaphthalene.

  In the present invention, the conditions for synthesizing the side chain hydroxyl group-containing resin (c) are not particularly limited, and can be performed under known conditions. For example, an epoxy compound (a) having at least two epoxy groups in one molecule, a phenol compound (b) having at least two phenolic hydroxyl groups in one molecule, and a solvent are charged into a flask while stirring. The side chain hydroxyl group-containing resin (c) can be obtained by heating at 100 to 150 ° C. At this time, a catalyst such as triphenylphosphine or a tertiary amino group-containing compound may be used as necessary.

  Next, the carboxyl group-containing resin (e) obtained in the second step of the present invention will be described. The carboxyl group-containing resin (e) can be obtained by reacting the side chain hydroxyl group-containing resin (c) with the polybasic acid anhydride (d), and the hydroxyl group in the side chain hydroxyl group-containing resin (c). And an acid anhydride group in the polybasic acid anhydride (d) are preferably reacted at a molar ratio of hydroxyl group / acid anhydride group = 1 / 0.1 to 1/1. If there are less acid anhydride groups than the above molar ratio range, the concentration of carboxyl groups that function as crosslinking points in the finally obtained photosensitive resin (A) will decrease, so the desired heat resistance and solubility in alkaline developer Is difficult to obtain. In addition, when there are more acid anhydride groups than the above molar ratio range, the excess polybasic acid anhydride (d) generates a by-product in the subsequent synthesis step, so the flexibility of the final coating film and solder heat resistance, Insulation reliability tends to decrease.

  The polybasic acid anhydride (d) used in the present invention is not particularly limited as long as it is a compound containing at least one acid anhydride group in the molecule. For example, phthalic anhydride, trimellitic anhydride, methyltetrahydrophthalic anhydride, methylhymic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, methylpentahydrophthalic anhydride, methyltrihydrophthalic anhydride, trialkyltetrahydro Examples thereof include compounds containing an acid anhydride group having an alicyclic structure such as phthalic anhydride, methylcyclohexene dicarboxylic acid anhydride, het acid anhydride, tetrabromophthalic anhydride, or an aromatic ring structure. Other compounds include succinic anhydride, maleic anhydride, glutaric anhydride, butyl succinic anhydride, hexyl succinic anhydride, octyl succinic anhydride, dodecyl succinic anhydride, butyl maleic anhydride, pentyl maleic acid Anhydride, hexylmaleic anhydride, octylmaleic anhydride, decylmaleic anhydride, dodecylmaleic anhydride, butylglutamic anhydride, hexylglutamic anhydride, heptylglutamic anhydride, octylglutamic anhydride, decylglutamic anhydride Products, dodecylglutamic acid anhydride, and the like. In the present invention, the polybasic acid anhydride (d) may be used alone or in combination.

  Of these, succinic anhydride, tetrahydrophthalic anhydride and the like are particularly preferable in the present invention because of their excellent patternability, pattern formability and coating film resistance.

  In the present invention, the synthesis conditions of the carboxyl group-containing resin (e) are not particularly limited, and can be performed under known conditions. For example, a side chain hydroxyl group-containing resin (c) is prepared by charging a flask with a side chain hydroxyl group-containing resin (c), a polybasic acid anhydride (d), and a solvent, and heating at 25 to 150 ° C. with stirring. Can be obtained. This reaction proceeds even in the absence of a catalyst, but a catalyst such as a tertiary amino group-containing compound may be used if necessary.

  Next, the hydroxyl group-containing resin (A-1) obtained in the third step of the present invention will be described. The hydroxyl group-containing resin (A-1) of the present invention can be obtained by reacting the carboxyl group-containing resin (e) with a compound (f) having an epoxy group or oxetane group and an ethylenically unsaturated group. The carboxyl group in the carboxyl group-containing resin (e) and the epoxy group or oxetane group in the compound (f) having an epoxy group or oxetane group and an ethylenically unsaturated group are converted into a carboxyl group / epoxy group or oxetane group. It is preferable to prepare it by reacting at a molar ratio of 1 / 0.1 to 1/1. When the epoxy group or oxetane group is less than the above molar ratio range, the double bond equivalent functioning as a photo-crosslinking point in the finally obtained photosensitive resin (A) becomes high. It becomes difficult to obtain resistance. Moreover, when there are more epoxy groups or oxetane groups than the range of the said molar ratio, it exists in the tendency for the flexibility of a final coating film to fall with the compound (f) which has an excess epoxy group or oxetane group, and an ethylenically unsaturated group. .

  The compound (f) having an epoxy group or oxetane group and an ethylenically unsaturated group used in the present invention may be any compound containing at least one epoxy group or oxetane group and an ethylenically unsaturated group in the molecule. There is no particular limitation. For example, glycidyl (meth) acrylate, glycidyl cinnamic acid, 4-hydroxybutyl (meth) acrylate glycidyl ether, glycidyl allyl ether, 2,3-epoxy-2-methylpropyl (meth) acrylate, (3,4-epoxycyclohexyl) Many hydroxyl-containing groups such as methyl (meth) acrylate, 4-vinyl-1-cyclohexene-1,2-epoxide, 1,3-butadiene monoepoxide, oxetanyl (meth) acrylate, oxetanylcinnamic acid, and pentaerythritol triacrylate Modification of most epoxide groups of polyfunctional acrylate groups by reacting epichlorohydrin with hydroxyl groups of functional acrylic monomers, and phenol novolac epoxy resins to acrylate groups with acrylic acid, etc. Epoxy of the compound which has two or more epoxy groups in the molecule to the carboxyl group of the polyfunctional acrylate group-containing monoepoxide and carboxyl group-containing polyfunctional acrylic monomer, in which one epoxy group remains in one molecule on average Polyfunctional acrylate group-containing monoepoxide obtained by reacting a part of the group, and the like. By reacting these epoxy group or oxetane group with the carboxyl group in the carboxyl group-containing resin (e), hydroxyl group is obtained. A group-containing resin (A-1) is obtained. In the present invention, the compound (f) having an epoxy group or oxetane group and an ethylenically unsaturated group may be used alone or in combination.

  Among them, glycidyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate glycidyl ether, and the like are particularly preferable in the present invention because they are highly reactive with carboxyl groups and are very excellent in photosensitivity.

  In the present invention, a compound having no ethylenically unsaturated group and having an epoxy group or oxetane group is used in combination with the compound (b) having an epoxy group or oxetane group and an ethylenically unsaturated group. You can also. In this case, it is possible to control the photosensitivity of the carboxyl group-containing photosensitive urethane resin (A) of the present invention more broadly. Examples of the compound having no ethylenically unsaturated group and having an epoxy group or oxetane group of the present invention include styrene oxide, phenyl glycidyl ether, o-phenylphenol glycidyl ether, p-phenylphenol glycidyl ether, glycidyl cinnamon. Mate, methyl glycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, decyl glycidyl ether, stearyl glycidyl ether, allyl glycidyl ether, glycidol, N-glycidyl phthalimide, 1,3-dibromophenyl glycidyl ether, Celoxide 2000 (Daicel Chemical Industries) And oxetane alcohol).

  In the present invention, the synthesis conditions of the hydroxyl group-containing resin (A-1) are not particularly limited, and can be performed under known conditions. For example, in the presence of oxygen, the flask is charged with the carboxyl group-containing resin (e), the compound (f) having an epoxy group or oxetane group and an ethylenically unsaturated group, and a solvent at 25 to 150 ° C. with stirring. The hydroxyl group-containing resin (A-1) can be obtained by heating. At this time, an ethylenically unsaturated group may be added so as not to add a reaction catalyst such as a tertiary amino group-containing compound or the like to promote the reaction, or to cause gelation due to polymerization reaction or progress of polymerization. It is also possible to use a polymerization inhibitor or molecular oxygen.

  As the polymerization inhibitor, hydroquinone, methylhydroquinone, pt-butylcatechol, 2-t-butylhydroquinone, 2,5-di-t-butylhydroquinone, trimethylhydroquinone, methoxyhydroquinone, p-benzoquinone, 2,5- Di-t-butylbenzoquinone, naphthoquinone, phenothiazine, N-oxyl compound and the like can be used. Further, even if molecular oxygen is present in the reaction vessel, there is an effect of inhibiting polymerization. For example, air or a mixed gas of air and an inert gas such as nitrogen may be blown into the reaction vessel so-called bubbling. In order to enhance the polymerization inhibition effect, it is preferable to use a polymerization inhibitor and molecular oxygen in combination.

  Next, the carboxyl group-containing photosensitive resin (A-2) obtained in the fourth step of the present invention will be described. The carboxyl group-containing photosensitive resin (A-2) of the present invention can be obtained by reacting the hydroxyl group-containing resin (A-1) with the polybasic acid anhydride (d). Prepared by reacting the hydroxyl group in A-1) with the acid anhydride group in the polybasic acid anhydride (d) at a molar ratio of hydroxyl group / acid anhydride group = 1 / 0.01 to 1/1. It is preferable to do. If there are less acid anhydride groups than the above molar ratio range, the concentration of carboxyl groups that function as crosslinking points in the finally obtained photosensitive resin (A) will decrease, so the desired heat resistance and solubility in alkaline developer Is difficult to obtain. Moreover, when there are more acid anhydride groups than the range of the said molar ratio, it exists in the tendency for the flexibility of a final coating film, solder heat resistance, and insulation reliability to fall with an excess polybasic acid anhydride (d).

  As described above, the polybasic acid anhydride (d) used in the present invention is not particularly limited as long as it is a compound containing at least one acid anhydride group in the molecule. You may use and you may use multiple together. Of these, succinic anhydride, tetrahydrophthalic anhydride and the like are particularly preferable in the present invention because of their excellent patternability, pattern formability and coating film resistance.

  In the present invention, the synthesis condition of the carboxyl group-containing photosensitive resin (A-2) is not particularly limited, and the hydroxyl group-containing resin (A-1) is added to the flask in the presence of oxygen in the same manner as in the third step. ), A polybasic acid anhydride (d), and a solvent are charged, and the reaction is preferably performed by heating and stirring at 25 to 150 ° C., and if necessary, a suitable reaction catalyst and an ethylenically unsaturated group A polymerization inhibitor can be newly added.

  It is preferable that the acid value of the photosensitive resin (A) of this invention obtained by the above process is 50-120 mgKOH / g, More preferably, it is 60-110 mgKOH / g. When the acid value is less than 50 mgKOH / g, it may be difficult to obtain sufficient patterning properties. For example, the film may remain as a residue in a portion where the film is dissolved and removed during development. On the other hand, when the acid value exceeds 120 mgKOH / g, the solubility of the coating film with respect to the developer is increased, and even the portion which is desired to be photocured and left as a pattern is dissolved, and the pattern shape may be deteriorated.

  It is preferable that the ethylenically unsaturated group equivalent of the photosensitive resin (A) of this invention is 200-5000 g / eq, More preferably, it is 300-3000 g / eq. When the ethylenically unsaturated group equivalent is less than 200 g / eq, the photosensitivity may be too high, and even the part to be removed by dissolving the film during development is cured by light, and a good pattern shape is obtained. There may not be. When the ethylenically unsaturated group equivalent exceeds 5000 g / eq, the photosensitivity may be too low, the portion to be photocured may not be sufficiently cured, and the pattern dissolves during development, thereby obtaining a good pattern shape. There may not be. The “ethylenically unsaturated group equivalent” as used in the present invention is a theoretical value calculated from the weight of raw materials used during the synthesis of the resin, and the weight of the resin is the ethylenically unsaturated group present in the resin. It is divided by the number of groups and corresponds to the weight of the resin per mole of ethylenically unsaturated groups, that is, the reciprocal of the ethylenically unsaturated group concentration.

  It is preferable that the weight average molecular weights of the photosensitive resin (A) of this invention are 2000-40000, More preferably, it is 3000-30000. When the weight average molecular weight is 2000 or more, the solder heat resistance and flexibility are excellent, and when the weight average molecular weight is 40000 or less, the patterning property can be improved.

  The solvent used for the synthesis of the photosensitive resin (A) can be appropriately selected according to the end use and the solubility of the reactant. In the dry film preparation step, it is preferable to use a low boiling point solvent in order to quickly dry the solvent. Examples of the low boiling point solvent in this case include methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate, tetrahydrofuran, toluene, isopropyl alcohol and the like.

  In the present invention, these solvents may be used alone or in combination, if necessary, and may be used in combination. Or a solvent may be added.

  The above-mentioned photosensitive resin (A) does not have an ester bond derived from half esterification with a dibasic acid anhydride or a urethane bond derived from the reaction of an isocyanate group and a hydroxyl group in the main chain, so that the main chain is chemically stable. Therefore, the obtained cover coat layer is excellent in various coating film resistance, exhibits excellent heat resistance even when exposed to high temperature conditions such as a solder bath, and also has excellent electrical insulation even under high temperature and high humidity. It is preferable to exhibit Furthermore, since the photosensitive resin (A) has a photosensitive group and a carboxyl group in the side chain, even when the amount of the photosensitive group and carboxyl group contained is small, it exhibits very good patterning properties. . The functional groups introduced into these side chains are more reactive than when directly connected to the main chain, and the amount of introduction can be adjusted arbitrarily compared to the case where they are introduced only at the ends of the main chain. Curability, patterning properties and coating film resistance can be exhibited.

(Thermosetting resin)
The thermosetting resin is a resin having a plurality of functional groups that can be used for a crosslinking reaction by heating. Examples of the functional group include a hydroxyl group, a phenolic hydroxyl group, a carboxyl group, an amino group, an epoxy group, an oxetanyl group, an oxazoline group, an oxazine group, an aziridine group, a thiol group, and a silanol group.
Examples of the thermosetting resin having the above functional group include acrylic resin, maleic acid resin, polybutadiene resin, polyester resin, condensation type polyester resin, addition type polyester resin, melamine resin, polyurethane resin, polyurethane urea resin, and epoxy resin. Oxetane resin, phenoxy resin, polyimide resin, polyamide resin, polyamideimide resin, phenolic resin, alkyd resin, amino resin, polylactic acid resin, oxazoline resin, benzoxazine resin, silicone resin, fluorine resin, and the like.

[Thermosetting agent]
The active energy ray-curable resin composition of the present invention preferably uses a thermosetting agent. The thermosetting agent forms a cover coat layer excellent in migration resistance and flexibility by thermally cross-linking with the carboxylic acid group and the hydroxyl group of the active energy ray curable resin or the thermosetting resin. The thermosetting agent has a plurality of functional groups capable of reacting with the functional groups of the active energy ray curable resin and the thermosetting resin. Examples of the thermosetting agent include known compounds such as an epoxy compound, an acid anhydride group-containing compound, an isocyanate compound, an aziridine compound, an amine compound, and a phenol compound, and an isocyanate compound is particularly preferable.

  The isocyanate compound is not particularly limited as long as it is a compound having an isocyanate group in the molecule. Specific examples of the diisocyanate compound include aromatic diisocyanates having 4 to 50 carbon atoms, aliphatic diisocyanates, araliphatic diisocyanates, and alicyclic diisocyanates.

  Examples of the aromatic diisocyanate include 1,3-phenylene diisocyanate, 4,4′-diphenyl diisocyanate, 1,4-phenylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6- Tolylene diisocyanate, 4,4'-toluidine diisocyanate, 2,4,6-triisocyanate toluene, 1,3,5-triisocyanate benzene, dianisidine diisocyanate, 4,4'-diphenyl ether diisocyanate, 4,4 ', 4 "-Triphenylmethane triisocyanate etc. can be mentioned.

  Examples of the aliphatic diisocyanate include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, dodecamethylene diisocyanate, 2 4,4-trimethylhexamethylene diisocyanate and the like.

  Examples of the araliphatic diisocyanate include ω, ω′-diisocyanate-1,3-dimethylbenzene, ω, ω′-diisocyanate-1,4-dimethylbenzene, ω, ω′-diisocyanate-1,4-diethylbenzene, 1 , 4-tetramethylxylylene diisocyanate, 1,3-tetramethylxylylene diisocyanate, and the like.

  Examples of the alicyclic diisocyanate include 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate [also known as isophorone diisocyanate], 1,3-cyclopentane diisocyanate, 1,3-cyclohexane diisocyanate, and 1,4-cyclohexane diisocyanate. , Methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, 4,4′-methylenebis (cyclohexyl isocyanate), 1,3-bis (isocyanatomethyl) cyclohexane, 1,4-bis (isocyanate methyl) A cyclohexane etc. can be mentioned.

  Specific examples of the isocyanate compound having one or three or more isocyanate groups in the molecule include (meth) acryloyloxyethyl isocyanate, 1,1 as a monofunctional isocyanate having one isocyanate group in one molecule. -Bis [(meth) acryloyloxymethyl] ethyl isocyanate, vinyl isocyanate, allyl isocyanate, (meth) acryloyl isocyanate, isopropenyl-α, α-dimethylbenzyl isocyanate and the like. In addition, 1,6-diisocyanatohexane, isophorone diisocyanate, 4,4′-diphenylmethane diisocyanate, polymeric diphenylmethane diisocyanate, xylylene diisocyanate, tolylene 2,4-diisocyanate, toluene diisocyanate, 2,4-diisocyanic acid Toluene, hexamethylene diisocyanate, 4-methyl-m-phenylene diisocyanate, naphthylene diisocyanate, paraphenylene diisocyanate, tetramethylxylylene diisocyanate, cyclohexylmethane diisocyanate, hydrogenated xylylene diisocyanate, cyclohexyl diisocyanate, tolidine diisocyanate, 2,2 , 4-Trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate Nitrate, m-tetramethylxylylene diisocyanate, p-tetramethylxylylene diisocyanate, diisocyanate ester compounds such as dimer acid diisocyanate and hydroxyl group, carboxyl group, and amide group-containing vinyl monomers are reacted in equimolar amounts. It can be used as an ester compound.

  Examples of the polyfunctional isocyanate having 3 or more isocyanate groups in one molecule include aliphatic polyisocyanates such as aromatic polyisocyanates and lysine triisocyanates, araliphatic polyisocyanates, and alicyclic polyisocyanates. Examples thereof include trimethylolpropane adducts of diisocyanate described above, burettes reacted with water, and trimers having an isocyanurate ring. Among these, a trimethylolpropane adduct of diisocyanate and a trimer having an isocyanurate ring are preferable. Furthermore, the migration resistance and flexibility can be improved by using a trimethylolpropane adduct of diisocyanate and a trimer having an isocyanurate ring in combination.

The blocked isocyanate compound is an isocyanate compound in which an isocyanate group is protected with a blocking agent such as ε-caprolactam or MEK oxime. Specific examples include those obtained by protecting the isocyanate group of the isocyanate compound with a blocking agent such as ε-caprolactam, MEK oxime, cyclohexanone oxime, pyrazole, phenol, etc. Among these, MEK oxime is preferable.
Among these, the isocyanate compound is preferably a blocked isocyanate compound. It is preferable to use a blocked isocyanate compound because the sheet life is improved.

  The dissociation temperature of the blocking agent of the blocked isocyanate compound is preferably 120 to 200 ° C, more preferably 130 to 180 ° C. By setting the dissociation temperature of the blocking agent of the blocked isocyanate compound to 120 ° C. or higher, it does not dissociate at the drying temperature when coating the active energy ray-curable resin composition on the transparent substrate, and has excellent patterning properties. A dry resist film having the following can be obtained. Further, by setting the dissociation temperature of the blocking agent to 200 ° C. or less, foaming in the cover coat layer can be suppressed during heat curing when forming the cover coat layer.

  The blocked isocyanate compound preferably has an isocyanate equivalent of 200 to 400 g / eq and 500 to 900 g / eq. Flexibility and migration resistance can be improved by using together block isocyanates having different isocyanate equivalents. The isocyanate equivalent referred to in the present invention is a value measured according to JIS K 7301.

The epoxy compound is a compound having two or more epoxy groups in one molecule. The property of the epoxy compound may be liquid or solid.
As the epoxy compound, for example, a glycidyl ether type epoxy compound, a glycidyl amine type epoxy compound, a glycidyl ester type epoxy compound, a cyclic aliphatic (alicyclic type) epoxy compound and the like are preferable.

  The molecular weight of the epoxy compound is preferably 100 to 2000, and more preferably 200 to 1500.

  Examples of the glycidyl ether type epoxy compound include bisphenol A type epoxy compound, bisphenol F type epoxy compound, bisphenol S type epoxy compound, bisphenol AD type epoxy compound, cresol novolac type epoxy compound, phenol novolac type epoxy compound, α-naphthol novolak. Type epoxy compound, bisphenol A type novolak type epoxy compound, dicyclopentadiene type epoxy compound, tetrabromobisphenol A type epoxy compound, brominated phenol novolac type epoxy compound, tris (glycidyloxyphenyl) methane, tetrakis (glycidyloxyphenyl) ethane Etc.

  Examples of the glycidylamine-type epoxy compound include tetraglycidyldiaminodiphenylmethane, triglycidylparaaminophenol, triglycidylmetaaminophenol, tetraglycidylmetaxylylenediamine, and the like.

  Examples of the glycidyl ester type epoxy compound include diglycidyl phthalate, diglycidyl hexahydrophthalate, diglycidyl tetrahydrophthalate, and the like.

Examples of the cycloaliphatic (alicyclic) epoxy compound include epoxycyclohexylmethyl-epoxycyclohexanecarboxylate, bis (epoxycyclohexyl) adipate, and the like.
Among these, as the epoxy compound, bisphenol A type epoxy compound, cresol novolak type epoxy compound, phenol novolak type epoxy compound, tris (glycidyloxyphenyl) methane, and tetrakis (glycidyloxyphenyl) ethane are preferable. By using these epoxy compounds, migration resistance and flexibility are further improved.

  The compounding amount of the epoxy compound is preferably 20% by weight or less and more preferably 15% by weight or less in the total amount (100% by weight) of the thermosetting agent. By setting the epoxy compound to 20% by weight or less, the curing reaction in the dry resist film is suppressed and the sheet life is improved, so that the patterning property can be improved.

  The blending amount of the thermosetting agent is preferably 30 to 150 parts by weight, and more preferably 50 to 110 parts by weight with respect to 100 parts by weight of the total of the active energy ray curable resin and the thermosetting resin. High migration resistance and flexibility can be obtained by blending 30 to 150 parts by weight of the curing agent with respect to 100 parts by weight of the total of the active energy ray curable resin and the thermosetting resin.

[Active energy ray polymerization initiator]
Examples of the active energy ray polymerization initiator include 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopro Acetophenone-based active energy ray polymerization initiators such as pan-1-one, 1,2-octadion-1- [4- (phenylthio)-, 2- (o-benzoyloxime)], ethanone, 1- [9-ethyl -6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (o- Cetyloxime) and other oxime ester active energy ray polymerization initiators, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzyldimethyl ketal and other benzoin active energy ray polymerization initiators, benzophenone, benzoylbenzoic acid, benzoyl Benzophenone-based active energy ray polymerization initiators such as methyl benzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, thioxanthone, 2-chlorothioxanthone, 2-methylthioxanone Thioxanthone-based active energy ray polymerization initiators such as Son, Isopropylthioxanthone, 2,4-Diisopropylthioxanthone, 2,4,6-Tri Loro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- ( p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2-piperonyl-4,6-bis (trichloromethyl) -s-triazine, 2,4-bis (trichloromethyl) -6-styryl -S-triazine, 2- (naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxy-naphth-1-yl) -4,6-bis (trichloro) Tria such as methyl) -s-triazine, 2,4-trichloromethyl- (piperonyl) -6-triazine, 2,4-trichloromethyl (4′-methoxystyryl) -6-triazine Active energy ray polymerization initiators, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, acylphosphine oxide-based active energy ray polymerization of bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide An initiator, a borate-based active energy ray polymerization initiator, a carbazole-based active energy ray polymerization initiator, an imidazole-based active energy ray polymerization initiator, or the like is used. These active energy ray polymerizable compounds can be used singly or as a mixture of two or more at any ratio as required.

  Of these, acylphosphine oxide-based active energy ray polymerization initiators and acetophenone-based active energy ray polymerization initiators are preferable because the bottom curability of the film is good and the migration resistance is improved. Specific examples of the acylphosphine oxide-based active energy ray polymerization initiator include Irgacure TPO (manufactured by BASF), Irgacure 819 (manufactured by BASF), and specific examples of the acetophenone-based active energy ray polymerization initiator include Irgacure. 907 (made by BASF), Irgacure 379 (made by BASF), Irgacure 379EG (made by BASF), etc. are mentioned.

  The active energy ray polymerization initiator is preferably used in an amount of 0.5 to 15 parts by weight with respect to 100 parts by weight of the solid content of the active energy ray curable resin.

The active energy ray-curable resin composition of the present invention further includes α-acyloxy ester, acylphosphine oxide, methylphenylglyoxylate, benzyl, 9,10-phenanthrenequinone, camphorquinone, as a sensitizer. A compound such as ethyl anthraquinone, 4,4′-diethylisophthalophenone, 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone, 4,4′-diethylaminobenzophenone may be used in combination. it can.
The sensitizer can be used in an amount of 0.1 to 10 parts by weight with respect to 100 parts by weight of the active energy ray polymerization initiator.

[Black colorant]
The dry resist film of the present invention contains a black colorant in order to enhance the light shielding property of the cover coat layer. The black colorant is preferably a black color pigment and a mixed colorant containing a plurality of pigments such as red, green, blue, yellow, purple, cyan and magenta. The mixed colorant can obtain black color by subtractive color mixing of a plurality of pigments.

  Examples of the black pigment include carbon black, ketjen black, carbon nanotube (CNT), perylene black, titanium black, iron black, and aniline black. Among these, from the viewpoint of improving jetness and migration resistance, perylene black, titanium black, iron black, and mixed colorants are preferable, and perylene black and titanium black are more preferable. Particularly preferred is titanium black.

The black colorant preferably has a specific gravity of 2 to 7 g / cm ³ and more preferably 4 to 6 g / cm ³ or more. When the specific gravity of the black colorant is 2 to 7 g / cm ³ , the black colorant contained is appropriately precipitated after the active energy ray-curable resin composition is applied to the transparent substrate. Thereby, when it dries and forms a dry resist film and a peelable sheet is affixed, as for the density | concentration of a black type colorant, a transparent base material surface will be dark and a peelable sheet surface will become thin.
Since the dry resist film has a peelable sheet peeled off to the signal circuit side and a cover coat layer is formed, if the black colorant component on the signal circuit side can be reduced, there is less impurity component and migration Resistance can be further improved.

  The black colorant preferably has an average primary particle size of 20 to 100 nm, more preferably 30 to 90 nm, and even more preferably 40 to 90 nm. By using the black colorant having the average primary particle diameter, the cover coat layer formed from the dry resist film is further improved in jet blackness and flexibility. In addition, when the particle shape of the black colorant has an average aspect ratio (major axis length / minor axis length) of 1.5 or more, the average primary particle diameter is obtained by averaging the major axis lengths.

  The powder resistance value of the black colorant is preferably 3 Ω · cm or more, and more preferably 5 Ω · cm or more. Migration resistance is further improved by setting the powder resistance value of the black colorant within the above range. The powder resistance value is a resistance value when pressed at a press pressure of 2 MPa using a powder resistance measurement system MCP-PD51 and a resistivity meter MCP-T610 manufactured by Mitsubishi Chemical Analytech.

The specific surface area of the black-based colorant is preferably ^{10~50m 2 / g, 15~40m 2 /} g is more preferable. By setting the specific surface area of the black colorant within the above range, the patterning property is further improved.
The specific surface area can be determined by the BET method using BELSORP-miniII manufactured by Nippon Bell Co., Ltd.

  The average primary particle diameter of the black colorant can be determined from an average value of about 20 primary particles that can be observed from an image enlarged to about 50,000 to 1,000,000 times with a transmission electron microscope (TEM).

  The following pigments can be used as the mixed colorant. “CI” means a color index (CI).

  Examples of red pigments and magenta pigments include C.I. I. Pigment Red 7, 14, 41, 48: 1, 48: 2, 48: 3, 48: 4, 57: 1, 81, 81: 1, 81: 2, 81: 3, 81: 4, 122, 146, 168, 176, 177, 178, 184, 185, 187, 200, 202, 208, 210, 242, 246, 254, 255, 264, 270, 272, and 279.

  Examples of the green pigment include C.I. I. Pigment green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55 and 58.

  Blue pigments and cyan pigments are exemplified by C.I. I. Pigment Blue 1, 1: 2, 9, 14, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56: 1, 60, 61, 61: 1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, 79 and the like.

  Examples of yellow pigments include C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 126, 127, 128, 129, 138, 139, 147, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 82,184,185,187,188,193,194,198,199,213 and 214, and the like.

  Examples of purple pigments include C.I. I. Pigment Violet 1, 1: 1, 2, 2: 2, 3, 3: 1, 3: 3, 5, 5: 1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, 50 and the like.

  The black colorant is preferably contained in an amount of 0.5 to 40% by weight, more preferably 1 to 30% by weight, in 100% by weight of the dry resist film. By including 0.5 to 40% by weight of the black colorant, it becomes easy to achieve both high jetness and migration test resistance.

[Inorganic filler]
The active energy ray-curable resin composition of the present invention preferably further contains an inorganic filler. By including the inorganic filler, the heat-resistant press bonding property is further improved. Examples of the inorganic filler include inorganic substances such as silica, alumina, aluminum hydroxide, magnesium hydroxide, barium sulfate, calcium carbonate, titanium oxide, zinc oxide, antimony trioxide, magnesium oxide, talc, montmorolinite, kaolin, and bentonite. Compounds.
Among these, as an inorganic filler, hydrophobic silica fine particles obtained by reacting a silanol group on the silica surface with a halogenated silane increase not only the heat-resistant pressure-bonding property but also the hydrophobicity of the film, thereby improving the migration resistance. It is preferable from the point of improving.

The BET specific surface area of the inorganic filler is preferably 50 to 300 m ² / g. By being in the said range, an inorganic filler is uniformly disperse | distributed to a dry resist film, and heat-resistant press-fit property improves.

  The average particle diameter (average particle diameter D50) of the inorganic filler is preferably 0.01 to 10 μm, and more preferably 0.05 to 8 μm. When the average particle diameter of the inorganic filler is 0.01 to 10 μm, the heat-resistant press bonding property can be further improved.

  It is preferable that content of an inorganic filler is 0.5 to 40 weight% in 100 weight% of solid content of an active energy ray curable resin composition. That is, it is preferably 0.5 to 40% by weight in 100% by weight of the resin layer of the dry resist film. More preferably, it is 1 to 30% by weight. If it is 0.5% by weight or more, the migration resistance is improved. Moreover, if it is 40 weight% or less, heat-resistant press-fit property will improve.

The active energy ray-curable resin composition includes pigments and dyes other than black colorants, and monomers, solvents, silane coupling agents, ion scavengers, antioxidants, tackifying resins, and plasticizers as necessary. , UV absorbers, antifoaming agents, leveling regulators, fillers, flame retardants, and the like.
The active energy ray-curable resin composition can be prepared by adding a solvent to the active energy ray-curable resin, the active energy ray polymerization initiator, and the black colorant, and mixing and stirring as necessary. For the stirring, for example, a known stirring device such as a disperse mat or a homogenizer can be used.

<Method for producing dry resist film>
The dry resist film of the present invention has a resin layer obtained by applying and drying an active energy ray-curable resin composition on one surface of a transparent substrate.
Furthermore, in order to protect the resin layer, it is common to laminate a peelable sheet to form a laminated structure of a transparent base material / resin layer / peelable sheet. Sometimes called a dry resist film with a substrate.
The dry film of the present invention may further have intermediate layers such as a cushion layer, an adhesive layer, a light absorption layer, and a gas barrier layer.

  The resin layer of the dry resist film is formed on the release surface of the transparent substrate, for example, knife coat, die coat, lip coat, roll coat, curtain coat, bar coat, gravure coat, flexo coat, dip coat, spray coat, spin coat. It can form by drying a solvent normally at the temperature of 40-120 degreeC after apply | coating the liquid active energy ray-curable resin composition melt | dissolved and disperse | distributed to the solvent by the method of these.

The transparent substrate preferably has a maximum light transmittance at a wavelength of 320 to 700 nm of 50% or more, and more preferably 60% or more. By using a transparent substrate having an average light transmittance of 50% or more at a wavelength of 320 to 700 nm, the active energy ray reaches the dry resist film and is cured efficiently, so that the patterning property is improved.
A polyethylene terephthalate film or a polyolefin film is suitably used as the transparent substrate having such transmittance.

  The peelable sheet is a film in which a release agent is coated on one or both sides of a polyethylene terephthalate film or an OPP film, and is a member to be bonded to protect the dry resist film. The light transmittance of the peelable sheet can be used without any particular limitation.

The thickness of the resin layer of the dry resist film is preferably 5 to 100 μm, and more preferably 10 to 70 μm.
The dry resist film of the present invention can be handled easily by forming a resin layer on a transparent substrate and further bonding a peelable sheet to the other surface and sandwiching the both sides.

<Printed wiring board>
Then, the printed wiring board which comprises the cover coat layer formed using the dry resist film of this invention is demonstrated.
The printed wiring board of the present invention comprises an electromagnetic wave shielding sheet, a cover coat layer, a substrate having signal wiring and an insulating substrate.
By having the cover coat layer formed using the dry resist film of this invention, it can be set as the printed wiring board with the electromagnetic wave shield sheet excellent in ion migration resistance, a flexibility, and jetness.

<Electromagnetic wave shield sheet>
The electromagnetic wave shielding sheet of the present invention includes a conductive layer and an insulating layer.
[Conductive layer]
The conductive layer of the electromagnetic wave shielding sheet is a layer that shields noise such as electromagnetic waves and is mainly attached to the cover coat layer of the FPC.
A conductive layer consists of two aspects, the 1st aspect of the conductive layer formed from the conductive adhesive, and the 2nd aspect which has a conductive layer formed from the metal layer and the conductive adhesive. The conductive adhesive layer has been described with conductive fine particles made of a conductive metal such as gold, platinum, silver, copper and nickel and alloys thereof, and the active energy ray resin composition which forms the dry resist film. A conductive resin composition in which a thermosetting resin and a curing agent are mixed is formed into a coating film.

  For the metal layer, for example, a conductive metal vapor-deposited film such as aluminum, copper, silver, or gold having a thickness of 0.005 to 10 μm, a metal foil, or the like is used.

[Insulation layer]
The insulating layer can be formed using an insulating resin composition.
The insulating resin composition can be formed by forming a coating film of an insulating resin composition containing a thermosetting resin and a thermosetting agent in the same manner as the conductive adhesive. In addition, a film obtained by molding an insulating resin such as polyester, polycarbonate, polyimide, polyphenylene sulfide, or the like can also be used.

  In the electromagnetic wave shielding sheet, the thermosetting resin and the thermosetting agent contained in the conductive layer exist in an uncured state, and a desired adhesive strength can be obtained by curing together with the cover coat layer by hot pressing. The uncured state includes a semi-cured state in which a part of the thermosetting agent is cured.

<Cover coat layer>
The cover coat layer is an insulating material that covers the signal wiring of the wiring board and protects it from the external environment. The cover coat layer of the present invention is formed using the dry resist film of the present invention, and is formed by active energy ray curing and heat curing of the resin layer of the dry resist film.

  The cover coat layer of the present invention has a resin layer formed from an active energy ray-curable resin composition containing an active energy ray-curable resin, an active energy ray polymerization initiator, and a black colorant. The cured product of the resin layer is formed from a dry resist film having a storage elastic modulus at 85 ° C. of 1.0E + 07 to 1.0E + 10 Pa.

  The thickness of the cover coat layer is preferably 5 to 100 μm, more preferably 10 to 70 μm. Flexibility and migration resistance can be improved by setting the thickness of the cover coat layer to a range of 5 to 100 μm.

The glass transition temperature (Tg) of the cover coat layer is preferably 40 ° C to 120 ° C, and 50 ° C to 1 ° C.
00 ° C. is more preferable. Flexibility and migration resistance can be improved by setting the glass transition temperature (Tg) of the cover coat layer to 40 ° C to 120 ° C.

<Board>
The substrate has signal wiring and an insulating base material.

  Examples of the signal wiring include a ground wiring for grounding and a wiring circuit for sending an electric signal to an electronic component. The signal wiring is generally formed by etching a copper foil.

  The insulating substrate is preferably a bendable plastic such as polyester, polycarbonate, polyimide, polyphenylene sulfide, liquid crystal polymer, and more preferably polyimide.

<Method for manufacturing printed printed wiring board with electromagnetic wave shield>
The manufacturing method of the printed wiring board with an electromagnetic wave shielding sheet of this invention is demonstrated.
The printed wiring board with an electromagnetic wave shielding sheet of the present invention includes a step of forming a signal wiring on an insulating substrate (step A), a step of laminating a dry resist film on the signal wiring (step B), and a resin layer of the dry resist film. And a step of forming a cover coat layer having an opening by thermosetting after development (step C), and a step of laminating an electromagnetic wave shielding sheet on the cover coat layer and hot pressing (step D). Can do. Each step will be specifically described below.

(Process A; Signal wiring formation process)
First, a ground wiring for grounding by etching a copper foil on an insulating substrate and a signal wiring including a wiring circuit for sending an electric signal to an electronic component are formed.

(Process B; Dry resist film lamination process)
Next, the peelable sheet of the dry resist film sandwiched between the transparent substrate and the peelable sheet is peeled off, and the exposed resin layer surface is pasted by a laminator so as to cover the signal wiring on the insulating substrate.

(Process C; Cover coat layer forming process)
Active energy rays are irradiated from the upper surface of the transparent substrate through a photomask formed in a desired pattern, and the resin layer of the dry resist film is cured with active energy rays.

As an active energy ray for curing the resin layer of the dry resist film, an electron beam, an ultraviolet ray, or a light beam having a wavelength of 350 to 500 nm can be used. A thermionic emission gun, a field emission gun, or the like can be used as the electron beam source to be irradiated. For example, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a gallium lamp, a xenon lamp, a carbon arc lamp, or the like can be used as the ultraviolet ray and a radiation source (light source) of 350 to 500 nm. Specifically, an ultra-high pressure mercury lamp, a xenon mercury lamp, or a metal halide lamp is often used because of the point light source and the stability of luminance. The active energy dose to be irradiated, can be set appropriately in the range of 5~2000mJ / cm ^2, it is preferably in the range on the easy of 50~1000mJ / cm ² management process. Further, these active energy rays can be used in combination with heat by infrared rays, far infrared rays, hot air, high-frequency heating or the like.

Thereafter, the transparent substrate is peeled off and developed with an aqueous alkaline solution to wash away the unirradiated portion, and an opening is formed on the ground wiring or at a necessary location.
In general, a hole in a coverlay film is formed by using a drill to form an opening having a diameter of 2 to 5 mm. However, by using the dry resist film in the present invention, the diameter of the opening is reduced to 0. It is possible to form a cover coat layer having an opening having a tapered development residue of 0.05 to 1 mm. By setting the opening diameter to 0.05 to 1 mm, for example, the area of the ground wiring can be greatly reduced, so that the FPC can be shortened.

  In development, an aqueous solution such as sodium carbonate or sodium hydroxide is used as an alkali developer, and an organic alkali such as dimethylbenzylamine or triethanolamine can also be used. An antifoaming agent or a surfactant can also be added to the developer.

  As a development processing method, a shower development method, a spray development method, a dip (immersion) development method, a paddle (liquid accumulation) development method, or the like can be applied.

  After the developer is washed with water, it is heated at 80 ° C. to 110 ° C. for 2 minutes to 10 minutes to remove unnecessary moisture, and then heated at 150 ° C. to 180 ° C. for 30 minutes to 2 hours and thermally cured to cover. A coat layer is formed. Even after heat curing, active energy rays can be irradiated as necessary.

(Process D; Hot press process)
Next, an electromagnetic wave shielding sheet punched into a predetermined size is laminated and temporarily attached to a part or the entire surface of the cover coat layer. Thereafter, the conductive layer of the electromagnetic wave shielding sheet is thermally cured and bonded by hot pressing. At this time, since the conductive adhesive layer flows into the opening of the cover coat layer formed on the ground wiring and is cured, the shielding property is further improved by conducting with the ground.

  The heat pressing of the electromagnetic wave shielding sheet and the wiring board is generally performed under conditions of a temperature of about 150 to 190 ° C., a pressure of about 1 to 3 MPa, and a time of about 1 to 60 minutes. The thermosetting resin and the curing agent react by hot pressing. In order to accelerate curing, post-curing may be performed at 150 to 190 ° C. for 30 to 90 minutes after hot pressing. In addition, an electromagnetic wave shield sheet may be called an electromagnetic wave shield layer after hot pressing.

  The printed wiring board of the present invention is preferably provided in an electronic device such as a notebook PC, a mobile phone, a smartphone, and a tablet terminal in addition to a liquid crystal display and a touch panel.

  EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated in detail, this invention is not limited only to a following example. The following “parts” and “%” are values based on “parts by weight” and “% by weight”, respectively.

A method for synthesizing the active energy ray-curable resin used in the examples is shown below.
[Active energy ray curable resin 1]
In a four-necked flask equipped with a stirrer, reflux condenser, nitrogen inlet tube, inlet tube, and thermometer, 64.8 parts of bisphenol A, 57.1 parts of YD8125 (manufactured by Nippon Steel Chemical Co., Ltd., bisphenol A type epoxy compound) EX861 (manufactured by Nagase ChemteX Corporation: polyethylene glycol diglycidyl ether) 128.1 parts, 1.25 parts triphenylphosphine as catalyst, 1.25 parts N, N-dimethylbenzylamine, 250 parts toluene as solvent The mixture was heated to 110 ° C. with stirring under a nitrogen stream and reacted for 8 hours to obtain a hydroxyl group-containing resin. Next, 54.6 parts of Ricacid SA (manufactured by Shin Nippon Rika Co., Ltd .: succinic anhydride) was added as an acid anhydride and reacted at 110 ° C. for 4 hours. After confirming that the absorption of the acid anhydride group disappeared by FT-IR measurement, it was cooled to room temperature. Next, the nitrogen from the nitrogen introduction tube was stopped in this flask and switched to introduction of dry air. While stirring, 26.0 parts of GMA (manufactured by NOF Corporation: glycidyl methacrylate), hydroquinone 0.165 as a polymerization inhibitor. Part was added and reacted at 80 ° C. for 8 hours. After completion of the reaction, methyl ethyl ketone was added to this solution to adjust the solid content to 50.0% to obtain an active energy ray-curable resin 1 solution.
The active energy ray-curable resin 1 is a hydroxyl group-containing photosensitive resin (A-1), the ethylenically unsaturated group equivalent is 1803 g / eq, the polystyrene-equivalent weight average molecular weight is 23500, and the resin solid content acid measured is actually measured. The value was 63 mgKOH / g.

[Active energy ray curable resin 2]
In a 4-neck flask equipped with a stirrer, reflux condenser, nitrogen inlet tube, inlet tube, and thermometer, 60.8 parts of bisphenol A, 43.4 parts of YD8125 (manufactured by Nippon Steel Chemical Co., Ltd., bisphenol A type epoxy compound) , EX861 (manufactured by Nagase ChemteX Corporation: polyethylene glycol diglycidyl ether) 145.8 parts, 1.25 parts of triphenylphosphine as a catalyst, 1.25 parts of DMBA, 250 parts of toluene as a solvent, and stirred under a nitrogen stream However, the temperature was raised to 110 ° C. and the reaction was performed for 8 hours to obtain a hydroxyl group-containing resin. Next, 49.8 parts of Ricacid SA (manufactured by Shin Nippon Rika Co., Ltd .: succinic anhydride) was added as an acid anhydride and reacted at 110 ° C. for 4 hours. After confirming that the absorption of the acid anhydride group disappeared by FT-IR measurement, it was cooled to room temperature. Next, the nitrogen from the nitrogen introduction tube was stopped in this flask and switched to introduction of dry air, while stirring, 41.1 parts of GMA (manufactured by NOF Corporation: glycidyl methacrylate), hydroquinone 0.17 as a polymerization inhibitor. Part was added and reacted at 80 ° C. for 8 hours. After completion of the reaction, 26.0 parts of Ricacid SA (manufactured by Shin Nippon Rika Co., Ltd .: succinic anhydride) was added as an acid anhydride to a flask in which dry air was introduced, and reacted at 80 ° C. for 4 hours. After confirming that the absorption of the acid anhydride group disappeared by FT-IR measurement, it was cooled to room temperature. Methyl ethyl ketone was added to this solution to adjust the solid content to 50.0% to obtain an active energy ray-curable resin 2 solution.
The active energy ray-curable resin 2 is a carboxyl group-containing photosensitive resin (A-2), the ethylenically unsaturated group equivalent is 1269 g / eq, the polystyrene-equivalent weight average molecular weight is 20200, and the acid content of the resin solid content by actual measurement The value was 73 mg KOH / g.

[Active energy ray curable resin 3]
A four-necked flask equipped with a stirrer, reflux condenser, nitrogen inlet pipe, inlet pipe, thermometer, bisphenol A type epoxy having an epoxy equivalent of 650, a softening point of 81.1 ° C., and a melt viscosity (150 ° C.) of 12.5 poise 371 parts of resin, 925 parts of epichlorohydrin, and 463 parts of dimethyl sulfoxide were added and dissolved uniformly, and then 52.8 parts of 98.5% aqueous sodium hydroxide solution was added at 70 ° C. over 100 minutes with stirring. After the addition, the reaction was further carried out at 70 ° C. for 3 hours. Subsequently, most of the excess unreacted epichlorohydrin and dimethyl sulfoxide are distilled off under reduced pressure, the reaction product containing by-product salt and dimethyl sulfoxide is dissolved in 750 parts of methyl isobutyl ketone, and further 10 parts of 30% aqueous sodium hydroxide solution. And reacted at 70 ° C. for 1 hour. After completion of the reaction, washing was performed twice with 200 parts of water. After separation of oil and water, methyl isobutyl ketone is recovered by distillation from the oil layer, and an epoxy resin having an epoxy equivalent of 287, a hydrolyzable chlorine content of 0.07%, a softening point of 64.2 ° C., and a melt viscosity (150 ° C.) of 7.1 poise. 340 parts were obtained.

Into a four-necked flask equipped with another stirrer, reflux condenser, nitrogen inlet pipe, inlet pipe and thermometer, 287 parts of this epoxy resin was added, and further 72 parts of acrylic acid, 0.3 part of methylhydroquinone, cyclohexanone 194 The reaction mixture was dissolved by heating and stirring at 90 ° C. Subsequently, the reaction liquid was cooled to 60 ° C., 1.7 parts of triphenylphosphine was added, and the reaction was performed at 100 ° C. for about 32 hours in the presence of oxygen to obtain a reaction product having an actually measured acid value of 1 mgKOH / g. Next, 78 parts of succinic anhydride and 42 parts of cyclohexanone were added thereto and reacted at 95 ° C. for about 6 hours. Cyclohexanone was added to this solution to adjust the solid content to 50.0% to obtain an active energy ray-curable resin 3 solution.
The active energy ray-curable resin 3 is a carboxyl group-containing photosensitive resin whose main skeleton is a bisphenol A type epoxy resin, the ethylenically unsaturated group equivalent is 450 g / eq, the polystyrene-equivalent weight average molecular weight is 7400, and the molecular weight distribution. The acid value of the resin solid content by 2.23 and actual measurement was 100 mgKOH / g.

  The physical properties of the active energy ray curable resins 1 to 3 are shown in Table 1.

Table 2 shows the physical property values of the black colorants 1 to 3.

Thermosetting resin: Urethane resin (acid value = 10 mg KOH / g, amine value = 0.1 mg KOH / g) Active energy ray polymerization initiator manufactured by Toyochem Co., Ltd .: 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide “ "Irgacure TPO" BASF sensitizer: 2,4-diethylthioxanthone "DETX-S" Nippon Kayaku thermosetting agent 1: IPDI nurate type MEK oxime block isocyanate compound "Desmodur BL-4265SN" (isocyanate equivalent = 337 g / eq) Thermosetting agent manufactured by Sumika Covestro Urethane Co., Ltd. 2: HDI adduct type MEK oxime block isocyanate compound “Duranate E402-B80B” (isocyanate equivalent = 560 g / eq) Thermosetting agent manufactured by Asahi Kasei Chemicals Co., Ltd. 3: Bisphenol A Epoxy compound “jER1001” (epoxy equivalent = 189 g / eq) manufactured by Mitsubishi Chemical Corporation inorganic filler 1: hydrophobic silica “SS50F (primary average particle size 25 nm)” Tosoh Silica Co., Ltd. inorganic filler 2: hydrophilic silica “AEROSILR200” (Average primary particle size 12 nm) “Inorganic filler 3 manufactured by Aerosil Co., Ltd .: Commercial ultrafine talc flame retardant having an average particle size of 3.8 μm: Aluminum phosphinate“ Exorit OP935 ”manufactured by Clariant

<Production of electromagnetic shielding sheet>
100 parts of thermosetting resin, 450 parts of conductive fine particles (dendritic particle D50 using copper as the core and silver as the coating layer D50 average particle size = 11.0 μm, manufactured by Fukuda Metal Foil Powder Industry Co., Ltd.), curing agent 15 parts of “JER828” (bisphenol A type epoxy compound epoxy equivalent = 189 g / eq, manufactured by Mitsubishi Chemical) and 2.0 parts of “Chemite PZ-33” (aziridine compound, manufactured by Nippon Shokubai Co., Ltd.) Then, a mixed solvent of toluene: isopropyl alcohol (weight ratio 2: 1) was added so that the nonvolatile content concentration was 40% by weight, and the mixture was stirred with a disper for 10 minutes to obtain a conductive resin composition. Next, the conductive resin composition was coated on a peelable sheet using a bar coater so that the dry thickness was 10 μm, and further dried in an electric oven at 100 ° C. for 2 minutes to obtain a conductive layer. .

  Separately, 100 parts of thermosetting resin, 15 parts of “JER828” (bisphenol A type epoxy compound epoxy equivalent = 189 g / eq, manufactured by Mitsubishi Chemical Corporation) as a curing agent, and “Chemite PZ-33” (aziridine compound, Nippon Shokubai) Insulating resin composition by adding a mixed solvent of toluene: isopropyl alcohol (weight ratio 2: 1) to a non-volatile content concentration of 40% by weight and stirring with a disper for 10 minutes. I got a thing. This insulating resin composition was coated on a peelable sheet using a bar coater so as to have a dry thickness of 15 μm, and further dried in an electric oven at 100 ° C. for 3 minutes to obtain an insulating layer. Furthermore, the electromagnetic wave shielding sheet was obtained by bonding together a conductive layer and an insulating layer with a laminator.

[Example 1]
100 parts by weight of active energy ray curable resin 1, 10 parts by weight of flame retardant, 3 parts by weight of black colorant 1 are charged into a container, and methyl ethyl ketone: methyl polyglycol = 1: 1 mixed so that the solid content is 50%. A solvent was added and dissolved and mixed uniformly. This was dispersed using a horizontal sand mill DYNO-MILL (manufactured by Shinmaru Enterprise Co., Ltd.) until the particle diameter by a grind gauge was less than 10 μm. Next, 100 parts by weight of the active energy ray-curable resin 1 of the dispersion coating liquid, 2 parts by weight of the active energy ray polymerization initiator, 0.5 parts by weight of the sensitizer, 5 parts by weight of the thermosetting agent 1, An active energy ray-curable resin composition was obtained by adding 35 parts by weight of thermosetting agent 2 and mixing them uniformly.

  The obtained active energy ray-curable resin composition was coated with a transparent substrate (polyethylene terephthalate (PET) film (Emblet S25, thickness 25 μm, 320 μm) so that the thickness after drying using a doctor blade was 45 μm. The maximum light transmittance of ˜700 nm was 60% or more, manufactured by Unitika Ltd.)) and dried at 100 ° C. for 5 minutes, and then cooled to room temperature to form a resin layer. Further, the obtained resin layer was separated into a release sheet (polyethylene terephthalate (PET) film coated with a release agent (PET75-AL5, thickness 75 μm, maximum light transmittance of 320 to 700 nm, 60% or more, manufactured by Lintec)) To obtain a dry resist film sandwiched between the transparent substrate and the peelable sheet.

[Examples 2-15, Comparative Examples 1-3]
Except having changed the composition of the active energy ray-curable resin composition as described in Table 1, the dry resist films of Examples 2 to 15 and Comparative Examples 1 to 3 were obtained in the same manner as in Example 1. It was.

The following physical properties of the obtained dry resist film were evaluated.
<Storage modulus, glass transition temperature (Tg)>
The storage elastic modulus and Tg of the cured product of the resin layer of the dry resist film were determined by the following methods.
Two samples were prepared by peeling off the peelable sheet from the dry resist film with a substrate, and the exposed resin layer surfaces were bonded together with a vacuum laminator (small pressure type vacuum laminator V-130 manufactured by Nichigo Morton). The vacuum lamination conditions were a heating temperature of 60 ° C., a vacuum time of 60 seconds, a vacuum ultimate pressure of 2 hPa, a pressure of 0.4 MPa, and a pressurization time of 60 seconds. Subsequently, active energy rays were irradiated on both surfaces of the obtained sample.
The irradiation conditions of active energy rays were as follows. Contact exposure method using Mylar film (125 μm PET film), use of short arc UV lamp, integrated exposure 500 mJ / cm ² . Next, one transparent substrate was peeled off, and the exposed resin layer surface was developed with a 1% aqueous sodium carbonate solution at a liquid temperature of 30 ° C. for 60 seconds, washed with water, and dried in a box oven at 100 ° C. for 2 minutes. Heat cured in a 160 ° C. box oven for 1 hour, cut into a size of 5 mm wide × 30 mm long, peeled off the other transparent substrate, and obtained a measurement sample for the cured product of the resin layer of the dry resist film It was. Subsequently, using a dynamic elastic modulus measuring apparatus DVA-200 (made by IT Measurement & Control Co., Ltd.), a deformation mode “tension”, a frequency of 10 Hz, a heating rate of 10 ° C./min, a measurement temperature range of 30 to 30 for a measurement sample. The measurement was performed at 300 ° C., and the storage elastic modulus and Tg at 85 ° C. were obtained.

<Light transmittance>
The peelable sheet of the dry resist film with the substrate was peeled off, and the light transmittance at a wavelength of 300 to 700 nm was measured using a spectrophotometer U-4100 (manufactured by Hitachi High-Technologies Corporation). At the time of measurement, the dry resist film was set so that incident light of each wavelength was incident from the transparent substrate.

<Migration test>
The migration test will be described with reference to FIG. By etching a laminate of a 12 μm thick copper foil and a 25 μm thick polyimide film, line / space = 0.05 mm / 0.05 mm on the polyimide film 1 as shown in the plan view of FIG. The cathode electrode comb signal wiring 2 having the cathode electrode connection point 2 'and the anode electrode comb signal wiring 3 having the anode electrode connection point 3' were formed. Next, the peelable sheet is peeled off from the dry resist film with the base material, and as shown in the plan view of FIG. 1 (2), the comb signal wiring 2 for the cathode electrode and the comb signal wiring 3 for the anode electrode are covered, and the cathode electrode The resin layer surface was overlaid so that the vicinity of the connection point 2 ′ and the vicinity of the anode electrode connection point 3 ′ were exposed, and the dry resist film was bonded to the laminate by vacuum lamination. The vacuum lamination conditions were a heating temperature of 60 ° C., a vacuum time of 60 seconds, a vacuum ultimate pressure of 2 hPa, a pressure of 0.4 MPa, and a pressurization time of 60 seconds. Furthermore, it exposed so that it might become the contact exposure system which uses a mylar film (125 micrometer PET film) from the transparent base material side of a dry resist film with a base material, use of a short arc UV lamp, and an integrated exposure amount of 500 mJ / cm < ² >. Subsequently, the PET mylar sheet and the transparent substrate were peeled off, and developed with a developing machine for 60 seconds (developer: sodium carbonate aqueous solution with a concentration of 1%, liquid temperature 30 ° C., spray pressure 0.2 MPa). After development, washed with water, dried in a box oven at 100 ° C. for 2 minutes, and then thermally cured (post-cure) the resin layer of the dry resist film with a hot air dryer at 160 ° C. for 1 hour. Got.
Further, the peelable sheet was peeled off from the conductive layer side of the obtained electromagnetic wave shielding sheet, and the exposed conductive layer surface was bonded onto the cover coat layer 4 so that a sample laminated as shown in the plan view of FIG. Obtained. In the obtained sample, the conductive layer 5b is electrically connected to the comb signal wiring 2 for the cathode electrode as described in the AA ′ sectional view of the sample shown in FIG.

The obtained sample was hot-pressed under the conditions of 150 ° C., 2.0 MPa, and 30 min to cure the thermosetting resin. Next, the anode was connected to the anode electrode connection point 3 ′ and the cathode electrode was connected to the cathode electrode connection point 2 ′ in an atmosphere of 85 ° C. to 85% RH (relative humidity). Application was continued for 500 hours. And the change of the resistance value until 500 hours passed was measured continuously. The “leak touch” described below means that there is a dielectric breakdown due to a short circuit, the resistance decreases instantaneously, and a current flows. If there is no leak touch, insulation does not decrease. The evaluation criteria are as follows.

A: Resistance value after 500 hours is 1 × 10 ⁷ Ω or more and no leak touch. Very good ○: Resistance value after 500 hours is 1 × 10 ⁷ Ω or more, and there is one leak touch. Good Δ: The resistance value after 500 hours passed is 1 × 10 ⁷ Ω or more, and there are two leak touches. There is no problem in practical use.
×: Resistance value after 500 hours is less than 1 × 10 ⁷ Ω, or
The resistance after 500 hours is 1 × 10 ⁷ Ω or more, and there are 3 or more leak touches. Not practical.

<Heat-resistant crimpability>
The peelable sheet of the dry resist film with the substrate was peeled off, and vacuum-laminated with a polyimide film (“Kapton 200EN” manufactured by Toray DuPont). Thereafter, in the same procedure as in the migration test, exposure, development and post-cure were performed to prepare a polyimide film with a cover coat layer (sample a). Next, a laminate (sample b) composed of an electromagnetic wave shield film / cover coat layer / polyimide film was prepared by attaching an electromagnetic wave shield sheet to the cover coat layer surface of sample a in the same procedure as in the migration test and hot pressing.
Sample a and sample b were cut by ion beam irradiation from the polyimide film side using a cross section polisher (manufactured by JEOL Ltd., SM-09010) to form a cross section of the cover coat layer. Using the laser microscope VK-X100 (manufactured by Keyence Corporation) and VK-H1XV (manufactured by Keyence Corporation) as an observation application, the thickness of the cover coat layer of sample a and sample b is measured, and the rate of change in thickness is obtained from the following formula. It was.

Thickness change rate = 100− (cover coat layer thickness of sample b / cover coat layer thickness of sample a × 100)

Based on the rate of change in thickness, the heat-resistant press bonding property was evaluated according to the following evaluation criteria.
A: Less than 2%. Good.
○: 2% or more and less than 5%. There is no problem in practical use.
X: 5% or more. Not practical.

<Flexibility>
The peelable sheet of the dry resist film with the base material was peeled off, and vacuum-laminated onto a circuit board with line / space = 0.05 mm / 0.05 mm. Thereafter, in the same procedure as in the migration test, exposure, development, and post-cure were performed to form a circuit board with a cover coat layer.
The circuit board with the cover coat layer is bent 180 degrees so that the cover coat layer is on the outside, and a weight of 500 g is placed on the bent portion for 5 seconds, and then the bent portion is returned to the original flat state and again 500 g The weight was placed for 5 seconds, and this was bent once. Whether or not a crack was generated in the cover coat layer was observed with a microscope “VHX-900” manufactured by Keyence Co., Ltd., and the number of times that the cover coat layer was bent without a crack was evaluated.
The number of folds until a crack was generated in a fold portion subjected to a load of 500 g was counted. The evaluation criteria are as follows.

A: 5 or more times. Very good.
○: 3 times or more and less than 5 times. Good Δ: 2 times or more and less than 3 times. There is no problem in practical use.
X: Less than 2 times. Not practical.

<Blackness>
The peelable sheet of the dry resist film with a substrate was peeled off, and the optical density was measured with a Macbeth densitometer (GRETAGD200-II) to obtain the optical density (OD) at a film thickness of 45 μm. The evaluation criteria are as follows.

A: 1.5 or more. Good.
○: 1 or more and less than 1.5. There is no problem in practical use.
X: Less than 1. Not practical.

<Patternability>
The peelable sheet was peeled off from the dry resist film with the base material, and vacuum-laminated on the copper surface of a copper-clad laminate (manufactured by Nippon Steel Chemical Co., Ltd .: ESPANEX MC-18-25-00FRM). The vacuum lamination conditions were a heating temperature of 60 ° C., a vacuum time of 60 seconds, a vacuum ultimate pressure of 2 hPa, a pressure of 0.4 MPa, and a pressurization time of 60 seconds. 120 μm PET Mylar sheet from the transparent substrate side of the dry resist film / development after exposure so that the accumulated light amount is 500 mJ / cm ^{2 through} a photomask in which circular black portions having a diameter of 0.1 mm are arranged at equal intervals on one surface The developing was carried out for 60 seconds under the following development conditions (1% Na ₂ CO ₃ aqueous solution having a liquid temperature of 30 ° C. and a spray pressure of 0.2 MPa).
After development, the plate was washed with water, dried in a box oven at 100 ° C. for 2 minutes, and then heat-cured (post-cure) for 1 hour in a hot air dryer at 160 ° C. to obtain a copper clad laminate with a cover coat layer having an opening. . Ten openings of the cover coat layer were observed with a scanning electron microscope (JSM-7800F manufactured by JEOL Ltd.), the diameter was measured, the average value was calculated, and evaluated as follows.

[Pattern accuracy T (%)]
= [Average value of diameter of opening] / [Black diameter of photomask] × 100

It can be said that the higher the pattern accuracy, the better the patterning because patterning can be performed as designed. Using this pattern accuracy, the patterning property was judged according to the following criteria.

◎ ・ ・ ・ Pattern accuracy T is 90% or more ○ ・ ・ ・ Pattern accuracy T is 70% or more and less than 90% Δ ・ ・ ・ Pattern accuracy T is 50% or more and less than 70% × ・ ・ ・ Pattern accuracy T is Less than 50%

  From the results of Tables 3 and 4, it was confirmed that the connection reliability was improved in the circuit in which the electromagnetic wave shield sheet was bonded by improving the ion migration resistance.

DESCRIPTION OF SYMBOLS 1 Polyimide film 2 Comb signal wiring 2 'for cathode electrodes Cathode electrode connection point 3 Comb signal wiring 3' for anode electrodes Anode electrode connection point 4 Cover coat layer 5 Electromagnetic wave shielding sheet 5a Insulating layer 5b Conductive layer

Claims (9)

A dry resist film for a printed wiring board comprising an electromagnetic wave shielding sheet, a cover coat layer formed from a dry resist film, and a substrate having a signal wiring and an insulating substrate,
Having a resin layer formed from an active energy ray-curable resin composition containing an active energy ray-curable resin, an active energy ray polymerization initiator, and a black colorant;
The cured product of the resin layer has a storage elastic modulus at 85 ° C. of 1.0E + 07 to 1.0E + 10 Pa.   2. The dry resist film according to claim 1, wherein an average light transmittance at a wavelength of 450 nm to 700 nm is 10% or less, and an average light transmittance at a wavelength of 300 to 450 nm is 5% or more.   The dry resist film according to claim 1 or 2, wherein the black colorant contains titanium black.   The dry resist film according to any one of claims 1 to 3, further comprising hydrophobic silica fine particles.   Printed wiring with an electromagnetic wave shielding sheet, comprising: an electromagnetic wave shielding sheet; a cover coat layer formed from the dry resist film according to any one of claims 1 to 4; and a substrate having a signal wiring and an insulating substrate. Board.   The printed wiring board with an electromagnetic wave shielding sheet according to claim 5, wherein the cover coat layer has an opening having an opening diameter of 0.05 to 1 mm.   An electronic device comprising the printed wiring board with an electromagnetic wave shielding sheet according to claim 5. Forming a signal wiring on an insulating substrate;
A process of laminating a dry resist film on the signal wiring;
A step of exposing a dry resist film and thermally curing after development to form a cover coat layer having an opening;
Laminating an electromagnetic wave shielding sheet on the cover coat layer, and hot pressing,
A method of manufacturing a printed wiring board with an electromagnetic wave shielding sheet manufactured by:
The dry film has a resin layer formed from an active energy ray-curable resin composition containing an active energy ray-curable resin, an active energy ray polymerization initiator, and a black colorant,
The cured product of the resin layer is a method for producing a printed wiring board with an electromagnetic wave shielding sheet, which has a storage elastic modulus at 85 ° C. of 1.0E + 07 to 1.0E + 10 Pa. The method for producing a printed wiring board with an electromagnetic wave shielding sheet according to claim 8, wherein the cover coat layer has an opening having an opening diameter of 0.05 to 1 mm.