KR20180103101A - Dry film and printed wiring board - Google Patents

Abstract

A dry film having a resin layer excellent in filling property and flatness, and a cured product obtained by curing the dry film. And a resin layer comprising an epoxy resin formed on the film, wherein the resin layer has a melt viscosity of 60 to 5500 dPa 占 퐏 at 100 占 폚 and a storage modulus of the resin layer of 80 To 5500 Pa, and the resin layer contains at least a liquid epoxy resin as the epoxy resin, and the content of the liquid epoxy resin is less than 60 mass% per the total mass of the epoxy resin.

Description

Dry film and printed wiring board

The present invention relates to a dry film and a printed wiring board, and more particularly to a dry film having a resin layer excellent in the filling property and the flatness, and a printed wiring board comprising a cured product obtained by curing the dry film.

BACKGROUND ART [0002] Dry films have been conventionally used as a protective film for a solder resist or an interlayer insulating layer formed on a printed wiring board used in electronic equipment or the like, or as means for forming an insulating layer (for example, Patent Documents 1 to 3). The dry film has a resin layer obtained by applying a curable resin composition having desired properties onto a carrier film and then drying the resin film. In general, a protective film for protecting a surface opposite to the carrier film is further laminated And is being distributed to the market. The protective film or insulating layer as described above can be formed on the printed wiring board by laminating the resin layer of the dry film to a substrate having a circuit pattern and then performing patterning or curing treatment.

Japanese Patent Application Laid-Open No. 7-15119 (claims) Japanese Patent Laid-Open No. 2002-162736 (claims) Japanese Patent Laying-Open No. 2003-131366 (claims)

When the resin layer of the dry film is laminated on the substrate, the resin layer may not be sufficiently filled with the unevenness of the circuit pattern on the substrate, and bubbles may be generated between the resin layer and the substrate. The adhesion of the substrate may be impaired.

Further, in order to make the outer surface of the resin layer of the dry film after lamination flat, vacuum laminates or presses were carried out, but the flatness was not sufficient because the unevenness of the circuit pattern on the substrate was transferred to the outer surface. Particularly, in recent years, with the trend of shortening the thickness of electronic devices, the printed wiring boards are also thinned, and the resin layer of the dry film is required to be further thinned. This makes it difficult to obtain the filling property of the resin layer on the substrate and the flatness of the outer surface of the resin layer even if vacuum laminating or pressing is performed.

It is therefore an object of the present invention to provide a printed wiring board comprising a dry film having a resin layer excellent in filling property and flatness, and a cured product obtained by curing the dry film.

The inventors of the present invention have conducted intensive studies in view of the above. As a result, they have found that a polyurethane resin having a melt viscosity at 100 ° C. of 60 to 5500 dPa · s, a storage elastic modulus at 100 ° C. of 10 to 5500 Pa and a liquid epoxy resin in an amount of 60% By weight of a dry film having a resin layer containing less than 0.01% by weight of the total weight of the resin composition. The present invention has been accomplished based on these findings.

That is, the dry film of the present invention is a dry film having a film and a resin layer containing an epoxy resin formed on the film, wherein the resin layer has a melt viscosity of 60 to 5500 dPa · s at 100 ° C, Wherein the resin layer has a storage elastic modulus at 100 占 폚 of 80 to 5500 Pa, the resin layer contains at least a liquid epoxy resin as the epoxy resin,

And the content of the liquid epoxy resin is less than 60 mass% with respect to the total mass of the epoxy resin.

In the dry film of the present invention, it is preferable that the amount of the residual solvent in the resin layer is 1.0 to 7.0 mass%.

The dry film of the present invention contains at least two kinds of organic solvents selected from the group consisting of N, N-dimethylformamide, toluene, cyclohexanone, aromatic hydrocarbons having 8 or more carbon atoms and methyl ethyl ketone in the resin layer .

The dry film of the present invention is characterized in that the resin layer contains at least one semi-solid epoxy resin selected from the group consisting of bisphenol A epoxy resin, naphthalene epoxy resin and phenol novolak epoxy resin as the epoxy resin .

In the dry film of the present invention, it is preferable that the resin layer contains a filler, and the average particle diameter of the filler is 0.1 to 10 mu m.

In the dry film of the present invention, it is preferable that the resin layer contains a filler and the content of the filler is 40 to 80 mass% per the total amount of the resin layer (when the resin layer contains a solvent, the total amount excluding the solvent).

In the dry film of the present invention, the resin layer includes a filler, and the filler is selected from the group consisting of a silane coupling agent having an epoxy group, a silane coupling agent having an amino group, a silane coupling agent having a mercapto group, a silane coupling agent having an isocyanate group, A silane coupling agent having a silyl group, a silane coupling agent having a silyl group, a silane coupling agent having a styryl group, a silane coupling agent having an acryl group, and a silane coupling agent having a methacrylic group.

The cured product of the present invention is characterized by being obtained by curing the resin layer of the dry film.

The printed wiring board of the present invention is characterized by comprising the cured product.

According to the present invention, it is possible to provide a printed wiring board comprising a dry film having a resin layer excellent in filling property and flatness, and a cured product obtained by curing the dry film.

BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic sectional view schematically showing one embodiment of the laminated structure of the present invention. Fig.
2 is a schematic sectional view schematically showing another embodiment of the laminated structure of the present invention.
3 is a schematic side view showing two test tubes used for liquid phase determination of an epoxy resin.

<Dry Film>

The dry film of the present invention is a dry film having a film and a resin layer formed on the film, wherein the resin layer has a melt viscosity of 60 to 5500 dPa 占 퐏 at 100 占 폚 and a storage elastic modulus of the resin layer of 100 占 폚 Is 80 to 5500 Pa, the resin layer contains at least a liquid epoxy resin as the epoxy resin, and the content of the liquid epoxy resin is less than 60 mass% with respect to the total amount of the epoxy resin. Although the detailed mechanism is not clear, by adjusting both the melt viscosity and the storage elastic modulus of the resin layer to the above range and making the ratio of the liquid epoxy resin contained in the resin layer to the total amount of the epoxy resin less than 60 mass% The flatness is remarkably improved.

Further, according to the dry film of the present invention, since a cured film having a flat surface can be formed, when a plating resist is formed thereon, the line of the plating resist can be prevented from being short-circuited and defective. That is, according to the dry film of the present invention, it is possible to obtain a cured product excellent in the formability of the plating resist. This makes it possible to form a high-precision conductive circuit on the resin layer.

On the other hand, when the melt viscosity of the resin layer of the dry film is less than 60 dPa · s at 100 ° C., or when the storage elastic modulus of the resin layer is less than 80 Pa at 100 ° C., bubbles are likely to be entangled during laminating of the dry film, It becomes difficult to obtain. On the other hand, when the melt viscosity of the resin layer exceeds 5500 dPa 에서 at 100 캜 or when the storage modulus of the resin layer exceeds 10000 캜 at 5500 Pa, it becomes difficult to obtain the flatness of the outer surface of the resin layer. The melt viscosity of the resin layer is preferably 400 to 3000 dPa · s at 100 ° C., and the storage elastic modulus of the resin layer at 100 ° C. is preferably 100 to 3500 Pa. Further, even when the content of the liquid epoxy resin is 60 mass% or more with respect to the total amount of the epoxy resin, it becomes difficult to obtain the landfill of the dry film and the flatness of the outer surface of the resin layer.

The melt viscosity of the resin layer is preferably 3,000 dPa 占 퐏 or less at 100 占 폚 and the storage elastic modulus of the resin layer is preferably 3000 占 폚 or less at 100 占 폚 because the flatness and the forming ability of the plating resist are excellent.

When the melt viscosity of the resin layer is 100 dPa 占 퐏 or more at 100 占 폚 and the storage elastic modulus of the resin layer is 100 Pa or more at 100 占 폚, bubbles are hardly entangled at the time of laminating,

It is more preferable that the resin layer has a melt viscosity of 500 to 3,000 dPa 占 퐏 at 100 占 폚 and a storage elastic modulus of the resin layer at 100 占 폚 of 500 to 3,000 Pa.

The method of adjusting the melt viscosity and the storage modulus of the resin layer is not particularly limited, but can be easily adjusted by selecting the amount of the filler, the particle diameter, the kind, and the like as described later. It can also be adjusted by a thermosetting component or a curing agent.

1 is a schematic cross-sectional view showing one embodiment of the dry film of the present invention. The dry film 11 is a two-layer structure in which a resin layer 12 is formed on a film 13. 2, in order to form the resin layer 22 on the first film 23 and protect the surface of the resin layer 22, the second film 24 is further laminated The dry film 21 may have a three-layer structure. If necessary, another resin layer may be formed between the film and the resin layer.

[Resin Layer]

The resin layer of the dry film of the present invention is generally referred to as a B-stage state and is obtained from a curable resin composition. Specifically, the resin layer of the dry film is obtained by applying the curable resin composition to a film and then drying it. The curing resin composition is not particularly limited in kind or amount of other components as long as the above melt viscosity, storage elastic modulus, and blending amount of liquid epoxy resin are satisfied. The film thickness of the resin layer is not particularly limited and may be, for example, from 1 to 200 m after drying, but the effect of the present invention can be remarkably obtained as the film thickness of the resin layer becomes thinner. Concretely, it is preferable that the film thickness of the resin layer is preferably 30 占 퐉 or less, more preferably 20 占 퐉 or less, and further preferably 15 占 퐉 or less because the effect of the present invention becomes easier to exhibit.

The resin layer includes an epoxy resin. The epoxy resin is a resin having an epoxy group, and all conventionally known ones can be used. A bifunctional epoxy resin having two epoxy groups in the molecule, and a polyfunctional epoxy resin having a large number of epoxy groups in the molecule. It may also be a hydrogenated epoxy resin. The resin layer contains, as the epoxy resin, a liquid epoxy resin in an amount of less than 60% by mass based on the total mass of the epoxy resin. The resin layer contains at least one of a solid epoxy resin and a semi-solid epoxy resin as an epoxy resin other than the liquid epoxy resin. In the present specification, the solid epoxy resin refers to an epoxy resin which is solid at 40 占 폚, and the semi-solid epoxy resin refers to an epoxy resin which is solid at 20 占 폚 and liquid at 40 占 폚, Resin.

The determination of the liquid phase shall be made in accordance with the Attachment 2 (Method for Confirmation of Liquid Phase) of the Ordinance of the Ministry of Justice (1989 Self-government Act No. 1) on the Testing and Characteristics of Dangerous Goods.

(1) Device

Constant temperature bath:

Use a stirrer, heater, thermometer, automatic thermostat (temperature controllable to ± 0.1 ℃) and a depth of 150mm or more.

In the determination of the epoxy resin used in the examples described later, a combination of a low-temperature constant-temperature water bath (type BU300) and a charging-type thermostat thermometer (type BF500) manufactured by Yamato Kagaku Co., (Type BF500) to the set temperature (20 ° C or 40 ° C) and put the thermometer (type BF500) at the set temperature ± 0.1 ° C. , But any device capable of performing the same adjustment can be used.

examiner:

As shown in Fig. 3, the test tube is made of a plain cylindrical transparent glass having an inner diameter of 30 mm and a height of 120 mm. Markers 31 and 32 are attached to portions of 55 mm and 85 mm from the bottom of the tube, A rubber stopper 33b having a hole for inserting and supporting a thermometer at the center is sealed in the same size with the same size as the test tube for liquid phase determination 30a sealed with a rubber stopper 33a. And a temperature measurement test tube 30b in which a thermometer 34 is inserted into the rubber stopper 33b is used. Hereinafter, a line drawn at a height of 55 mm from the bottom of the tube is referred to as "A line", and a line at a height of 85 mm from the bottom of the tube is referred to as "B line".

As the thermometer 34, a temperature range of 0 to 50 占 폚 is to be measured, while a thermometer 34 (SOP-58 scale range: 20 to 50 占 폚) specified in JIS B7410 (1982) Anything that can be done.

(2) Procedure for conducting tests

A sample left to stand for 24 hours or more under atmospheric pressure at a temperature of 20 ± 5 ° C was placed in a liquid phase determination test tube 30a shown in Figure 3 (a) and a temperature measurement test tube 30b shown in Figure 3 (b) Put in line. The two test tubes 30a and 30b are placed upright in the low-temperature and constant-temperature water bath so that the line B is below the water surface. Make sure that the bottom of the thermometer is 30 mm below the A line.

After the sample temperature reaches the set temperature ± 0.1 ° C, the sample remains unchanged for 10 minutes. After 10 minutes, the liquid test tube (30a) was taken out of the low temperature and constant temperature water bath, immediately dropped on a horizontal test stand, and the time when the tip of the liquid surface in the test tube moved from line A to line B was measured with a stopwatch And records it. The sample is judged to be liquid if the time measured at the set temperature is 90 seconds or less, and if it exceeds 90 seconds, it is determined to be solid.

Examples of the solid epoxy resin include naphthalene type epoxy resins such as HP-4700 (naphthalene type epoxy resin) manufactured by DIC, EXA4700 (tetrafunctional naphthalene type epoxy resin) manufactured by DIC, NC-7000 (polyfunctional solid epoxy resin containing naphthalene skeleton) manufactured by Nippon Kayaku Co., Epoxy resin; Epoxides (phenol type epoxy resin) of phenols such as EPPN-502H (trisphenol epoxy resin) manufactured by Nippon Kayaku Co., Ltd. and condensates of aromatic aldehyde having phenolic hydroxyl group; Dicyclopentadiene aralkyl type epoxy resins such as Epiclon HP-7200H (multifunctional solid epoxy resin containing dicyclopentadiene skeleton) manufactured by DIC Corporation; Biphenylaralkyl type epoxy resins such as NC-3000H (polyfunctional solid epoxy resin containing biphenyl skeleton) manufactured by Nihon Kayakusa; Biphenyl / phenol novolak type epoxy resins such as NC-3000L manufactured by Nihon Kayakusa; Novolak type epoxy resins such as Epiclon N660 manufactured by DIC, Epiclon N690, and EOCN-104S manufactured by Nippon Kayaku Co., Ltd.; Biphenyl-type epoxy resins such as YX-4000 manufactured by Mitsubishi Chemical Corporation; A phosphorus-containing epoxy resin such as TX0712 made by Sumitomo Chemical Co., Ltd.; Tris (2,3-epoxypropyl) isocyanurate such as TEPIC manufactured by Nissan Kagaku Kogyo Co., Ltd., and the like.

Examples of the semi-solid epoxy resin include Epiclon 860, Epiclon 900-IM, Epiclon EXA-4816, Epiclon EXA-4822 manufactured by DIC, Araldite AER280 manufactured by Asahi Chiba, A bisphenol A type epoxy resin such as jER834, jER872 manufactured by Kagaku Co., and ELA-134 manufactured by Sumitomo Chemical Co., Ltd.; Naphthalene-type epoxy resins such as Epiclon HP-4032 manufactured by DIC Corporation; And phenol novolak type epoxy resins such as Epiclon N-740 manufactured by DIC Corporation.

As the semi-solid epoxy resin, at least one selected from the group consisting of bisphenol A type epoxy resin, naphthalene type epoxy resin and phenol novolak type epoxy resin is preferably included. By including their semi-solid epoxy resin, the cured product has a high glass transition temperature (Tg), low CTE, and excellent crack resistance.

Examples of the liquid epoxy resin include epoxy resins such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, phenol novolak type epoxy resin, tert-butyl-catechol type epoxy resin, glycidylamine type epoxy resin, Epoxy resins, and alicyclic epoxy resins.

The epoxy resin may be used in combination of two or more. The blending amount of the epoxy resin is preferably 5 to 50 mass%, more preferably 5 to 40 mass%, and still more preferably 5 to 35 mass%, based on the entire resin layer of the dry film excluding the solvent. The content of the liquid epoxy resin is preferably 5 to 45% by mass, more preferably 5 to 40% by mass, and particularly preferably 5 to 30% by mass, based on the total mass of the epoxy resin.

The resin layer preferably contains a filler. By containing the filler, the heat characteristics of the dry film can be improved by matching the heat intensity with the conductor layer such as copper around the insulating layer. As the filler, conventionally known inorganic fillers and organic fillers can be used, and although not limited to specific ones, inorganic fillers that suppress curing shrinkage of the coating film and contribute to improvement in properties such as adhesion and hardness are preferable. Examples of the inorganic filler include barium sulfate, barium titanate, barium titanate zirconate, strontium titanate, calcium titanate, calcium zirconate, magnesium titanate, bismuth titanate, neodymium titanate, barium titanate tin, Clay, neobulk silica particles, boehmite, magnesium carbonate, calcium carbonate, titanium oxide, aluminum oxide, aluminum hydroxide, silicon nitride, aluminum nitride, aluminum nitride, And metallic powders such as copper, tin, zinc, nickel, silver, palladium, aluminum, iron, cobalt, gold and platinum.

Among these fillers, mention may be made of barium titanate, barium titanate, barium titanate, strontium titanate, calcium titanate, calcium zirconate, magnesium titanate, bismuth titanate, barium titanate neodymium, barium titanate tin, If it is used, it is preferable because the dielectric constant can be increased and the concealability of the circuit can be improved.

The inorganic filler is preferably spherical particles. The average particle diameter of the filler is preferably 0.1 to 10 mu m. In the present specification, the average particle diameter of the filler is not only the particle diameter of the primary particles but also the average particle diameter including the particle diameter of the secondary particles (aggregated particles). The average particle diameter can be obtained by a laser diffraction particle diameter distribution measuring apparatus. Nanotrac waves manufactured by Nikkiso Co., Ltd. and the like can be given as a measuring device by the laser diffraction method.

The inorganic filler is preferably surface-treated. As the surface treatment, surface treatment with a coupling agent is preferred. As the coupling agent, a silane coupling agent, a titanium coupling agent, a zirconium coupling agent, an aluminum coupling agent and the like can be used. Among them, a silane coupling agent is preferable.

As the silane coupling agent, a silane coupling agent having an epoxy group as an organic group, a silane coupling agent having an amino group, a silane coupling agent having a mercapto group, a silane coupling agent having an isocyanate group, a silane coupling agent having a vinyl group, A silane coupling agent having a methacryl group, a silane coupling agent having an acryl group, or the like can be used. In particular, a silane coupling agent having an epoxy group and a silane coupling agent having an amino group are preferable from the viewpoint of excellent adhesion with an underlayer circuit.

The inorganic filler may be surface-treated without introducing organic groups such as alumina treatment.

The surface-treated inorganic filler may be incorporated in the resin layer of the dry film in a surface-treated state. When the inorganic filler is surface-treated in the composition, However, it is preferable to mix an inorganic filler that has been surface-treated beforehand in adjusting the curable resin composition. By blending an inorganic filler that has been surface-treated in advance, the flatness after curing of the resin layer and the formation of the plating resist are further improved, and the dielectric tangent after the humidification is excellent. When surface treatment is carried out in advance, it is preferable to blend a preliminary dispersion liquid in which an inorganic filler is preliminarily dispersed in a solvent, and the surface-treated inorganic filler is preliminarily dispersed in a solvent, and the preliminary dispersion is added to the composition, It is more preferable to add the preliminary dispersion liquid to the composition after thoroughly surface-treating the preliminary dispersion liquid in the solvent.

Here, when the silica surface-treated with a silane coupling agent having a vinyl group in advance is blended, dielectric tangent after humidification is excellent. In addition, when alumina surface-treated with a silane coupling agent having a vinyl group in advance is mixed, heat radiation is excellent.

The blending amount of the filler is preferably 25 to 85% by mass, more preferably 40 to 85% by mass, based on the entire resin layer of the dry film excluding the solvent. When the compounding amount of the filler is 25 to 85% by mass, the filling property is excellent. When it is 25 mass% or more, the coefficient of linear expansion can be lowered, and the heat radiation property is excellent.

When two or more kinds of fillers are used in combination, it is preferable because flatness and formation of a plating resist are excellent. Here, when the filler includes a nanofiller having an average primary particle diameter of 100 nm or less, the filling efficiency of the filler can be increased. Thereby, the dielectric tangent after humidification can be lowered, the coefficient of linear expansion can be made smaller, and the crack resistance in a cooling / heating cycle after reflow can be improved.

The amount of the residual solvent in the resin layer is preferably 1.0 to 7.0 mass%, more preferably 3.0 to 5.0 mass%, still more preferably 3.5 to 4.5 mass%. When the residual solvent content is 7.0% by mass or less, the molar ratio at the time of thermosetting is suppressed and the surface flatness is improved. Further, the melt viscosity becomes too low to prevent the resin from flowing down, and the flatness is improved. When the amount of the residual solvent is 1.0% by mass or more, the fluidity at the time of lamination is good, and the flatness and the filling property are improved. When the residual solvent is 3.0 to 5.0% by mass, the handling properties and film properties of the dry film are excellent.

It is preferable that the resin layer contains at least two kinds of organic solvents selected from the group consisting of N, N-dimethylformamide, toluene, cyclohexanone, aromatic hydrocarbons having 8 or more carbon atoms, and methyl ethyl ketone. When a resin composition containing such an organic solvent is used for forming the resin layer, a drying margin is easily obtained. That is, the drying time can be increased, and the degree of freedom of the drying time is improved.

The curable resin composition is a thermosetting resin composition containing an epoxy resin such as a liquid epoxy resin. As a specific example thereof, a photocurable thermosetting resin composition containing a photocurable thermosetting resin composition, a thermosetting resin composition and a photopolymerization initiator, , A photo-curable thermosetting resin composition containing a photoacid generator, a negative-type photo-curable thermosetting resin composition and a positive photo-curable thermosetting resin composition, an alkali developing type photo-curable thermosetting resin composition, a solvent- A thermosetting resin composition, a swelling and peeling thermosetting resin composition, and a dissolution and peeling thermosetting resin composition, but is not limited thereto. Examples of the epoxy resin such as liquid epoxy resin include those exemplified as the epoxy resin contained in the resin layer.

(Photo-curable thermosetting resin composition)

As an example of the photocurable thermosetting resin composition, a resin composition containing a carboxyl group-containing resin and a photopolymerization initiator in addition to an epoxy resin will be described below.

The carboxyl group-containing resin can be made alkali-developable by including a carboxyl group. In addition to the carboxyl group, from the viewpoint of photocurability and resistance to development, it is preferable to have an ethylenically unsaturated bond in the molecule, but only a carboxyl group-containing water not having an ethylenically unsaturated bond may be used. When the carboxyl group-containing resin has no ethylenically unsaturated bond, it is necessary to use a compound having at least one ethylenic unsaturated bond (photosensitive monomer) in the molecule in order to make the composition photo-curable. As the ethylenically unsaturated bond, those derived from acrylic acid or methacrylic acid or a derivative thereof are preferable. Among the carboxyl group-containing resins, a carboxyl group-containing resin having a copolymerization structure, a carboxyl group-containing resin having a urethane structure, a carboxyl group-containing resin starting from an epoxy resin, and a carboxyl group- Specific examples of the carboxyl group-containing resin include the following compounds (any of oligomers or polymers) listed below.

(1) reacting a bifunctional or higher polyfunctional epoxy resin as described below with (meth) acrylic acid, reacting a hydroxyl group in the side chain with a dibasic acid anhydride such as phthalic anhydride, tetrahydrophthalic anhydride or hexahydrophthalic anhydride, A carboxyl group-containing photosensitive resin added thereto. Here, the bifunctional or higher polyfunctional epoxy resin is preferably a solid.

(2) a method in which a (meth) acrylic acid is reacted with a polyfunctional epoxy resin obtained by epoxidizing a hydroxyl group of a bifunctional epoxy resin as described below with epichlorohydrin, and a carboxyl group containing a dibasic acid anhydride Photosensitive resin. Here, the bifunctional epoxy resin is preferably a solid.

(3) reacting an epoxy compound having two or more epoxy groups in one molecule with a compound having at least one alcoholic hydroxyl group and one phenolic hydroxyl group in one molecule and an unsaturated group-containing monocarboxylic acid such as (meth) acrylic acid And reacting the alcoholic hydroxyl group of the obtained reaction product with a polybasic acid anhydride such as maleic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride or adipic acid.

(4) A process for producing a polyurethane resin composition, which comprises mixing a bisphenol A, bisphenol F, bisphenol S, novolac phenolic resin, poly-p-hydroxystyrene, condensate of naphthol and aldehyde, condensate of dihydroxynaphthalene and aldehyde, Containing monocarboxylic acid such as (meth) acrylic acid is reacted with a reaction product obtained by reacting a compound having at least two phenolic hydroxyl groups with an alkylene oxide such as ethylene oxide or propylene oxide to give a reaction product of polybasic acid A carboxyl group-containing photosensitive resin obtained by reacting an anhydride.

(5) reacting an unsaturated group-containing monocarboxylic acid with a reaction product obtained by reacting a compound having two or more phenolic hydroxyl groups in one molecule with a cyclic carbonate compound such as ethylene carbonate or propylene carbonate, A carboxyl group-containing photosensitive resin obtained by reacting an anhydride.

(6) A process for producing a polyisocyanate compound, which comprises reacting a diisocyanate compound such as an aliphatic diisocyanate, a branched aliphatic diisocyanate, an alicyclic diisocyanate or an aromatic diisocyanate with a polycarbonate-based polyol, a polyether- A terminal carboxyl group-containing urethane resin obtained by reacting an acid anhydride with a terminal of a urethane resin by a heavier reaction of a diol compound such as an A-alkylene oxide adduct diol, a phenolic hydroxyl group and a compound having an alcoholic hydroxyl group.

(7) In the synthesis of a carboxyl group-containing urethane resin by diisocyanate and a carboxyl group-containing dialcohol compound containing a carboxyl group such as dimethylolpropionic acid or dimethylolbutyric acid and a diol compound, a hydroxyalkyl (meth) acrylate or the like A carboxyl group-containing urethane resin obtained by adding a compound having one hydroxyl group and at least one (meth) acryloyl group in a molecule to a terminal (meth) acrylate.

(8) In the synthesis of a carboxyl group-containing urethane resin by the reaction of a diisocyanate with a carboxyl group-containing dialcohol compound and a diol compound, an isomeric reaction product of isophorone diisocyanate and pentaerythritol triacrylate, (Meth) acryloyl group-containing urethane resin obtained by adding a compound having two or more isocyanato groups and at least one (meth) acryloyl group.

(9) A carboxyl group-containing photosensitive resin obtained by copolymerization of an unsaturated carboxylic acid such as (meth) acrylic acid with an unsaturated group-containing compound such as styrene,? -Methylstyrene, lower alkyl (meth) acrylate or isobutylene.

(10) A process for producing a polyester resin, which comprises reacting a polyfunctional oxetane resin with a dicarboxylic acid such as adipic acid, phthalic acid or hexahydrophthalic acid and reacting the resultant polyester resin with a carboxyl group-containing polyester resin obtained by adding a dibasic acid anhydride to the resulting primary hydroxyl group A carboxyl group-containing photosensitive resin obtained by adding a compound having one epoxy group and at least one (meth) acryloyl group in a molecule such as glycidyl (meth) acrylate and? -Methyl glycidyl (meth) acrylate.

(11) A carboxyl group-containing photosensitive resin to which a compound having a cyclic ether group and a (meth) acryloyl group in one molecule is added to the carboxyl group-containing resin of any one of the above-mentioned (1) to (10).

Herein, the term (meth) acrylate is generically referred to as acrylate, methacrylate and mixtures thereof, and the same applies to other similar expressions below.

The acid value of the carboxyl group-containing resin is preferably 40 to 150 mgKOH / g. When the acid value of the carboxyl group-containing resin is 40 mgKOH / g or more, the alkali development is improved. Further, by setting the acid value to 150 mgKOH / g or less, normal resist pattern drawing can be easily performed. More preferably 50 to 130 mg KOH / g.

The blending amount of the carboxyl group-containing resin is preferably 20 to 60% by mass based on the whole amount of the resin layer of the dry film excluding the solvent. When the content is 20% by mass or more, the coating film strength can be improved. When the content is 60% by mass or less, the viscosity is appropriate and the processability is improved. More preferably from 20 to 50% by mass.

As the photopolymerization initiator, known photopolymerization initiators can be used. Among them, oxime ester photopolymerization initiators having an oxime ester group,? -Aminoacetophenone photopolymerization initiators, acylphosphine oxide photopolymerization initiators and titanocene photopolymerization initiators are preferable. One type of photopolymerization initiator may be used alone, or two or more types may be used in combination.

The blending amount of the photopolymerization initiator is, for example, 0.1 to 30 parts by mass based on 100 parts by mass of the carboxyl group-containing resin.

When the oxime ester-based photopolymerization initiator is used, the blending amount is preferably 0.01 to 5 parts by mass based on 100 parts by mass of the carboxyl group-containing resin. When the amount is 0.01 part by mass or more, the photocurability on copper becomes more certain and the coating film properties such as chemical resistance are improved. When the amount is 5 parts by mass or less, the light absorption at the surface of the coating film is suppressed, and the hardness of the core portion tends to be improved. More preferably, it is 0.5 to 3 parts by mass based on 100 parts by mass of the carboxyl group-containing resin.

When the? -aminoacetophenone-based photopolymerization initiator or the acylphosphine oxide-based photopolymerization initiator is used, the blending amount of each is preferably 0.01 to 15 parts by mass relative to 100 parts by mass of the carboxyl group-containing resin. When the amount is 0.01 part by mass or more, the photocurability on copper becomes more certain, and coating film properties such as chemical resistance are improved. When the amount is 15 parts by mass or less, a sufficient outgass reduction effect is obtained, light absorption at the surface of the cured coating is suppressed, and the curing property of the core portion is also improved. More preferably, it is 0.5 to 10 parts by mass based on 100 parts by mass of the carboxyl group-containing resin.

A photoinitiator or a sensitizer may be used in combination with the photopolymerization initiator. Examples of the photoinitiator or sensitizer include benzoin compounds, acetophenone compounds, anthraquinone compounds, thioxanthone compounds, ketal compounds, benzophenone compounds, tertiary amine compounds and xanthone compounds. These compounds may be used as a photopolymerization initiator, but they are preferably used in combination with a photopolymerization initiator. The photoinitiator or sensitizer may be used alone or in combination of two or more.

The photo-curable thermosetting resin composition may contain a thermosetting component other than an epoxy resin for the purpose of improving properties such as heat resistance and insulation reliability. Examples of such thermosetting components include known thermosetting resins such as isocyanate compounds, block isocyanate compounds, amino resins, maleimide compounds, benzoxazine resins, carbodiimide resins, cyclocarbonate compounds, polyfunctional oxetane compounds and episulfide resins Can be used.

The blending amount of the thermosetting component is preferably 10 to 100 parts by mass relative to 100 parts by mass of the carboxyl group-containing resin.

The photo-curable thermosetting resin composition preferably contains a thermosetting catalyst. Examples of such thermosetting catalysts include imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, Imidazole derivatives such as 1-cyanoethyl-2-phenylimidazole and 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole; Amines such as dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N-dimethylbenzylamine and 4- Compounds, hydrazine compounds such as adipic acid dihydrazide and sebacic acid dihydrazide; And phosphorus compounds such as triphenylphosphine. Further, it is also possible to use at least one selected from the group consisting of guanamine, acetoguanamine, benzoguanamine, melamine, 2,4-diamino-6-methacryloyloxyethyl-S-triazine, Azine, 2-vinyl-4,6-diamino-S-triazine isocyanuric acid adduct, 2,4-diamino-6-methacryloyloxyethyl-S-triazine, isocyanuric acid S-triazine derivatives such as adducts may be used. Preferably, a compound that also functions as such an adhesion-imparting agent is used in combination with a thermosetting catalyst.

The blending amount of the thermosetting catalyst is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 15.0 parts by mass based on 100 parts by mass of the epoxy resin.

The photocurable thermosetting resin composition may contain a photosensitive monomer in addition to the above-mentioned carboxyl group-containing resin, photopolymerization initiator and epoxy resin. The photosensitive monomer is a compound having at least one ethylenic unsaturated bond in the molecule. The photosensitive monomer is to assist the photo-curing of the carboxyl group-containing resin by irradiation with active energy rays.

(Meth) acrylate, urethane (meth) acrylate, carbonate (meth) acrylate, epoxy (meth) acrylate and the like can be given as examples of the compound used as the photosensitive monomer. And the like. Specific examples thereof include hydroxyalkyl acrylates such as 2-hydroxyethyl acrylate and 2-hydroxypropyl acrylate; Diacrylates of glycols such as ethylene glycol, methoxytetraethylene glycol, polyethylene glycol and propylene glycol; Acrylamides such as N, N-dimethyl acrylamide, N-methylol acrylamide and N, N-dimethylaminopropylacrylamide; Aminoalkyl acrylates such as N, N-dimethylaminoethyl acrylate and N, N-dimethylaminopropyl acrylate; Polyhydric alcohols such as hexanediol, trimethylol propane, pentaerythritol, dipentaerythritol and tris-hydroxyethylisocyanurate, or ethylene oxide adducts thereof, propylene oxide adducts, or? -Caprolactone adducts Polyhydric acrylates; Phenoxy acrylate, bisphenol A diacrylate and phenols thereof; ethylene oxide adducts or propylene oxide adducts; Polyhydric acrylates of glycidyl ethers such as glycerin diglycidyl ether, glycerin triglycidyl ether, trimethylol propane triglycidyl ether and triglycidyl isocyanurate; The present invention is not limited to the above, and acrylates and melamine acrylates in which a polyol such as a polyether polyol, a polycarbonate diol, a hydroxyl-terminated polybutadiene, or a polyester polyol is directly acrylated or urethane acrylated through a diisocyanate, and And at least one of the respective methacrylates corresponding to the acrylate may be appropriately selected and used.

Cresol novolak type epoxy resin and the like, an epoxy acrylate resin obtained by reacting an acrylic acid with a polyfunctional epoxy resin, and a curing agent such as a hydroxyacrylate such as pentaerythritol triacrylate and an isophorone di An epoxy urethane acrylate compound obtained by reacting a half urethane compound of diisocyanate such as isocyanate may be used as a photosensitive monomer. Such an epoxy acrylate resin can improve photo-curability without deteriorating the touch-dry composition.

The compounding amount of the compound having an ethylenically unsaturated bond in the molecule used as the photosensitive monomer is preferably 5 to 100 parts by mass, more preferably 5 to 70 parts by mass based on 100 parts by mass of the carboxyl group-containing resin. When the compounding amount of the compound having an ethylenically unsaturated bond is 5 parts by mass or more, the photo-curability of the photo-curable thermosetting resin composition is improved. By adjusting the blending amount to 100 parts by mass or less, the hardness of the coating film can be improved.

The photo-curable thermosetting resin composition preferably contains a filler in addition to the above-described components, and may contain other components such as a colorant, an elastomer, and a thermoplastic resin. Hereinafter, these components will also be described.

In the photo-curable thermosetting resin composition, a filler may be added if necessary in order to increase the physical strength and the like of the resulting cured product. The filler is not particularly limited, and examples thereof include those exemplified as fillers contained in the resin layer. The fillers may be used singly or as a mixture of two or more kinds.

The addition amount of the filler is preferably 500 parts by mass or less, more preferably 0.1 to 400 parts by mass, particularly preferably 0.1 to 300 parts by mass, based on 100 parts by mass of the carboxyl group-containing resin. When the addition amount of the filler is 500 parts by mass or less, the viscosity of the photo-curable thermosetting resin composition is not excessively high, the printing property is good, and the cured product is hard to be detached.

The photo-curable thermosetting resin composition may contain a coloring agent. As the colorant, known colorants such as red, blue, green, yellow, black and white can be used, and any of pigments, dyes and pigments can be used. However, from the viewpoint of reducing the environmental burden and influencing the human body, it is preferable not to contain a halogen.

The amount of the colorant to be added is not particularly limited, but is preferably 10 parts by mass or less, particularly preferably 0.1 to 7 parts by mass, based on 100 parts by mass of the carboxyl group-containing resin.

In addition, the photo-curable thermosetting resin composition may be blended with an elastomer for the purpose of imparting flexibility to the obtained cured product, improving the curability of the cured product, and the like. Examples of the elastomer include a polyester elastomer, a polyurethane elastomer, a polyester urethane elastomer, a polyamide elastomer, a polyester amide elastomer, an acrylic elastomer, and an olefin elastomer. A resin obtained by modifying an epoxy group of some or all of the epoxy resins having various skeletons with both terminal carboxylic acid modified butadiene-acrylonitrile rubbers can also be used. The epoxy-containing polybutadiene elastomer, the acrylic-containing polybutadiene elastomer, the hydroxyl group-containing polybutadiene elastomer, and the hydroxyl group-containing isoprene elastomer may also be used. The elastomer may be used singly or as a mixture of two or more kinds.

The amount of the elastomer to be added is preferably 50 parts by mass or less, more preferably 1 to 30 parts by mass, and particularly preferably 5 to 30 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin. When the addition amount of the elastomer is 50 parts by mass or less, the alkali developability of the photo-curable thermosetting resin composition becomes satisfactory, and the potable pause time is not shortened.

If necessary, components such as a block copolymer, an adhesion promoter, an antioxidant, and an ultraviolet absorber may be added to the photo-curable thermosetting resin composition. They can use materials known in the field of electronic materials. It is also possible to use known thickening agents such as fine silica, hydrotalcite, organic bentonite and montmorillonite, antifoaming agents such as silicone, fluorine and high molecular weight, leveling agents, silane coupling agents such as imidazole, thiazole and triazole, At least one kind of additive for known additives such as a fluorescent whitening agent and the like can be blended.

The organic solvent that can be used is not particularly limited, and examples thereof include ketones, aromatic hydrocarbons, glycol ethers, glycol ether acetates, esters, alcohols, aliphatic hydrocarbons and petroleum solvents. More specifically, ketones such as methyl ethyl ketone, cyclohexanone, methyl butyl ketone, methyl isobutyl ketone and methyl ethyl ketone; Aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; Methylcellosolve, butylcellosolve, carbitol, methylcarbitol, butylcarbitol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, dipropylene Glycol ethers such as glycol monomethyl ether, dipropylene glycol diethyl ether and triethylene glycol monoethyl ether; Esters such as ethyl acetate, butyl acetate, isobutyl acetate, ethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate and propylene glycol butyl ether acetate; Alcohols such as ethanol, propanol, 2-methoxypropanol, n-butanol, isobutyl alcohol, isopentyl alcohol, ethylene glycol and propylene glycol; Aliphatic hydrocarbons such as octane and decane; Petroleum solvents such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha and solvent naphtha, and N, N-dimethylformamide (DMF), tetrachlorethylene and terpentine. Further, a solvent # 100, Solvent # 150, manufactured by Shell Chemicals Japan Ltd., manufactured by Maruzen Sekiyu Kagaku Co., Ltd., Swazol 1000, Swazol 1500, Solvesso 100 manufactured by Standard Sekiyu Osaka Hatsubai Show, Solvesso 150, Organic solvents such as Shellolsol A100, Shellolsol A150, Idemitsu Kosan 100, and Ipzol 150 may be used. These organic solvents may be used singly or as a mixture of two or more kinds.

As a method for producing a printed wiring board using a dry film having a resin layer made of a photo-curable thermosetting resin composition, conventionally known methods may be used. For example, in the case of a dry film in which a resin layer is sandwiched between a first film and a second film as shown in Fig. 2, a printed wiring board can be manufactured by the following method. The second film is peeled off from the dry film to expose the resin layer and the resin layer of the dry film is laminated on the substrate on which the circuit pattern is formed using a vacuum laminator or the like to perform pattern exposure on the resin layer. The first film may be peeled off either before or after exposure after lamination. Thereafter, an alkali development is performed to form a patterned resin layer on the substrate, and the patterned resin layer is cured by light irradiation and heat to form a cured coating, whereby a printed wiring board can be manufactured.

(Thermosetting resin composition)

As an example of the thermosetting resin composition, a resin composition containing an epoxy resin without containing a photocurable component will be described below.

The thermosetting resin composition is preferably blended with a filler, and the physical strength and the like of the resulting cured product can be increased. The filler is not particularly limited, and examples thereof include those exemplified as fillers contained in the resin layer. The fillers may be used singly or as a mixture of two or more kinds.

The organic solvent that can be used is not particularly limited, and examples thereof include organic solvents exemplified in the above-described photo-curable thermosetting resin composition. The organic solvent may be used singly or as a mixture of two or more kinds.

The thermosetting resin composition may contain a curing agent. Examples of the curing agent include phenol resins, polycarboxylic acids and acid anhydrides thereof, cyanate ester resins, active ester resins, maleimide compounds, and alicyclic olefin polymers. The curing agent may be used alone or in combination of two or more. Here, by using at least a cyanate ester resin or an active ester resin, the dielectric tangent after humidification can be lowered. Further, by using at least a cyanate ester resin or a maleimide compound, the crack resistance in a cooling / heating cycle after reflow is improved.

When the resin layer contains a thermosetting resin composition, bubbles are generated severely when cured at a high temperature. However, according to the dry film of the present invention, the phenol resin, the active ester resin, the cyanate ester resin, Even when a curing agent is contained, bubbles are hardly generated after curing. It is also preferable that the curing agent has a structure of at least one of a biphenyl skeleton and a naphthol skeleton.

Examples of the phenol resin include phenol novolac resins, alkylphenol novolac resins, bisphenol A novolak resins, dicyclopentadiene type phenol resins, Xylok type phenol resins, terpene modified phenol resins, cresol / naphthol resins, polyvinyl phenols, / Naphthol resin, an? -Naphthol skeleton-containing phenol resin, a triazine skeleton-containing cresol novolak resin, a biphenylaralkyl-type phenol resin, a xylylene-type phenol novolac resin, Can be used in combination.

Among the above-mentioned phenolic resins, those having a hydroxyl equivalent of 130 g / eq. Or more, more preferably 150 g / eq. Or more. The hydroxyl equivalent is 130 g / eq. Examples of the phenol resin include dicyclopentadiene skeleton phenol novolak resin (GDP series, manufactured by Gunyonagaku Kasei), xylo-type phenol novolac resin (MEH-7800, manufactured by Meiwa Kasei Kasei), biphenylaralkyl (SN-series, manufactured by Shinnittetsu Sumikin), a triazine skeleton-containing cresol novolak resin (LA-3018-50P, manufactured by DIC), a novolak type epoxy resin (MEH- And the like.

The cyanate ester resin is a compound having two or more cyanate ester groups (-OCN) in one molecule. As the cyanate ester resin, all conventionally known resins can be used. Examples of the cyanate ester resin include phenol novolak type cyanate ester resins, alkylphenol novolak type cyanate ester resins, dicyclopentadiene type cyanate ester resins, bisphenol A type cyanate ester resins, bisphenol F type cyanate ester resins Naphthoate ester resin, and bisphenol S type cyanate ester resin. In addition, some of them may be trierized prepolymers.

The active ester resin is a resin having two or more active ester groups in one molecule. The active ester resin is generally obtained by a condensation reaction of a carboxylic acid compound and a hydroxy compound. Among them, an active ester compound obtained by using a phenol compound or a naphthol compound as a hydroxy compound is preferable. Examples of the phenol compound or naphthol compound include hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, phenol phthaline, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o- Cresol, catechol, alpha -naphthol, beta naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone , Tetrahydroxybenzophenone, fluoroglucine, benzenetriol, dicyclopentadienyldiphenol, phenol novolak, and the like. The active ester resin may also be a naphthalene diol alkyl / benzoic acid type.

The maleimide compound is a compound having a maleimide skeleton, and all conventionally known ones can be used. The maleimide compound is preferably one having at least two maleimide skeletons, and may be selected from the group consisting of N, N'-1,3-phenylene dimaleimide, N, N'-1,4-phenylenedimaleimide, N, N'- Bis (maleimide) ethane, 1,6-bismaleimide hexane, 1,6-bismaleimide- (2,2,4-trimethyl) hexane, 2, Dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, 4-methyl (4-methylphenyl) Bis (3-ethyl-5-methyl-4-maleimidophenyl) methane, bisphenol A diphenyl ether bismaleimide, polyphenylmethane maleimide and oligomers thereof, And a diamine condensate having a mid skeleton. The oligomer is an oligomer obtained by condensing a maleimide compound as a monomer in the maleimide compound described above. The maleimide compounds may be used singly or in combination of two or more.

The curing agent preferably has a ratio of a functional group capable of thermosetting reaction such as an epoxy group of a thermosetting component and a functional group in a curing agent that reacts with the functional group to a ratio of a functional group capable of reacting with a functional group / . &Lt; / RTI &gt; By setting the functional group (equivalence ratio) capable of a functional group / thermosetting reaction of the curing agent within the above range, it is possible to prevent roughening of the film surface in the desmear process. More preferably, the functional group (equivalence ratio) capable of reacting with the functional group / thermosetting agent of the curing agent is 0.2 to 1.5, more preferably the functional group (equivalent ratio) of the curing agent capable of reacting with the functional group / thermosetting reaction is 0.3 to 1.0.

When the functional group equivalent (g / eq.) Of the phenol resin, cyanate ester resin, active ester resin or maleimide compound is 200 or more, the warpage can be reduced.

The thermosetting resin composition may further contain a thermoplastic resin in order to improve the mechanical strength of the resulting cured coating film. The thermoplastic resin is preferably soluble in a solvent. When it is soluble in a solvent, the flexibility of the dry film is improved, and generation of cracks and falling of the powder can be suppressed. Examples of the thermoplastic resin include a thermoplastic polyhydroxypolyether resin, a phenoxy resin which is a condensation product of epichlorohydrin and various bifunctional phenol compounds, or a hydroxyl group of a hydroxy ether moiety existing in the skeleton thereof, with various acid anhydrides or acid chlorides Esterified phenoxy resins, polyvinyl acetal resins, polyamide resins, polyamideimide resins, and block copolymers. The thermoplastic resin may be used alone or in combination of two or more.

The blending amount of the thermoplastic resin is 0.5 to 20 mass%, preferably 0.5 to 10 mass%, based on the entire resin layer excluding the solvent. When the blending amount of the thermoplastic resin is out of the above range, it becomes difficult to obtain a uniform roughened surface state.

In addition, the thermosetting resin composition may contain rubber-like particles as required. Examples of such rubber-like particles include polybutadiene rubber, polyisoprene rubber, urethane-modified polybutadiene rubber, epoxy-modified polybutadiene rubber, acrylonitrile-modified polybutadiene rubber, carboxyl-group-modified polybutadiene rubber, acrylonitrile modified with a carboxyl group or hydroxyl group Butadiene rubber, crosslinked rubber particles thereof, and core-shell type rubber particles. These may be used singly or in combination of two or more. These rubber-like particles are added in order to improve the flexibility of the resulting cured coating, improve crack resistance, enable surface roughening treatment with an oxidizing agent, and improve the adhesion strength with copper foil and the like.

The average particle diameter of the rubber-like particles is preferably in the range of 0.005 to 1 mu m, more preferably in the range of 0.2 to 1 mu m. The average particle diameter of the rubber-like particles in the present invention can be obtained by a laser diffraction particle diameter distribution measuring apparatus. For example, rubber-like particles are uniformly dispersed in an appropriate organic solvent by ultrasonic waves or the like, and the particle size distribution of the rubber-like particles is prepared on the basis of mass by using Nanotrac wave manufactured by Nikkiso Co., Ltd. and the median diameter of the rubber- Can be measured.

The blending amount of the rubber-like particles is preferably 0.5 to 10 mass%, more preferably 1 to 5 mass%, based on the entire resin layer excluding the solvent. If it is 0.5% by mass or more, crack resistance is obtained, and the adhesion strength with the conductor pattern and the like can be improved. When it is 10 mass% or less, the CTE is lowered and the glass transition temperature (Tg) is increased to improve the curing property.

The resin layer of the dry film of the present invention may contain a curing accelerator. The curing accelerator promotes the thermosetting reaction and is used for further improving properties such as adhesion, chemical resistance and heat resistance. Specific examples of such curing accelerators include imidazoles and derivatives thereof; Guanamine such as acetoguanamine and benzoguanamine; Polyamines such as diaminodiphenylmethane, m-phenylenediamine, m-xylenediamine, diaminodiphenylsulfone, dicyandiamide, urea, urea derivatives, melamine and polybasic hydrazide; Organic acid salts and / or epoxy adducts thereof; Amine complexes of boron trifluoride; Triazine derived products such as ethyldiamino-S-triazine, 2,4-diamino-S-triazine and 2,4-diamino-6-xylyl-S-triazine; (N-methyl) melamine, 2,4,6-tris (dimethylaminophenol), tetra (dimethylaminophenol), N, N-dimethyloctylamine, N-benzyldimethylamine, pyridine, N-methylmorpholine, Amines such as methyl guanidine and m-aminophenol; Polyphenols such as polyvinyl phenol, polyvinyl phenol bromide, phenol novolac, and alkylphenol novolak; Organic phosphines such as tributylphosphine, triphenylphosphine, and tris-2-cyanoethylphosphine; Phosphonium salts such as tri-n-butyl (2,5-dihydroxyphenyl) phosphonium bromide, and hexadecyl tributylphosphonium chloride; Quaternary ammonium salts such as benzyltrimethylammonium chloride and phenyltributylammonium chloride; The polybasic acid anhydride; A photocationic polymerization catalyst such as diphenyl iodonium tetrafluoroborate, triphenylsulfonium hexafluoroantimonate, 2,4,6-triphenylthiopyrylium hexafluorophosphate and the like; Styrene-maleic anhydride resin; Condensation reaction products of phenyl isocyanate and dimethyl amine, equimolar reaction products of organic polyisocyanates such as tolylene diisocyanate and isophorone diisocyanate with dimethylamine, metal catalysts, and other known curing accelerators. Of the curing accelerators, phosphonium salts are preferred in view of obtaining BHAST resistance.

The curing accelerator may be used alone or in combination of two or more. The use of the curing accelerator is not essential, but when curing is to be particularly promoted, the curing accelerator may be used in an amount of preferably 0.01 to 5 parts by mass based on 100 parts by mass of the thermosetting component. In the case of the metal catalyst, the amount is preferably 10 to 550 ppm, more preferably 25 to 200 ppm based on 100 parts by mass of the thermosetting component.

The thermosetting resin composition may further contain a conventionally known colorant such as phthalocyanine blue, phthalocyanine green, iodine green, disazo yellow, crystal violet, titanium oxide, carbon black and naphthalene black, asbestos, , Antistatic agents such as antistatic agents, antistatic agents, antistatic agents, antistatic agents, antistatic agents, antistatic agents, antistatic agents, antistatic agents, antistatic agents, antistatic agents, antistatic agents, Can be used.

As a method for producing a printed wiring board using a dry film having a resin layer made of a thermosetting resin composition, conventionally known methods may be used. For example, in the case of a dry film in which a resin layer is sandwiched between a first film and a second film as shown in Fig. 2, a printed wiring board can be manufactured by the following method. The second film is peeled off from the dry film, heat laminated on the circuit board on which the circuit pattern is formed, and then thermally cured. The thermosetting may be cured in an oven or cured by hot plate pressing. The copper foil or the circuit-formed substrate may be laminated at the same time when the substrate on which the circuit is formed and the dry film of the present invention are laminated or hot plate pressed. A printed wiring board can be manufactured by forming a pattern or a via hole by laser irradiation or drilling at a position corresponding to a predetermined position on a substrate on which a circuit pattern is formed and exposing the circuit wiring. At this time, when the remaining components (smear) can not be completely removed on the pattern or the circuit wiring in the via-hole, the desmear treatment is performed. The first film may be peeled at any time after lamination, after thermal curing, after laser processing, or after desmear treatment.

(Photo-curable thermosetting resin composition containing photo-base generator)

As an example of a photo-curable thermosetting resin composition containing a photo-base generator (hereinafter, also referred to as a photo-base generator-containing composition), a composition comprising an alkali developable resin and a photo base generator in addition to an epoxy resin is described below do.

The alkali developable resin is a resin containing at least one functional group selected from the group consisting of a phenolic hydroxyl group, a thiol group and a carboxyl group and capable of being developed into an alkali solution, preferably a compound having two or more phenolic hydroxyl groups, a carboxyl group containing resin, And compounds having a carboxyl group, and compounds having two or more thiol groups.

As the carboxyl group-containing resin, a resin containing a known carboxyl group can be used. The resin composition can be made alkali-developable by the presence of a carboxyl group. In addition to the carboxyl group, a compound having an ethylenically unsaturated bond in the molecule may be used. In the present invention, however, it is preferable to use only a carboxyl group-containing water having no ethylenically unsaturated bond as the carboxyl group-containing resin.

Specific examples of the carboxyl group-containing resin that can be used in the present invention include, in addition to the compounds (1) to (11) listed as the carboxyl group-containing resin contained in the photocurable thermosetting resin composition, the compounds listed below (either oligomer or polymer ).

(12) aliphatic diisocyanates such as aliphatic diisocyanates, branched aliphatic diisocyanates, alicyclic diisocyanates, and aromatic diisocyanates, carboxyl group-containing dialcohol compounds such as dimethylolpropionic acid and dimethylolbutanoic acid, and polycarbonate-series polyols, Containing urethane resin obtained by a mid-portion reaction of a diol compound such as a polyester polyol, a polyolefin polyol, an acrylic polyol, a bisphenol A alkylene oxide adduct diol, a compound having a phenolic hydroxyl group and an alcoholic hydroxyl group .

(13) A thermosetting resin composition comprising a diisocyanate and a bifunctional epoxy resin, such as a bisphenol A epoxy resin, a hydrogenated bisphenol A epoxy resin, a bisphenol F epoxy resin, a bisphenol S epoxy resin, a biquileneol epoxy resin or a biphenol epoxy resin (Meth) acrylate or a partial acid anhydride thereof, a carboxyl group-containing dialcohol compound and a diol compound.

(14) A method for producing a resin composition, which comprises adding a compound having one hydroxyl group and at least one (meth) acryloyl group in a molecule such as hydroxyalkyl (meth) acrylate during synthesis of the resin of the above (12) (Meth) acrylated carboxyl group-containing urethane resin.

(15) A process for producing a resin composition comprising the steps of: (1) preparing a resin having an isocyanate group and at least one (meth) acryloyl group in a molecule, such as a molar reaction product of isophorone diisocyanate and pentaerythritol triacrylate, (Meth) acrylate obtained by adding a compound to a carboxyl group-containing urethane resin.

(16) A method for producing a polyfunctional epoxy resin composition, which comprises reacting a polyfunctional epoxy resin as described above with a saturated monocarboxylic acid, adding a carboxyl group in which a dibasic acid anhydride such as phthalic anhydride, tetrahydrophthalic anhydride, or hexahydrophthalic anhydride is added to a hydroxyl group present in the side chain Suzy. Here, the polyfunctional epoxy resin is preferably solid.

(17) A carboxyl group-containing polyester resin in which a dicarboxylic acid is reacted with a polyfunctional oxetane resin as described below, and dibasic acid anhydride is added to the generated primary hydroxyl group.

(18) A carboxyl group-containing resin obtained by reacting a reaction product obtained by reacting a compound having a plurality of phenolic hydroxyl groups in a molecule with an alkylene oxide such as ethylene oxide or propylene oxide, with a polybasic acid anhydride.

(19) reacting a saturated monocarboxylic acid with a reaction product obtained by reacting a compound having a plurality of phenolic hydroxyl groups in one molecule with an alkylene oxide such as ethylene oxide or propylene oxide, reacting the resultant reaction product with a polybasic acid anhydride The obtained carboxyl-containing resin.

(20) A method in which a reaction product obtained by reacting a compound having a plurality of phenolic hydroxyl groups in a molecule with a cyclic carbonate compound such as ethylene carbonate or propylene carbonate is reacted with a saturated monocarboxylic acid, the reaction product obtained is reacted with a polybasic acid anhydride The obtained carboxyl-containing resin.

(21) A carboxyl group-containing resin obtained by reacting a reaction product obtained by reacting a compound having a plurality of phenolic hydroxyl groups in a molecule with a cyclic carbonate compound such as ethylene carbonate or propylene carbonate, with a polybasic acid anhydride.

(22) A process for producing an epoxy compound having a plurality of epoxy groups in a molecule by reacting a compound having at least one alcoholic hydroxyl group and one phenolic hydroxyl group in a molecule such as p-hydroxyphenethyl alcohol with a saturated monocarboxylic acid And a polybasic acid anhydride such as maleic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride or adipic acid is reacted with the alcoholic hydroxyl group of the obtained reaction product.

(23) A process for producing an epoxy compound having a plurality of epoxy groups in one molecule by reacting a compound having at least one alcoholic hydroxyl group and one phenolic hydroxyl group in one molecule such as p-hydroxyphenethyl alcohol with an alcoholic A carboxyl group-containing resin obtained by reacting a hydroxyl group with a polybasic acid anhydride such as maleic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, or adipic acid.

(24) The positive resist composition as described in any one of (12) to (23) above, further comprising one or more epoxy groups in the molecule such as glycidyl (meth) acrylate and? -Methyl glycidyl A carboxyl group-containing resin obtained by adding a compound having a (meth) acryloyl group.

The above-described alkali-developable resin has a large number of carboxyl groups and hydroxyl groups in the side chain of the backbone polymer, so that development with an aqueous alkaline solution becomes possible.

The hydroxyl group equivalent or carboxyl group equivalent of the alkali developable resin is preferably 80 to 900 g / eq., More preferably 100 to 700 g / eq. The hydroxyl group equivalent or the carboxyl group equivalent is 900 g / eq. Or less, the adhesion of the pattern layer is obtained, and alkali development is facilitated. On the other hand, when the hydroxyl group equivalent or the carboxyl group equivalent is 80 g / eq. , The dissolution of the light irradiation portion by the developer is suppressed, the lines are not thin more than necessary, and normal resist patterns are easily drawn, which is preferable. When the carboxyl group equivalent or the phenol group equivalent is large, development is possible even when the content of the alkali developable resin is small, which is preferable.

The acid value of the alkali developable resin is preferably 40 to 150 mgKOH / g. When the acid value of the alkali developable resin is 40 mgKOH / g or more, the alkali develops satisfactorily. Further, by setting the acid value to 150 mgKOH / g or less, normal resist pattern drawing can be easily performed. More preferably 50 to 130 mg KOH / g.

The blending amount of the alkali developable resin is preferably 20 to 60% by mass based on the whole amount of the resin layer of the dry film excluding the solvent. When the content is 20% by mass or more, the coating film strength can be improved. When it is 60 mass% or less, the viscosity becomes appropriate and the coating property is improved. And more preferably from 30 to 50 mass%.

The photobase generator is a compound which produces one or more basic substances capable of functioning as a catalyst for the addition reaction of the heat-reactive compound by changing the molecular structure or cleaving the molecules by irradiation of light such as ultraviolet rays or visible light. As the basic substance, for example, secondary amine and tertiary amine can be mentioned.

As the photobase generator, for example, an? -Amino acetophenone compound, an oxime ester compound, an acyloxyimino group, an N-formylated aromatic amino group, a N-acylated aromatic amino group, a nitrobenzylcarbamate group, And a compound having a substituent such as a carboxylate group and a carboxylate group.

These photobase generators may be used alone or in combination of two or more. The blending amount of the photo-base generator in the photo-base generator-containing composition is preferably 1 to 50 parts by mass, more preferably 1 to 40 parts by mass, per 100 parts by mass of the heat-reactive compound. When it is 1 part by mass or more, development is preferable because it is easy.

In the photobase generator-containing composition, a filler is preferably blended, and the physical strength and the like of the resulting cured product can be increased. The filler is not particularly limited, and examples thereof include those exemplified as fillers contained in the resin layer. The fillers may be used singly or as a mixture of two or more kinds.

The organic solvent that can be used is not particularly limited, and examples thereof include organic solvents exemplified as the above-mentioned photo-curable thermosetting resin composition. The organic solvent may be used singly or as a mixture of two or more kinds.

If necessary, components such as a mercapto compound, an adhesion promoter, an antioxidant, and an ultraviolet absorber may be added to the photobase generator-containing composition. They can use materials known in the field of electronic materials.

The photobase generator-containing composition may contain a known thickener such as finely divided silica, hydrotalcite, organic bentonite or montmorillonite, a defoaming agent such as a silicone type, a fluorine type or a high molecular type and / or a leveling agent, a silane coupling agent, Additives such as known additives can be formulated.

As a method for producing a printed wiring board using a dry film having a resin layer composed of a composition containing a photobase generator, conventionally known methods may be used. For example, in the case of a dry film in which a resin layer is sandwiched between a first film and a second film as shown in Fig. 2, a printed wiring board can be manufactured by the following method. The second film is peeled off from the dry film to expose the resin layer and a dry film is laminated on the substrate on which the circuit pattern is formed using a vacuum laminator or the like. Thereafter, the photo-base generating agent contained in the photo-base generating agent-containing resin composition is activated by light irradiation in the negative pattern shape to cure the light irradiated portion and remove the unexposed portion by alkali development to form a negative type pattern layer can do. The first film may be peeled at any time after lamination or after exposure. Further, it is preferable to heat the resin layer after light irradiation and before development. Thereby, the resin layer can be sufficiently cured, and a pattern layer having further excellent curing properties can be obtained. It is preferable that the heating after the light irradiation and before the development is a temperature at which the unirradiated portion does not thermally cure. In addition, after development, it is preferable to perform thermal curing (post curing). After development, ultraviolet irradiation may be performed to activate the remaining photoacid generators without activation during light irradiation, followed by thermosetting (postcuring).

(Positive photosensitive thermosetting resin composition)

As an example of the positive photosensitive thermosetting resin composition, a resin composition containing a compound capable of generating a carboxyl group upon irradiation with light in addition to an epoxy resin will be described below.

Among the compounds which generate a carboxyl group by light irradiation, it is preferable to use a naphthoquinone diazide compound. The naphthoquinone diazide compound has been conventionally used in a system which suppresses the alkali solubility of a carboxyl group or the like by forming a complex with a carboxyl group or a phenolic hydroxyl group and dissociates the complex by subsequent light irradiation to thereby exhibit alkali solubility. In this case, if the naphthoquinone diazide compound remains in the film, the complex may dissociate due to light irradiation and the solubility may be expressed. Therefore, in the semiconductor field, etc., the remaining naphthoquinone diazide compound is finally And was removed by blowing off at a high temperature. However, in the field of printed wiring boards, such a high temperature can not be applied, and since it can not be used as a permanent coating film from the standpoint of stability, a naphthoquinone diazide compound has not been practically used. In the present invention, when a naphthoquinone diazide compound is used as a compound which generates a carboxyl group by light irradiation, the naphthoquinone diazide compound remaining in the unexposed portion is introduced into the crosslinking structure during the thermosetting reaction and stabilized Therefore, the film toughness, that is, the bending resistance and the electric characteristics can be improved without causing the problem of removal as in the conventional case. Particularly, the naphthoquinone diazide compound as a compound which generates a carboxyl group by light irradiation can be obtained by effectively using a polyamideimide resin and a thermosetting component while ensuring satisfactory developability and resolution, .

Specific examples of the naphthoquinone diazide compound include a naphthoquinone diazide adduct of tris (4-hydroxyphenyl) -1-ethyl-4-isopropylbenzene (for example, (E.g., TS533, TS567, TS583, TS593 manufactured by Nippon Shokubai Co., Ltd.) and naphthoquinonediazide adducts of tetrahydroxybenzophenone (BS550, BS570, BS599 available from Sanbo Kagaku Kagaku Co., Ltd.).

In the positive photosensitive thermosetting resin composition, a filler is preferably blended, and the physical strength and the like of the resulting cured product can be increased. The filler is not particularly limited, and examples thereof include those exemplified as fillers contained in the resin layer. The fillers may be used singly or as a mixture of two or more kinds.

Specific examples of the alkali developable resin contained in the positive photosensitive thermosetting resin composition include the carboxyl group-containing resin exemplified in the above-mentioned photo-curable thermosetting resin composition and the alkali developable resin exemplified in the above photoacid generator-containing composition .

The positive photosensitive thermosetting resin composition may contain a thermosetting component other than the epoxy resin for the purpose of improving properties such as heat resistance and insulation reliability. As the thermosetting component, known thermosetting resins such as an isocyanate compound, a block isocyanate compound, an amino resin, a maleimide compound, a benzoxazine resin, a carbodiimide resin, a cyclocarbonate compound, a polyfunctional oxetane compound, Can be used.

The organic solvent that can be used is not particularly limited, and examples thereof include the organic solvents exemplified as the photocurable thermosetting resin composition. The organic solvent may be used singly or as a mixture of two or more kinds.

The positive photosensitive thermosetting resin composition preferably contains a filler. The filler is not particularly limited, and examples thereof include those exemplified as fillers contained in the resin layer. The fillers may be used singly or as a mixture of two or more kinds.

The positive photosensitive thermosetting resin composition may contain other components such as a block copolymer, a colorant, an elastomer, and a thermoplastic resin in addition to the above components. Further, components such as adhesion promoter, antioxidant, and ultraviolet absorber may be further added to the positive photosensitive thermosetting resin composition, if necessary. They can use materials known in the field of electronic materials. Further, at least one of a thickener such as fine silica, hydrotalcite, organic bentonite, and montmorillonite, a defoaming agent such as silicon, fluorine, and high molecular weight, and a leveling agent, and a silane such as imidazole, thiazole, At least one kind of additive for publicly known agents such as coupling agents, rust inhibitors, fluorescent whitening agents and the like can be added.

As a method for producing a printed wiring board using a dry film having a resin layer made of a positive photosensitive thermosetting resin composition, conventionally known methods may be used. For example, in the case of a dry film in which a resin layer is sandwiched between a first film and a second film as shown in Fig. 2, a printed wiring board can be manufactured by the following method. The second film is peeled off from the dry film to expose the resin layer and a dry film is laminated on the substrate on which the circuit pattern is formed using a vacuum laminator or the like. Thereafter, a positive pattern layer can be formed by irradiating light to the resin layer in a positive pattern shape, alkali development of the resin layer, and removal of the irradiated portion. The first film may be peeled at any time after lamination or after exposure. After the development, the resin layer is heat-cured (post-cured), and the unirradiated portion is cured to produce a printed wiring board. In the positive photosensitive thermosetting resin composition, since the acid generated by light irradiation changes to a composition that is soluble in an alkali developer, positive pattern formation by alkaline development becomes possible.

[film]

When a dry film having a resin layer sandwiched between a carrier film and a protective film is laminated, in many cases, the protective film is peeled and laminated so that the surface of the resin layer on the side in contact with the protective film is in contact with the substrate. However, in some cases, the carrier film is peeled off and the surface of the resin layer on the side in contact with the carrier film is laminated so as to be in contact with the base material. In the present invention, it is preferable that the resin layer is sandwiched between the first film and the second film by the carrier film and the protective film as shown in Fig. The film on the side in contact with the side of the resin layer (that is, the laminate side) which is in contact with the substrate when the substrate is laminated is the second film, and the side of the second film contacting with the resin layer has an arithmetic average surface roughness Ra of 0.1 To 1.2 탆, more preferably 0.3 to 1.2 탆, and still more preferably 0.4 to 1.2 탆. The arithmetic mean surface roughness Ra means a value measured in accordance with JIS B0601. The second film may be either a carrier film or a protective film. Preferably, the first film is a carrier film and the second film is a protective film.

The carrier film has a role of supporting the resin layer of the dry film and is a film to which the curable resin composition is applied when the resin layer is formed. Examples of the carrier film include a thermoplastic resin such as a polyester film such as polyethylene terephthalate and polyethylene naphthalate, a polyimide film, a polyamideimide film, a polyethylene film, a polytetrafluoroethylene film, a polypropylene film and a polystyrene film And a surface-treated paper or the like can be used. Among them, a polyester film can be preferably used from the viewpoints of heat resistance, mechanical strength, handleability and the like. The thickness of the carrier film is not particularly limited, but is appropriately selected depending on the application in the range of about 10 to 150 mu m. The surface of the carrier film on which the resin layer is formed may be subjected to a releasing treatment. A sputter or an ultra-thin copper foil may be formed on the surface of the carrier film on which the resin layer is formed.

The protective film is formed on the surface opposite to the carrier film of the resin layer for the purpose of preventing adhesion of dust to the surface of the resin layer of the dry film and improving handling properties. As the protective film, for example, a film composed of the thermoplastic resin exemplified in the above carrier film, a paper treated with a surface treatment, or the like can be used, and among these, a polyester film, a polyethylene film and a polypropylene film are preferable. The thickness of the protective film is not particularly limited, but is appropriately selected depending on the application in the range of about 10 to 150 mu m. The surface of the protective film on which the resin layer is formed may be subjected to a releasing treatment.

When a thermoplastic resin film is used as the second film having the arithmetic mean surface roughness Ra as described above, it is preferable to add a filler to the resin at the time of film formation, blast the film surface, The surface can be formed into a predetermined shape by coating, chemical etching or the like, and a thermoplastic resin film having the arithmetic average surface roughness Ra can be obtained. For example, when the filler is added to the resin, the arithmetic average surface roughness Ra can be controlled by adjusting the particle diameter and the addition amount of the filler. In the case of performing the blast treatment, the arithmetic mean surface roughness Ra can be controlled by adjusting the processing conditions such as the blast material and the blast pressure. Commercially available thermoplastic resin films having such surface roughness may be used. For example, Lamia X42, Lumirror X43, Lumirror X44, Enbelt PTH-12, Enbelt PTH-25, Blet PTHA-25, Enbret PTH-38, ALPAN MA-411, MA-420, E-201F and ER-440 manufactured by Oji-Fiftech.

In the first film, it is preferable that the arithmetic average surface roughness Ra of the surface in contact with the resin layer is 0.1 탆 or less. When the thickness is 0.1 탆 or less, the surface flatness of the resin layer after curing becomes good and the gloss becomes good. Further, if there is a difference in arithmetic average surface roughness Ra between the first film and the second film, it is easy to recognize which of the films is in appearance (presence or absence of gloss), thereby making it possible to prevent mistakes in operation.

Further, in order to facilitate peeling of the second film, the thickness A of the first film is preferably larger than the thickness B of the second film. More preferably, the difference (A-B) between the thickness A and the thickness B is 1 占 퐉 or more. Further, if the thicknesses of the first film and the second film are different from each other, it is easy to recognize which of the films is touched or out of sight, thereby making it possible to prevent mistakes in operation.

The thickness of the first film is preferably 10 to 100 mu m, more preferably 15 mu m or more. When the thickness is 10 mu m or more, even if heat treatment is performed without laminating the first film after laminating the dry film to the substrate, the first film is hardly shrunk, the thickness becomes uneven due to heat shrinkage, It is possible to prevent deterioration of the quality caused by flowing the resin layer along the stripes and causing streaks in the resin layer.

In the case where the resin layer of the dry film of the present invention includes the photosensitive resin composition, it is preferable to use a light-transmitting material such as the thermoplastic resin as the first film so that the first film can be exposed without peeling . In this case, the thickness of the first film is preferably 45 占 퐉 or less. When the thickness is 45 μm or less, the undercut is reduced. More preferably, it is 40 mu m or less.

The dry film of the present invention can be preferably used for forming a permanent protective film of a printed wiring board, and can be suitably used for forming a solder resist layer, an interlayer insulating layer, and a coverlay of a flexible printed wiring board. In addition, since the dry film of the present invention is excellent in the filling property, it can be suitably used for a printed circuit board having a microcircuit such as a package substrate having a large influence of bubbles. In particular, Can be suitably used for a printed wiring board having a circuit. Further, even in the case of employing a vacuum laminate in which bubbles are likely to occur as a method of laminating a dry film, the dry film of the present invention can be suitably used. The resin layer cured product of the dry film of the present invention is preferably used for forming an interlayer insulating layer because of its excellent formability of a plating resist. A wiring board may be formed by bonding wires using the dry film of the present invention. It can also be used as a sealing resin for a semiconductor chip. And can be used for forming the outermost layer of the core-less substrate and the interlayer insulating layer.

Example

EXAMPLES Hereinafter, the present invention will be described in detail with reference to Examples, Comparative Examples and Test Examples. However, it is needless to say that the present invention is not limited to the following Examples. In the following, "parts" and "%" are on a mass basis unless otherwise specified.

[Adjustment of surface treated inorganic filler]

(Adjustment of surface treated silica A to D and adjustment of surface treated alumina A, B)

100 g of each of the inorganic fillers and 2000 g of an aqueous alcohol solution (water: alcohol = 1: 9 by weight) were added to the flask and stirred at room temperature for 30 minutes at a rotation speed of 300 rpm to obtain a slurry. Subsequently, each silane coupling agent was prepared in an amount of 1 wt% based on the weight of the inorganic filler. The slurry was slowly dropped into the slurry for 10 minutes so that the droplets would not scatter, and the slurry was stirred at 300 rpm for 10 minutes. Thereafter, the surface-treated filler was removed by performing a circular qualitative filter paper. Subsequently, the surface-treated inorganic filler was spread in a shallow tray and dried at 110 DEG C for 60 minutes to obtain an inorganic filler surface-treated with a silane coupling agent. The inorganic fillers and silane coupling agents used are described in the annotations in Table 1 below.

(Examples 1 to 34 and Comparative Examples 1 to 12)

&Lt; Preparation of dry film &

Each component was compounded by the formulations shown in the examples and comparative examples described in Tables 1, 3, 5, 7, 9, 11, 13, and 15, and the components were mixed and dispersed by roll milling to obtain a solution having a viscosity of 0.5 to 20 dPa ((rotational viscometer, 25 占 폚). Subsequently, the film was applied to a carrier film (Lamierer S10, thickness 38 mu m, no surface treatment, Ra = 0.03 mu m, manufactured by Toray Industries Co., Ltd.) using a bar coater so that the film thickness of the dry film became 15 mu m after drying. Subsequently, drying was carried out at 85 캜 for 5 to 15 minutes so that the residual solvent amount in the hot air circulating type drying furnace was 3.5 to 4.5%, thereby forming a curable resin layer on the carrier film. Subsequently, a protective film (MA-411, thickness: 15 mu m, Ra = 0.45 mu m, manufactured by Ojifec) was roll laminated on the dry film surface at a set temperature of 70 DEG C to obtain a three-layer structure dry film.

&Lt; Storage elastic modulus G 'and melt viscosity of resin layer >

Each of the dry films prepared above was peeled off the protective film, and the resin layer of two dry films was superposed and thermocompression-bonded with a one-chamber vacuum laminator MVLP-500 (manufactured by Meikisha Co., Ltd.) Mu] m. At that time, in order to prevent heat from being applied to the film, the film was laminated by laminating at a temperature of 40 ° C and a pressure of 0.5 MPa for 1 minute. Next, the carrier-film was peeled off with a visco-viscoelasticity measuring device Leostress RS-6000 (manufactured by HAAKE), and the temperature-viscoelasticity of each resin layer was measured. The measurement conditions were a temperature rise mode of 5 占 폚 / min, an oscillation mode deformation amount of 8%, a frequency of 1Hz, a parallel plate having a measurement sensor? Of 20 mm, and a gap of 300 占 퐉 between sensors. By thickening the resin layer with respect to the gap, a sufficient resin thickness can be secured between the gaps even during heating. From the curve of the temperature-storage elastic modulus G 'and the viscosity? Measured by the above-mentioned method, the storage elastic modulus and the melt viscosity at 100 ° C were defined as "the storage modulus G' of the resin layer and the" melt viscosity of the resin layer " . The measurement results are shown in the table.

&Lt; Filling property (FLS (fine line & space)) >

A double-sided printed wiring board on which a fine circuit of a comb pattern having a copper thickness of 10 占 퐉, L (line: wiring width) / S (space: spacing width) = 5/5 占 퐉 and an aspect ratio of 2.0 was formed, -8101 etching treatment corresponding to 0.5 占 퐉 was performed. Subsequently, a dry film having a thickness of 15 占 퐉 produced as described above was laminated on a substrate on which L / S was formed, using a batch type vacuum pressure laminator MVLP-500 (manufactured by Meikisha). Lamination was conducted under the conditions of 5 kgf / cm ² , 100 ° C, 1 minute, 1 Torr, and then leveled at 10 kgf / cm ² at 100 ° C for 1 minute in a hot plate press process. After laminating, it was confirmed whether air bubbles (voids) were formed at the boundary between the lines and spaces after peeling the carrier film. The evaluation by this method was called &quot; after lamination &quot;. Subsequently, the evaluation of the occurrence of bubbles in the same manner under the condition of curing the resin layer was made &quot; after curing &quot;. The curing conditions are detailed in the following section. The evaluation criteria are as follows.

○: No void was confirmed.

?: 1 to 5 voids were confirmed.

X: The viscosity and the modulus of elasticity were high, so that it could not be buried in a substrate having fine lines.

&Lt; Flatness of Substrate after Curing >

The reason why the curing system is thermosetting with respect to the resin layer of each of the dry films laminated on the substrate on which the microcircuit is formed by the method described in the &quot; Filling property (generated bubble generation FLS) &quot; , And then thermally cured at 180 DEG C for 30 minutes in a hot air circulation type drying furnace and then thermally cured at 200 DEG C for 60 minutes to completely cure the resin layer.

On the other hand, in the case where the curing system was optically and thermosetting, the carrier film was peeled from the carrier film after the photocuring with an exposure dose of 300 mJ / cm ² (i line, Usio projection exposure apparatus) so that the fine line portion was completely exposed. Subsequently, development was carried out for 60 seconds at a solution temperature of 30 ° C at a pressure of 0.2 MPa with a 1 wt% sodium carbonate aqueous solution. Subsequently, exposure was performed at 1000 mJ / cm ² using a high-pressure mercury lamp irradiation device. Thereafter, the resin layer was thermally cured at 180 DEG C for 60 minutes in a hot-air circulation type drying furnace to completely cure the resin layer.

The surface roughness of the surface of the cured film in the direction perpendicular to the fine lines was measured with a contact type surface roughness measuring device (SE-300, manufactured by Kosaka Kagaku Co., Ltd.) on the substrate completely cured by each curing method, Irregularities were measured. The evaluation criteria are as follows.

?: On the fine circuit, irregularities have a maximum tolerance of less than 0.3 占 퐉. No copper burning of the microcircuits was observed.

?: On the fine circuit, the maximum unevenness is less than 0.3 占 퐉.

DELTA: On the fine circuit, the maximum unevenness is 0.3 mu m or more and less than 1.0 mu m.

X: On the fine circuit, the maximum irregularity has a tolerance of 1.0 占 퐉 or more.

××: On the fine circuit, the maximum unevenness is 5.0 μm or more. The unevenness of the circuit was remarkable.

&Lt; Adhesion with a ground circuit >

Electrolytic copper foil GTS-MP-18 占 퐉 (manufactured by Furukawa Electric Co., Ltd.) was etched to a thickness of 0.5 占 퐉 by CZ-8101 manufactured by Mack Co.

Thereafter, the respective dry films were laminated by the method described in &quot; Filling property (generation of bubbles FLS) &quot;, and then the resin layer was completely cured by the method of &quot; flatness of substrate after curing &quot; Thereafter, the adhesive layer was cured at room temperature by using a two-component adhesive Araldite on the side of the resin layer and overlaid on the H-out plate of 1.6 mmt FR-4 to obtain a three-layer structure of the CZ treated copper foil- . The obtained substrate was evaluated for adhesion to CZ treated surfaces of respective resin layers in accordance with JIS-C-6481 test method for copper clad laminate and measuring method of peel strength (test piece width 10 mm, direction at 90 °, speed 50 mm / min) Were measured. The judgment criteria are as follows.

?: Adhesive strength of 5.0 N / cm or more.

?: Adhesive strength of 3.0 N / cm or more and less than 5.0 N / cm.

X: The viscosity or the modulus of elasticity was high, and evaluation samples could not be produced.

&Lt; Formability of plating resist &

A plating resist was formed on the surface of the cured substrate produced by the method described in &quot; Flatness of Substrate after Curing &quot;

Specifically, the cured substrate thus prepared was subjected to swelling at 60 ° C for 5 minutes, permanganic acid at 80 ° C for 20 minutes, and reduction at 50 ° C for 5 minutes using a permanganate desmear treatment (manufactured by Atotech Co., Ltd., Sucuregent MV series for vertical dismers) , And the surface of the substrate was roughened. Subsequently, a copper seed layer having a thickness of 0.3 탆 was formed on the surface of the substrate by using an electroless copper plating treatment (alkaline ion type Pd made by Uemura Kogyo Co., Ltd.). Subsequently, the surface of the copper seed layer was subjected to alkali degreasing. Subsequently, a plating resist POTEC RY-3625 (plating resist for SAP, made by Hitachi Chemical Co., Ltd., thickness: 25 mu m) Overlaid on the surface. Subsequently, a pattern of L / S = 10/10 占 퐉 was formed in a glass dry plate negative mask L / S pattern (an area of 20 mm × 20 mm) by EXP-2960 (manufactured by Oak Seisakusho Co., Negative mask) was used to form a negative pattern on the substrate surface at an exposure dose of 100 mJ / cm ² . Subsequently, development was carried out at 30 DEG C for 30 seconds with a 1 wt% aqueous solution of sodium carbonate to form a L / S pattern on the surface of the substrate. The obtained substrate was observed using SEM. 100 parts were randomly extracted in the range of 20 mm x 20 mm to evaluate the formability of the plating resist (confirmation of the presence or absence of a state where a defective development occurred due to a recess in a line or a recessed portion). The judgment criteria are as follows.

Good: Good formability.

?: L / S formation failure (line shortage, development failure) was observed at more than one point and less than 10 points.

X: Defective formation of L / S (missing of line, defective development) was observed at 10 or more points.

Xx: Since the legs are not flat, the pattern value as the design value can not be formed.

&Lt; Dielectric tangent after humidification >

A dry film having a thickness of 15 占 퐉 of the resin layer prepared by the method described in < Production of dry film > was formed on the polished surface of electrolytic copper foil GTS-MP-18 占 퐉 (manufactured by Furukawa Circuit Wheel Co., Ltd.) FLS), and then the resin layer was completely cured by the method of &quot; flatness of substrate after curing &quot;. Thereafter, the cured product was peeled from the copper foil to obtain a cured product having a thickness of 15 탆.

The resulting cured product was stored in a high-temperature, high-humidity bath set at a temperature of 85 ° C and a humidity of 85% RH for 100 hours. Using a SPDR dielectric resonator and a network analyzer (all manufactured by Agilent) The dielectric loss tangent at the time of humidification of GHz was measured. The judgment criteria are as follows.

◎ ◎: The dielectric loss tangent at 5 GHz is less than 0.005.

?: The dielectric loss tangent at 5 GHz is 0.005 or more and less than 0.01.

?: The dielectric loss tangent at 5 GHz is 0.01 or more and less than 0.015.

DELTA: dielectric loss tangent at 5 GHZ of 0.015 or more and less than 0.02.

X: dielectric loss tangent at 5 GHz of 0.02 or more.

<Heat dissipation characteristics>

The cured product of 15 占 퐉 obtained in the same manner as the <dielectric loss tangent after humidification> was measured for the thermal conductivity of the cured product in accordance with the method described in JIS-R1611. The judgment criteria are as follows.

◎: Thermal conductivity is 1 W / m · K or more.

○: Thermal conductivity is 0.3 W / m · K or more and less than 1 W / m · K.

?: Thermal conductivity is less than 0.3 W / m? K.

X: The viscosity or the modulus of elasticity was high, and evaluation samples could not be produced.

<Thermal Expansion Coefficient>

The cured product of 15 占 퐉 obtained in the same manner as in the <dielectric loss tangent after humidification> was peeled off from the copper foil, and then the sample was cut into a measurement size (size of 3 mm x 10 mm) and supplied to TMA6100 manufactured by Seiko Instruments. The TMA measurement was carried out twice in succession, with the temperature of the sample being raised at a rate of 10 DEG C / min from the room temperature of 5 g in the test weight. (CTE (? 1)) in a region of Tg or less in the second time. The judgment criteria are as follows.

◎ ◎: Less than 10ppm CTE below glass transition temperature.

◎: CTE of 10 ppm or more and less than 17 ppm below glass transition temperature.

?: The CTE below the glass transition temperature is 17 ppm or more and less than 30 ppm.

?: CTE of 30 ppm or higher at or below the glass transition temperature.

X: The viscosity or the modulus of elasticity was high, and evaluation samples could not be produced.

&Lt; Substrate warpage &

On a copper clad laminate (MCL-E-770G, Hitachi Kasei, copper having a thickness of 18 m and a thickness of 200 mm and a size of 100 mm x 100 mm and subjected to an etching treatment equivalent to CZ-8101 1 m as a pretreatment) , A resin film having a thickness of 15 mu m was laminated on one side of the substrate using a vacuum laminator and then the carrier film was peeled off and the resin layer was completely cured by using a hot air circulation type drying furnace . For each of the obtained substrates, the four corners of the substrate were measured with respect to the amount of warpage using a nogris, and evaluation was made according to the following criteria.

◎: The maximum value of warpage is less than 3mm.

○: The maximum value of the warp is 3mm or more and less than 15mm.

?: The maximum value of the warp is 15 mm or more.

X: The viscosity or the modulus of elasticity was high, and evaluation samples could not be produced.

<Reflow + TCT (Thermal Cycling Test)>

Each of Examples and Comparative Examples by using the dry film thickness (thickness of the resin 15㎛) a batch type vacuum pressure laminator MVLP-500 (May Fuki claim), the copper in 5kgf / cm ^2, 80 ℃ of the copper-clad laminate for 1 minute , And 1 Torr. Thereafter, the carrier film was peeled and heated in a hot-air circulation type drying furnace, and the resin layer was cured at 180 DEG C for 30 minutes. Thereafter, vias were formed using a CO ₂ laser processing machine (manufactured by Hitachi Biomekanics Co., Ltd.) so as to have a top diameter of 65 μm and a bottom diameter of 50 μm.

Regarding the curing system being optically and thermosetting, exposure and development are carried out by using a negative pattern of? 65 占 퐉 by the method described in <Flatness of Substrate after Curing>, and then ultraviolet irradiation and final curing are carried out to form vias Respectively.

Subsequently, the obtained via pattern was subjected to treatment in the order of a commercially available wet permanganic acid dismear (manufactured by ATOTECH), electroless copper plating (through cup PEA, manufactured by Uemura Kogyo Co., Ltd.) and electrolytic copper plating treatment, A copper thickness of 25 mu m, and a copper plating treatment so as to fill the via portion. Subsequently, the substrate was thermally cured at 200 DEG C for 60 minutes in a hot-air circulation type drying furnace to obtain a test substrate on which a fully cured copper plating treatment was performed. The obtained test substrate was subjected to a heat treatment for 3 cycles of reflow treatment under the conditions of a lead-free assembly (peak temperature 270 DEG C for 10 seconds), followed by one cycle consisting of -65 DEG C for 30 minutes and 150 DEG C for 30 minutes, Respectively. After the lapse of 2000 and 3000 cycles, in order to observe the state of the via bottom or the wall surface by an optical microscope, the center portion of the via was cut and polished by a precision cutter to observe the cross-sectional state. The evaluation criteria were evaluated as follows. The number of observed vias was 100 holes.

A: No crack occurred after 3000 cycles.

?: No crack occurred after the end of 2000 cycles. 1 to 5 cracks occurred in 3000 cycles.

DELTA: 1 to 5 cracks occurred after the end of 2000 cycles.

X: The test piece could not be produced because the melt viscosity and the storage elastic modulus exceeded the optimum range.

<Relative dielectric constant>

A dry film having a thickness of 15 占 퐉 of the resin layer prepared by the method described in < Production of dry film > was formed on the polished surface of electrolytic copper foil GTS-MP-18 占 퐉 (manufactured by Furukawa Circuit Wheel Co., Ltd.) FLS), and then the resin layer was completely cured by the method of < flatness of the substrate after curing >. Thereafter, the cured product was peeled from the copper foil to obtain a cured product having a thickness of 15 탆.

The obtained cured product was measured for dielectric constant at 1 GHz at 23 DEG C using an SPDR dielectric resonator and a network analyzer (all manufactured by Agilent). The judgment criteria are as follows.

⊚: relative dielectric constant at 1 GHz is 10.0 or more.

?: The relative dielectric constant at 1 GHz is 5.0 or more and less than 10.0.

&Lt; Circuit concealment >

A cured film was formed on the microcircuit substrate by the method described in < Filling property (generation of bubbles FLS) > < Flatness of substrate after curing >, and then the carrier film was peeled to obtain a printed wiring board.

With respect to the obtained evaluation substrate, the discoloration of the copper circuit on the cured film was visually confirmed, and the concealability of the circuit was evaluated. The judgment criteria are as follows.

⊚: discoloration is not confirmed.

X: Discoloration was confirmed.

* 1: HP-820 manufactured by DIC, alkylphenol type liquid epoxy resin, epoxy equivalent: 225 g / eq

* 2: NC-3000L manufactured by Nihon Kayakusa, biphenyl aralkyl type solid epoxy resin, epoxy equivalent: 275 g / eq

* 3: CG-500 manufactured by Osaka Gas Chemical Co., fluorene solid epoxy resin, epoxy equivalent: 311 g / eq

* 4: TGIC manufactured by Nissan Kagaku Co., triglycidyl isocyanurate (solid epoxy resin), epoxy equivalent: 99 g / eq

* 5: Mitsubishi Chemical Corporation 1003, Bis-A type solid epoxy resin, epoxy equivalent: 720 g / eq

* 6: TD-2131 manufactured by DIC, phenol novolak resin, hydroxyl equivalent: 104 g / eq

* 7: MEH-7851-4H manufactured by Meiwa Chemical Industries, Ltd., biphenylaralkyl type phenol resin, hydroxyl equivalent: 240 g / eq

* 8: LA-3018 manufactured by DIC, phenol novolac resin containing ATN, hydroxyl equivalent: 151 g / eq

* 9: Malka linker M, polyvinyl phenol, hydroxyl equivalent of 120 g / eq, manufactured by Maruzen Chemical Industries, Ltd.

* 10: PT-30 manufactured by Lonza Japan, novolac cyanate ester resin, cyanate equivalent: 124 g / eq

* 11: BA-3000, Bis-A type cyanate ester resin manufactured by Lonza Japan, cyanate equivalent: 284 g / eq

* 12: BMI-1100 manufactured by Daiwa Kasei Kogyo Co., Ltd., N, N'-diphenylmethane bismaleimide, maleimide equivalent: 179 g / eq

* 13: MIR-3000 manufactured by Nippon Kayaku Co., bismaleimide containing biphenyl skeleton, maleimide equivalent: 275 g / eq

* 14: PC-1100-02 manufactured by Air Water Co., polyfunctional active ester resin, active ester equivalent: 154 g / eq

* 15: EXB9416 manufactured by DIC, naphthol end, active ester resin containing dicyclopentadiene skeleton, active ester equivalent: 220 g / eq

* 16: RMA-11902 manufactured by Nippon Nyuga Co., Ltd., a photosensitive carboxyl group-containing resin (solid content: 65%) having an acrylic group using phenol resin as a starting material,

* 17: A-DCP manufactured by Shin Nakamura Kagaku Kogyo Co., dicyclopentadiene skeletal acrylic acid monomer

* 18: HPS-500 manufactured by Doagosei Co., Ltd., spherical silica having D50 =

* 19: HPS-1000 manufactured by Toagosei Co., Ltd., spherical silica having D50 =

* 20: Surface treated silica A (1 wt% aminosilane-treated product of nano-silica (average primary particle diameter (D50) = 50 nm) manufactured by Admatechs Co.,

* 21: FB-5SDX manufactured by Denki Kagaku Kogyo Co., Ltd., D50 = 4.9 탆 spherical silica

* 22: Surface-treated silica B (HPS-500 / KBE-1003, 1 wt% vinylsilane treated product of HPS-500)

* 23: Surface-treated silica C (HPS-500 / KBE-9103, 1 wt% amino silane treated product of HPS-500)

* 24: Surface-treated silica D (HPS-1000 / KBE-1003, HPS-1000 treated with 1 wt% vinyl silane)

* 25: Surface-treated silica E (FB-5SDX / KBE-9103, 1 wt% amino silane treated product of FB-5SDX)

* 26: ASFP-20 manufactured by Denki Kagaku Kogyo Co., Ltd., spherical alumina with D50 = 0.3 탆

* 27: DAM-03 manufactured by Denki Kagaku Kogyo Co., Ltd., spherical alumina having D50 = 3.7 탆

* 28: Surface treated alumina A (ASFP-20 / KBE-1003, 1 wt% vinylsilane treated product of ASFP-20)

* 29: Surface treated alumina B (DAM-03 / KBE-1003, DAM-03 1 wt% vinyl silane treated product)

* 30: Fuseless WX made by Tatsumori Co., D50 = 1.5 mu m pseudomorphic silica

* 31: KBE-1003 manufactured by Shin-Etsu Chemical Co., Ltd., vinyltriethoxysilane

* 32: KBE-402 manufactured by Shin-Etsu Chemical Co., Ltd., 3-glycidoxypropylmethyldiethoxysilane

* 33: KBE-9103 from Shin-Etsu Chemical Co., Ltd., 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine

* 34 Irgacure 369 manufactured by BASF Japan, alpha -aminoalkylphenone-based photopolymerization initiator

* 35: Cobalt acetylacetonate 1 wt%, DMF solution

* 36: Shikoku Kasei Co., Ltd. 2E4MZ-AP, imidazole

* 37: YL7600 manufactured by Mitsubishi Chemical Corporation, phenoxy resin containing a low-molecular skeleton

* 38: Cyclohexanone

* 39: DMF (N, N-dimethylformamide)

* 40: Izpol 100 manufactured by Idemitsu Kosan Co., Ltd., aromatic high boiling point solvent

* 42: EPICLON 860 manufactured by DIC, bisphenol A type semi-solid epoxy resin, epoxy equivalent: 245 g / eq

* 43: HP-4032 manufactured by DIC, naphthalene type semi-solid epoxy resin, epoxy equivalent: 150 g / eq

* 44: N-740 manufactured by DIC, phenol novolac type semi-solid epoxy resin, epoxy equivalent: 180 g / eq

* 45: Made by Sakai Kagaku Kogyo Co., Ltd. BT-03B D50 = 0.3 탆

* 46: Ishihara Mountain Taipei CR-97 D50 = 0.25 mu m

* 47: CZ-03 D50 made by Sakai Kagaku Kogyo Co., Ltd. = 0.3 탆

From the results shown in the above table, it can be seen that the dry films of Examples 1 to 34 are excellent in the filling property and flatness of the resin layer. On the other hand, the dry film of Comparative Examples 1 to 11, in which the melt viscosity of the resin layer does not satisfy 60 to 5500 dPa 占 퐏 at 100 占 폚, or the storage elastic modulus of the resin layer does not satisfy 80 to 5500 Pa at 100 占 폚, The dry film of Comparative Example 12 having a liquid epoxy resin content of 60% by mass or more had poor fillability and flatness.

11 Two-layer structure dry film
12 resin layer
13 film
21 Three-layer structure dry film
22 resin layer
23 First film
24 Second film
30a Test tube for liquid determination
30b Test tube for temperature measurement
31 Line (A line)
32 Mark line (line B)
33a, 33b Rubber plug
34 Thermometers

Claims (9)

A dry film having a film and a resin layer containing an epoxy resin formed on the film,
Wherein the resin layer has a melt viscosity of 60 to 5500 dPa 占 퐏 at 100 占 폚,
Wherein the resin layer has a storage elastic modulus at 100 DEG C of 80 to 5500 Pa,
Wherein the resin layer contains at least a liquid epoxy resin as the epoxy resin,
Wherein the content of the liquid epoxy resin is less than 60% by mass based on the total mass of the epoxy resin. The dry film according to claim 1, wherein the amount of the residual solvent in the resin layer is 1.0 to 7.0% by mass. The method according to claim 1, wherein the resin layer contains at least two organic solvents selected from the group consisting of N, N-dimethylformamide, toluene, cyclohexanone, aromatic hydrocarbons having 8 or more carbon atoms, and methyl ethyl ketone Lt; / RTI &gt; The epoxy resin composition according to claim 1, wherein the resin layer further comprises at least one semi-solid epoxy resin selected from the group consisting of a bisphenol A epoxy resin, a naphthalene epoxy resin and a phenol novolak epoxy resin as the epoxy resin By weight. The method of claim 1, wherein the resin layer comprises a filler,
Wherein the filler has an average particle diameter of 0.1 to 10 mu m. The method of claim 1, wherein the resin layer comprises a filler,
Wherein the filler is contained in an amount of 40 to 80% by mass based on the entire amount of the resin layer (when the resin layer contains a solvent, the total amount excluding the solvent). The method of claim 1, wherein the resin layer comprises a filler,
Wherein the filler is selected from the group consisting of a silane coupling agent having an epoxy group, a silane coupling agent having an amino group, a silane coupling agent having a mercapto group, a silane coupling agent having an isocyanate group, a silane coupling agent having a vinyl group, A silane coupling agent having a group and a silane coupling agent having an acryl group. A cured product obtained by curing a resin layer of the dry film according to any one of claims 1 to 7. A printed wiring board comprising the cured product according to claim 8.

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