JP6937701B2 - Dry film and printed wiring board - Google Patents

Description

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

Conventionally, a dry film has been used as one of means for forming a protective film or an insulating layer such as a solder resist or an interlayer insulating layer provided on a printed wiring board used in an electronic device or the like (for example, Patent Documents 1 to 3). .. The dry film has a resin layer obtained by applying a curable resin composition having desired properties on the carrier film and then performing a drying step, and generally protects the surface opposite to the carrier film. Protective films for this purpose are further laminated and distributed on the market. The protective film and the insulating layer as described above can be formed on the printed wiring board by laminating the resin layer of the dry film on the base material having the circuit pattern and then performing patterning and curing treatment.

Japanese Unexamined Patent Publication No. 7-15119 (Claims) JP-A-2002-162736 (Claims) Japanese Unexamined Patent Publication No. 2003-131366 (Claims)

When laminating the resin layer of the dry film on the base material, the resin layer may not be sufficiently embedded in the unevenness of the circuit pattern on the base material, and bubbles may be generated between the resin layer and the base material. In some cases, such bubbles impair the adhesion between the resin layer and the base material.

Further, vacuum laminating and pressing are performed in order to flatten the outer surface of the resin layer of the dry film after laminating, but the unevenness of the circuit pattern on the base material is transferred to the outer surface. , The flatness was not enough. In particular, due to the recent trend toward lighter, thinner, shorter and smaller electronic devices, it is required that the printed wiring board be made thinner and the resin layer of the dry film be made even thinner. This makes it difficult to obtain the embedding property of the resin layer in the base material and the flatness of the outer surface of the resin layer even if vacuum laminating or pressing is performed.

Therefore, an object of the present invention is to provide a dry film having a resin layer excellent in embedding property and flatness, and a printed wiring board provided with a cured product obtained by curing the dry film.

As a result of diligent studies in view of the above, the present inventors have 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 is 60 with respect to the total amount of epoxy resin. We have found that the above problems can be solved by using a dry film having a resin layer contained in an amount of less than mass%, and have completed the present invention.

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, and the melt viscosity of the resin layer is 60 to 5500 dPa · s at 100 ° C. The storage elastic coefficient of the resin layer is 80 to 5500 Pa at 100 ° C., and the resin layer contains at least a liquid epoxy resin as the epoxy resin.
The content of the liquid epoxy resin is less than 60% by mass with respect to the total mass of the epoxy resin.

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

The dry film of the present invention 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 in the resin layer. Is preferable.

In the dry film of the present invention, the resin layer is at least one semi-solid epoxy resin selected from the group consisting of bisphenol A type epoxy resin, naphthalene type epoxy resin and phenol novolac type epoxy resin as the epoxy resin. It is preferable to include it.

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

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

In the dry film of the present invention, the resin layer contains a filler, and the filler contains a silane coupling agent having an epoxy group, a silane coupling agent having an amino group, a silane coupling agent having a mercapto group, and an isocyanate group. Surface treatment with at least one of a silane coupling agent having a vinyl group, a silane coupling agent having a vinyl group, a silane coupling agent having a styryl group, a silane coupling agent having an acrylic group, and a silane coupling agent having a methacryl group. It is preferable that it is.

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 dry film having a resin layer excellent in embedding property and flatness, and a printed wiring board provided with a cured product obtained by curing the dry film.

It is a schematic cross-sectional view which shows typically one Embodiment of the laminated structure of this invention. It is a schematic cross-sectional view which shows typically another embodiment of the laminated structure of this invention. It is a schematic side view which shows the two test tubes used for the liquid 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, and the melt viscosity of the resin layer is 60 to 5500 dPa · s at 100 ° C., and the resin layer. The storage elasticity of the resin is 80 to 5500 Pa at 100 ° C., the resin layer contains at least a liquid epoxy resin as the epoxy resin, and the content of the liquid epoxy resin is 60% by mass with respect to the total amount of the epoxy resin. It is characterized by being less than. Although the detailed mechanism is not clear, both the melt viscosity and the storage elastic modulus of the resin layer should be adjusted within the above ranges, and the ratio of the liquid epoxy resin contained in the resin layer to the total amount of epoxy resin should be less than 60% by mass. Remarkably improves embedding and flatness.

Further, according to the dry film of the present invention, a cured film having a flat surface can be formed, so that when a plating resist is formed on the cured film, it is possible to suppress missing lines of the plating resist and development defects. .. That is, according to the dry film of the present invention, a cured product having excellent formability of a plating resist can be obtained. This also makes it possible to form a high-definition 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 the storage elastic modulus of the resin layer is less than 80 Pa at 100 ° C. It becomes difficult to obtain. On the other hand, when the melt viscosity of the resin layer exceeds 5500 dPa · s at 100 ° C. or the storage elastic modulus of the resin layer exceeds 5500 Pa at 100 ° C., 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 is preferably 100 to 3500 Pa · s at 100 ° C. Further, even when the content of the liquid epoxy resin is 60% by mass or more with respect to the total amount of the epoxy resin, it becomes difficult to obtain the embedding property of the dry film and the flatness of the outer surface of the resin layer.

When the melt viscosity of the resin layer is 3000 dPa · s or less at 100 ° C. and the storage elastic modulus of the resin layer is 3000 Pa · s or less at 100 ° C., it is preferable because the flatness and the formability of the plating resist are excellent.

When the melt viscosity of the resin layer is 100 dPa · s or more at 100 ° C. and the storage elastic modulus of the resin layer is 100 Pa · s or more at 100 ° C., it is preferable that air bubbles are less likely to be entrained during laminating and the embedding property is more excellent. ..

It is more preferable that the melt viscosity of the resin layer is 500 to 3000 dPa · s at 100 ° C. and the storage elastic modulus of the resin layer is 500 to 3000 Pa · s at 100 ° C.

The method for adjusting the melt viscosity and the storage elastic modulus of the resin layer is not particularly limited, but as described later, it can be easily adjusted by selecting the blending amount, particle size, type, etc. of the filler. It can also be adjusted by a thermosetting component or a curing agent.

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

[Resin layer]
The resin layer of the dry film of the present invention is in a state 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 through a drying step after applying the curable resin composition to the film. The type and amount of other components of the curable resin composition are not particularly limited as long as they satisfy the melt viscosity, storage elastic modulus and the amount of the liquid epoxy resin. The film thickness of the resin layer is not particularly limited, and for example, the film thickness after drying may be 1 to 200 μm, but the thinner the resin layer, the more remarkable the effect of the present invention can be obtained. Specifically, the thickness of the resin layer is preferably 30 μm or less, more preferably 20 μm or less, still more preferably 15 μm or less, because the effect of the present invention is more likely to be exhibited.

The resin layer contains an epoxy resin. The epoxy resin is a resin having an epoxy group, and any conventionally known resin can be used. Examples thereof include a bifunctional epoxy resin having two epoxy groups in the molecule, a polyfunctional epoxy resin having many epoxy groups in the molecule, and the like. It may be a hydrogenated epoxy resin. The resin layer contains a liquid epoxy resin as the epoxy resin in a content 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 that is solid at 40 ° C., and the semi-solid epoxy resin refers to an epoxy resin that is solid at 20 ° C. and liquid at 40 ° C., and is a liquid epoxy resin. Refers to an epoxy resin that is liquid at 20 ° C.

Judgment of liquidity is carried out in accordance with the "Liquid confirmation method" of Attachment 2 of the Ministerial Ordinance on Dangerous Goods Testing and Properties (Ministerial Ordinance No. 1 of 1989).
(1) Equipment constant temperature water tank:
Use a stirrer, heater, thermometer, and automatic temperature controller (those that can control the temperature at ± 0.1 ° C) with a depth of 150 mm or more.
In the determination of the epoxy resin used in the examples described later, about 22 liters of tap water was used in combination with a low-temperature constant temperature water tank (model BU300) manufactured by Yamato Scientific Co., Ltd. and a charging constant temperature device Thermomate (model BF500). In a low temperature constant temperature water tank (model BU300), turn on the power of the thermomate (model BF500) attached to it, set it to the set temperature (20 ° C or 40 ° C), and set the water temperature to the set temperature ± 0.1 ° C. Fine adjustment was made with Thermomate (model BF500), but any device that can make similar adjustments can be used.

Test tube:
As shown in FIG. 3, the test tube is made of flat-bottomed cylindrical transparent glass having an inner diameter of 30 mm and a height of 120 mm, and marked lines 31 and 32 are attached at heights of 55 mm and 85 mm from the tube bottom, respectively. , The liquid judgment test tube 30a in which the mouth of the test tube is sealed with rubber 1000 33a, and the rubber stopper 33b which has the same size and is similarly marked and has a hole in the center for inserting and supporting the thermometer. The test tube 30b for temperature measurement is used in which the mouth of the test tube is sealed and the thermometer 34 is inserted in the rubber stopper 33b. Hereinafter, the marked line having a height of 55 mm from the bottom of the pipe is referred to as "line A", and the marked line having a height of 85 mm from the bottom of the pipe is referred to as "line B".
As the thermometer 34, the one for freezing point measurement (SOP-58 scale range 20 to 50 ° C.) specified in JIS B7410 (1982) "Glass thermometer for petroleum test" is used, but the temperature is 0 to 50 ° C. Anything that can measure the range will do.

(2) Test implementation procedure Samples left for 24 hours or more under atmospheric pressure at a temperature of 20 ± 5 ° C. are subjected to a liquid determination test tube 30a shown in FIG. 3A and a temperature measurement test shown in FIG. 3B. Put up to line A in each tube 30b. The two test tubes 30a and 30b are placed upright in a low-temperature constant-temperature water tank so that the B line is below the water surface. The thermometer should have its lower end 30 mm below line A.
After the sample temperature reaches the set temperature ± 0.1 ° C, keep it as it is for 10 minutes. After 10 minutes, take out the liquid judgment test tube 30a from the low temperature constant temperature water tank, immediately lay it horizontally on a horizontal test table, and use a stopwatch to measure the time when the tip of the liquid level in the test tube moves from line A to line B. Measure and record. As for the sample, those having a measured time of 90 seconds or less at a set temperature are judged to be liquid, and those having a measured time of more than 90 seconds are judged to be solid.

As the solid epoxy resin, 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., Ltd. Naphthalene type epoxy resin such as EPPN-502H (Trisphenol epoxy resin) manufactured by Nippon Kayaku Co., Ltd .; Epoxy product of condensate of phenols such as EPPN-502H (Trisphenol epoxy resin) and aromatic aldehyde having phenolic hydroxyl group (Trisphenol type epoxy resin) Dicyclopentadiene aralkyl type epoxy resin such as Epicron HP-7200H (dicyclopentadiene skeleton-containing polyfunctional solid epoxy resin); Biphenyl aralkyl such as NC-3000H (biphenyl skeleton-containing polyfunctional solid epoxy resin) manufactured by Nippon Kayaku Co., Ltd. Type epoxy resin; Biphenyl / phenol novolac type epoxy resin such as NC-3000L manufactured by Nippon Kayaku Co., Ltd .; Novolac type epoxy resin such as Epicron N660 and Epicron N690 manufactured by DIC Co., Ltd .; EOCN-104S manufactured by Nippon Kayaku Co., Ltd .; Biphenyl type epoxy resins such as YX-4000; phosphorus-containing epoxy resins such as TX0712 manufactured by Nippon Steel & Sumitomo Metal Corporation; tris (2,3-epoxypropyl) isocyanurate such as TEPIC manufactured by Nissan Chemical Industry Co., Ltd. and the like can be mentioned.

Examples of the semi-solid epoxy resin include Epicron 860 manufactured by DIC, Epicron 900-IM, Epicron EXA-4816, Epicron EXA-4822, Araldite AER280 manufactured by Asahi Ciba, Epototo YD-134 manufactured by Toto Kasei Co., Ltd., and jER834 manufactured by Mitsubishi Chemical Co., Ltd. Examples thereof include bisphenol A type epoxy resins such as jER872 and ELA-134 manufactured by Sumitomo Chemical Industries; naphthalene type epoxy resins such as Epicron HP-4032 manufactured by DIC; and phenol novolac type epoxy resins such as Epicron N-740 manufactured by DIC. ..
The semi-solid epoxy resin preferably contains at least one selected from the group consisting of bisphenol A type epoxy resin, naphthalene type epoxy resin and phenol novolac type epoxy resin. By containing these semi-solid epoxy resins, the glass transition temperature (Tg) of the cured product is high, the CTE is low, and the crack resistance is excellent.

Examples of the liquid epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, phenol novolac type epoxy resin, tert-butyl-catechol type epoxy resin, glycidylamine type epoxy resin, and aminophenol type epoxy resin. , Alicyclic epoxy resin and the like.

Two or more types of epoxy resins can be used in combination. The blending amount of the epoxy resin is preferably 5 to 50% by mass, more preferably 5 to 40% by mass, and further 5 to 35% by mass based on the total amount of the resin layer of the dry film excluding the solvent. preferable. 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 thermal characteristics of the dry film can be improved by matching the thermal strength with the conductor layer such as copper around the insulating layer. Conventionally known inorganic fillers and organic fillers can be used as the filler, and the filler is not limited to a specific one, but an inorganic filler that suppresses curing shrinkage of the coating film and contributes to improvement of properties such as adhesion and hardness is preferable. Examples of the inorganic filler include barium sulfate, barium titanate, barium titanate, strontium titanate, calcium titanate, calcium zirconate, magnesium titanate, bismuth titanate, barium neodymium titanate, and barium tin titanate. Lead titanate, amorphous silica, crystalline silica, fused silica, spherical silica and other silica, talc, clay, Neuburg silica soil particles, boehmite, magnesium carbonate, calcium carbonate, titanium oxide, aluminum oxide, aluminum hydroxide, silicon nitride , Constituent pigments such as aluminum nitride, and metal powders such as copper, tin, zinc, nickel, silver, palladium, aluminum, iron, cobalt, gold, and platinum.
Among the above fillers, barium titanate, barium titanate, strontium titanate, calcium titanate, calcium zirconate, magnesium titanate, bismuth titanate, barium neodymium titanate, barium tin titanate, lead titanate, oxidation The use of titanium is preferable because the dielectric constant can be increased and the concealment of the circuit can be improved.
The inorganic filler is preferably spherical particles. The average particle size of the filler is preferably 0.1 to 10 μm. In the specification of the present application, the average particle size of the filler is an average particle size including not only the particle size of the primary particles but also the particle size of the secondary particles (aggregates). The average particle size can be determined by a laser diffraction type particle size distribution measuring device. Examples of the measuring device by the laser diffraction method include Nanotrac wave manufactured by Nikkiso Co., Ltd.

The inorganic filler is preferably surface-treated. As the surface treatment, a surface treatment with a coupling agent is preferable. 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. Of these, a silane coupling agent is preferable.

Examples of the silane coupling agent include 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, and a vinyl group as organic groups. A silane coupling agent having a styrene group, a silane coupling agent having a styryl group, a silane coupling agent having a methacryl group, a silane coupling agent having an acrylic group, and 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 because they are excellent in adhesion to the underlying circuit.

Further, the inorganic filler may be surface-treated such as alumina treatment without introducing an organic group.

The surface-treated inorganic filler may be blended in the resin layer of the dry film in the surface-treated state, and when preparing the curable resin composition, the surface-treated inorganic filler and the surface treatment agent are separately separated. Although the inorganic filler may be surface-treated in the composition by blending, it is preferable to blend the inorganic filler which has been surface-treated in advance when preparing the curable resin composition. By blending the inorganic filler that has been surface-treated in advance, the flatness of the resin layer after curing and the formability of the plating resist are further improved, and the dielectric loss tangent after humidification is excellent. In the case of surface treatment in advance, it is preferable to mix a pre-dispersion liquid in which an inorganic filler is pre-dispersed in a solvent. It is more preferable to sufficiently surface-treat the untreated inorganic filler when pre-dispersing it in a solvent, and then add the pre-dispersion liquid to the composition.
Here, if silica that has been surface-treated with a silane coupling agent having a vinyl group in advance is blended, the dielectric loss tangent after humidification is excellent. Further, when alumina which has been surface-treated with a silane coupling agent having a vinyl group in advance is blended, heat dissipation 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 total amount of the resin layer of the dry film excluding the solvent. When the blending amount of the filler is 25 to 85% by mass, the embedding property is excellent. When it is 25% by mass or more, the coefficient of linear expansion can be lowered and the heat dissipation characteristics are excellent.
Further, it is preferable to use two or more kinds of fillers in combination because they are excellent in flatness and formability of the plating resist. Here, when the filler contains a nanofiller having an average primary particle size of 100 nm or less, the filling efficiency of the filler can be increased. As a result, the dielectric loss tangent after humidification can be lowered, the coefficient of linear expansion can be reduced, and the crack resistance during the cooling and heating cycle after reflow can be improved.

The amount of residual solvent in the resin layer is preferably 1.0 to 7.0% by mass, more preferably 3.0 to 5.0% by mass, and 3.5 to 4.5% by mass. Is even more preferable. When the residual solvent is 7.0% by mass or less, bumping during thermosetting is suppressed and the flatness of the surface is improved. Further, it is possible to prevent the resin from flowing due to the melt viscosity being lowered too much, and the flatness is improved. When the residual solvent is 1.0% by mass or more, the fluidity at the time of laminating is good, and the flatness and embedding property are good. Further, when the residual solvent is 3.0 to 5.0% by mass, the handleability of the dry film and the coating film characteristics are excellent.

It is preferable that 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. When a resin composition containing such an organic solvent is used for forming the resin layer, it becomes easy to obtain a drying margin. That is, the drying time can be lengthened, and the degree of freedom in the drying time is improved.

The curable resin composition is a thermosetting resin composition containing an epoxy resin such as a liquid epoxy resin, and as specific examples, a photocurable thermosetting resin composition, a thermosetting resin composition, and photopolymerization initiation. Photocurable thermosetting resin composition containing an agent, photocurable thermosetting resin composition containing a photobase generator, photocurable thermosetting resin composition containing a photoacid generator, negative type Photocurable thermosetting resin composition, positive photosensitive thermosetting resin composition, alkali-developed photocurable thermosetting resin composition, solvent-developed photocurable thermosetting resin composition, swelling peeling type Examples thereof include, but are not limited to, a thermosetting resin composition and a melt-release type thermosetting resin composition. Examples of the epoxy resin such as the liquid epoxy resin include those exemplified as the epoxy resin contained in the resin layer.

(Photocurable 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 the epoxy resin will be described below.

The carboxyl group-containing resin can be made alkaline developable because it contains a carboxyl group. Further, from the viewpoint of photocurability and development resistance, it is preferable to have an ethylenically unsaturated bond in the molecule in addition to the carboxyl group, but only a carboxyl group-containing resin having no ethylenically unsaturated bond is used. You may. When the carboxyl group-containing resin does not have an ethylenically unsaturated bond, a compound having one or more ethylenically unsaturated bonds (photosensitive monomer) is used in combination in order to make the composition photocurable. There is a need. The ethylenically unsaturated bond is preferably derived from acrylic acid or methacrylic acid or a derivative thereof. 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 using an epoxy resin as a starting material, and a carboxyl group-containing resin using a phenol compound as a starting material are available. preferable. Specific examples of the carboxyl group-containing resin include compounds (either oligomers or polymers) listed below.

(1) A (meth) acrylic acid is reacted with a bifunctional or higher polyfunctional epoxy resin as described later, and phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, etc. are added to the hydroxyl groups present in the side chain. Carboxyl group-containing photosensitive resin to which basic acid anhydride is added. Here, the bifunctional or higher polyfunctional epoxy resin is preferably solid.

(2) A (meth) acrylic acid is reacted with a polyfunctional epoxy resin obtained by further epoxidizing a hydroxyl group of a bifunctional epoxy resin as described later with epichlorohydrin, and a dibasic acid anhydride is added to the generated hydroxyl group. Carboxyl group-containing photosensitive resin. Here, the bifunctional epoxy resin is preferably solid.

(3) An epoxy compound having two or more epoxy groups in one molecule, a compound having at least one alcoholic hydroxyl group and one phenolic hydroxyl group in one molecule, and non-hydride such as (meth) acrylic acid. Polybases such as maleic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, adipic acid, etc., with respect to the alcoholic hydroxyl group of the reaction product obtained by reacting with a saturated group-containing monocarboxylic acid. A carboxyl group-containing photosensitive resin obtained by reacting an acid anhydride.

(4) Two or more in one molecule such as bisphenol A, bisphenol F, bisphenol S, novolak type phenol resin, poly-p-hydroxystyrene, condensate of naphthol and aldehydes, condensate of dihydroxynaphthalene and aldehydes, etc. A reaction obtained by reacting a reaction product obtained by reacting a compound having a phenolic hydroxyl group with an alkylene oxide such as ethylene oxide or propylene oxide with an unsaturated group-containing monocarboxylic acid such as (meth) acrylic acid. A carboxyl group-containing photosensitive resin obtained by reacting a product with a polybasic acid anhydride.

(5) An unsaturated group-containing monocarboxylic acid is reacted 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 the obtained reaction product with a polybasic acid anhydride.

(6) Diisocyanate compounds such as aliphatic diisocyanates, branched aliphatic diisocyanates, alicyclic diisocyanates, and aromatic diisocyanates, and polycarbonate-based polyols, polyether-based polyols, polyester-based polyols, polyolefin-based polyols, acrylic-based polyols, and bisphenol A-based An alkylene oxide adduct diol, a terminal carboxyl group-containing urethane resin obtained by reacting an acid anhydride with an acid anhydride at the end of a urethane resin obtained by a double addition reaction of a diol compound such as a compound having an alkylene oxide adduct diol, a phenolic hydroxyl group and an alcoholic hydroxyl group.

(7) Molecules such as hydroxyalkyl (meth) acrylate during the synthesis of a carboxyl group-containing urethane resin by a double addition reaction between a diisocyanate, a carboxyl group-containing dialcohol compound such as dimethylolpropionic acid and dimethylolbutyric acid, and a diol compound. A carboxyl group-containing urethane resin obtained by adding a compound having one hydroxyl group and one or more (meth) acryloyl groups to the terminal (meth) acrylic.

(8) During the synthesis of the carboxyl group-containing urethane resin by the double addition reaction of the diisocyanate, the carboxyl group-containing dialcohol compound, and the diol compound, 1 in the molecule such as an isophorone diisocyanate and a pentaerythritol triacrylate equimolar reaction product. A carboxyl group-containing urethane resin that is terminally (meth) acrylicated by adding a compound having one isocyanate group and one or more (meth) acryloyl groups.

(9) Carboxyl group-containing photosensitive obtained by copolymerization of an unsaturated carboxylic acid such as (meth) acrylic acid with an unsaturated group-containing compound such as styrene, α-methylstyrene, lower alkyl (meth) acrylate, and isobutylene. resin.

(10) A carboxyl group-containing polyester resin obtained by reacting a polyfunctional oxetane resin with a dicarboxylic acid such as adipic acid, phthalic acid, or hexahydrophthalic acid, and adding a dibasic acid anhydride to the generated primary hydroxyl group. Further, a carboxyl group-containing photosensitive resin obtained by adding a compound having one epoxy group and one or more (meth) acryloyl groups to one molecule such as glycidyl (meth) acrylate and α-methylglycidyl (meth) acrylate. ..

(11) A carboxyl group-containing photosensitive resin obtained by adding a compound having a cyclic ether group and a (meth) acryloyl group in one molecule to the carboxyl group-containing resin according to any one of (1) to (10) described above.

Here, (meth) acrylate is a general term for acrylate, methacrylate and a mixture 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, alkaline development becomes good. Further, by setting the acid value to 150 mgKOH / g or less, it is possible to easily draw a normal resist pattern. More preferably, it is 50 to 130 mgKOH / g.

The blending amount of the carboxyl group-containing resin is preferably 20 to 60% by mass based on the total amount of the resin layer of the dry film excluding the solvent. The coating film strength can be improved by setting the content to 20% by mass or more. Further, when the content is 60% by mass or less, the viscosity becomes appropriate and the workability is improved. More preferably, it is 20 to 50% by mass.

Known photopolymerization initiators can be used, and among them, an oxime ester-based photopolymerization initiator having an oxime ester group, an α-aminoacetophenone-based photopolymerization initiator, and an acylphosphine oxide-based photopolymerization initiator are used. Agents and titanosen-based photopolymerization initiators are preferred. 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 with respect to 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 with respect to 100 parts by mass of the carboxyl group-containing resin. By setting the amount to 0.01 parts by mass or more, the photocurability on copper becomes more reliable, and the coating film characteristics such as chemical resistance are improved. Further, when the amount is 5 parts by mass or less, light absorption on the surface of the coating film is suppressed, and the curability of the deep part tends to be improved. More preferably, it is 0.5 to 3 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin.

When the α-aminoacetophenone-based photopolymerization initiator or the acylphosphine oxide-based photopolymerization initiator is used, the blending amount thereof may be 0.01 to 15 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin. preferable. By setting the amount to 0.01 parts by mass or more, the photocurability on copper becomes more reliable, and the coating film characteristics such as chemical resistance are improved. Further, by setting the amount to 15 parts by mass or less, a sufficient effect of reducing outgas can be obtained, light absorption on the surface of the cured film is suppressed, and the curability of the deep portion is also improved. More preferably, it is 0.5 to 10 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin.

A photoinitiator or sensitizer may be used in combination with the photopolymerization initiator described above. Examples of the photoinitiator aid or sensitizer include benzoin compounds, acetophenone compounds, anthraquinone compounds, thioxanthone compounds, ketal compounds, benzophenone compounds, tertiary amine compounds, and xanthone compounds. Although these compounds may be used as a photopolymerization initiator, they are preferably used in combination with a photopolymerization initiator. In addition, one type of photoinitiator aid or sensitizer may be used alone, or two or more types may be used in combination.

The photocurable 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. Examples of such thermosetting components include known and commonly used thermosetting resins such as isocyanate compounds, blocked 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 with respect to 100 parts by mass of the carboxyl group-containing resin.

The photocurable thermosetting resin composition preferably contains a thermosetting catalyst. Examples of such a thermocuring catalyst include imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole. , 1- (2-Cyanoethyl) -2-ethyl-4-methylimidazole and other imidazole derivatives; dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N Examples thereof include amine compounds such as -dimethylbenzylamine, 4-methyl-N, N-dimethylbenzylamine, hydrazine compounds such as adipate dihydrazide and sebacic acid dihydrazide; and phosphorus compounds such as triphenylphosphine. In addition, guanamine, acetoguanamine, benzoguanamine, melamine, 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino-S-triazine, 2-vinyl-4,6-diamino S-triazine derivatives such as -S-triazine-isocyanuric acid adduct and 2,4-diamino-6-methacryloyloxyethyl-S-triazine-isocyanulic acid adduct can also be used, preferably as these adhesion-imparting agents. A compound that also functions is used in combination with a thermosetting catalyst.

The blending amount of the thermosetting catalyst is preferably 0.1 to 20 parts by mass, and more preferably 0.5 to 15.0 parts by mass with respect to 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 one or more ethylenically unsaturated bonds in the molecule. The photosensitive monomer assists the photocuring of the carboxyl group-containing resin by irradiation with active energy rays.

Examples of the compound used as the photosensitive monomer include commonly known polyester (meth) acrylate, polyether (meth) acrylate, urethane (meth) acrylate, carbonate (meth) acrylate, and epoxy (meth) acrylate. Specifically, 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; N, N-dimethylacrylamide. , N-methylol acrylamide, acrylamides such as N, N-dimethylaminopropyl acrylamide; aminoalkyl acrylates such as N, N-dimethylaminoethyl acrylate, N, N-dimethylaminopropyl acrylate; Polyhydric alcohols such as pentaerythritol, dipentaerythritol, tris-hydroxyethyl isocyanurate or polyhydric acrylates such as their ethireoxyside adducts, propylene oxide adducts, or ε-caprolactone adducts; phenoxyacrylates, bisphenol A di. Acrylate and polyvalent acrylates such as ethylene oxide adducts or propylene oxide adducts of these phenols; Polyvalent acrylates; Not limited to the above, acrylates and melamine acrylates obtained by directly acrylated polyols such as polyether polyols, polycarbonate diols, hydroxyl group-terminated polybutadienes, and polyester polyols, or urethane acrylates via diisocyanates, and the acrylates. Can be appropriately selected and used from at least one of each methacrylate corresponding to the above.

An epoxy acrylate resin obtained by reacting a polyfunctional epoxy resin such as cresol novolac type epoxy resin with acrylic acid, and a hydroxy acrylate such as pentaerythritol triacrylate and a diisocyanate half urethane such as isophorone diisocyanate on the hydroxyl group of the epoxy acrylate resin. An epoxy urethane acrylate compound obtained by reacting the compound or the like may be used as the photosensitive monomer. Such an epoxy acrylate-based resin can improve the photocurability without lowering the dryness to the touch.

The 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 with respect to 100 parts by mass of the carboxyl group-containing resin. It is a ratio. By setting the blending amount of the compound having an ethylenically unsaturated bond to 5 parts by mass or more, the photocurability of the photocurable thermosetting resin composition is improved. Further, the hardness of the coating film can be improved by setting the blending amount to 100 parts by mass or less.

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

A filler can be added to the photocurable thermosetting resin composition, if necessary, in order to increase the physical strength of the obtained cured product. The filler is not particularly limited, and examples thereof include those exemplified as the filler contained in the resin layer. The filler may be used alone or as a mixture of two or more.

The amount of the filler added is preferably 500 parts by mass or less, more preferably 0.1 to 400 parts by mass, and particularly preferably 0.1 to 300 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin. When the amount of the filler added is 500 parts by mass or less, the viscosity of the photocurable thermosetting resin composition does not become too high, the printability is good, and the cured product is less likely to become brittle.

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

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

Further, in the photocurable thermosetting resin composition, an elastomer can be blended for the purpose of imparting flexibility to the obtained cured product, improving the brittleness of the cured product, and the like. Examples of the elastomer include polyester-based elastomers, polyurethane-based elastomers, polyester-urethane-based elastomers, polyamide-based elastomers, polyesteramide-based elastomers, acrylic-based elastomers, and olefin-based elastomers. Further, a resin obtained by modifying a part or all of the epoxy groups of the epoxy resin having various skeletons with both-terminal carboxylic acid-modified butadiene-acrylonitrile rubber can also be used. Further, epoxy-containing polybutadiene-based elastomers, acrylic-containing polybutadiene-based elastomers, hydroxyl group-containing polybutadiene-based elastomers, hydroxyl group-containing isoprene-based elastomers, and the like can also be used. The elastomer may be used alone or as a mixture of two or more.

The amount of the elastomer 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 amount of the elastomer added is 50 parts by mass or less, the alkali developability of the photocurable thermosetting resin composition is good, and the developable pot life is unlikely to be shortened.

In addition, components such as block copolymers, adhesion promoters, antioxidants, and ultraviolet absorbers can be added to the photocurable thermosetting resin composition, if necessary. As these, those known in the field of electronic materials can be used. In addition, known and commonly used thickeners such as fine silica, hydrotalcite, organic bentonite, and montmorillonite, defoaming agents such as silicone-based, fluorine-based, and polymer-based, leveling agents, imidazole-based, thiazole-based, triazole-based, etc. At least one of known and commonly used additives such as a silane coupling agent, a rust preventive, and a fluorescent whitening agent 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. be able to. 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 tetramethyl benzene; cellosolve, methyl cellosolve, butyl cellosolve, carbitol and methyl. Glycol ethers such as carbitol, butyl carbitol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, and triethylene glycol monoethyl ether. Classes; 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, propylene glycol butyl ether acetate; ethanol, propanol, Alcohols such as 2-methoxypropanol, n-butanol, isobutyl alcohol, isopentyl alcohol, ethylene glycol, propylene glycol; aliphatic hydrocarbons such as octane and decane; petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, solvent naphtha, etc. In addition to petroleum-based solvents and the like, N, N-dimethylformamide (DMF), tetrachloroethylene, televisionn oil and the like can be mentioned. In addition, Maruzen Petrochemical Co., Ltd. Swazole 1000, Swazole 1500, Standard Petrochemical Osaka Sales Office Co., Ltd. Solbesso 100, Solvesso 150, Sankyo Chemical Co., Ltd. Solvent # 100, Solvent # 150, Shell Chemicals Japan Co., Ltd. , Idemitsu Kosan Co., Ltd. Ipsol No. 100, Ipsol No. 150 and other organic solvents may be used. Such an organic solvent may be used alone or as a mixture of two or more.

As a method for producing a printed wiring board using a dry film having a resin layer made of a photocurable thermosetting resin composition, a conventionally known method 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 by using a vacuum laminator or the like, and the resin layer is exposed to the pattern. .. The first film may be peeled off either after laminating and before exposure or after exposure. After that, a patterned resin layer is formed on the substrate by performing alkaline development, and the patterned resin layer is cured by light irradiation and heat to form a cured film to manufacture a printed wiring board. Can be done.

(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.

It is preferable to add a filler to the thermosetting resin composition, and the physical strength of the obtained cured product can be increased. The filler is not particularly limited, and examples thereof include those exemplified as the filler contained in the resin layer. The filler may be used alone or as a mixture of two or more.

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

The thermosetting resin composition can contain a curing agent. Examples of the curing agent include phenol resins, polycarboxylic acids and their acid anhydrides, cyanate ester resins, active ester resins, maleimide compounds, alicyclic olefin polymers and the like. As the curing agent, one type may be used alone or two or more types may be used in combination. Here, by using at least a cyanate ester resin or an active ester resin, the dielectric loss tangent after humidification can be lowered. Further, by using at least a cyanate ester resin or a maleimide compound, crack resistance during a cold cycle after reflow is improved.
When the resin layer is made of a thermosetting resin composition, bubbles are likely to be generated when it is cured at a high temperature, but according to the dry film of the present invention, it is cured at a high temperature such as a phenol resin, an active ester resin, and a cyanate ester resin. Even when a curing agent that requires the above is contained, bubbles are unlikely to be generated after curing. Further, the curing agent preferably has at least one structure of a biphenyl skeleton and a naphthol skeleton.

Examples of the phenol resin include phenol novolac resin, alkylphenol volac resin, bisphenol A novolac resin, dicyclopentadiene type phenol resin, Xylok type phenol resin, terpene-modified phenol resin, cresol / naphthol resin, polyvinylphenols, phenol / naphthol resin. , Α-naphthol skeleton-containing phenol resin, triazine skeleton-containing cresol novolac resin, biphenyl aralkyl type phenol resin, Zyroc type phenol novolac resin, and other conventionally known ones can be used alone or in combination of two or more. ..
Among the phenolic resins, the hydroxyl group equivalent is 130 g / eq. The above is preferable, and 150 g / eq. The above is more preferable. The hydroxyl group equivalent is 130 g / eq. Examples of the above-mentioned phenol resin include dicyclopentadiene skeleton phenol novolac resin (GDP series, manufactured by Gunei Chemical Co., Ltd.), zylock type phenol novolac resin (MEH-7800, manufactured by Meiwa Kasei Co., Ltd.), and biphenyl aralkyl type novolak resin (MEH). -7851, manufactured by Meiwa Kasei Co., Ltd.), naphthol aralkyl type curing agent (SN series, manufactured by Nippon Steel & Sumitomo Metal Corporation), triazine skeleton-containing cresol novolac resin (LA-3018-50P, manufactured by DIC Co., Ltd.) 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, any conventionally known resin can be used. Examples of the cyanate ester resin include phenol novolac type cyanate ester resin, alkylphenol novolac type cyanate ester resin, dicyclopentadiene type cyanate ester resin, bisphenol A type cyanate ester resin, bisphenol F type cyanate ester resin, and bisphenol S type cyanate ester resin. Can be mentioned. Further, it may be a prepolymer in which a part is triazine-ized.

The active ester resin is a resin having two or more active ester groups in one molecule. The active ester resin can generally be obtained by a condensation reaction of a carboxylic acid compound and a hydroxy compound. Of these, an active ester compound obtained by using a phenol compound or a naphthol compound as the hydroxy compound is preferable. Examples of the phenol compound or naphthol compound include hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, phenolphthaline, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenol, tetrahydroxybenzophenone, fluoroglusin, benzenetriol , Dicyclopentadienyldiphenol, phenol novolac and the like. Further, the active ester resin may be a naphthalenediol alkyl / benzoic acid type.

The maleimide compound is a compound having a maleimide skeleton, and any conventionally known compound can be used. The maleimide compound preferably has two or more maleimide skeletons, N, N'-1,3-phenylenedi maleimide, N, N'-1,4-phenylenedi maleimide, N, N'-4,4-. Diphenylmethane bismaleimide, 1,2-bis (maleimide) ethane, 1,6-bismaleimide hexane, 1,6-bismaleimide- (2,2,4-trimethyl) hexane, 2,2'-bis- [4- (4-Maleimidephenoxy) phenyl] propane, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethanebismaleimide, 4-methyl-1,3-phenylenebismaleimide, bis (3-ethyl) -5-Methyl-4-maleimidephenyl) methane, bisphenol A diphenyl ether bismaleimide, polyphenylmethane maleimide, and oligomers thereof, and more preferably at least one of diamine condensates having a maleimide skeleton. .. The oligomer is an oligomer obtained by condensing a maleimide compound, which is a monomer of the above-mentioned maleimide compound. The maleimide compound may be used alone or in combination of two or more.

In the curing agent, the ratio of a functional group capable of a thermosetting reaction such as an epoxy group of a thermosetting component to a functional group in the curing agent that reacts with the functional group is the functional group / thermosetting reaction of the curing agent. It is preferable to blend in a ratio such that the functional group (equivalent ratio) that can be used is 0.2 to 2. By setting the functional group (equivalent ratio) capable of the functional group / thermosetting reaction of the curing agent within the above range, roughening of the film surface in the desmear step can be prevented. More preferably, the functional group of the curing agent / the functional group capable of the thermosetting reaction (equivalent ratio) = 0.2 to 1.5, and more preferably the functional group of the curing agent / the functional group capable of the thermosetting reaction (equivalent ratio). Equivalent ratio) = 0.3 to 1.0.
When the functional group equivalent (g / eq.) Of the phenol resin, cyanate ester resin, active ester resin, and maleimide compound is 200 or more, the warpage can be reduced.

The thermosetting resin composition can further contain a thermoplastic resin in order to improve the mechanical strength of the obtained cured 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 the generation of cracks and powder falling can be suppressed. As the thermoplastic resin, various acid anhydrides or acid chlorides are used for the thermoplastic polyhydroxypolyether resin, the phenoxy resin which is a condensate of epichlorohydrin and various bifunctional phenol compounds, or the hydroxyl group of the hydroxyether portion existing in the skeleton thereof. Examples thereof include phenoxy resins, polyvinyl acetal resins, polyamide resins, polyamideimide resins, and block copolymers that have been esterified. 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% by mass, preferably 0.5 to 10% by mass, based on the total amount of the resin layer excluding the solvent. If the blending amount of the thermoplastic resin is out of the above range, it becomes difficult to obtain a uniform roughened surface state.

Further, the thermosetting resin composition can contain rubber-like particles, if necessary. Examples of such rubber-like particles include polybutadiene rubber, polyisopropylene rubber, urethane-modified polybutadiene rubber, epoxy-modified polybutadiene rubber, acrylonitrile-modified polybutadiene rubber, carboxyl group-modified polybutadiene rubber, carboxyl group-modified or hydroxyl-modified acrylonitrile butadiene rubber, and Examples thereof include cross-linked rubber particles and core-shell type rubber particles, and one type can be used alone or in combination of two or more types. These rubber-like particles are added to improve the flexibility of the obtained cured film, improve crack resistance, enable surface roughening treatment with an oxidizing agent, and improve the adhesion strength with copper foil and the like. Will be done.

The average particle size of the rubber-like particles is preferably in the range of 0.005 to 1 μm, more preferably in the range of 0.2 to 1 μm. The average particle size of the rubber-like particles in the present invention can be determined by a laser diffraction type particle size distribution measuring device. For example, rubber-like particles are uniformly dispersed in an appropriate organic solvent by ultrasonic waves, etc., and the particle size distribution of the rubber-like particles is prepared on the basis of mass using Nanotrac wave manufactured by Nikkiso Co., Ltd., and the median diameter is defined as the average particle size. It can be measured by doing.

The blending amount of the rubber-like particles is preferably 0.5 to 10% by mass, more preferably 1 to 5% by mass, based on the total amount of the resin layer excluding the solvent. When it is 0.5% by mass or more, crack resistance can be obtained and the adhesion strength with the conductor pattern or the like can be improved. When it is 10% by mass or less, the coefficient of thermal expansion (CTE) decreases, the glass transition temperature (Tg) increases, and the curing characteristics are improved.

The resin layer of the dry film of the present invention can contain a curing accelerator. The curing accelerator accelerates the thermosetting reaction, and is used to further improve properties such as adhesion, chemical resistance, and heat resistance. Specific examples of such a curing accelerator include imidazole and its derivatives; guanamines such as acetoguanamine and benzoguanamine; diaminodiphenylmethane, m-phenylenediamine, m-xylenediamine, diaminodiphenylsulphon, dicyandiamide, urea, urea derivatives, etc. Polyamines such as melamine, polybasic hydrazide; these organic acid salts and / or epoxy adducts; amine complexes of boron trifluoride; ethyldiamino-S-triazine, 2,4-diamino-S-triazine, 2,4- Triazine derivatives such as diamino-6-xysilyl-S-triazine; trimethylamine, triethanolamine, N, N-dimethyloctylamine, N-benzyldimethylamine, pyridine, N-methylmorpholin, hexa (N-methyl) melamine, Amines such as 2,4,6-tris (dimethylaminophenol), tetramethylguanidine, m-aminophenol; polyphenols such as polyvinylphenol, polyvinylphenol bromide, phenol novolac, alkylphenol novolac; tributylphosphine, triphenylphosphine , Organic phosphines such as tris-2-cyanoethylphosphine; phosphonium salts such as tri-n-butyl (2,5-dihydroxyphenyl) phosphonium bromide, hexadecyltributylphosphonium chloride; Tertiary ammonium salts; the polybasic acid anhydrides; photocationic polymerization catalysts such as diphenyliodonium tetrafluoroboroate, triphenylsulfonium hexafluoroantimonate, 2,4,6-triphenylthiopyrylium hexafluorophosphate; styrene- Maleic anhydride resin; isomolar reactants of phenylisocyanate and dimethylamine, equimolar reactants of organic polyisocyanate and dimethylamine such as tolylene diisocyanate and isophorone diisocyanate, and conventionally known curing accelerators such as metal catalysts can be mentioned. .. Among the curing accelerators, phosphonium salts are preferable because BHAST resistance can be obtained.

As the curing accelerator, one type may be used alone or two or more types may be mixed. The use of a curing accelerator is not essential, but when it is particularly desired to accelerate curing, it can be preferably used in the range of 0.01 to 5 parts by mass with respect to 100 parts by mass of the thermosetting component. In the case of a metal catalyst, 10 to 550 ppm is preferable in terms of metal with respect to 100 parts by mass of the thermosetting component, and 25 to 200 ppm is preferable.

If necessary, the thermosetting resin composition further comprises a conventionally known colorant such as phthalocyanine blue, phthalocyanine green, iodin green, disazo yellow, crystal violet, titanium oxide, carbon black, naphthalene black, and asbestos. Adhesion of conventionally known thickeners such as Orben, Benton, and fine powder silica, antifoaming agents such as silicone-based, fluorine-based, and polymer-based and / or leveling agents, thiazole-based, triazole-based, and silane coupling agents. Conventionally known additives such as an imparting agent, a flame retardant, a titanate type, and an aluminum type 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, a conventionally known method 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 from the dry film, heat-laminated on the circuit board on which the circuit pattern is formed, and then thermosetting. The thermosetting may be cured in an oven or may be cured by a hot plate press. When laminating or hot plate pressing the base material on which the circuit is formed and the dry film of the present invention, the copper foil or the base material on which the circuit is formed can be laminated at the same time. A printed wiring board can be manufactured by forming a pattern or a via hole by laser irradiation or a drill at a position corresponding to a predetermined position on a substrate on which a circuit pattern is formed to expose the circuit wiring. At this time, if there is a residual component (smear) that cannot 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 off either after laminating, after thermosetting, after laser processing, or after desmear treatment.

(Photocurable thermosetting resin composition containing a photobase generator)
As an example of a photocurable thermosetting resin composition containing a photobase generator (hereinafter, also referred to as a photobase generator-containing composition), in addition to an epoxy resin, an alkali-developable resin and a photobase generator The composition containing the above will be described below.

The alkali-developable resin is a resin containing one or more functional groups of phenolic hydroxyl group, thiol group and carboxyl group and can be developed with an alkaline solution, preferably a compound having two or more phenolic hydroxyl groups, carboxyl. Examples thereof include a group-containing resin, a compound having a phenolic hydroxyl group and a carboxyl group, and a compound having two or more thiol groups.

As the carboxyl group-containing resin, a known resin containing a carboxyl group can be used. The presence of the carboxyl group allows the resin composition to be alkaline developable. In addition to the carboxyl group, a compound having an ethylenically unsaturated bond in the molecule may be used, but in the present invention, the carboxyl group-containing resin is a carboxyl group-containing resin having no ethylenically unsaturated bond. It is preferable to use only.

Specific examples of the carboxyl group-containing resin that can be used in the present invention include the following (1) to (11) as the carboxyl group-containing resin contained in the photocurable thermosetting resin composition. Examples include the listed compounds (either oligomers and polymers).

(12) 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, polycarbonate-based polyols and polyether-based compounds. A carboxyl group-containing urethane resin obtained by a double addition reaction of a diol compound such as a polyol, a polyester-based polyol, a polyolefin-based polyol, an acrylic polyol, a bisphenol A-based alkylene oxide adduct diol, and a compound having a phenolic hydroxyl group and an alcoholic hydroxyl group.

(13) Diisocyanate and bifunctional epoxy resin such as bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bixylenel type epoxy resin, biphenol type epoxy resin ( Meta) A carboxyl group-containing urethane resin obtained by a double addition reaction of an acrylate or a modified partial acid anhydride thereof, a carboxyl group-containing dialcohol compound, and a diol compound.

(14) During the synthesis of the resin according to (12) or (13), a compound having one hydroxyl group and one or more (meth) acryloyl groups in a molecule such as hydroxyalkyl (meth) acrylate was added to the terminal (14). Meta) Acryloylated carboxyl group-containing urethane resin.

(15) During the synthesis of the resin according to (12) or (13), one isocyanate group and one or more (meth) acryloyl groups are added to the molecule, such as an isophorone diisocyanate and pentaerythritol triacrylate isomorphic reaction product. A carboxyl group-containing urethane resin that is terminal (meth) acrylicized by adding the compound to be possessed.

(16) A saturated monocarboxylic acid is reacted with the polyfunctional epoxy resin as described above, and a dibasic acid anhydride such as phthalic anhydride, tetrahydrophthalic anhydride, or hexahydrophthalic anhydride is added to the hydroxyl group existing in the side chain. Carboxyl anhydride-containing resin. Here, the polyfunctional epoxy resin is preferably solid.

(17) A carboxyl group-containing polyester resin obtained by reacting a polyfunctional oxetane resin as described later with a dicarboxylic acid and adding a dibasic acid anhydride to the generated primary hydroxyl group.

(18) A carboxyl group-containing resin obtained by reacting a polybasic acid anhydride 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. ..

(19) A saturated monocarboxylic acid is reacted 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, and the obtained reaction product is abundant. A carboxyl group-containing resin obtained by reacting a basic acid anhydride.

(20) A reaction product obtained by 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 a cyclic carbonate compound such as ethylene carbonate or propylene carbonate. A carboxyl group-containing resin obtained by reacting with a polybasic acid anhydride.

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

(22) An epoxy compound having a plurality of epoxy groups in one molecule, a compound having at least one alcoholic hydroxyl group and one phenolic hydroxyl group in one molecule such as p-hydroxyphenethyl alcohol, and a saturated monocarboxylic acid. The reaction product is reacted with an 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. Carboxyl group-containing resin obtained by.

(23) An epoxy compound having a plurality of epoxy groups in one molecule is reacted with at least one alcoholic hydroxyl group in one molecule such as p-hydroxyphenethyl alcohol and a compound having one phenolic hydroxyl group. A carboxyl group obtained by 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. Containing resin.

(24) In addition to the resin according to any one of (12) to (23) above, one epoxy group and one or more (meth) acryloyl in a molecule such as glycidyl (meth) acrylate and α-methylglycidyl (meth) acrylate. A carboxyl group-containing resin obtained by adding a compound having a group.

Since the alkaline developable resin as described above has a large number of carboxyl groups, hirodoxy groups, etc. in the side chain of the backbone polymer, it can be developed with an alkaline aqueous solution.
The hydroxyl group equivalent or the carboxyl group equivalent of the alkali-developable resin is 80 to 900 g / eq. Is more preferable, and more preferably 100 to 700 g / eq. Is. The hydroxyl group equivalent or the carboxyl group equivalent is 900 g / eq. In the following cases, the adhesion of the pattern layer is obtained, and alkaline development becomes easy. On the other hand, the hydroxyl group equivalent or the carboxyl group equivalent is 80 g / eq. In the above case, dissolution of the light-irradiated portion by the developing solution is suppressed, the line is not thinned more than necessary, and a normal resist pattern can be easily drawn, which is preferable. Further, when the carboxyl group equivalent or the phenol group equivalent is large, development is possible even when the content of the alkaline developable resin is small, which is preferable.

The acid value of the alkaline developable resin is preferably 40 to 150 mgKOH / g. When the acid value of the alkaline developable resin is 40 mgKOH / g or more, the alkaline development becomes good. Further, by setting the acid value to 150 mgKOH / g or less, it is possible to easily draw a normal resist pattern. More preferably, it is 50 to 130 mgKOH / g.

The blending amount of the alkaline developable resin is preferably 20 to 60% by mass based on the total amount of the resin layer of the dry film excluding the solvent. The coating film strength can be improved by setting the content to 20% by mass or more. Further, when the content is 60% by mass or less, the viscosity becomes appropriate and the coatability is improved. More preferably, it is 30 to 50% by mass.

The photobase generator is one or more kinds that can function as a catalyst for the addition reaction of the above-mentioned heat-reactive compound by changing the molecular structure by irradiation with light such as ultraviolet rays or visible light or by cleaving the molecule. It is a compound that produces a basic substance. Examples of the basic substance include secondary amines and tertiary amines.

Examples of the photobase generator include α-aminoacetophenone compound, oxime ester compound, acyloxyimino group, N-formylated aromatic amino group, N-acylated aromatic amino group, nitrobenzyl carbamate group, and alcoholic benzyl carbamate. Examples thereof include compounds having a substituent such as a group.

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

It is preferable to add a filler to the photobase generator-containing composition, and the physical strength of the obtained cured product can be increased. The filler is not particularly limited, and examples thereof include those exemplified as the filler contained in the resin layer. The filler may be used alone or as a mixture of two or more.

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

If necessary, the photobase generator-containing composition may further contain components such as a mercapto compound, an adhesion accelerator, an antioxidant, and an ultraviolet absorber. As these, those known in the field of electronic materials can be used.
In addition, the above-mentioned photobase generator-containing composition includes known and commonly used thickeners such as fine powder silica, hydrotalcite, organic bentonite, and montmorillonite, and defoaming agents such as silicone-based, fluorine-based, and polymer-based. Alternatively, known and commonly used additives such as leveling agents, silane coupling agents, and rust preventives can be blended.

As a method for producing a printed wiring board using a dry film having a resin layer made of a photobase generator-containing composition, a conventionally known method 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 dry film is laminated on the substrate on which the circuit pattern is formed by using a vacuum laminator or the like. After that, the photobase generator contained in the photobase generator-containing resin composition is activated by negative-type patterned light irradiation to cure the light-irradiated portion, and the unirradiated portion is removed by alkaline development to remove the negative. A pattern layer of the mold can be formed. The first film may be peeled off either after lamination or after exposure. Further, it is preferable to heat the resin layer after light irradiation and before development. As a result, the resin layer can be sufficiently cured to obtain a pattern layer having further excellent curing characteristics. The heating after light irradiation and before development is preferably at a temperature at which the unirradiated portion is not thermoset. Further, it is preferable to perform thermosetting (post-cure) after development. After the development, the photobase generator that remains unactivated during the light irradiation may be activated by irradiating with ultraviolet rays, and then thermosetting (post-cure) may be performed.

(Positive Photosensitive Thermosetting Resin Composition)
As an example of the positive photosensitive thermosetting resin composition, a resin composition containing a compound that generates a carboxyl group by light irradiation in addition to the epoxy resin will be described below.

Among the compounds that 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 in which alkali solubility such as a carboxyl group is suppressed by forming a complex with a carboxyl group or a phenolic hydroxyl group, and the complex is dissociated by subsequent light irradiation to express alkali solubility. ing. In this case, if the naphthoquinone diazide compound remains in the membrane, the complex may be dissociated by light irradiation and become soluble. Therefore, in the semiconductor field or the like, the remaining naphthoquinone diazide compound is finally blown off at a high temperature. It was removed by that. However, in the field of printed wiring boards, naphthoquinone diazide compounds have not been practically used because such high temperatures cannot be applied and they cannot be used as permanent coating films from the viewpoint of stability. In the present invention, when a naphthoquinone diazide compound is used as a compound that generates a carboxyl group by light irradiation, the naphthoquinone diazide compound remaining in the unexposed portion is incorporated into the crosslinked structure and stabilized during the thermosetting reaction. The film toughness, that is, the bending resistance and the electrical characteristics can be improved without causing the problem of removal as in the conventional case. In particular, by using a naphthoquinone diazide compound as a compound that generates a carboxyl group by light irradiation in combination with a polyamide-imide resin and a thermosetting component, flexibility is effective while ensuring good developability and resolution. It can be improved to the above, which is preferable.

Specific examples of the naphthoquinone diazide compound include a naphthoquinone diazide adduct of tris (4-hydroxyphenyl) -1-ethyl-4-isopropylbenzene (for example, TS533, TS567, TS583, TS593 manufactured by Sanpo Chemical Laboratory Co., Ltd.). ), A naphthoquinone diazide adduct of tetrahydroxybenzophenone (for example, BS550, BS570, BS599 manufactured by Sanpo Chemical Laboratory Co., Ltd.) and the like can be used.

It is preferable to add a filler to the positive photosensitive thermosetting resin composition, and the physical strength of the obtained cured product can be increased. The filler is not particularly limited, and examples thereof include those exemplified as the filler contained in the resin layer. The filler may be used alone or as a mixture of two or more.

Specific examples of the alkali-developable resin contained in the positive photosensitive thermosetting resin composition include the carboxyl group-containing resin exemplified in the photocurable thermosetting resin composition and the photobase generator-containing composition. Examples thereof include an alkali-developable resin exemplified by the material.

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 and commonly used thermosetting resins such as isocyanate compounds, blocked isocyanate compounds, amino resins, maleimide compounds, benzoxazine resins, carbodiimide resins, cyclocarbonate compounds, polyfunctional oxetane compounds, and episulfide resins can be used. ..

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

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

The positive photosensitive thermosetting resin composition may contain other components such as block copolymers, colorants, elastomers, and thermoplastic resins in addition to the above-mentioned components. Further, the positive photosensitive thermosetting resin composition may further contain components such as an adhesion accelerator, an antioxidant, and an ultraviolet absorber, if necessary. As these, those known in the field of electronic materials can be used. In addition, at least one of known and commonly used thickeners such as fine silica, hydrotalcite, organic bentonite, and montmorillonite, antifoaming agents such as silicone-based, fluorine-based, and polymer-based and leveling agents, imidazole, and thiazole. At least one of known and commonly used additives such as a silane coupling agent such as a system or a triazole system, a rust preventive agent, and a fluorescent whitening agent can be blended.

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, a conventionally known method 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, the resin layer is exposed, and the dry film is laminated on the substrate on which the circuit pattern is formed by using a vacuum laminator or the like. After that, the resin layer is irradiated with light in a positive pattern, the resin layer is alkaline-developed, and the light-irradiated portion is removed to form the positive pattern layer. The first film may be peeled off either after lamination or after exposure. Further, after development, the resin layer is heat-cured (post-cured) and the unirradiated portion is cured, so that the printed wiring board can be manufactured. In the positive photosensitive thermosetting resin composition, the composition is changed to a composition soluble in an alkaline developer by the acid generated by light irradiation, so that a positive pattern can be formed by alkaline development.

[the film]
When laminating a dry film having a resin layer sandwiched between a carrier film and a protective film, in many cases, the protective film is peeled off and the surface of the resin layer on the side in contact with the protective film is the base. Laminated to contact the material. However, in some cases, the carrier film is peeled off and laminated so that the surface of the resin layer on the side in contact with the carrier film comes into 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. Further, the film on the side in contact with the surface of the resin layer (that is, the laminated surface) that comes into contact with the base material when laminating on the base material is the second film, and the surface of the second film in contact with the resin layer is The arithmetic mean surface roughness Ra is preferably 0.1 to 1.2 μm, more preferably 0.3 to 1.2 μm, and even more preferably 0.4 to 1.2 μm. 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 polyester films such as polyethylene terephthalate and polyethylene naphthalate, polyimide films, polyamideimide films, polyethylene films, polytetrafluoroethylene films, polypropylene films, and films made of thermoplastic resins such as polystyrene films. Surface-treated paper or the like can be used. However, among these, 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 in the range of approximately 10 to 150 μm according to the application. The surface of the carrier film on which the resin layer is provided may be subjected to a mold release treatment. Further, a sputtered or ultrathin copper foil may be formed on the surface of the carrier film on which the resin layer is provided.

The protective film is provided on the surface opposite to the carrier film of the resin layer for the purpose of preventing dust and the like from adhering to the surface of the resin layer of the dry film and improving handleability. As the protective film, for example, a film made of the thermoplastic resin exemplified in the carrier film, surface-treated paper and 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 in the range of approximately 10 to 150 μm according to the application. The surface of the protective film on which the resin layer is provided may be subjected to a mold release treatment.

When a thermoplastic resin film is used as the second film having the arithmetic average surface roughness Ra as described above, a filler may be added to the resin when the film is formed, or the film surface may be blasted. Alternatively, the surface can be formed into a predetermined shape by hairline processing, matte coating, chemical etching, or the like, and a thermoplastic resin film having the above-mentioned arithmetic average surface roughness Ra can be obtained. For example, when the filler is added to the resin, the arithmetic mean surface roughness Ra can be controlled by adjusting the particle size and the amount of the filler added. Further, in the case of blasting, the arithmetic mean surface roughness Ra can be controlled by adjusting the processing conditions such as the blasting material and the blasting pressure. As the thermoplastic resin film having such a surface roughness, a commercially available one may be used. For example, Toray Industries, Inc. Lumirror X42, Lumirror X43, Lumirror X44, Unitika Ltd. Emblet PTH-12, Emblet PTH. -25, Embret PTHA-25, Embret PTH-38, Alfan MA-411, MA-420, E-201F and ER-440 manufactured by Oji F-Tex Co., Ltd. can be mentioned.

The first film preferably has an arithmetic average surface roughness Ra of the surface in contact with the resin layer of 0.1 μm or less. When it is 0.1 μm or less, the flatness of the surface of the resin layer after curing becomes good, and the glossiness also becomes good. In addition, if there is a difference in the arithmetic mean surface roughness Ra of the first film and the second film, it becomes easier to recognize which film by appearance (whether or not there is gloss), and it is possible to prevent work mistakes. can.

Further, the thickness A of the first film is preferably larger than the thickness B of the second film because the second film can be easily peeled off. More preferably, the difference (AB) between the thickness A and the thickness B is 1 μm or more. Further, if there is a difference in thickness between the first film and the second film, it becomes easier to recognize which film is to the touch or the appearance, and it is possible to prevent a mistake in work.

The thickness of the first film is preferably 10 to 100 μm, more preferably 15 μm or more. When the thickness is 10 μm or more, even if the dry film is laminated on the base material and then heat-treated without peeling the first film, the first film does not easily shrink due to heat, and the thickness becomes uneven due to heat shrinkage or heat. It is possible to prevent quality deterioration such that the resin layer flows along the streaks generated in the first film due to the shrinkage and streaks are also generated in the resin layer.

When the resin layer of the dry film of the present invention is made of a photosensitive resin composition, light such as the above-mentioned thermoplastic resin is used as the first film so that the first dry film can be exposed without peeling. It is preferable to use a permeable material. In that case, the thickness of the first film is preferably 45 μm or less. When it is 45 μm or less, the undercut is reduced. More preferably, it is 40 μm or less.

The dry film of the present invention can be preferably used for forming a permanent protective film for a printed wiring board, and above all, can be preferably used for forming a solder resist layer, an interlayer insulating layer, and a coverlay for a flexible printed wiring board. Further, since the dry film of the present invention is excellent in embedding property, it can be suitably used for a printed wiring board provided with a fine circuit such as a package substrate which is greatly affected by air bubbles, and particularly L / S = 10/10 μm or less. It can be suitably used for a printed wiring board provided with the fine circuit of. Further, the dry film of the present invention can be preferably used even when a vacuum laminating method in which air bubbles are likely to occur is adopted as the method for laminating the dry film. Further, since the cured product of the resin layer of the dry film of the present invention is excellent in the formability of the plating resist, it is preferable to use it for forming the interlayer insulating layer. A wiring board may be formed by bonding wirings using the dry film of the present invention. It can also be used as a sealing resin for semiconductor chips. It can also be used to form the outermost layer and interlayer insulating layer of a coreless substrate.

Hereinafter, the present invention will be specifically described with reference to Examples, Comparative Examples, and Test Examples of the present invention, but it goes without saying that the present invention is not limited to the following Examples. In the following, "part" and "%" are all based on mass unless otherwise specified.

[Adjustment of surface-treated inorganic filler]
(Adjustment of surface-treated silicas A to D and adjustment of surface-treated aluminas A and B)
100 g of each inorganic filler and 2000 g of an aqueous alcohol solution (water: alcohol = 1: 9 weight ratio) were added to the flask, and the mixture was stirred at room temperature at a rotation speed of 300 rpm for about 30 minutes to form a slurry. Next, 1 wt% of each silane coupling agent was prepared with respect to the weight of the inorganic filler, and the slurry was slowly added dropwise to the slurry over 10 minutes so that the droplets did not scatter, and the slurry was stirred for 10 minutes at 300 rpm. Then, a circular qualitative filter paper was performed and the surface-treated filler was taken out. Next, the surface-treated inorganic filler was spread on a shallow tray and dried at 110 ° 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 notes in Table 1 below.

(Examples 1 to 34 and Comparative Examples 1 to 12)
<Making dry film>
Each component was blended according to the formulations shown in Examples and Comparative Examples shown in Tables 1, 3, 5, 7, 9, 11, 13 and 15 below, dispersed on a roll mill, and had a viscosity of 0.5 to 20 dPa · s (rotation). The curable resin composition was adjusted so as to have a viscometer (5 rpm, 25 ° C.). Then, using a bar coater, the dry film was applied onto a carrier film (Lumirror S10, thickness 38 μm, no surface treatment, Ra = 0.03 μm, manufactured by Toray Industries, Inc.) so that the film thickness of the dry film was 15 μm after drying. .. Next, it was dried in a hot air circulation type drying oven at 85 ° C. for 5 to 15 minutes so that the amount of residual solvent was 3.5 to 4.5%, and a curable resin layer was formed on the carrier film. Next, a protective film (MA-411, thickness 15 μm, Ra = 0.45 μm, manufactured by Oji F-Tex Co., Ltd.) was rolled on the surface of the dry coating film at a set temperature of 70 ° C. to obtain a dry film having a three-layer structure.

<Storage modulus G'and melt viscosity of the resin layer>
For each of the dry films produced above, the protective film was peeled off, and the resin layers of the two dry films were laminated and thermocompression bonded with a 1-chamber vacuum laminator MVLP-500 (manufactured by Meiki Co., Ltd.). The thickness of the layer was set to 350 μm. At that time, in order not to apply heat to the film, the film was laminated at a temperature of 40 ° C. and a pressure of 0.5 MPa for 1 min. Next, the carrier film was peeled off with a viscosity / viscoelasticity measuring device Leostress RS-6000 (manufactured by HAAKE), and then the temperature-viscoelasticity of each resin layer was measured. The measurement conditions were a temperature rise mode of 5 ° C./min, an oscillation mode strain amount of 8%, a frequency of 1 Hz, a parallel plate with a measurement sensor of Φ20 mm, and a gap of 300 μm between the sensors. By making the resin layer thicker than the gap, a sufficient resin thickness can be secured between the gaps even during heating. From the curve of temperature-storage elastic modulus G'and viscosity η measured by the above method, the storage elastic modulus and melt viscosity at 100 ° C. were determined by "residual storage elastic modulus G'" and "resin layer It was defined as "melt viscosity". The measurement results are shown in the table.

<Embedability (Foam generation FLS (Fine line &space))>
As a pretreatment on a double-sided printed wiring board on which a fine circuit of a comb tooth pattern with a copper thickness of 10 μm, L (line: wiring width) / S (space: spacing width) = 5/5 μm, and an aspect ratio of 2.0 is formed. An etching treatment equivalent to 0.5 μm was performed by a CZ-8101 treatment manufactured by MEC. Next, the dry film having a thickness of 15 μm produced above was laminated on a substrate on which L / S was formed using a batch type vacuum pressure laminator MVLP-500 (manufactured by Meiki Co., Ltd.). Laminating conditions were 5 kgf / cm ² , 100 ° C., 1 minute, 1 Torr, and then ^{leveling was performed in a hot plate pressing step at 10 kgf / cm 2} , 100 ° C., 1 minute. After laminating, air entered the boundary between the line and the space, and it was confirmed at 100 places whether or not air bubbles (voids) were generated after the carrier film was peeled off. What was evaluated by this method was defined as "after laminating". Next, when the resin layer was cured and the presence or absence of bubbles was evaluated in the same manner, it was defined as "after curing". The curing conditions will be described in detail in the next section. The evaluation criteria are as follows.
◯: No void was confirmed.
Δ: 1 to 5 voids were confirmed.
X: The viscosity and elastic modulus were high, and it could not be embedded in a substrate having fine wires.

<Flatness of substrate after curing>
Regarding the resin layer of each dry film laminated on the substrate on which the fine circuit is formed by the method described in the above <Embedability (Bubble generation FLS)>, if the curing system is thermosetting, After the carrier film was peeled off, it was heat-cured at 180 ° C. for 30 minutes in a hot air circulation type drying furnace, and then heat-cured at 200 ° C. for 60 minutes to completely cure the resin layer.
On the other hand, if the curing system is light / thermosetting, it is photocured with an exposure amount of 300 mJ / cm ² (i-line, Ushio projection exposure machine) so that the thin line portion is completely exposed from the carrier film. After that, the carrier film was peeled off. Next, development was carried out for 60 seconds at a 1 wt% sodium carbonate aqueous solution, a pressure of 0.2 MPa, and a liquid temperature of 30 ° C. Next, 1000 mJ / cm ² exposure was performed with a high-pressure mercury lamp irradiator. Then, it was heat-cured at 180 ° C. for 60 minutes in a hot air circulation type drying oven to completely cure the resin layer.
For the substrate completely cured by each curing method, the length of the surface irregularities of the cured film in the direction perpendicular to the thin line was measured with a contact type surface roughness measuring device (SE-300, manufactured by Kosaka Laboratory Co., Ltd.). The unevenness on the cured film was measured with a width of 20 mm. The evaluation criteria are as follows.
⊚: Concavities and convexities have a maximum tolerance of less than 0.3 μm on a fine circuit. At the same time, no copper burning of the fine circuit was observed.
◯: Concavities and convexities have a maximum tolerance of less than 0.3 μm on a fine circuit.
Δ: The maximum unevenness on the fine circuit is 0.3 μm or more and less than 1.0 μm.
X: The maximum unevenness on the fine circuit is 1.0 μm or more.
XX: The maximum unevenness on the fine circuit is 5.0 μm or more. The unevenness of the circuit was noticeable.

<Adhesion with the underlying circuit>
The glossy surface of the electrolytic copper foil GTS-MP-18 μm (manufactured by Furukawa Circuit Foil Co., Ltd.) was subjected to an etching treatment equivalent to 0.5 μm by the CZ-8101 treatment manufactured by MEC.
After that, each dry film is laminated on the treated surface side by the method described in <Embedability (Bubble generation FLS)>, and then by the method of <Flatness of the substrate after curing>. The resin layer was completely cured. After that, a two-component adhesive Araldite was used on the resin layer side, and the adhesive layer was bonded to a 1.6 mmt FR-4 etchout plate, and the adhesive layer was cured at room temperature. CZ-treated copper foil-resin layer-FR4 material 3 A layered structure was obtained. The obtained substrate was subjected to CZ treatment of each resin layer in accordance with JIS-C-6481 copper-clad laminate test method and peel strength measurement method (test piece width 10 mm, 90 ° direction, speed 50 mm / min). The adhesive strength with the surface was measured. The judgment criteria are as shown below.
⊚: Adhesive strength is 5.0 N / cm or more.
◯: Adhesive strength is 3.0 N / cm or more and less than 5.0 N / cm.
X: The viscosity or elastic modulus was high, and the evaluation sample could not be prepared.

<Formability of plating resist>
With respect to the cured substrate produced by the method described in <Flatness of the substrate after curing>, a plating resist was further formed on the surface thereof and evaluated.
Specifically, the produced cured substrate was subjected to permanganate desmear treatment (Atotech, Securigant MV series for vertical desmear), swelling at 60 ° C for 5 minutes, permanganate at 80 ° C for 20 minutes, and reduction at 50 ° C. The surface of the substrate was roughened by the partial treatment. Next, an electroless copper plating treatment (manufactured by C. Uyemura & Co., Ltd., alkaline ion type Pd) was used to form a copper seed layer having a thickness of 0.3 μm on the surface of the substrate. Then, after the surface of the copper seed layer was degreased with alkali, the plating resist Fortec RY-3625 (manufactured by Hitachi Kasei Kogyo Co., Ltd., plating resist for SAP, thickness 25 μm) was used under a pressure condition of 110 ° C. and 0.4 MPa using a roll laminator. The surface of the substrate was laminated with. Next, with EXP-2960 (Parallel light exposure machine manufactured by ORC Manufacturing Co., Ltd.), a glass dry plate negative mask L / S pattern (L / S = 10/10 μm pattern is formed in an area of 20 mm × 20 mm). A negative pattern was formed on the surface of the substrate at an exposure of 100 mJ / cm ^{2 using a negative mask).} Next, development was carried out at 30 ° C. for 30 seconds in a 1 wt% sodium carbonate aqueous solution to form an L / S pattern on the substrate surface. The obtained substrate was observed using SEM. Randomly extract 100 points in the range of 20 mm x 20 mm, and evaluate the formability of the plating resist (confirm whether there are lines that are skipped or development defects are generated due to dents). rice field. The judgment criteria are as shown below.
◯: Good formability.
Δ: Poor L / S formation (missing lines, poor development) was observed at one or more and less than 10 locations.
X: Poor L / S formation (missing lines, poor development) was observed at 10 or more locations.
XX: Since the base was not flat, the pattern could not be formed according to the design value.

<Dissipation factor after humidification>
A dry film having a thickness of 15 μm as a resin layer prepared by the method described in <Preparation of dry film> is placed on a glossy surface of electrolytic copper foil GTS-MP-18 μm (manufactured by Furukawa Circuit Foil Co., Ltd.). Lamination was performed by the method described in FLS)>, and then the resin layer was completely cured by the method of <flatness of the substrate after curing>. Then, the cured product was peeled off from the copper foil to obtain a cured product having a thickness of 15 μm.
The obtained cured product was stored in a high-temperature and high-humidity bath set at a temperature of 85 ° C. and a humidity of 85% RH for 100 hours, and within 10 minutes of removal, an SPDR dielectric resonator and a network analyzer (both manufactured by Agilent) were used. Was used to measure the dielectric loss tangent when humidified at 5.1 GHz at 23 ° C. The judgment criteria are as shown below.
◎ ◎: 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.
Δ: The dielectric loss tangent at 5 GHz is 0.015 or more and less than 0.02.
X: The dielectric loss tangent at 5 GHz is 0.02 or more.

<Heat dissipation characteristics>
The 15 μm cured product obtained by the same method as <dielectric loss tangent after humidification> was measured for thermal conductivity of the cured product in accordance with the method described in JIS-R1611. The judgment criteria are as shown below.
⊚: 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.
Δ: Thermal conductivity is less than 0.3 W / m · K.
X: The viscosity or elastic modulus was high, and the evaluation sample could not be prepared.

<Coefficient of thermal expansion>
After peeling the cured product of 15 μm obtained by the same method as <dielectric loss tangent after humidification> from the copper foil, a sample was cut out to the measurement size (size of 3 mm × 10 mm) and used for TMA6100 manufactured by Seiko Instruments Inc. bottom. In the TMA measurement, the test load was 5 g, the sample was heated above room temperature at a heating rate of 10 ° C./min, and the sample was measured twice in succession. It was evaluated as the coefficient of thermal expansion (CTE (α1)) in the region below Tg in the second time. The judgment criteria are as shown below.
◎ ◎: CTE below the glass transition temperature is less than 10 ppm.
⊚: CTE below the glass transition temperature is 10 ppm or more and less than 17 ppm.
◯: CTE below the glass transition temperature is 17 ppm or more and less than 30 ppm.
Δ: CTE below the glass transition temperature is 30 ppm or more.
X: The viscosity or elastic modulus was high, and the evaluation sample could not be prepared.

<Board warp>
<Preparation of dry film on a copper-clad laminate (MCL-E-770G, Hitachi Kasei Co., Ltd., copper thickness 18 μm, etching treatment equivalent to CZ-8101 1 μm was performed as a pretreatment) with a thickness of 200 μm and a size of 100 × 100 mm. >, A dry film having a resin thickness of 15 μm was laminated on one side of the substrate using a vacuum laminator, then the carrier film was peeled off, and then the resin layer was completely cured using a hot air circulation drying furnace. I let you. The obtained substrate was evaluated by measuring the amount of warpage at the four corners of the substrate using calipers and following the following criteria.
⊚: The maximum value of warpage is less than 3 mm.
◯: The maximum value of warpage is 3 mm or more and less than 15 mm.
Δ: The maximum value of warpage is 15 mm or more.
X: The viscosity or elastic modulus was high, and the evaluation sample could not be prepared.

<Reflow + TCT (Thermal Cycling Test)>
^{The dry film thickness (resin thickness 15 μm) of each example and comparative example was 5 kgf / cm 2} , 80 on copper of a copper-clad laminate using a batch type vacuum pressure laminator MVLP-500 (manufactured by Meiki Co., Ltd.). Laminating was performed under the conditions of ° C., 1 minute, and 1 Torr. Then, the carrier film was peeled off and heated in a hot air circulation type drying oven, and the resin layer was cured at 180 ° C. for 30 minutes. Then, using a CO ₂ laser machine (manufactured by Hitachi Via Mechanics), vias were formed so that the top diameter was 65 μm and the bottom diameter was 50 μm.
If the curing system is light / thermosetting, exposure and development are performed using a negative pattern of Φ65 μm by the method described in <Flatness of substrate after curing>, and then ultraviolet irradiation and main curing are performed. And formed vias.
Next, the obtained via pattern was treated in the order of commercially available wet permanganate desmear (manufactured by ATOTECH), electroless copper plating (Sulcup PEA, manufactured by Uemura Kogyo Co., Ltd.), and electrolytic copper plating, and then the resin layer. A copper plating treatment was performed on the top so as to fill the via portion with a copper thickness of 25 μm. Next, the test substrate was thermally cured at 200 ° C. for 60 minutes in a hot air circulation type drying oven to obtain a completely cured copper-plated test substrate. The obtained test substrate was subjected to thermal shock for 3 cycles of reflow treatment under lead-free assembly conditions (peak temperature 270 ° C. for 10 seconds), and then subjected to thermal shock at −65 ° C. for 30 minutes and at 150 ° C. for 30 minutes for 1 minute. A cold cycle treatment was applied as a cycle. After 2000 and 3000 cycles, in order to observe the state of the via bottom and the wall surface with an optical microscope, the central part of the via was cut and polished with a precision cutting machine, and the cross-sectional state was observed. The evaluation criteria were evaluated according to the following. The number of observed vias was 100 holes.
⊚: No crack occurred after 3000 cycles.
◯: No cracks occurred after 2000 cycles. Cracks occur in 1 to 5 places in 3000 cycles.
Δ: After 2000 cycles, cracks occurred in 1 to 5 places.
X: A test piece could not be manufactured because the melt viscosity and the storage elastic modulus exceeded the optimum range.

<Relative permittivity>
A dry film having a thickness of 15 μm as a resin layer prepared by the method described in <Preparation of dry film> is placed on a glossy surface of electrolytic copper foil GTS-MP-18 μm (manufactured by Furukawa Circuit Foil Co., Ltd.). Lamination was performed by the method described in FLS)>, and then the resin layer was completely cured by the method of <flatness of the substrate after curing>. Then, the cured product was peeled off from the copper foil to obtain a cured product having a thickness of 15 μm.
The obtained cured product was measured for a relative permittivity of 1 GHz at 23 ° C. using an SPDR dielectric resonator and a network analyzer (both manufactured by Agilent). The judgment criteria are as shown below.
⊚: The relative permittivity at 1 GHz is 10.0 or more.
◯: The relative permittivity at 1 GHz is 5.0 or more and less than 10.0.

<Circuit concealment>
A cured film was formed on the fine circuit board by the methods described in <Embedability (FLS for generating bubbles)> and <Flatness of the substrate after curing>, and then the carrier film was peeled off to obtain a printed wiring board.
With respect to the obtained evaluation substrate, the discoloration of the copper circuit from the cured film was visually confirmed, and the concealing property of the circuit was evaluated. The judgment criteria are as shown below.
⊚: No discoloration is confirmed.
X: Discoloration was confirmed.

＊１：ＤＩＣ社製ＨＰ−８２０、アルキルフェノール型液状エポキシ樹脂、エポキシ当量：２２５ｇ／ｅｑ
＊２：日本化薬社製ＮＣ−３０００Ｌ、ビフェニルアラルキル型固形エポキシ樹脂、エポキシ当量：２７５ｇ／ｅｑ
＊３：大阪ガスケミカル社製ＣＧ−５００、フルオレン系固形エポキシ樹脂、エポキシ当量：３１１ｇ／ｅｑ
＊４：日産化学社製ＴＧＩＣ、トリグリシジルイソシアヌラート（固形エポキシ樹脂）、エポキシ当量：９９ｇ／ｅｑ
＊５：三菱化学社製１００３、Ｂｉｓ−Ａ型固形エポキシ樹脂、エポキシ当量：７２０ｇ／ｅｑ
＊６：ＤＩＣ社製ＴＤ−２１３１、フェノールノボラック樹脂、水酸基当量：１０４ｇ／ｅｑ
＊７：明和化成社製ＭＥＨ−７８５１−４Ｈ、ビフェニルアラルキル型フェノール樹脂、水酸基当量：２４０ｇ／ｅｑ
＊８：ＤＩＣ社製ＬＡ−３０１８、ＡＴＮ含有フェノールノボラック樹脂、水酸基当量：１５１ｇ／ｅｑ
＊９：丸善化学社製マルカリンカーＭ、ポリビニルフェノール、水酸基当量１２０ｇ／ｅｑ
＊１０：ロンザジャパン社製ＰＴ−３０、ノボラック型シアネートエステル樹脂、シアネート当量：１２４ｇ／ｅｑ
＊１１：ロンザジャパン社製ＢＡ−３０００、Ｂｉｓ−Ａ型シアネートエステル樹脂、シアネート当量：２８４ｇ／ｅｑ
＊１２：大和化成工業社製ＢＭＩ−１１００、Ｎ，Ｎ’−ジフェニルメタンビスマレイミド、マレイミド当量：１７９ｇ／ｅｑ
＊１３：日本化薬社社製ＭＩＲ−３０００、ビフェニル骨格含有ビスマレイミド、マレイミド当量：２７５ｇ／ｅｑ
＊１４：エア・ウォータ社製ＰＣ−１１００−０２、多官能型活性エステル樹脂、活性エステル当量：１５４ｇ／ｅｑ
＊１５：ＤＩＣ社製ＥＸＢ９４１６、ナフトール末端、ジシクロペンタジエン骨格含有活性エステル樹脂、活性エステル当量：２２０ｇ／ｅｑ
＊１６：日本乳化剤社製ＲＭＡ−１１９０２、フェノール樹脂を出発原料とするアクリル基を有する感光性カルボキシル基含有樹脂（固形分：６５％）
＊１７：新中村化学工業社製Ａ−ＤＣＰ、ジシクロペンタジエン骨格アクリル酸モノマー＊１８：東亜合成社製ＨＰＳ−５００、Ｄ５０＝０．５μｍの球状シリカ
＊１９：東亜合成社製ＨＰＳ−１０００、Ｄ５０＝１．０μｍの球状シリカ
＊２０：上記で調整した表面処理されたシリカＡ（アドマテックス社製ナノシリカ（平均一次粒径（Ｄ５０）＝５０ｎｍ）の１ｗｔ％のアミノシラン処理品）
＊２１：電気化学工業社製ＦＢ−５ＳＤＸ、Ｄ５０＝４．９μｍの球状シリカ
＊２２：上記で調整した表面処理されたシリカＢ（ＨＰＳ−５００／ＫＢＥ−１００３、ＨＰＳ−５００の１ｗｔ％ビニルシラン処理品）
＊２３：上記で調整した表面処理されたシリカＣ（ＨＰＳ−５００／ＫＢＥ−９１０３、ＨＰＳ−５００の１ｗｔ％アミノシラン処理品）
＊２４：上記で調整した表面処理されたシリカＤ（ＨＰＳ−１０００／ＫＢＥ−１００３、ＨＰＳ−１０００の１ｗｔ％ビニルシラン処理品）
＊２５：上記で調整した表面処理されたシリカＥ（ＦＢ−５ＳＤＸ／ＫＢＥ−９１０３、ＦＢ−５ＳＤＸの１ｗｔ％アミノシラン処理品）
＊２６：電気化学工業社製ＡＳＦＰ−２０、Ｄ５０＝０．３μｍの球状アルミナ
＊２７：電気化学工業社製ＤＡＭ−０３、Ｄ５０＝３．７μｍの球状アルミナ
＊２８：上記で調整した表面処理されたアルミナＡ（ＡＳＦＰ−２０／ＫＢＥ−１００３、ＡＳＦＰ−２０の１ｗｔ％ビニルシラン処理品）
＊２９：上記で調整した表面処理されたアルミナＢ（ＤＡＭ−０３／ＫＢＥ−１００３、ＤＡＭ−０３の１ｗｔ％ビニルシラン処理品）
＊３０：龍森社製ヒューズレックスＷＸ、Ｄ５０＝１．５μｍの不定形シリカ
＊３１：信越化学社製ＫＢＥ−１００３、ビニルトリエトキシシラン
＊３２：信越化学社製ＫＢＥ−４０２、３−グリシドキシプロピルメチルジエトキシシラン
＊３３：信越化学社製ＫＢＥ−９１０３、３−トリエトキシシリル−Ｎ−（１，３−ジメチル−ブチリデン）プロピルアミン
＊３４：ＢＡＳＦジャパン社製イルガキュア３６９、α-アミノアルキルフェノン系光重
合開始剤
＊３５：コバルトアセチルアセトナート１ｗｔ％、ＤＭＦ溶液
＊３６：四国化成社製２Ｅ４ＭＺ−ＡＰ、イミダゾール
＊３７：三菱化学社製ＹＬ７６００、低誘電骨格含有フェノキシ樹脂
＊３８：シクロヘキサノン
＊３９：ＤＭＦ（Ｎ，Ｎ−ジメチルホルムアミド）
＊４０：出光興産社製 イプゾール１００、 芳香族系高沸点溶剤

* 1: HP-820 manufactured by DIC Corporation, alkylphenol type liquid epoxy resin, epoxy equivalent: 225 g / eq
* 2: NC-3000L manufactured by Nippon Kayaku Co., Ltd., biphenyl aralkyl type solid epoxy resin, epoxy equivalent: 275 g / eq
* 3: CG-500 manufactured by Osaka Gas Chemical Co., Ltd., fluorene-based solid epoxy resin, epoxy equivalent: 311 g / eq
* 4: TGIC manufactured by Nissan Chemical Industries, Ltd., 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: DIC TD-2131, phenol novolac resin, hydroxyl group equivalent: 104 g / eq
* 7: MEH-7851-4H manufactured by Meiwakasei Workers, biphenyl aralkyl type phenol resin, hydroxyl group equivalent: 240 g / eq
* 8: LA-3018 manufactured by DIC, ATN-containing phenol novolac resin, hydroxyl group equivalent: 151 g / eq
* 9: Marukalinker M manufactured by Maruzen Chemical Co., Ltd., polyvinylphenol, hydroxyl group equivalent 120 g / eq
* 10: Lonza Japan PT-30, novolac type cyanate ester resin, cyanate equivalent: 124 g / eq
* 11: BA-3000 manufactured by Lonza Japan, Bis-A type cyanate ester resin, cyanate equivalent: 284 g / eq
* 12: Daiwa Kasei Kogyo Co., Ltd. BMI-1100, N, N'-diphenylmethanebismaleimide, maleimide equivalent: 179 g / eq
* 13: MIR-3000 manufactured by Nippon Kayaku Co., Ltd., biphenyl skeleton-containing bismaleimide, maleimide equivalent: 275 g / eq
* 14: Air Water PC-1100-02, polyfunctional active ester resin, active ester equivalent: 154 g / eq
* 15: EXB9416 manufactured by DIC Corporation, naphthol terminal, dicyclopentadiene skeleton-containing active ester resin, active ester equivalent: 220 g / eq
* 16: RMA-11902 manufactured by Nippon Emulsifier Co., Ltd., a photosensitive carboxyl group-containing resin having an acrylic group using a phenol resin as a starting material (solid content: 65%)
* 17: A-DCP manufactured by Shin-Nakamura Chemical Industry Co., Ltd., dicyclopentadiene skeleton acrylic acid monomer * 18: HPS-500 manufactured by Toagosei Co., Ltd., spherical silica with D50 = 0.5 μm * 19: HPS-1000 manufactured by Toagosei Co., Ltd. D50 = 1.0 μm spherical silica * 20: Surface-treated silica A prepared above (1 wt% aminosilane-treated product of Admatex nanosilica (average primary particle size (D50) = 50 nm))
* 21: FB-5SDX manufactured by Denki Kagaku Kogyo Co., Ltd., D50 = 4.9 μm spherical silica * 22: 1 wt% vinylsilane treatment of surface-treated silica B (HPS-500 / KBE-1003, HPS-500) prepared above. Product)
* 23: Surface-treated silica C (HPS-500 / KBE-9103, HPS-500 1 wt% aminosilane-treated product) prepared above.
* 24: Surface-treated silica D (HPS-1000 / KBE-1003, HPS-1001 wt% vinylsilane-treated product) prepared above.
* 25: Surface-treated silica E (FB-5SDX / KBE-9103, FB-5SDX 1 wt% aminosilane-treated product) prepared above.
* 26: ASFP-20 manufactured by Denki Kagaku Kogyo Co., Ltd., D50 = 0.3 μm spherical alumina * 27: DAM-03 manufactured by Denki Kagaku Kogyo Co., Ltd., D50 = 3.7 μm spherical alumina * 28: Surface treatment adjusted above 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% vinylsilane-treated product) prepared above.
* 30: Hugheslex WX manufactured by Ryumori Co., Ltd., D50 = 1.5 μm amorphous silica * 31: KBE-1003 manufactured by Shin-Etsu Chemical Co., Ltd., vinyl triethoxysilane * 32: KBE-402, 3-glycid manufactured by Shin-Etsu Chemical Co., Ltd. Xypropylmethyldiethoxysilane * 33: KBE-9103, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine manufactured by Shin-Etsu Chemical Co., Ltd. * 34: Irgacure 369, α-aminoalkyl manufactured by BASF Japan. Phenone-based photopolymerization initiator * 35: cobalt acetylacetonate 1 wt%, DMF solution * 36: Shikoku Kasei Co., Ltd. 2E4MZ-AP, imidazole * 37: Mitsubishi Chemical Co., Ltd. YL7600, low dielectric skeleton-containing phenoxy resin * 38: cyclohexanone * 39: DMF (N, N-dimethylformamide)
* 40: Idemitsu Kosan Co., Ltd. Ipsol 100, aromatic high boiling point solvent

＊４２：ＤＩＣ社製ＥＰＩＣＬＯＮ ８６０、ビスフェノールＡ型半固形エポキシ樹脂、エポキシ当量：２４５ｇ／ｅｑ
＊４３：ＤＩＣ社製ＨＰ−４０３２、ナフタレン型半固形エポキシ樹脂、エポキシ当量：１５０ｇ／ｅｑ
＊４４：ＤＩＣ社製Ｎ−７４０、フェノールノボラック型半固形エポキシ樹脂、エポキシ当量：１８０ｇ／ｅｑ

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

＊４５： 堺化学工業製ＢＴ−０３Ｂ Ｄ５０＝０．３μｍ

＊４６：石原産業製タイペークＣＲ−９７ Ｄ５０＝０．２５μｍ
＊４７：堺化学工業製ＣＺ−０３ Ｄ５０＝０．３μｍ

* 45: Sakai Chemical Industry BT-03B D50 = 0.3 μm

* 46: Ishihara Sangyo Typake CR-97 D50 = 0.25 μm
* 47: Sakai Chemical Industry CZ-03 D50 = 0.3 μm

＊４８：ラミネート不可

* 48: Cannot be laminated

From the results shown in the above table, it can be seen that the dry films of Examples 1 to 34 are excellent in embedding property and flatness of the resin layer. On the other hand, the dry films of Comparative Examples 1 to 11 and the resin layer in which the melt viscosity of the resin layer does not satisfy 60 to 5500 dPa · s at 100 ° C. or the storage elastic modulus of the resin layer does not satisfy 80 to 5500 Pa at 100 ° C. The dry film of Comparative Example 12 having a liquid epoxy resin content of 60% by mass or more was inferior in embedding property 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 Liquidity judgment test tube 30b Temperature measurement test tube 31 Marked line (line A) )
32 Mark line (B line)
33a, 33b Rubber stopper 34 Thermometer

Claims (9)

A dry film having a film and a resin layer containing an epoxy resin formed on the film.
The melt viscosity of the resin layer is 60 to 5500 dPa · s at 100 ° C.
The storage elastic modulus of the resin layer is 80 to 5500 Pa at 100 ° C.
The resin layer contains at least a liquid epoxy resin as the epoxy resin.
The content of the liquid epoxy resin, Ri the epoxy resin to the total mass of less than 60% by mass per
Dry film characterized Rukoto used in applications for forming a plating resist on the cured film obtained by curing the resin layer. The dry film according to claim 1, wherein the amount of residual solvent in the resin layer is 1.0 to 7.0% by mass. The claim is characterized in that 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. The dry film according to 1 or 2. The resin layer further contains, as the epoxy resin, at least one semi-solid epoxy resin selected from the group consisting of bisphenol A type epoxy resin, naphthalene type epoxy resin and phenol novolac type epoxy resin. Item 3. The dry film according to any one of Items 1 to 3. The resin layer contains a filler and contains
The dry film according to any one of claims 1 to 4, wherein the average particle size of the filler is 0.1 to 10 μm. The resin layer contains a filler and contains
The dry film according to any one of claims 1 to 5, wherein the blending amount of the filler is 40 to 80% by mass per the total amount of the resin layer (the total amount excluding the solvent when the resin layer contains a solvent). The resin layer contains a filler and contains
The filler is 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, and styryl. The dry according to any one of claims 1 to 6, which is surface-treated with at least one of a silane coupling agent having a group, a silane coupling agent having a methacrylic group, and a silane coupling agent having an acrylic group. the film. A cured product obtained by curing the 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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