TWI721070B - Dry film and printed wiring board - Google Patents

Abstract

The present invention provides a dry film having a resin layer with excellent embedding properties and flatness, and a printed wiring board provided with a cured product obtained by curing the dry film. A dry film, which is a dry film having a film and a resin layer containing an epoxy resin formed on the film, the melt viscosity of the aforementioned resin layer is 60~5500dPa at 100°C. s, the storage elastic modulus of the aforementioned resin layer is 80~5500Pa at 100°C, the aforementioned resin layer contains at least liquid epoxy resin as the aforementioned epoxy resin, and the content of the aforementioned liquid epoxy resin is in the aforementioned epoxy resin In the total mass, less than 60% by mass.

Description

Dry film and printed wiring board

The present invention relates to a dry film and a printed wiring board, and more specifically relates to a dry film having a resin layer with excellent embedding properties and flatness, and a printed wiring board provided with a cured product obtained by curing the dry film.

In the past, one of the methods for forming protective films or insulating layers such as solder resists or interlayer insulating layers used on printed wiring boards used in electronic devices has been the use of dry films (for example, Patent Documents 1 to 3). The dry film has a resin layer obtained by coating a curable resin composition with desired characteristics on a carrier film and then undergoing a drying step. Generally speaking, a protective film used to protect the side opposite to the carrier film is further In the state of being laminated, circulate in the market. After the resin layer of the dry film is laminated on the substrate with the circuit pattern, patterning or hardening treatment is applied to form the protective film or insulating layer as described above on the printed wiring board.

[Prior technical literature] 〔Patent Literature〕

Patent Document 1: Japanese Patent Application Publication No. 7-15119 (Patent Application range)

Patent Document 2: Japanese Patent Laid-Open No. 2002-162736 (Scope of Patent Application)

Patent Document 3: Japanese Patent Application Publication No. 2003-131366 (Scope of Patent Application)

Summary of the invention

When laminating the resin layer of the dry film on the substrate, the resin layer cannot be fully buried in the unevenness of the circuit pattern on the substrate, and air bubbles may be generated between the resin layer and the substrate. It may impair the adhesion between the resin layer and the substrate.

In order to flatten the outer surface of the resin layer of the laminated dry film, vacuum lamination or pressing is performed. However, since the unevenness of the circuit pattern on the substrate is transferred to the outer surface, the flatness is insufficient.

Especially in recent years, the trend of lighter, thinner, shorter and smaller electronic devices, and the thinning of printed wiring boards, is required to be thinner than the resin layer of dry film. Thereby, even if vacuum lamination or pressing is performed, it is difficult to obtain the embedding property of the resin layer of the base material or the flatness of the outer surface of the resin layer.

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

In view of the above situation, the inventors of the present invention carefully reviewed the results and found that the foregoing problems can be solved by using a dry film with the following resin layer, and completed the present invention, wherein the resin layer has a melt viscosity at 100°C. 60~5500dPa. s, the storage elastic modulus at 100°C is 10 to 5500 Pa, and the resin layer containing liquid epoxy resin is less than 60% by mass relative to the total amount of epoxy resin.

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 60~5500dPa at 100°C. s, the storage elastic modulus of the aforementioned resin layer is 80-5500 Pa at 100°C, and the aforementioned resin layer contains at least liquid epoxy resin as the aforementioned epoxy resin, The content of the liquid epoxy resin is less than 60% by mass in the total mass of the epoxy resin.

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

The dry film of the present invention, wherein the aforementioned resin layer contains a group selected from the group consisting of N,N-dimethylformamide, toluene, cyclohexanone, aromatic hydrocarbons with 8 or more carbon atoms, and methyl ethyl ketone At least two kinds of organic solvents are preferred.

The dry film of the present invention, wherein the resin layer further contains at least one semi-solid epoxy resin selected from the group consisting of bisphenol A epoxy resin, naphthalene epoxy resin, and phenol novolac epoxy resin, as The aforementioned epoxy resin is preferred.

In the dry film of the present invention, the resin layer contains a filler, and the average particle size of the filler is preferably 0.1-10 μm.

In the dry film of the present invention, the resin layer contains a filler, and the blending amount of the filler is preferably 40-80% by mass of the total amount of the resin layer (when the resin layer contains a solvent, the total amount of the solvent is excluded).

In the dry film of the present invention, the resin layer contains a filler, and the filler is a silane coupling agent with epoxy groups, a silane coupling agent with amine groups, a silane coupling agent with mercapto groups, a silane coupling agent with isocyanate groups, and It is preferable that at least any one of vinyl silane coupling agent, styrene group-containing silane coupling agent, methacryl group-containing silane coupling agent, and acryl group-containing silane coupling agent be subjected to surface treatment.

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

The printed wiring board of the present invention is characterized by having a cured product as described above.

According to the present invention, a dry film having a resin layer with excellent embedding properties and flatness, and a printed wiring board having a cured product obtained by curing the dry film can be provided.

11‧‧‧Two-layer dry film

12‧‧‧Resin layer

13‧‧‧Film

21‧‧‧Three-layer dry film

22‧‧‧Resin layer

23‧‧‧First film

24‧‧‧Second film

30a‧‧‧Test tube for liquid state determination

30b‧‧‧Test tube for temperature measurement

31‧‧‧Marking line (A line)

32‧‧‧Marking line (B line)

33a, 33b‧‧‧Rubber plug

34‧‧‧Thermometer

[Figure 1] Schematic representation of one embodiment of the laminated structure of the present invention Schematic section view.

[Fig. 2] A schematic cross-sectional view schematically showing another embodiment of the laminated structure of the present invention.

[Fig. 3] A schematic side view showing two test tubes for judging the liquid state of 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 60~5500dPa at 100°C. s, the storage elastic modulus of the aforementioned resin layer is 80~5500Pa at 100°C, the aforementioned resin layer contains at least liquid epoxy resin as the aforementioned epoxy resin, and the content of the aforementioned liquid epoxy resin is in the aforementioned epoxy resin Among the total mass, it is characterized by less than 60 mass%. The detailed mechanism is unknown, but by adjusting both the melt viscosity of the resin layer and the storage elastic modulus to the above ranges, and the ratio of the liquid epoxy resin contained in the resin layer to the total amount of epoxy resin is set to not Up to 60% by mass, significantly improving embedding and flatness.

In addition, according to the dry film of the present invention, a cured film with a flat surface can be formed. Therefore, when a plating resist is formed on the dry film, it is possible to suppress the lack of line of the plating resist or poor development. That is, according to the dry film of the present invention, a cured product with excellent plating resistance can be obtained. Thereby, a high-definition conductive circuit can also be formed on the resin layer.

In contrast, the melt viscosity of the resin layer of the dry film does not reach 60dPa at 100°C. If s is not reached or the storage elastic modulus of the resin layer is less than 80 Pa at 100°C, air bubbles will be easily involved in the lamination of dry films, making it difficult to obtain embedding properties. In addition, the melt viscosity of the resin layer exceeds 5500dPa at 100°C. When s or the storage elastic modulus of the resin layer exceeds 5500 Pa at 100°C, it is difficult to obtain the flatness of the outer surface of the resin layer. The melt viscosity of the resin layer is 400~3000dPa at 100℃. s is better, and the storage elastic modulus of the resin layer is preferably 100~3500 Pa at 100°C. In addition, when the content of the liquid epoxy resin is 60% by mass or more relative to the total amount of the epoxy resin, it is difficult to obtain the embedding property of the dry film and the flatness of the outer surface of the resin layer.

The melt viscosity of the aforementioned resin layer is 3000dPa at 100°C. s or less, when the storage elastic modulus of the aforementioned resin layer is 3000 Pa or less at 100°C, the flatness and the formability of the plating resist are excellent, which is preferable.

The melt viscosity of the aforementioned resin layer is 100dPa at 100°C. s or more, when the storage elastic modulus of the aforementioned resin layer is 100 Pa or more at 100°C, air bubbles are less likely to be involved during lamination, and the embedding property is more excellent, so it is preferable.

The melt viscosity of the aforementioned resin layer is 500~3000dPa at 100℃. s. It is better that the storage elastic modulus of the aforementioned resin layer is 500~3000Pa at 100°C.

The method of adjusting the melt viscosity and storage elastic modulus of the resin layer is not particularly limited. As described later, by selecting the blending amount, particle size, and The type, etc., can be easily adjusted. Moreover, it can also be adjusted by thermosetting components or hardeners.

Fig. 1 shows a schematic cross-sectional view of an embodiment of the dry film of the present invention. The resin layer 12 is a two-layer dry film 11 formed on the film 13. Furthermore, as shown in FIG. 2, a resin layer 22 is formed on the first film 23. In order to protect the surface of the resin layer 22, it may be a dry film 21 with a three-layer structure further laminated with a second film 24. 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 generally called a B-stage state, and is obtained from a curable resin composition. Specifically, the resin layer of the dry film is obtained by coating the curable resin composition on the film and then going through a drying step. When the aforementioned curable resin composition satisfies the aforementioned melt viscosity, storage modulus of elasticity, and the blending amount of the liquid epoxy resin, the types or blending amounts of other components are not particularly limited. The film thickness of the resin layer is not particularly limited. For example, the film thickness after drying may be 1 to 200 μm. However, the thinner the film thickness of the resin layer, the more remarkable the effect of the present invention can be obtained. Specifically, the film thickness of the resin layer is preferably 30 μm or less, more preferably 20 μm or less, and still more preferably 15 μm or less, since it becomes easier to exhibit the effects of the present invention, which is preferable.

The aforementioned resin layer contains epoxy resin. The epoxy resin is a resin having an epoxy group, and conventionally known ones can be used. Examples include bifunctional epoxy resins having two epoxy groups in the molecule, multifunctional epoxy resins having many epoxy groups in the molecule, and the like. Moreover, it may be a hydrogenated epoxy resin. before The resin layer contains a liquid epoxy resin in a content of less than 60% by mass in the total mass of the epoxy resin as the epoxy resin. The aforementioned 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 this manual, solid epoxy resin means solid epoxy resin at 40°C, semi-solid epoxy resin means solid epoxy resin at 20°C and liquid epoxy resin at 40°C, liquid epoxy Resin refers to a liquid epoxy resin at 20°C.

The determination of the liquid state is based on the second "method of confirming liquid state" of the provincial ordinance on the test and properties of dangerous substances (the first year of the Heisei Provincial Autonomous Province Order No. 1).

(1) Device Constant temperature water tank:

Use those with a mixer, heater, thermometer, and automatic temperature regulator (the temperature can be controlled by ±0.1°C), and the depth is 150mm or more.

In addition, in the determination of the epoxy resin used in the following examples, a combination of a low-temperature constant-temperature water tank (model BU300) manufactured by Yamato Science Co., Ltd. and an input constant-temperature device Thermomate (model BF500) was used, and approximately 22 liters of tap water was placed in a low-temperature constant-temperature water tank. In the water tank (type BU300), turn on the power of the Thermomate (type BF500) assembled here, set it to the set temperature (20°C or 40°C), and fine-tune the water temperature with the Thermomate (type BF500) to the set temperature ±0.1°C, But as long as it is a device that can be adjusted in the same way, it can be used.

Test tube:

The test tube is shown in Figure 3. The flat-bottomed cylindrical transparent glass with an inner diameter of 30mm and a height of 120mm is made of transparent glass. The marks 31 and 32 are made at the height of 55mm and 85mm from the bottom of the tube, respectively, and the rubber plug 33a is sealed test. The test tube 30a for judging the liquid state of the nozzle and the same size is also marked with the same size, and inserted with the center opening. The rubber plug 33b supporting the hole for the thermometer seals the test nozzle, and the test tube 30b for temperature measurement of the thermometer 34 is inserted into the rubber plug 33b. Hereinafter, the marking line with a height of 55mm from the bottom of the tube is called "A line", and the marking line with a height of 85mm from the tube bottom is called "B line".

The thermometer 34 uses the freezing point measurement specified by JIS B7410 (1982) "Glass Thermometer for Petroleum Tests" (SOP-58 scale range 20~50℃), but as long as it can be measured in the temperature range of 0~50℃ can.

(2) The order of implementation of the test

Place the sample that has been left for more than 24 hours under the atmospheric pressure at a temperature of 20±5°C into the test tube 30a for liquid state determination shown in Fig. 3(a) and the test tube 30b for temperature measurement shown in Fig. 3(b). Until the A line. The two test tubes 30a and 30b were placed in a low-temperature constant-temperature water tank, and the line B was allowed to stand still under the water surface. Make the lower end of the thermometer 30mm lower than the A line.

After the sample temperature reaches the set temperature ±0.1°C, keep this state for 10 minutes. After 10 minutes, take out the test tube 30a for judging the liquid state from the low temperature and constant temperature water tank, and then place it horizontally on a horizontal test bench. Use a stopwatch to measure the time for the tip of the liquid in the test tube to move from line A to line B, and record it . test When the material is at the set temperature, the one that is within 90 seconds of the measurement is judged to be liquid, and the one that exceeds 90 seconds is judged to be solid.

Examples of solid epoxy resins include HP-4700 (naphthalene type epoxy resin) manufactured by DIC, EXA4700 (4-functional naphthalene epoxy resin) manufactured by DIC, and NC-7000 (multifunctional solid containing naphthalene skeleton) manufactured by Nippon Kayaku Co., Ltd. Epoxy resins such as naphthalene type epoxy resins; EPPN-502H (trisphenol epoxy resin) manufactured by Nippon Kayaku Co., Ltd. Epoxides of condensation products of phenols and aromatic aldehydes with phenolic hydroxyl groups (Triphenol type epoxy resin); Dicyclopentadiene aralkyl type epoxy resin such as EPICLON HP-7200H (multifunctional solid epoxy resin containing dicyclopentadiene skeleton) manufactured by DIC; Nippon Kayaku Biphenyl aralkyl type epoxy resin such as NC-3000H (multifunctional solid epoxy resin containing biphenyl skeleton) manufactured by the company; Biphenyl/phenol novolac type ring such as NC-3000L manufactured by Nippon Kayaku Co., Ltd. Oxygen resin; Novolac type epoxy resin such as EPICLON N660, EPICLON N690 manufactured by DIC, EOCN-104S manufactured by Nippon Kayaku Co.; Biphenyl type epoxy resin such as YX-4000 manufactured by Mitsubishi Chemical Corporation; Nippon Steel & Sumikin Phosphorus-containing epoxy resins such as TX0712 manufactured by Chemical Corporation; Ginseng (2,3-epoxypropyl) cyanuric acid esters such as TEPIC manufactured by Nissan Chemical Industry Co., Ltd.

Examples of semi-solid epoxy resins include EPICLON860, EPICLON900-IM, EPICLONEXA-4816, EPICLON EXA-4822 manufactured by DIC, araldite AER280 manufactured by Asahi Ciba, EPOTOHTO YD-134 manufactured by Toto Kasei Co., Ltd., jER834, jER872 manufactured by Mitsubishi Chemical Corporation, and Sumitomo ELA-134, etc. made by Chemical Industry Corporation Phenolic A type epoxy resin; Naphthalene type epoxy resin such as EPICLON HP-4032 manufactured by DIC Company; Phenolic novolak type epoxy resin such as EPICLON N-740 manufactured by DIC Company.

The semi-solid epoxy resin preferably contains at least one selected from the group consisting of bisphenol A epoxy resin, naphthalene epoxy resin, and phenol novolac epoxy resin. By containing these semi-solid epoxy resins, the glass transition temperature (Tg) of the hardened product is high, the CTE is reduced, and the crack resistance is excellent.

Liquid epoxy resins include bisphenol A epoxy resins, bisphenol F epoxy resins, bisphenol AF epoxy resins, phenol novolac epoxy resins, and tert-butyl-catechol epoxy resins. Resin, epoxy propyl amine type epoxy resin, amino phenol type epoxy resin, alicyclic epoxy resin, etc.

Two or more types of epoxy resins can be used in combination. The blending amount of the epoxy resin is based on the total amount of the resin layer of the dry film after excluding the solvent, and is preferably 5-50% by mass, more preferably 5-40% by mass, and still more preferably 5-35% by mass. In addition, 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 in the entire mass of the epoxy resin.

The aforementioned resin layer system preferably contains a filler. Because it contains fillers, the thermal properties of the dry film can be improved by matching the copper conductor layer and the thermal strength around the insulating layer. As the filler, conventionally known inorganic fillers and organic fillers can be used, and they are not limited to specific ones. It is preferable to suppress the curing shrinkage of the coating film and to help improve the adhesion, hardness and other characteristics of the inorganic filler. Inorganic fillers include, for example, barium sulfate, barium titanate, barium zirconate titanate, strontium titanate, calcium titanate, calcium zirconate, magnesium titanate, bismuth titanate, barium neodymium titanate, barium tin titanate, titanium Lead acid, amorphous silica, crystalline silica, fused silica, spherical silica, etc., silica, talc, clay, silica (Neuburger Kieselerde) particles, diaspore (Boehmite) , Magnesium carbonate, calcium carbonate, titanium oxide, aluminum oxide, aluminum hydroxide, silicon nitride, aluminum nitride and other extender pigments or, copper, tin, zinc, nickel, silver, palladium, aluminum, iron, cobalt, gold, Metal powder such as platinum.

Among the above fillers, barium titanate, barium titanate zirconate, strontium titanate, calcium titanate, calcium zirconate, magnesium titanate, bismuth titanate, barium neodymium titanate, barium tin titanate, lead titanate, In the case of titanium oxide, it can increase the dielectric rate and improve the concealment of the circuit, so it is preferred.

The inorganic filler is preferably spherical particles. The average particle size of the filler is preferably 0.1-10 μm. In addition, in the specification of this case, the average particle size of the filler is not only the particle size of the primary particles, but also the average particle size of the particle size of the secondary particles (aggregates). The average particle size can be obtained by a laser diffraction particle size distribution measuring device. The measurement device by the laser diffraction method includes the Nanotrac wave manufactured by Nikkiso Co., Ltd. and the like.

The aforementioned inorganic fillers are preferably surface-treated. The surface treatment is preferably a surface treatment using a coupling agent. As the coupling agent, silane coupling agent, titanium coupling agent, zirconium coupling agent, aluminum coupling agent, etc. can be used. Among them, a silane coupling agent is preferred.

As the silane coupling agent, a silane coupling agent with an epoxy group as an organic group, a silane coupling agent with an amine group, a silane coupling agent with a mercapto group, a silane coupling agent with an isocyanate group, a silane coupling agent with a vinyl group, Styrene-based silane coupling agent, with methacrylic acid Base silane coupling agent, acryl-based silane coupling agent, etc. In particular, the adhesion to the underlying circuit is excellent, and a silane coupling agent having an epoxy group and a silane coupling agent having an amine group are preferred.

In addition, the inorganic filler can be subjected to surface treatment such as alumina treatment without introducing organic groups.

The surface-treated inorganic filler can be surface-treated and blended in the resin layer of the dry film. When preparing the curable resin composition, the surface-untreated inorganic filler and the surface treatment agent are separately blended. In the composition, The inorganic filler may be surface-treated, but when preparing a curable resin composition, it is better to prepare an inorganic filler that has been surface-treated in advance. By mixing the inorganic filler that has been surface-treated in advance, the flatness of the resin layer after curing and the formation of the plating resist can be improved, and the dielectric tangent after humidification is excellent. In the case of surface treatment in advance, it is better to prepare a preliminary dispersion liquid in which the inorganic filler is pre-dispersed in a solvent. The inorganic filler after the surface treatment is pre-dispersed in the solvent, and the preliminary dispersion liquid is prepared in the composition, or the surface is untreated When the inorganic filler is pre-dispersed in a solvent, it is better to mix the pre-dispersed liquid into the composition after sufficient surface treatment.

Here, when silicon dioxide surface-treated with a silane coupling agent having a vinyl group is prepared, the dielectric tangent after humidification is excellent. In addition, when alumina surface-treated with a vinyl-containing silane coupling agent is prepared in advance, heat dissipation is excellent.

The blending amount of the filler is based on the total amount of the resin layer of the dry film after removing the solvent, preferably 25 to 85% by mass, more preferably 40 to 85% by mass. When the blending amount of the filler is 25 to 85% by mass, the embedding property is excellent. At 25% by mass or more, the coefficient of linear expansion can be reduced and the heat dissipation characteristics are excellent.

In addition, when two or more types of fillers are used in combination, the flatness and the formability of the plating resist are excellent, which is preferable. Here, when the filler contains nanofillers with an average primary particle diameter of 100 nm or less, the filling efficiency of the filler can be improved. In this way, the dielectric tangent after humidification can be reduced, the coefficient of linear expansion can be reduced, and the crack resistance during the thermal cycle after reflow can be improved.

The amount of residual solvent in the aforementioned resin layer is preferably 1.0 to 7.0% by mass, more preferably 3.0 to 5.0% by mass, and still more preferably 3.5 to 4.5% by mass. When the residual solvent is 7.0% by mass or less, sudden boiling during thermal hardening can be suppressed, and the surface flatness is good. In addition, it is possible to prevent the melt viscosity from being excessively lowered and the resin to flow, and the flatness is good. When the residual solvent is 1.0% by mass or more, the fluidity during lamination is good, and the flatness and embedding properties are good. In addition, 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.

The aforementioned resin layer contains at least two organic solvents selected from the group consisting of N,N-dimethylformamide, toluene, cyclohexanone, aromatic hydrocarbons with 8 or more carbon atoms, and methyl ethyl ketone Better. When a resin composition containing such an organic solvent is used for the formation of the resin layer, it becomes easy to obtain a drying margin. That is, the drying time can be extended, and the degree of freedom of the drying time can be increased.

The aforementioned curable resin composition is a thermosetting resin composition containing epoxy resin such as liquid epoxy resin. Specific examples include photocuring thermosetting resin composition, thermosetting resin composition, and photopolymerization. The light-curing thermosetting resin composition of the initiator, the light-curing thermosetting resin composition containing the photoalkali generator, the one containing the photoacid generator Photocurable thermosetting resin composition, negative type photocuring thermosetting resin composition, positive type photosensitive thermosetting resin composition, alkali development type photocuring thermosetting resin composition, solvent development type light The curable thermosetting resin composition, the swelling peeling type thermosetting resin composition, and the dissolving peeling type thermosetting resin composition, but are not limited to these. Moreover, epoxy resins, such as a liquid epoxy resin, are exemplified by the epoxy resin contained in the aforementioned resin layer.

(Photocurable thermosetting resin composition)

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

Since the carboxyl group-containing resin contains a carboxyl group, it can be alkali-developable. In addition, from the viewpoint of photocurability or development resistance, it is preferable to have ethylenically unsaturated bonds in the molecule in addition to the carboxyl group, and it is also possible to use only carboxyl group-containing resins that do not have ethylenically unsaturated bonds. When the carboxyl group-containing resin does not have an ethylenically unsaturated bond, in order to make the composition photocurable, a compound (photosensitive monomer) having one or more ethylenically unsaturated bonds in the molecule must be used in combination. The ethylenically unsaturated bond is preferably derived from acrylic acid or methacrylic acid or their derivatives. Among the carboxyl-containing resins, carboxyl-containing resins with copolymerized structure, carboxyl-containing resins with urethane structure, carboxyl-containing resins with epoxy resin as starting material, carboxyl-containing resins with phenol compound as starting material Resin is better. Specific examples of the carboxyl group-containing resin include the following compounds (which may be either oligomer or polymer).

(1) Reacting a bifunctional or bifunctional or more polyfunctional epoxy resin as described later with (meth)acrylic acid to make a binary system such as phthalic anhydride, tetrahydrophthalic anhydride, and hexahydrophthalic anhydride The acid (DIBASIC ACID) anhydride is added to the carboxyl group-containing photosensitive resin that exists in the hydroxyl group of the side chain. Here, the bifunctional or bifunctional or more polyfunctional epoxy resin is preferably in a solid form.

(2) The hydroxyl group of the bifunctional epoxy resin described below is then epoxidized with epichlorohydrin and the multifunctional epoxy resin is reacted with (meth)acrylic acid, and the resulting hydroxyl group is added with a carboxyl group containing dibasic acid anhydride Photosensitive resin. Here, the bifunctional epoxy resin is preferably in a solid form.

(3) Unsaturation of epoxy compounds having two or more epoxy groups in one molecule, compounds having at least one alcoholic hydroxyl group and one phenolic hydroxyl group in one molecule, and (meth)acrylic acid, etc. For the reaction of the alcoholic hydroxyl group of the resulting reaction product with maleic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, adipic acid, etc. The polybasic acid anhydride reacts to obtain a carboxyl group-containing photosensitive resin.

(4) Make bisphenol A, bisphenol F, bisphenol S, novolac type phenol resin, poly-p-hydroxystyrene, condensate of naphthol and aldehyde, condensate of dihydroxy naphthalene and aldehyde, etc. A reaction product obtained by reacting a compound having two or more phenolic hydroxyl groups in a molecule with an epoxide such as ethylene oxide and propylene oxide, and an unsaturated group-containing monocarboxylic acid such as (meth)acrylic acid A carboxyl group-containing photosensitive resin obtained by reacting the reaction product obtained by the reaction with a polybasic acid anhydride.

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

(6) Diisocyanate compounds such as aliphatic diisocyanates, branched aliphatic diisocyanates, alicyclic diisocyanates, and aromatic diisocyanates, and polycarbonate polyols, polyether polyols, and polyester polyols , Polyolefin-based polyols, acrylic polyols, bisphenol A-based alkylene oxide adducts, diols, compounds with phenolic hydroxyl groups and alcoholic hydroxyl groups, etc. by addition polymerization The end of the urethane resin of the polyaddition reaction is reacted with an acid anhydride to form a carboxyl-containing urethane resin at the end.

(7) In the synthesis of carboxyl-containing urethane resins by addition polymerization of carboxyl-containing diol compounds such as diisocyanate, dimethylolpropionic acid, dimethylolbutyric acid, and diol compounds , Add hydroxyalkyl (meth)acrylate and other compounds having one hydroxyl group and one or more (meth)acrylic acid groups in the molecule, and carry out terminal (meth)acrylation of carboxyl-containing amino formic acid Ester resin.

(8) In the synthesis of diisocyanate and carboxyl-containing diol compound and diol compound by addition polymerization of carboxyl-containing urethane resin, one of isophorone diisocyanate and pentaerythritol triacrylate is added Mole reactants, etc., a compound having one isocyanate group and one or more (meth)acrylic groups in the molecule, and the terminal (meth)acrylic acid Acrylated carboxyl-containing urethane resin.

(9) Copolymerization of unsaturated carboxylic acids such as (meth)acrylic acid and unsaturated group-containing compounds such as styrene, α-methylstyrene, lower alkyl (meth)acrylate, diisobutylene, etc. The carboxyl-containing photosensitive resin.

(10) For polyfunctional oxetane resin and dicarboxylic acid such as adipic acid, phthalic acid, hexahydrophthalic acid, etc., the carboxyl group-containing polyester with dibasic acid anhydride added to the primary hydroxyl group Resins, with glycidyl (meth)acrylate, α-methylglycidyl (meth)acrylate, etc., which have one epoxy group and more than one (methyl) per molecule ) A carboxyl group-containing photosensitive resin formed from an acrylic compound.

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

In addition, (meth)acrylate here refers to a general term of acrylate, methacrylate, and their mixture, and the same applies to other similar descriptions below.

The acid value of the carboxyl group-containing resin is preferably 40 to 150 mgKOH/g. By setting the acid value of the carboxyl group-containing resin to 40 mgKOH/g or more, alkali development becomes good. In addition, by setting the acid value to 150 mgKOH/g or less, it is easy to draw a normal resist pattern. More preferably, it is 50~130mgKOH/g.

The compounding amount of the carboxyl-containing resin is based on the total amount of the resin layer of the dry film after removing the solvent, and is preferably 20-60% by mass. By setting it to 20 Above mass%, the strength of the coating film can be improved. In addition, by setting it to 60% by mass or less, the viscosity is appropriate and the workability is improved. More preferably, it is 20-50% by mass.

As the photopolymerization initiator, known ones 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 oxyphosphorus-based photopolymerization initiator are preferred. Initiator, titanocene-based photopolymerization initiator. A photopolymerization initiator can be used individually by 1 type or in combination of 2 or more types.

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

The compounding amount when using the oxime ester-based photopolymerization initiator is preferably 0.01 to 5 parts by mass relative to 100 parts by mass of the carboxyl group-containing resin. By setting it to 0.01 parts by mass or more, the photocuring property on copper is more reliable, and the coating film properties such as chemical resistance are improved. In addition, by setting it as 5 parts by mass or less, light absorption on the surface of the coating film is suppressed, and there is also a tendency to improve the curability of the deep part. It is more preferably 0.5 to 3 parts by mass relative to 100 parts by mass of the carboxyl group-containing resin.

When an α-aminoacetophenone-based photopolymerization initiator or an acetoxyphosphorus-based photopolymerization initiator is used, the respective compounding amount is based on 100 parts by mass of the carboxyl group-containing resin, preferably 0.01-15 parts by mass. By setting it to 0.01 parts by mass or more, the photocuring property on copper is more reliable, and the coating film properties such as chemical resistance are improved. In addition, by setting it to 15 parts by mass or less, sufficient outgas reduction effect can be obtained, and light absorption on the surface of the cured film is further suppressed, and the tendency of deep curability is also improved. It is more preferably 0.5 to 10 parts by mass relative to 100 parts by mass of the carboxyl group-containing resin.

In combination with the above-mentioned photopolymerization initiator, a photoinitiator or sensitizer can also be used. Light initiation aids or sensitizers, including benzidine compounds, acetophenone compounds, anthraquinone compounds, thioxanthone compounds, acetal compounds, benzophenone compounds, tertiary amine compounds, and xanthone compounds Wait. These compounds can also be used as photopolymerization initiators, but they are preferably used in combination with photopolymerization initiators. In addition, a photo-initiating aid or a sensitizer may be used alone or in combination of two or more kinds.

The photocurable thermosetting resin composition may contain thermosetting components other than epoxy resin for the purpose of improving the characteristics of heat resistance and insulation reliability. For this thermosetting component, isocyanate compounds, blocked isocyanate compounds, amino resins, maleimide compounds, benzoxazine resins, CARBODIIMIDE resins, cyclic carbonate compounds can be used , Polyfunctional oxetane compounds, episulfide resins and other conventionally used thermosetting resins.

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

The photocurable thermosetting resin composition system is better than the thermosetting catalyst. Such thermosetting catalysts include, for example, imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanide Dicyandiamide, benzyldimethylamine, 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole and other imidazole derivatives; dicyandiamide, benzyldimethylamine, 4- (Dimethylamino)-N,N-dimethylbenzylamine, 4-methoxy-N,N-dimethylbenzylamine, 4-methyl-N,N-dimethylbenzyl Amination of amines, etc. Hydrazine compounds such as dihydrazine adipic acid and sebacic acid diamine; phosphorus compounds such as triphenylphosphine, etc. In addition, guanamine, acetoguanamine, benzoguanamine, melamine, 2,4-diamino-6-methacryloxyethyl-S-triazine, 2-vinyl-2, 4-Diamino-S-triazine, 2-vinyl-4,6-diamino-S-triazine. Isocyanuric acid adduct, 2,4-diamino-6-methacryloyloxyethyl-S-triazine. S-triazine derivatives such as isocyanuric acid adducts are preferably used in combination with a thermosetting catalyst as a compound that also functions as an adhesion imparting agent.

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

In addition to the aforementioned carboxyl group-containing resin, photopolymerization initiator, and epoxy resin, the photocurable thermosetting resin composition may also contain a photosensitive monomer. A compound having at least one ethylenic unsaturated bond in the photosensitive single-system molecule. The photosensitive single system is irradiated with active energy rays to help the light hardening of the carboxyl-containing resin.

Compounds that can be used as photosensitive monomers include, for example, conventionally known polyester (meth)acrylates, polyether (meth)acrylates, urethane (meth)acrylates, and carbonate (meth)acrylates. Base) acrylate, epoxy (meth)acrylate, etc. Specifically, hydroxyalkyl acrylates such as 2-hydroxyethyl acrylate and 2-hydroxypropyl acrylate; ethylene glycol, methoxytetraethylene glycol, polyethylene glycol, propylene glycol, etc. Alcohol diacrylates; acrylamides such as N,N-dimethyl acrylamide, N-methylol acrylamide, N,N-dimethylaminopropyl acrylamide, etc. Class; N,N-dimethylaminoethyl acrylate, N,N-dimethylaminopropyl acrylate and other amino alkyl acrylates; hexanediol, trimethylolpropane, pentaerythritol , Dipentaerythritol, ginseng-hydroxyethyl trimeric isocyanate and other polyols or these ethylene oxide adducts, propylene oxide adducts, or ε-caprolactone adducts and other polyacrylates ; Phenoxy acrylate, bisphenol A diacrylate, and polyacrylates such as ethylene oxide adducts or propylene oxide adducts of these phenols; glycerol diglycidyl ether , Glycerol triglycidyl ether, trimethylolpropane triglycidyl ether, triglycidyl triglycidyl isocyanate, etc. Polyacrylates of glycidyl ether; not limited to the foregoing, it can be polyether polyol , Polycarbonate diol, hydroxyl-terminated polybutadiene, polyester polyol and other polyols are directly acrylated, or urethane acrylated acrylates and melamine acrylates through diisocyanate, And any one of at least one of each methacrylate corresponding to the aforementioned acrylate is appropriately selected and used.

An epoxy acrylate resin that reacts a multifunctional epoxy resin such as a cresol novolak type epoxy resin with acrylic acid or an epoxy acrylate resin such as the hydroxyl group of the epoxy acrylate resin and a hydroxy acrylate such as pentaerythritol triacrylate and the like The epoxy urethane acrylate compound, etc., which react with the half urethane compound of the diisocyanate such as isophorone diisocyanate, can also be used as a photosensitive monomer. This epoxy acrylate-based resin does not reduce the dryness to the touch, and can improve the photocurability.

The compounding amount of the compound having an ethylenically unsaturated bond in the molecule used as the photosensitive monomer is preferably 5-100 parts by mass, and more preferably 5-70 parts by mass relative to 100 parts by mass of the carboxyl group-containing resin. By setting the compounding amount of the compound having an ethylenically unsaturated bond to 5 parts by mass or more, the photocurability of the photocurable thermosetting resin composition can be improved. In addition, by setting the blending amount to 100 parts by mass or less, the hardness of the coating film can be increased.

In addition to the above-mentioned components, the photocurable thermosetting resin composition may preferably contain fillers, and may also contain other components such as colorants, elastomers, and thermoplastic resins. These ingredients are explained below.

In the photocurable thermosetting resin composition, fillers may be blended as necessary in order to improve the physical strength of the cured product obtained. The filler is not particularly limited, and examples thereof include those exemplified for the filler contained in the aforementioned resin layer. The filler can be used singly or as a mixture of two or more.

The addition amount of the filler is based on 100 parts by mass of the carboxyl group-containing resin, 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. When the amount of filler added is 500 parts by mass or less, the viscosity of the photocurable thermosetting resin composition will not become too high, the printability will be good, and the cured product will not easily become brittle.

The photocurable thermosetting resin composition may contain a coloring agent. As the coloring agent, conventional coloring agents such as red, blue, green, yellow, black, and white can be used, and can be any of pigments, dyes, and pigments. However, from the viewpoint of reducing the burden on the environment and affecting the human body, it is preferable to contain halogen.

The addition amount of the coloring agent is not particularly limited, and it is preferably 10 parts by mass or less, particularly preferably 0.1-7 parts by mass relative to 100 parts by mass of the carboxyl group-containing resin.

In addition, in the photocurable thermosetting resin composition, in order to For the purpose of imparting flexibility to the obtained hardened product and improving the brittleness of the hardened product, an elastomer can be formulated. Elastomers include, for example, polyester elastomers, polyurethane elastomers, polyester urethane elastomers, polyamide elastomers, polyester amide elastomers, and acrylic elastomers. , Olefin-based elastomers, etc. In addition, resins in which part or all of epoxy groups of epoxy resins having various skeletons are modified with carboxylic acid-modified butadiene-acrylonitrile rubber at both ends can also be used. In addition, epoxy-containing polybutadiene-based elastomers, acrylic-containing polybutadiene-based elastomers, hydroxyl-containing polybutadiene-based elastomers, hydroxyl-containing isoprene-based elastomers, and the like can also be used. Elastomers can be used singly or as a mixture of two or more types.

The addition amount of the elastomer is relative to 100 parts by mass of the carboxyl group-containing resin, preferably 50 parts by mass or less, more preferably 1-30 parts by mass, and particularly preferably 5-30 parts by mass. When the addition amount of the elastomer is 50 parts by mass or less, the alkali developability of the photocurable thermosetting resin composition is good, and it can be developed so that the time is not easily shortened.

In addition, in the photocurable thermosetting resin composition, components such as block copolymers, adhesion promoters, antioxidants, and ultraviolet absorbers may be blended as necessary. These conventional objects can be used in the field of electronic materials. In addition, it can be formulated with conventionally used tackifiers such as micropowder silica, hydrotalcite, organic bentonite, microcrystalline kaolinite, defoaming agents, leveling agents, etc. of polysiloxane, fluorine, and polymer systems, etc. At least one of the conventionally used additives such as imidazole series, thiazole series, triazole series, etc., silane coupling agents, rust inhibitors, fluorescent whitening agents, etc.

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-based solvents. More specifically, ketones such as methyl ethyl ketone, cyclohexanone, methyl butyl ketone, methyl isobutyl ketone, methyl ethyl ketone, etc.; toluene, xylene, tetramethyl benzene, etc. Of aromatic hydrocarbons; cellosolve, methyl cellosolve, butyl cellosolve, carbitol, methyl carbitol, butyl carbitol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethyl Glycol ethers such as glycol monobutyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, triethylene glycol monoethyl ether, etc.; ethyl acetate, butyl acetate, isobutyl acetate, ethyl acetate Glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol butyl ether acetate and other esters; ethanol, propanol, 2-methoxy Alcohols such as propanol, n-butanol, isobutanol, isoamyl alcohol, ethylene glycol, and propylene glycol; aliphatic hydrocarbons such as octane and decane; petroleum ether, naphtha, hydrogenated naphtha, solvent naphtha In addition to other petroleum-based solvents, there are N,N-dimethylformamide (DMF), tetrachloroethylene, turpentine, etc. In addition, Swasol 1000 and Swasol 1500 manufactured by Maruzen Petrochemical Company, SOLVESSO 100 and SOLVESSO 150 manufactured by Standard Petroleum Osaka Sales Office, solvent#100, solvent#150 manufactured by Sankyo Chemical Co., Ltd., shellsol A100, shellsolA150 manufactured by Shell Chemicals Japan Co., Ltd. can be used. , Idemitsu Kosan Co.'s Ipsol No. 100, Ipsol No. 150 and other organic solvents. This organic solvent can be used singly or as a mixture of two or more types.

The use of light-curable thermosetting resin composition The manufacturing method of the printed wiring board of the dry film of the resin layer can be made by a conventionally known method. For example, in the case of a dry film in which a resin layer is interposed between the first film and the second film as shown in FIG. 2, a printed wiring board can be manufactured as follows. The second film is peeled from the dry film to expose the resin layer. On the substrate on which the circuit pattern is formed, the resin layer of the dry film is laminated using a vacuum laminator or the like, and the resin layer is pattern-exposed. The first film can be peeled off either before or after exposure after lamination. Then, by performing alkali development, a patterned resin layer is formed on the substrate, and the patterned resin layer is cured by light irradiation and heat, and by forming a cured film, a printed wiring board can be manufactured.

(Thermosetting resin composition)

As an example of a thermosetting resin composition, a resin composition containing no photocurable component and containing an epoxy resin will be described below.

It is better to mix fillers in the thermosetting resin composition, which can improve the physical strength of the cured product obtained. The filler is not particularly limited, and examples thereof include those exemplified for the filler contained in the aforementioned resin layer. The filler can be used singly or as a mixture of two or more types.

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

The thermosetting resin composition may contain a curing agent. Examples of hardeners include phenol resins, polycarboxylic acids and their anhydrides, cyanate ester resins, active ester resins, maleimide compounds, and alicyclic olefin polymers. Hardener can One type is used alone or two or more types are used in combination. Here, by using at least a cyanate ester resin or an active ester resin, the dielectric tangent after humidification can be reduced. In addition, by using at least a cyanate ester resin or a maleimide compound, the crack resistance during the cooling and heating cycle after reflow can be improved.

When the resin layer is made of a thermosetting resin composition, it is easy to generate bubbles when cured at a high temperature. However, the dry film according to the present invention requires high temperature even if it contains phenol resin, active ester resin, cyanate ester resin, etc. In the case of hardening agent, it is not easy to produce bubbles after hardening. In addition, the curing agent preferably has at least any structure of a biphenyl skeleton and a naphthol skeleton.

As the aforementioned phenol resin, phenol novolak resin, alkylphenol novolak resin, bisphenol A novolak resin, dicyclopentadiene type phenol resin, Xylok type phenol resin, terpene-modified phenol resin, cresol/ Naphthol resin, polyvinyl phenols, phenol/naphthol resin, phenol resin containing α-naphthol skeleton, cresol novolak resin containing triazine skeleton, biphenyl aralkyl phenol resin, Zilog phenol novolak Conventionally known resins such as resins are used singly or in combination of two or more.

Among the aforementioned phenol resins, those having a hydroxyl equivalent of 130 g/eq. or more are preferable, and those having a hydroxyl equivalent of 150 g/eq. or more are more preferable. Phenolic resins having a hydroxyl equivalent of 130g/eq. or more include, for example, dicyclopentadiene skeleton phenol novolac resin (GDP series, manufactured by Kunei Chemical Co., Ltd.), Zilog type phenol novolac resin (MEH-7800, Meiwa Chemical Co., Ltd.) Made), biphenyl aralkyl type novolac resin (MEH-7851, made by Meiwa Chemical Co., Ltd.), naphthol aralkyl type hardener (SN series, made by Nippon Steel & Sumikin Co., Ltd.), cresol containing triazine skeleton Novolac resin (LA-3018-50P, manufactured by DIC) Wait.

The aforementioned cyanate ester resin is a compound having two or more cyanate ester groups (-OCN) in one molecule. As the cyanate ester resin, conventionally known ones can be used. Examples of cyanate ester resins include phenol novolac type cyanate ester resins, alkylphenol novolac type cyanate ester resins, dicyclopentadiene type cyanate ester resins, bisphenol A type cyanate ester resins, and bisphenol F. Type cyanate ester resin, bisphenol S type cyanate ester resin. In addition, it may be a prepolymer partially triazineized.

The aforementioned 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 the condensation reaction of a carboxyl compound and a hydroxyl compound. Among them, an active ester compound obtained by using a phenol compound or a naphthol compound as the hydroxyl compound is preferred. Phenol compounds or naphthol compounds, including hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenolphthalein, 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, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucinol, benzenetriol, dicyclopentadienediol, phenol novolac, etc. In addition, the active ester resin may be a naphthalene glycol alkyl/benzoic acid type.

The aforementioned maleimine compound is a compound having a maleimine skeleton, and conventionally known compounds can be used. The maleimide compound is preferably one having a maleimine skeleton of 2 or more, more preferably N,N'-1,3-phenylene dimaleimide, N,N'-1, 4-phenylene dimaleimide, N,N'-4,4-diphenylmethane bismaleimide, 1,2-bis(maleimide) Amine) ethane, 1,6-bismaleimide hexane, 1,6-bismaleimide-(2,2,4-trimethyl)hexane, 2,2'-bis- [4-(4-Maleiminophenoxy)phenyl]propane, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleic Amide, 4-methyl-1,3-phenylene bismaleimide, bis(3-ethyl-5-methyl-4-maleimide phenyl)methane, bisphenol A Diphenyl ether bismaleimide, polyphenylmethane maleimide, and at least any one of these oligomers and diamine condensates having a maleimine skeleton.

The aforementioned oligomer is an oligomer obtained by condensing a maleimine compound which is a monomer in the above-mentioned maleimine compound. The maleimide compound can be used individually by 1 type or in combination of 2 or more types.

The aforementioned curing agent is the functional group of the curing agent/the functional group capable of heat curing reaction based on the ratio of the functional group that can be heat-cured, such as epoxy group of the thermosetting component, and the functional group in the curing agent that reacts with the functional group ( Equivalent ratio)=0.2~2 is better. By setting the functional group of the hardening agent/the functional group capable of thermal curing reaction (equivalent ratio) within the above range, it is possible to prevent the roughening of the film surface in the desmear step. More preferably, the functional group of the hardener/the functional group capable of thermal hardening reaction (equivalent ratio)=0.2~1.5, and more preferably the functional group of the hardener/the functional group capable of thermal hardening reaction (the equivalent ratio)=0.3~1.0 .

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.

In order to increase the mechanical strength of the cured film obtained, the thermosetting resin composition may further contain a thermoplastic resin. Thermoplastic Tree The fat is soluble in solvents. When it is soluble in solvents, it can improve the softness of the dry film and inhibit the occurrence of cracks or powder falling. Thermoplastic resins include thermoplastic polyhydroxypolyether resins or phenoxy resins that are condensates of epichlorohydrin and various bifunctional phenol compounds, or use various acid anhydrides or acid chlorides for the hydroxyl groups present in the hydroxy ether portion of the skeleton. Phenoxy resins, polyvinyl acetal resins, polyamide resins, polyimide imine resins, block copolymers, etc. in which the product is esterified. Thermoplastic resin can be used individually by 1 type or in combination of 2 or more types.

The blending amount of the thermoplastic resin is based on the total amount of the resin layer after the solvent is removed, and is 0.5-20% by mass, preferably 0.5-10% by mass. When the blending amount of the thermoplastic resin is outside the above range, it becomes difficult to obtain a uniform roughened surface state.

In addition, the thermosetting resin composition may contain rubber-like particles as necessary. Such rubbery particles can include polybutadiene rubber, polyisopropylene rubber, urethane modified polybutadiene rubber, epoxy modified polybutadiene rubber, and acrylonitrile modified polybutadiene. Rubber, carboxyl modified polybutadiene rubber, carboxyl or hydroxyl modified acrylonitrile butadiene rubber and their cross-linked rubber particles, shell-core rubber particles, etc., can be used alone or in combination of two or more use.

These rubbery particles of silicon can be added in order to improve the flexibility of the cured film obtained, or to improve the crack resistance, or to roughen the surface with an oxidizing agent to improve the adhesion strength with copper foil.

The average particle diameter 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. Rubber-like particles in the present invention The average particle size can be obtained by a laser diffraction particle size distribution measuring device. For example, the rubber-like particles are uniformly dispersed in a suitable organic solvent by ultrasonic waves, and the Nanotrac wave manufactured by Nikkiso Co., Ltd. is used to produce the particle size distribution of the rubber-like particles on a mass basis. The median diameter can be used as The average particle size is measured.

The compounding amount of the rubber-like particles is based on the total amount of the resin layer after the solvent is removed, and is preferably 0.5-10% by mass, more preferably 1-5% by mass. In the case of 0.5% by mass or more, crack resistance can be obtained. It can improve the adhesion strength with conductor pattern etc. In the case of 10% by mass or less, the coefficient of thermal expansion (CTE) decreases, the glass transition temperature (Tg) increases, and the hardening characteristics are improved.

The resin layer of the dry film of the present invention may contain a hardening accelerator. The hardening accelerator is one that promotes the thermal hardening reaction and is used to further improve the characteristics of adhesion, chemical resistance, and heat resistance. Specific examples of such hardening accelerators include imidazole and its derivatives; guanamines such as acetoguanamine and benzoguanamine; diaminodiphenylmethane, m-phenylenediamine, and m-xylene Polyamines such as diamine, diaminodiphenyl sulfide, dicyandiamide, urea, urea derivatives, melamine, polyhydrazine, etc.; these organic acid salts and/or epoxy adducts; trifluoride Amine complexes of boron; ethyldiamino-S-triazine, 2,4-diamino-S-triazine, 2,4-diamino-6-xylyl-S-triazine, etc. Triazine derivatives; trimethylamine, triethanolamine, N,N-dimethyloctylamine, N-benzyldimethylamine, pyridine, N-methylmorpholine, hexa(N-methyl) ) Melamine, 2,4,6-ginseng (dimethylaminophenol), tetramethylguanidine, m-aminophenol and other amines; polyvinylphenol, polyvinylphenol bromide, phenol novolac Polyphenols such as paint, alkylphenol novolac; organic phosphines such as tributylphosphine, triphenylphosphine, ginseng-2-cyanoethylphosphine; tri-n-butyl(2,5-di Phosphonium salts such as hydroxyphenyl)phosphonium bromide and cetyltributylphosphonium chloride; quaternary ammonium salts such as benzyltrimethylammonium chloride and phenyltributylammonium chloride; the aforementioned Polybasic acid anhydride; photocationic polymerization catalysts such as diphenyliodonium tetrafluoroborate, triphenylsulfonium hexafluoroantimonate, 2,4,6-triphenylthiopyrylium (Thiopyrylium) hexafluorophosphate, etc.; benzene Ethylene-maleic anhydride resin; molar reaction of phenyl isocyanate and dimethylamine or organic polyisocyanate of phenyl tolylene diisocyanate, isophorone diisocyanate and dimethylamine Hardening accelerators known in the past as materials, metal catalysts, etc. Among the hardening accelerators, the point at which BHAST resistance can be obtained, and phosphonium salts are preferred.

A hardening accelerator can be used individually by 1 type or in mixture of 2 or more types. The use of a hardening accelerator is not essential, but particularly when it is desired to accelerate hardening, it is preferably used in the range of 0.01 to 5 parts by mass relative to 100 parts by mass of the thermosetting component. In the case of a metal catalyst, it is preferably 10 to 550 ppm in terms of metal, and more preferably 25 to 200 ppm based on 100 parts by mass of the thermosetting component.

Thermosetting resin composition, phthalocyanine can be used if necessary. Blue, phthalocyanine. Green, iodine. Green, bis-azo yellow, crystal violet, titanium oxide, carbon black, naphthalene black and other known coloring agents, asbestos, Orben, Bentonite, micronized silica and other conventionally known tackifiers , Polysiloxane, fluorine, polymer, etc. defoaming agent and/or leveling agent, thiazole, triazole, silane coupling agent, etc. Conventional additives such as additives, flame retardants, titanate series, and aluminum series.

The method of manufacturing a printed wiring board using a dry film having a resin layer made of a thermosetting resin composition may use a conventionally known method. For example, in the case of a dry film in which a resin layer is interposed between the first film and the second film as shown in FIG. 2, a printed wiring board can be manufactured as follows. The second film is peeled off from the dry film, and laminated on the circuit board on which the circuit pattern is formed by heating, and then thermally cured. Thermal hardening can be hardened in an oven or hardened by pressing with a hot plate. When laminating the circuit-formed substrate and the dry film of the present invention or hot plate pressing, the copper foil or the circuit-forming substrate can be laminated at the same time. At the position corresponding to the specific position on the substrate with the circuit pattern formed, a pattern or via hole is formed by laser irradiation or a drilling machine, and a printed wiring board can be manufactured by exposing the circuit wiring. At this time, if there are components (residues) that cannot be completely removed on the circuit wiring in the via hole, the desmear treatment is performed. The first film can be peeled off after being laminated, thermally hardened, and after laser processing or slag removal.

(Photocurable thermosetting resin composition containing photoalkali generator)

Regarding an example of a photocurable thermosetting resin composition containing a photobase generator (hereinafter also referred to as a composition containing a photobase generator), in addition to epoxy resins, it also includes alkali developable resins and photobase generators. The composition of the agent is as follows.

Alkali developable resin contains at least one functional group among phenolic hydroxyl group, mercapto group and carboxyl group, and can be developed by alkaline solution, preferably A compound having two or more phenolic hydroxyl groups, a carboxyl group-containing resin, a compound having a phenolic hydroxyl group and a carboxyl group, and a compound having two or more mercapto groups.

As the carboxyl group-containing resin, conventional resins containing carboxyl group can be used. Due to the presence of carboxyl groups, the resin composition can be made alkali developable. In addition to the carboxyl group, a compound having an ethylenically unsaturated bond in the molecule can also be used. However, in the present invention, it is preferable to use only a carboxyl group-containing resin that does not have an ethylenically unsaturated bond in the carboxyl group-containing resin.

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

(12) Diisocyanates such as aliphatic diisocyanates, branched aliphatic diisocyanates, alicyclic diisocyanates, aromatic diisocyanates, etc. and carboxyl-containing groups such as dimethylol propionic acid and dimethylol butyric acid Diol compounds and polycarbonate polyols, polyether polyols, polyester polyols, polyolefin polyols, acrylic polyols, bisphenol A-based alkylene oxide adduct diols, phenols Carboxyl group-containing urethane resin obtained by polyaddition reaction of diol compounds such as hydroxy and alcoholic hydroxy compounds.

(13) Diisocyanate and bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisxylenol type epoxy resin, The polyaddition reaction of (meth)acrylates of bifunctional epoxy resins, such as bifunctional epoxy resins, or partial acid anhydride modified products, carboxyl-containing diol compounds and diol compounds The resulting urethane resin containing carboxyl groups.

(14) In the synthesis of the resin of (12) or (13) above, a compound having one hydroxyl group and one or more (meth)acryloyl groups in the molecule such as hydroxyalkyl (meth)acrylate is added, Carboxyl-containing urethane resin formed by terminal (meth)acrylation.

(15) In the synthesis of the resin of (12) or (13) above, a molar reactant such as isophorone diisocyanate and pentaerythritol triacrylate is added, and the molecule has one isocyanate group and one or more ( A meth)acrylic compound is a carboxyl-containing urethane resin formed by terminal (meth)acrylation.

(16) Make the aforementioned multifunctional epoxy resin react with saturated monocarboxylic acid, and add phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, etc. to the hydroxyl group present in the side chain A carboxyl group-containing resin of anhydride. Here, the solid form of the multifunctional epoxy resin is preferable.

(17) The polyfunctional oxetane resin described later is reacted with a dicarboxylic acid to produce a carboxyl group-containing polyester resin with a dibasic acid anhydride added to the primary hydroxyl group.

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

(19) The reaction product obtained by reacting a compound having plural phenolic hydroxyl groups in one molecule with alkylene oxide such as ethylene oxide and propylene oxide, and the reaction product obtained by reacting with saturated monocarboxylic acid, and then with Polyacid Carboxyl group-containing resin obtained by anhydride reaction.

(20) The reaction product obtained by reacting a compound having plural phenolic hydroxyl groups in one molecule with a cyclic carbonate compound such as ethylene carbonate and propylene carbonate, and the reaction product obtained by reacting with saturated monocarboxylic acid, and then Carboxyl group-containing resin obtained by reacting with polybasic acid anhydride.

(21) A carboxyl group-containing resin obtained by reacting a compound having plural phenolic hydroxyl groups in one molecule with a cyclic carbonate compound such as ethylene carbonate and propylene carbonate, and then reacting with a polybasic acid anhydride.

(22) An epoxy compound having plural epoxy groups in one molecule and a compound having at least one alcoholic hydroxyl group and one phenolic hydroxyl group in one molecule such as p-hydroxyphenethyl alcohol are reacted with saturated monocarboxylic acid The alcoholic hydroxyl group of the reaction product is a carboxyl-containing resin obtained by reacting with maleic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, adipic acid and other polybasic acid anhydrides.

(23) One of the reaction products obtained by reacting an epoxy compound having plural epoxy groups in one molecule with a compound having at least one alcoholic hydroxyl group and one phenolic hydroxyl group in one molecule such as p-hydroxyphenethyl alcohol Alcoholic hydroxyl group is a carboxyl-containing resin obtained by reacting with maleic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, adipic acid and other polybasic acid anhydrides.

(24) For any of the resins (12) to (23) above, further addition of glycidyl (meth)acrylate, α-methylglycidyl (meth)acrylate, etc., has 1 epoxy group and more than 1 The (meth)acrylic acid compound is a carboxyl-containing resin.

The alkali-developable resin mentioned above is in the main chain. The side chain of the polymer has many carboxyl groups or hydroxyl groups, etc., so it can be developed by an aqueous alkali solution.

In addition, the hydroxyl equivalent or carboxyl equivalent of the alkali developable resin is preferably 80 to 900 g/eq., and more preferably 100 to 700 g/eq. When the hydroxyl equivalent or carboxyl equivalent is 900 g/eq. or less, the adhesion of the pattern layer can be obtained, and alkali development becomes easy. In addition, when the hydroxyl equivalent or carboxyl equivalent is 80 g/eq. or more, the dissolution of the light-irradiated part by the developer is suppressed, the line does not become excessively thin, and the normal resist pattern drawing becomes easy, so Better. In addition, when the carboxyl group equivalent or the phenol group equivalent is large, even if the content of the alkali developable resin is small, the image can be developed, which is preferable.

The acid value of the alkali developable resin is preferably 40 to 150 mgKOH/g. By setting the acid value of the alkali-developable resin to 40 mgKOH/g or more, alkali development becomes good. In addition, by setting the acid value to 150 mgKOH/g or less, a normal resist pattern can be easily drawn. More preferably, it is 50~130mgKOH/g.

The blending amount of the alkali-developable resin is based on the total amount of the resin layer of the dry film from which the solvent has been removed, and is preferably 20-60% by mass. By setting it as 20% by mass or more, the strength of the coating film can be improved. In addition, by setting it to 60% by mass or less, the viscosity becomes appropriate and the coatability is improved. More preferably, it is 30-50% by mass.

The photobase generator is irradiated with light such as ultraviolet light or visible light, and the molecular structure changes, or the molecule cracks, to produce more than one kind of alkali that can act as a catalyst for the addition reaction of the above-mentioned thermally reactive compound. The compound of the substance. Examples of basic substances include secondary amines and tertiary amines.

The photobase generator includes, for example, α-aminoacetophenone compounds, oxime ester compounds, or hydroxylimino groups having acyl groups, N-formylated aromatic amine groups, N-acylated aromatic amine groups, and nitro groups. Compounds with substituents such as benzyl carbamate groups and alkoxy benzyl carbamate groups.

The aforementioned photobase generators can be used singly or in combination of two or more kinds. The compounding amount of the photobase generator in the composition containing the photobase generator is preferably 1-50 parts by mass, and more preferably 1-40 parts by mass relative to 100 parts by mass of the thermally reactive compound. If it is 1 part by mass or more, development becomes easy, so it is preferable.

In the composition containing the photobase generator, it is better to mix fillers, which can improve the physical strength of the resulting hardened product. The filler is not particularly limited, and examples thereof include those exemplified for the filler contained in the aforementioned resin layer. The filler can be used singly or as a mixture of two or more.

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

In the composition containing the photobase generator, components such as sulfhydryl compounds, adhesion promoters, antioxidants, ultraviolet absorbers, etc. can be adjusted when necessary. These can be used conventionally in the field of electronic materials.

In addition, in the above-mentioned composition containing photoalkali generators, conventionally used tackifiers such as micropowdered silica, hydrotalcite, organic bentonite, microcrystalline kaolinite, silicone, fluorine, and polymer can be blended. It is the conventionally used additives such as defoamer and/or leveling agent, silane coupling agent, rust inhibitor, etc.

The method of manufacturing a printed wiring board having a dry film of a resin layer formed of a composition containing a photobase generator may be a conventionally known method. For example, in the case of a dry film in which a resin layer is interposed between the first film and the second film as shown in FIG. 2, a printed wiring board can be manufactured as follows. The second film is peeled 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, using a vacuum laminator or the like. Then, it is irradiated with light in a negative pattern to activate the photobase generator contained in the resin composition containing the photobase generator to harden the light-irradiated part, and remove the unirradiated part by alkali development. Form a negative pattern layer. The first film can be peeled off either after laminating or after exposure. Furthermore, it is preferable to heat the resin layer after light irradiation and before development. Thereby, the resin layer is fully cured, and a patterned layer with excellent curing characteristics can be obtained. In addition, the temperature at which the non-irradiated part is not thermally cured after the light irradiation and before the image development is preferable. Furthermore, it is preferable to perform thermal curing (post curing) after development. After the image development, by irradiating with ultraviolet rays, the photobase generator that is not activated during the light irradiation and the remaining photobase generator may be activated, and then thermal curing (post-curing) may be performed.

(Positive photosensitive thermosetting resin composition)

An example of a positive photosensitive thermosetting resin composition is a resin composition containing a compound that generates a carboxyl group by light irradiation in addition to an epoxy resin, as described below.

Among the compounds that generate a carboxyl group by light irradiation, a naphthoquinonediazide compound is preferably used. Naphthoquinone diazide compounds, used in the past to borrow By forming a complex with a carboxyl group or a phenolic hydroxyl group, the alkali solubility of the carboxyl group is inhibited, and by subsequent light irradiation, the complex is dissociated, and the system exhibits alkali solubility. At this time, when the naphthoquinone diazide compound remains in the film, the complex compound is dissociated due to light irradiation, and there is a concern that it will exhibit solubility. Therefore, in the semiconductor field, the remaining naphthoquinone diazide compound is finally scattered at high temperature. Remove. However, in the field of printed wiring boards, such high temperatures cannot be applied, and from the standpoint of stability, it cannot be used as a permanent coating film. Therefore, naphthoquinonediazide compounds are not actually used. 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 part is incorporated into the cross-linked structure during the thermosetting reaction In addition, it is stabilized, so it does not cause the problems that have been removed as in the past, and the film strength and toughness, that is, the bending resistance or electrical properties can be improved. In particular, the use of a naphthoquinonediazide compound, which is a compound that generates a carboxyl group by light irradiation, together with a polyamide imide resin and a thermosetting component can ensure good developability or resolution, and effectively improve flexibility, so Better.

The naphthoquinone diazide compound, specifically, the naphthoquinone diazide adduct of (4-hydroxyphenyl)-1-ethyl-4-isopropylbenzene (for example, Sambo Chemical Research Institute TS533, TS567, TS583, TS593 manufactured by the company) or naphthoquinone diazide adduct of tetrahydroxybenzophenone (for example, BS550, BS570, BS599 manufactured by Sanbao Chemical Research Institute) and the like.

In the positive photosensitive thermosetting resin composition, it is better to mix fillers, which can improve the physical strength of the cured product obtained. The filler is not particularly limited, and examples thereof include those exemplified for the filler contained in the aforementioned resin layer. fill The materials can 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 aforementioned photocurable thermosetting resin composition and the aforementioned composition containing the photobase generator. Illustrative alkali developable resin and the like.

The positive photosensitive thermosetting resin composition may contain thermosetting components other than epoxy resin for the purpose of improving characteristics such as heat resistance and insulation reliability. Thermosetting components can use isocyanate compounds, blocked isocyanate compounds, amino resins, maleimide compounds, benzoxazine resins, carbodiimide resins, cyclic carbonate compounds, and polyfunctional oxetane compounds. , Episulfide resin and other conventionally used thermosetting resins.

The organic solvent that can be used is not particularly limited, and examples thereof include the organic solvents exemplified in the aforementioned photocurable thermosetting resin composition. The organic solvent can be used singly 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 for the filler contained in the aforementioned resin layer. The filler can be used alone or as a mixture of two or more types.

In addition to the above-mentioned components, the positive photosensitive thermosetting resin composition may also contain other components such as block copolymers, colorants, elastomers, and thermoplastic resins. In addition, in the positive photosensitive thermosetting resin composition, components such as adhesion promoters, antioxidants, and ultraviolet absorbers may be blended as necessary. These can be used conventionally in the field of electronic materials. In addition, it can also be formulated with conventionally used tackifiers such as micronized silica, hydrotalcite, organic bentonite, and microcrystalline kaolin, as well as defoamers and flattening agents such as silicone, fluorine, and polymer. At least any one of the conventionally used additives such as imidazole-based, thiazole-based, triazole-based silane coupling agents, rust inhibitors, fluorescent whitening agents, etc.

The method of manufacturing a printed wiring board using a dry film having a resin layer made of a positive photosensitive thermosetting resin composition can use a conventionally known method. For example, in the case of a dry film in which a resin layer is interposed between the first film and the second film as shown in FIG. 2, a printed wiring board can be manufactured as follows. The second film is peeled 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, using a vacuum laminator or the like. Then, the resin layer is irradiated with positive patterned light, the resin layer is subjected to alkali development, and the light irradiated portion is removed to form a positive patterned layer. The first film can be peeled off either after laminating or after exposure. In addition, after development, the resin layer is thermally cured (post-curing), and by curing the unirradiated portion, a printed wiring board can be manufactured. The positive-type photosensitive thermosetting resin composition is changed into a composition soluble in an alkali developer by an acid generated by light irradiation, so that a positive-type pattern can be formed by alkali development.

[film]

When laminating a dry film with a resin layer sandwiched between a carrier film and a protective film, in most cases, the protective film is peeled off, and the resin layer on the side contacting the protective film is laminated with the base material. However, the carrier film is also peeled off, and the resin layer on the side in contact with the carrier film is in contact with the substrate. To be laminated. The present invention uses a carrier film and a protective film. As shown in FIG. 2, the resin layer is preferably sandwiched between the first film and the second film. In addition, when laminating on a substrate, the film on the side in contact with the resin layer (ie, the laminated surface) of the substrate is the second film, and the surface in contact with the aforementioned resin layer of the second film is the arithmetic average surface roughness Ra is preferably 0.1 to 1.2 μm, more preferably 0.3 to 1.2 μm, and still more preferably 0.4 to 1.2 μm. In addition, the arithmetic mean surface roughness Ra refers to the value measured in accordance with JIS B0601. The second film can be any of a carrier film and a protective film. Preferably, the first film is a carrier film, and the second film is a protective film.

The carrier film refers to a film that has the function of supporting the resin layer of the dry film, and when the resin layer is formed, a film coated with a curable resin composition. The carrier film can use, for example, polyester film such as polyethylene terephthalate or polyethylene naphthalate, polyimide film, polyimide film, polyethylene film, and polytetrafluoroethylene film. , Polypropylene film, polystyrene film and other thermoplastic resin films and surface-treated paper, etc. Among these, from the viewpoints of heat resistance, mechanical strength, handleability, etc., a polyester film is preferably used. The thickness of the carrier film is not particularly limited, and it is probably in the range of 10~150μm, which is appropriately selected according to the application. The surface where the resin layer is provided with the carrier film can also be subjected to mold release treatment. In addition, the surface where the resin layer of the carrier film is provided can be sputtered or formed into an ultra-thin copper foil.

The protective film is to prevent dust and the like from adhering to the surface of the resin layer of the dry film, and to improve the workability, is set on the opposite side of the carrier film of the resin layer. As the protective film, for example, a film made of a thermoplastic resin as exemplified in the aforementioned carrier film, a surface-treated paper, etc. can be used. Among the others, a polyester film, a polyethylene film, and a polypropylene film are preferred. The thickness of the protective film is not particularly limited, it is probably in the range of 10~150μm, which is suitable for the application. The surface of the resin layer where the protective film is provided can also be demoulded.

When a thermoplastic resin film is used for the second film with the arithmetic average surface roughness Ra as described above, filler is added to the resin when the film is formed, or the surface of the film is blasted, or by hairline Treatment (Hairline Finish), matte coating (matte coating) or chemical etching, etc. can make the surface form a specific shape, and a thermoplastic resin film with the above-mentioned arithmetic average surface roughness Ra can be obtained. For example, when a filler is added to the resin, the arithmetic average surface roughness Ra can be controlled by adjusting the particle size or the amount of the filler. In addition, in the case of sandblasting, the arithmetic average surface roughness Ra can be controlled by adjusting the processing conditions such as sandblasting material or sandblasting pressure. Commercially available products can also be used for thermoplastic resin films having such surface roughness. For example, lumirror X42, lumirror X43, lumirror X44 made by Toray, EMBLETPTH-12 made by Unitika, EMBLETPTH-25, EMBLETPTHA-25, EMBLETPTH can be mentioned. -38. AlphanMA-411, MA-420, E-201F and ER-440 manufactured by Oji F-Tex.

The arithmetic mean surface roughness Ra of the surface of the first film in contact with the aforementioned resin layer is preferably 0.1 μm or less. In the case of less than 0.1 μm, the surface flatness of the cured resin layer becomes good, and the gloss becomes good. In addition, when the arithmetic average surface roughness Ra of the first film and the second film are different, it is easy to recognize which is thinner by visual inspection (presence of gloss) Membrane can prevent negligence in operation.

In addition, since the second film becomes easy to peel off, the thickness A of the first film is preferably greater than the thickness B of the second film. More preferably, the difference (A-B) between thickness A and thickness B is 1 μm or more. In addition, when there is a difference in thickness between the first film and the second film, it is easy to identify which film is touched or visually, which can prevent errors in operation.

The thickness of the first film is preferably 10-100 μm, but more preferably 15 μm or more. In the case of 10μm or more, after the dry film is laminated on the substrate, the first film is heat-treated without peeling off the first film. The first film is not easy to undergo thermal shrinkage, which can prevent uneven thickness due to thermal shrinkage, or thermal shrinkage. With the streaks produced by the first film, the resin layer produces flow, and the resin layer also produces grain quality deterioration.

When the resin layer of the dry film of the present invention is made of a photosensitive resin composition, in order to expose the first dry film without peeling off, it is preferable to use a light-transmitting material such as the above-mentioned thermoplastic resin for the first film . At this time, the thickness of the first film is preferably 45 μm or less. Under 45μm, the undercut can be reduced. More preferably, it is 40 μm or less.

The dry film of the present invention can be suitably used to form a permanent protective film for a printed wiring board, and can also be suitably used to form a solder resist layer, an interlayer insulating layer, and a cover lay of a flexible printed wiring board. In addition, the dry film of the present invention is excellent in embedding properties, so it can be applied to printed wiring boards with fine circuits such as packaging substrates that have a large influence of bubbles, and especially suitable for fine circuits with L/S=10/10μm or less Printed wiring board. In addition, The dry film of the present invention can also be suitably used in the case of vacuum lamination which is easy to generate bubbles as the lamination method of the dry film. In addition, the cured product of the resin layer of the dry film of the present invention is excellent in the formability of a plating resist, so it is preferably used to form an interlayer insulating layer. Using the dry film of the present invention, a wiring board can also be formed by bonding wiring. In addition, it can also be used as an encapsulating resin for semiconductor wafers. It can also be used to form the outermost layer or interlayer insulating layer of a coreless substrate.

Example

Hereinafter, examples, comparative examples, and test examples of the present invention will be given to specifically explain the present invention, but the present invention is not limited to the following examples. In addition, in the following, "parts" and "%" are all quality standards when specifically stated.

[Preparation of surface-treated inorganic fillers] (The preparation of surface-treated silica A~D and the preparation of surface-treated alumina A and B)

In the flask, 100 g of each inorganic filler and 2000 g of alcohol aqueous solution (water:alcohol=1:9 weight ratio) are added, and the mixture is stirred at a rotation speed of 300 rpm for about 30 minutes at room temperature to form a slurry. Secondly, relative to the weight of the inorganic filler, the respective silane coupling agent is prepared at 1 wt% to prevent droplets from flying off, drip slowly into the slurry for 10 minutes, and stir the slurry for 10 minutes at 300 rpm. Then, use round qualitative filter paper to take out the surface-treated filler. Next, diffuse the surface-treated inorganic filler on the shallow pan (tray), dried at 110°C for 60 minutes to obtain an inorganic filler surface-treated with a silane coupling agent. The inorganic filler and silane coupling agent used are described in the notes to Table 1 below.

(Examples 1 to 34 and Comparative Examples 1 to 12) <Production of dry film>

In the following Tables 1, 3, 5, 7, 9, 11, 13 and 15 described in the Examples and Comparative Examples, the ingredients were mixed and dispersed by a roller mill to adjust the viscosity to 0.5-20dPa. s (rotary viscometer 5rpm, 25°C) curable resin composition. Next, using a coating bar, apply to a carrier film (lumirror S10, thickness 38 μm, no surface treatment, Ra=0.03 μm, manufactured by Toray Corporation) so that the film thickness of the dry film becomes 15 μm after drying. Next, use a hot air circulation type drying oven to dry at 85°C for 5 to 15 minutes, and the residual solvent amount used will be 3.5 to 4.5% to form a curable resin layer 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 applied to the dry coating film surface, and roll-laminated at a set temperature of 70° C. to obtain a dry film with a three-layer structure.

<Storage elastic modulus G'and melt viscosity of resin layer>

Regarding each dry film produced above, after peeling off the protective film, use a 1-cavity company vacuum laminator MVLP-500 (manufactured by Meiji Co., Ltd.) to superimpose two resin layers of the dry film and perform thermocompression bonding to make the resin layer The thickness becomes 350μm. At this time, in order to avoid heating the film, lamination was performed for 1 minute at a temperature of 40°C and a pressure of 0.5 MPa to overlap the film. Secondly, in terms of viscosity. The viscoelasticity measuring device RheoStress RS-6000 (manufactured by HAAKE) peeled off the carrier film, and then measured the temperature-viscoelasticity of the respective resin layer. The measurement conditions were performed in a heating mode of 5°C/min, an oscillation mode (oscillation mode) strain of 8%, a frequency of 1 Hz, a parallel plate of measuring sensor Φ20mm, and a gap between sensors of 300 μm. Regarding the gap, by increasing the thickness of the resin layer, a sufficient resin thickness can also be ensured between the gaps during heating. From the temperature-storage elastic modulus G'and viscosity η measured by the aforementioned method, the storage elastic modulus and melt viscosity at 100°C are taken as the "storage elastic modulus G'of the resin layer" and "resin Melt viscosity of the layer". The measurement results are shown in the table.

<Embedding (FLS (thin line width/spacing))>

A double-sided printed circuit board with a copper thickness of 10μm, L (line: wiring width)/S (space (space): interval width) = 5/5μm, and an aspect ratio of 2.0 with a comb-tooth pattern fine circuit , Carry out pretreatment: Treat with CZ-8101 made by Merk Company, and carry out 0.5μm equivalent etching treatment. Next, the dry film with a thickness of 15 μm produced as described above was laminated on the substrate on which the L/S was formed using a batch-type vacuum pressure laminator MVLP-500 (manufactured by Meiji Co., Ltd.). The lamination conditions ^{are heating lamination under the conditions of 5kgf/cm 2} , 100°C, 1 minute, and 1 Torr, and secondly, in the hot plate pressing step, ^{flattening under the conditions of 10kgf/cm 2} , 100°C, and 1 minute. After lamination, air enters the line width/spacing interface. After peeling off the carrier film at 100 points, check whether bubbles (voids) are generated. Those evaluated in this way are regarded as "after lamination". Next, the presence or absence of bubbles was evaluated in the same way as the state in which the resin layer was cured, and it was referred to as "after curing". The hardening conditions are detailed as shown in the next item. The evaluation criteria are as follows.

○: No gaps are confirmed.

△: 1~5 gaps are confirmed.

×: The viscosity and elastic modulus are high and cannot be embedded in a substrate with fine lines.

<The flatness of the hardened substrate>

Regarding the resin layer of each dry film laminated on the substrate on which the micro-circuit is formed by the method described in the above-mentioned <embedding (bubble generation FLS)>, and the curing system is thermosetting, the carrier film After peeling, using a hot-air circulation type drying oven, thermal curing was performed at 180°C for 30 minutes, and then thermal curing was performed at 200°C for 60 minutes to completely cure the resin layer.

In addition, the hardening system is light. The thermosetting type is from the carrier film, so that the thin line part is completely exposed, and ^{the light is cured with an exposure amount of 300mJ/cm 2} (i-line, oxtail projection exposure machine), and then the carrier film is peeled off. Next, develop with a 1 wt% sodium carbonate aqueous solution, a pressure of 0.2 MPa, and a liquid temperature of 30°C for 60 seconds. Next, a high-pressure mercury lamp irradiation device was used to perform 1000 mJ/cm ² exposure. Then, heat curing was performed at 180°C for 60 minutes in a hot air circulation type drying furnace to completely cure the resin layer.

For the substrates that are completely cured by the respective curing methods, the surface irregularities of the cured film in the direction perpendicular to the thin line are measured with a contact-type surface roughness measuring device (SE-300, manufactured by Kosaka Laboratory Co., Ltd.) in a width of 20 mm in length, Measure the unevenness on the hardened film. The evaluation criteria are as follows.

◎: On the fine circuit, the unevenness does not reach the maximum tolerance of 0.3μm. Not seen The copper of the fine circuit is burnt.

○: On the fine circuit, the unevenness does not reach the maximum tolerance of 0.3μm.

△: On the fine circuit, the maximum unevenness is a tolerance of 0.3μm or more and less than 1.0μm.

×: On the fine circuit, the maximum unevenness is 1.0 μm or more tolerance.

××: On fine circuits, the maximum unevenness is 5.0 μm or more tolerance. The unevenness of the circuit is obvious.

<Adhesion to the bottom circuit>

The glossy surface of the electrolytic copper foil GTS-MP-18μm (manufactured by Furukawa Circuit Foil) was treated with CZ-8101 manufactured by Merk, and an etching treatment equivalent to 0.5μm was performed.

Then, for the treatment surface side, the respective dry films are laminated by the method described in <embedding (bubble generation FLS)>, and secondly, the resin layer is completed by the method of <flatness of the substrate after curing> hardening. Then, a 2-component adhesive araldite was used on the resin layer side and attached to a 1.6mmtFR-4 etching board, and the adhesive layer was cured at room temperature to obtain a three-layer structure of CZ-treated copper foil-resin layer-FR4 material. For the obtained substrate, measure the relationship between the resin layer and the CZ treatment surface according to the JIS-C-6481 copper-laminated laminate test method and the peel strength measurement method (test piece width 10mm, 90° direction, speed 50mm/min) Follow force. The criterion system is as follows.

⊚: The adhesive force is 5.0 N/cm or more.

○: The adhesive force is 3.0 N/cm or more and less than 5.0 N/cm.

×: The viscosity or modulus of elasticity is high, and an evaluation sample cannot be produced.

<Formation of anti-plating agent>

For the hardened substrate produced by the method described in <The flatness of the substrate after hardening>, a plating resist was further formed on the surface and evaluated.

Specifically, the produced hardened substrate is treated with permanganic acid desmear (manufactured by atotech, Securiganth MV series for vertical desmear), swelled at 60°C for 5 minutes, and permanganic acid is used at 80°C for 5 minutes. The surface of the substrate was subjected to a roughening treatment at 20 minutes of treatment at 50°C, and reduction treatment at 50°C for 5 minutes. Next, an electroless copper plating process (manufactured by Uemura Industry Co., Ltd., alkali ion type Pd) was used to form a copper seed layer with a thickness of 0.3 μm on the surface of the substrate. Then, after alkali degreasing the surface of the copper seed layer, apply the anti-plating agent fortech RY-3625 (manufactured by Hitachi Chemical Co., Ltd., anti-plating agent for SAP, thickness 25μm) using a roll laminator at 110°C, 0.4MPa Under pressure conditions, it is attached to the surface of the substrate. Next, use the EXP-2960 (Orc Manufacturing Co., Ltd., parallel light exposure machine) to use a glass dry plate negative mask (negative mask) L/S pattern (20mm×20mm area, L/S=10 /10μm pattern negative mask), and with an exposure amount of 100mJ/cm ² , a negative pattern is formed on the surface of the substrate. Secondly, a 1wt% sodium carbonate aqueous solution was used to develop at 30°C for 30 seconds to form an L/S pattern on the surface of the substrate. The obtained substrate was observed by SEM. Randomly extract 100 places within the range of 20mm×20mm to evaluate the formation of the anti-plating agent (check whether the line is missing or the state of poor development due to dents). The judgment criteria are as follows.

○: The formability is good.

△: Poor L/S formation (line missing, poor development) was found to be more than one and less than ten.

×: L/S formation failures (line missing, poor development) were found in 10 or more places.

××: The bottom layer is not flat, so there is no pattern like the design value.

<Dielectric tangent after humidification>

A dry film with a thickness of 15μm in the resin layer produced by the method described in <Production of dry film> is used on the glossy surface of the electrolytic copper foil GTS-MP-18μm (manufactured by Furukawa Circuit Foil Co., Ltd.) with <embedding (bubble) The occurrence of FLS) is laminated by the method described in, and secondly, the resin layer is 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 with a thickness of 15 μm.

The cured product obtained is stored in a high temperature and high humidity tank set at a temperature of 85°C and a humidity of 85%RH for 100 hours. Within 10 minutes after taking it out, use an SPDR dielectric resonator and a network analyzer (both from agilent) Manufacture), measure the dielectric tangent of 5.1GHz humidification at 23℃. The criterion system is as follows.

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

◎: The dielectric tangent of 5GHz is 0.005 or more and less than 0.01.

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

△: The dielectric tangent of 5GHZ is more than 0.015 and less than 0.02.

×: The dielectric tangent at 5 GHz is 0.02 or more.

<Heat dissipation characteristics>

The 15μm hardened product obtained by the same method as the <dielectric tangent after humidification> was measured according to the method described in JIS-R1611 to measure the thermal conductivity of the hardened product (Thermal Conductivity). The criterion system is as follows.

◎: The thermal conductivity is 1W/m. Above K.

○: The thermal conductivity is 0.3W/m. Above K, less than 1W/m. K.

△: The thermal conductivity is less than 0.3W/m. K.

×: The viscosity or modulus of elasticity is high, and an evaluation sample cannot be produced.

<Coefficient of Thermal Expansion>

After peeling the cured product of 15 μm from the copper foil by the same method as the "dielectric tangent after humidification", the sample was cut into a measurement size (3mm×10mm size) and supplied to TMA6100 manufactured by Seiko Instruments. The TMA measurement system is to measure the temperature of the sample from room temperature at a heating rate of 10°C/min under a test load of 5g, and two consecutive measurements. It is evaluated as the second thermal expansion coefficient (CTE(α1)) in the region below Tg. The criterion system is as follows.

◎◎: The CTE below the glass transition temperature is less than 10 ppm.

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

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

△: The CTE below the glass transition temperature is 30 ppm or more.

×: The viscosity or modulus of elasticity is high, and an evaluation sample cannot be produced.

<Substrate warpage>

On a copper-laminated laminate (MCL-E-770G, Hitachi Chemical Co., Ltd., copper thickness 18μm, pre-treatment: CZ-8101 equivalent to 1μm etching treatment) with a thickness of 200μm and a size of 100×100mm, use <Production of dry film> A dry film with a resin thickness of 15 μm produced by the described method is laminated on one side of the substrate using a vacuum laminator, and then the carrier film is peeled off, and then the resin layer is completely cured using a hot air circulation drying oven. For the obtained substrate, the amount of warpage at the 4 corners of the substrate was measured using a Vernier Caliper, and the evaluation was performed based on the following criteria.

◎: The maximum warpage is less than 3mm.

○: The maximum warpage is 3mm or more and less than 15mm.

△: The maximum value of warpage is 15 mm or more.

×: The viscosity or modulus of elasticity is high, and an evaluation sample cannot be produced.

<Reflow+TCT (Thermal Cycling Test)>

The dry film thickness (resin thickness of 15μm) of each example and comparative example was used in a batch-type vacuum pressure laminator MVLP-500 (manufactured by Meiji Corporation) at a rate of 5kgf/cm ² , 80°C, 1 minute, 1 Torr Under the conditions, it is laminated on the copper of the copper-clad laminate. Then, the carrier film was peeled off and heated in a hot-air circulation type drying oven to harden the resin layer at 180°C for 30 minutes. Then, a CO ₂ laser processing machine (manufactured by Hitachi Viamechanics) was used to form vias with a top diameter of 65 μm and a bottom diameter of 50 μm.

The hardening system is light. For the thermosetting type, use the method described in <The flatness of the substrate after curing>, using a 65μm negative pattern, exposure and development, followed by ultraviolet radiation and this curing to form via holes.

Secondly, the obtained via pattern is processed in the order of commercially available wet permanganic acid desmear (manufactured by ATOTECH), electroless copper (THRU-CUP PEA, manufactured by Uemura Industrial Co.), and copper electroplating. , Provide copper with a thickness of 25μm on the resin layer, and apply copper plating to fill the via hole. Next, heat curing was carried out at 200° C. for 60 minutes in a hot-air circulation type drying furnace to obtain a test substrate subjected to a fully cured copper plating treatment. The obtained test substrate was subjected to 3 cycles of heat shock under lead-free assembly conditions (peak temperature of 270°C, 10 seconds), and then subjected to 1 cycle at -65°C for 30 minutes and 150°C for 30 minutes. Heat and cold cycle processing. After 2000 and 3000 cycles, in order to observe the state of the bottom or wall surface of the guide hole with an optical microscope, it was cut with a precision cutter, and the center part of the guide hole was polished to observe the cross-sectional state. The evaluation criteria are based on the following evaluations. The number of observation guide holes is 100 holes.

◎: After 3000 cycles, no cracks occurred.

○: No cracks occurred after the end of the 2000 cycle. 1 to 5 cracks occurred at 3000 cycles.

△: After the end of the 2000 cycle, 1 to 5 cracks occurred.

×: The melt viscosity and storage elastic modulus exceed the optimum range, so the test piece cannot be produced.

<Specific Dielectric Rate>

On the glossy surface of electrolytic copper foil GTS-MP-18μm (manufactured by Furukawa Circuit Foil Co., Ltd.), laminate the resin produced by the method described in <embedding property (foam generation FLS)> with the method described in <dry film production> A dry film with a layer thickness of 15μm, and secondly, the resin layer is completely cured by the method of <Finishing the substrate after curing>. Then, the cured product was peeled from the copper foil to obtain a cured product having a thickness of 15 μm.

For the obtained cured product, SPDR dielectric resonator and network analyzer (both manufactured by Gilent) were used to measure the specific dielectric rate of 1 GHz at 23°C. The criterion system is as follows.

⊚: The specific permittivity at 1 GHz is 10.0 or more.

○: The specific permittivity at 1 GHz is 5.0 or more and less than 10.0.

<Circuit concealment>

After forming a cured film on a fine circuit board by the methods described in the above-mentioned <embedding (bubble generation FLS)> and <flatness of the substrate after curing>, the carrier film is peeled off to obtain a printed wiring board.

For the obtained evaluation substrate, the discoloration of the copper circuit from the cured film was visually confirmed, and the concealment of the circuit was evaluated. The judgment criteria are as follows.

◎: No discoloration was confirmed.

×: Discoloration is confirmed.

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

*2: NC-3000L, biphenyl aralkyl type solid Shape epoxy resin, epoxy equivalent: 275g/eq

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

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

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

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

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

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

*9: MARUKA LYNCUR M manufactured by Maruzen Chemical Co., polyvinylphenol, hydroxyl equivalent 120g/eq

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

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

*12: BMI-1100, N,N'-diphenylmethane bismaleimide, maleimine equivalent manufactured by Daiwa Chemical Industry Co., Ltd.: 179g/eq

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

*14: PC-1100-02 manufactured by AIR WATER, multifunctional active ester resin, active ester equivalent: 154g/eq

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

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

*17: A-DCP, dicyclopentadiene skeleton acrylic monomer manufactured by Shinnakamura Chemical Industry Co., Ltd.

*18: HPS-500 manufactured by Toagosei Co., Ltd., spherical silica with D50=0.5μm

*19: HPS-1000 manufactured by Toagosei Co., Ltd., spherical silica with D50=1.0μm

*20: The above-prepared surface-treated silica A (Nanosilica manufactured by Admatechs (Average primary particle size (D50)=50nm) 1wt% aminosilane-treated product)

*21: FB-5SDX, D50=4.9μm spherical silicon dioxide manufactured by Electrochemical Industry Co., Ltd.

*22: Surface-treated silicon dioxide B prepared above (HPS-500/KBE-1003, HPS-500 1wt% vinyl silane treated product)

*23: Surface-treated silicon dioxide C prepared above (HPS-500/KBE-9103, HPS-500 1wt% aminosilane treated product)

*24: The surface-treated silicon dioxide D prepared above (HPS-1000/KBE-1003, HPS-1000 1wt% vinyl silane treated product)

*25: The surface-treated silicon dioxide E prepared above (FB-5SDX/KBE-9103, FB-5SDX 1wt% aminosilane treated product)

*26: ASFP-20 made by Electrochemical Industry Corporation, D50=0.3μm spherical alumina

*27: DAM-03, D50=3.7μm spherical alumina manufactured by Electrochemical Industry Corporation

*28: The surface-treated alumina A prepared above (ASFP-20/KBE-1003, ASFP-20 1wt% vinyl silane treated product)

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

*30: FUSELEX WX made by Ronson, D50=1.5μm amorphous silica

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

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

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

*34: IRGACURE369 made by BASF Japan, α-aminoalkyl phenone (phenone)-based photopolymerization initiator

*35: Cobalt acetone 1wt%, DMF solution

*36: 2E4MZ-AP, imidazole manufactured by Shikoku Chemical Co., Ltd.

*37: YL7600 made by Mitsubishi Chemical Corporation, phenoxy resin containing low dielectric skeleton

*38: Cyclohexanone

*39: DMF (N,N-dimethylformamide)

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

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

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

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

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

*46: TIPAQUE CR-97 D50=0.25μm manufactured by Ishihara Sangyo

*47: CZ-03 D50=0.3μm manufactured by Sakai Chemical Industry

*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 have excellent embedding properties and flatness of the resin layer. In addition, the melt viscosity of the resin layer does not meet the requirements of 60~5500dPa at 100℃. s or the storage elastic modulus of the resin layer does not satisfy the dry film of Comparative Examples 1 to 11 at 100°C of 80 to 5500 Pa, and Comparative Example 12 where the content of the liquid epoxy resin in the resin layer is 60% by mass or more Dry film, poor embedding and flatness.

Claims (9)

A dry film, which is a dry film having a film and a resin layer containing an epoxy resin formed on the film, the melt viscosity of the aforementioned resin layer is 60~5500dPa at 100°C. s, the storage elastic modulus of the aforementioned resin layer is 80~5500Pa at 100°C, the aforementioned resin layer contains at least liquid epoxy resin as the aforementioned epoxy resin, and the content of the aforementioned liquid epoxy resin is in the aforementioned epoxy resin The total mass is less than 60% by mass, and it is used for the purpose of forming a plating resist on the cured film obtained by curing the aforementioned resin layer. For example, the dry film of item 1 in the scope of patent application, wherein the amount of residual solvent in the aforementioned resin layer is 1.0~7.0% by mass. For example, the dry film of the first item of the scope of patent application, wherein the aforementioned resin layer contains selected from the group consisting of N,N-dimethylformamide, toluene, cyclohexanone, aromatic hydrocarbons with a carbon number of 8 or more, and methyl ethyl At least 2 kinds of organic solvents from the group of base ketones. For example, the dry film of item 1 in the scope of patent application, wherein the aforementioned resin layer further contains at least one semi-solid selected from the group consisting of bisphenol A epoxy resin, naphthalene epoxy resin and phenol novolac epoxy resin. Epoxy resin is the aforementioned epoxy resin. For example, the dry film of item 1 in the scope of patent application, in which the aforementioned resin layer contains fillers, The average particle size of the aforementioned filler is 0.1~10μm. For example, the dry film of the first item in the scope of patent application, wherein the resin layer contains a filler, and the blending amount of the filler is 40 to 80% by mass of the total amount of the resin layer (when the resin layer contains a solvent, the total amount of the solvent is excluded). For example, the dry film of the first item in the scope of patent application, wherein the resin layer contains a filler, and the filler is a silane coupling agent with an epoxy group, a silane coupling agent with an amine group, a silane coupling agent with a mercapto group, and an isocyanate group At least one of a silane coupling agent, a silane coupling agent with a vinyl group, a silane coupling agent with a styrene group, a silane coupling agent with a methacryl group and a silane coupling agent with an acryl group is subjected to surface treatment. A hardened product obtained by hardening the resin layer of a dry film as in any one of items 1 to 7 in the scope of the patent application. A printed wiring board, which is provided with a cured product as in item 8 of the scope of the patent application.

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