WO2020195843A1 - Dry film, cured article, and electronic component - Google Patents

Abstract

A dry film 11 includes a curable resin layer 12 made of a light-shielding curable resin composition containing: a polymer resin having a glass transition point of 20°C or less and a weight average molecular weight of 10,000 or greater; a coloring agent; and an inorganic filler. When the thickness of the curable resin layer 12 is X (μm), the largest particle diameter of aggregate particles of the inorganic filler is X/2 (μm) or less. The dry film 11 has excellent light-shielding performance, and is configured such that warping is suppressed and burrs and chipping during dicing can also be suppressed.

Description

Dry films, cured products, and electronic components

The present invention relates to dry films, cured products, and electronic components.

Conventionally, a dry film (laminated film) has been used as one of means for forming a protective film or an insulating layer such as a solder resist or an interlayer insulating layer provided on a printed wiring board used in an electronic device or the like (for example, a patent document). 1). The dry film has a resin layer obtained by applying a resin composition having desired properties on a carrier film and then performing a drying step, and generally, for protecting the surface opposite to the carrier film. Protective film is further laminated and is distributed on the market. A printed wiring board having a protective film or an insulating layer as described above can be manufactured by attaching a resin layer of a dry film to a substrate (hereinafter, also referred to as “laminate”) and then performing patterning and curing treatment. it can.

Japanese Unexamined Patent Publication No. 2015-010179

Dry films are also used as encapsulants for semiconductor chips. After the dry film laminated on the semiconductor wafer is cured to form a sealing material, dicing is performed using, for example, a blade-type cutting machine to cut into individual semiconductor chips. During this dicing, burrs may be generated at the cut end portion of the sealing material, or the sealing material may be chipped. Further, after the semiconductor chip is sealed, the film thickness of the sealing material on the chip becomes thin, but even in such a case, a light-shielding property for blocking light from the outside and protecting the semiconductor chip is required. There is.
Further, a resin having a high light-shielding property is required for a partition wall in an optical sensor module and a material arranged around each RGB light emitting element in a display using a micro LED. However, conventional resins are not always required. The light blocking effect was not sufficient. In addition, the dry film may be required to have low light transmittance in other applications such as black solder resist.
Further, the dry film is required to have less warpage when cured on the substrate so that the resin layer is sufficiently adhered to the substrate.

Therefore, an object of the present invention is to provide a dry film, a cured product, and an electronic component which are excellent in light-shielding property, suppress warpage, and can suppress burrs and chips during dicing.

As a result of diligent research to solve the above problems, the present inventors have a light-shielding property containing a polymer resin having a glass transition point of 20 ° C. or less and a weight average molecular weight of 10,000 or more, a colorant, and an inorganic filler. It is a dry film provided with a curable resin layer made of a curable resin composition, and has excellent dispersibility because the maximum particle size of the aggregated particles of the inorganic filler is less than half the thickness of the curable resin layer. We have found that it has sufficient light-shielding properties, suppresses warpage, and can suppress burrs and chips during dying, and has arrived at the present invention.

That is, the dry film of the present invention is cured by a light-shielding curable resin composition containing a polymer resin having a glass transition point of 20 ° C. or less and a weight average molecular weight of 10,000 or more, a colorant, and an inorganic filler. Equipped with a sex resin layer,
When the thickness of the curable resin layer is X (μm), the maximum particle size of the aggregated particles of the inorganic filler is X / 2 (μm) or less.
In the present invention, the light-shielding property means that the transmittance is less than 0.5% in the entire wavelength region of the light wavelength of 380 to 780 nm at a film thickness of 40 μm of the curable resin layer.

In the dry film of the present invention, the maximum particle size of the aggregated particles of the inorganic filler is preferably 10 μm or less, and the blending amount of the inorganic filler is 0.1 to 0.1 to the solid content of the light-shielding curable resin composition. It is preferably 70% by mass, and the blending amount of the colorant is preferably 0.3 to 20% by mass with respect to the solid content of the light-shielding curable resin composition, and the glass transition point is 20 ° C. or less. Moreover, the blending amount of the polymer resin having a weight average molecular weight of 10,000 or more is preferably 1 to 35% by mass with respect to the solid content of the light-shielding curable resin composition, and the curable resin layer is further added. It preferably contains a liquid epoxy resin.

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

The electronic component of the present invention is characterized by having the cured product.

According to the present invention, it is possible to provide a dry film, a cured product, and an electronic component which are excellent in light-shielding property, suppress warpage, and can suppress burrs and chips during dicing.

It is the schematic sectional drawing which shows one Embodiment of the dry film of this invention schematically. It is a figure which represented the color of a colorant with the a * value and b * value in the L * a * b * color system as coordinate axes.

Hereinafter, the dry film, cured product, and electronic component of the present invention will be described in more detail.
FIG. 1 is a schematic cross-sectional view of the dry film 11 according to the embodiment of the present invention. The dry film 11 shown in FIG. 1 has a three-layer structure in which a curable resin layer 12 is formed on a carrier film 13 and a protective film 14 is laminated. If necessary, the dry film 11 may be provided with another resin layer between the protective film and the curable resin layer, or between the support film and the curable resin layer.

<Curable resin layer>
The dry film of the present invention is a curable resin composed of a light-shielding curable resin composition containing a polymer resin having a glass transition point of 20 ° C. or less and a weight average molecular weight of 10,000 or more, a colorant, and an inorganic filler. When the layer is provided and the thickness of the curable resin layer is X (μm), the maximum particle size of the aggregated particles of the inorganic filler is X / 2 (μm) or less.

The inorganic filler suppresses the curing shrinkage of the obtained cured product, and improves various properties such as adhesion, hardness, and crack resistance by matching the coefficient of linear expansion (CTE) with the conductor layer such as copper around the insulating layer. Can be made to. However, the inorganic filler aggregates when a light-shielding curable resin composition is prepared and made into an ink. According to the research by the present inventors, it has been found that when the aggregated particles of the aggregated inorganic filler are large, burrs and chips are likely to occur during dicing. Further, the light-shielding property (low transmittance) of the cured product is improved by including a colorant such as carbon black in the curable resin composition. According to the research by the present inventors, it has been found that when the aggregated particles of the aggregated inorganic filler are large, the inorganic filler easily scatters light in the cured product, which is disadvantageous in light shielding property. Therefore, when the thickness of the curable resin layer is X (μm), the maximum particle size of the aggregated particles of the inorganic filler is X / 2 (μm) or less, so that burrs and chips during dicing are suppressed. In addition, the light-shielding property can be improved even in the thin film on the semiconductor chip.

Further, the curable resin layer contains a polymer resin having a glass transition point of 20 ° C. or less and a weight average molecular weight of 10,000 or more, thereby suppressing aggregation of the colorant and the inorganic filler and dispersing the colorant and the inorganic filler. The property can be improved, sedimentation can be suppressed, and both the light-shielding property and the long-term stability of the curable resin composition can be improved. Further, the warp of the cured product can be suppressed.
The curable resin layer of the dry film is in a state generally referred to as a B stage state, and is obtained from a light-shielding curable resin composition. Hereinafter, each component will be described.

[Polymer resin with a glass transition point of 20 ° C or less and a weight average molecular weight of 10,000 or more]
The glass transition point of the polymer resin having a glass transition point of 20 ° C. or lower and a weight average molecular weight of 10,000 or more is preferably −40 to 20 ° C., more preferably −15 to 15 ° C., and −5. It is particularly preferably at ~ 15 ° C. When the temperature is −5 to 15 ° C., the warpage of the cured product can be satisfactorily suppressed.
Further, the higher the weight average molecular weight of the polymer resin, the greater the effect of preventing the colorant and the inorganic filler from settling. Therefore, it is preferably 100,000 or more, and more preferably 200,000 or more. The upper limit is, for example, 1 million or less, and preferably 500,000 or less.

Examples of the polymer resin include polymer resins having one or more skeletons selected from a butadiene skeleton, an amide skeleton, an imide skeleton, an acetal skeleton, a carbonate skeleton, an ester skeleton, a urethane skeleton, an acrylic skeleton and a siloxane skeleton. .. For example, polymer resins having a butadiene skeleton ("G-1000", "G-3000", "GI-1000", "GI-3000" manufactured by Nippon Soda, "R-45EPI" manufactured by Idemitsu Kosan Co., Ltd., Daicel Co., Ltd. "PB3600", "Epofriend AT501", Clay Valley "Ricon130", "Ricon142", "Ricon150", "Ricon657", "Ricon130MA"), a polymer resin having a butadiene skeleton and a polyimide skeleton (Japanese Patent Laid-Open No. 2006) (As described in Japanese Patent Application Laid-Open No. -37083), polymer resin having an acrylic skeleton ("SG-P3", "SG-600LB", "SG-280", "SG-790", "SG-K2" manufactured by Nagase ChemteX Corporation. , "SN-50" manufactured by Negami Kogyo Co., Ltd., "AS-3000E", "ME-2000") and the like.

The polymer resin is preferably an acrylic copolymer having a glass transition point of 20 ° C. or less and a weight average molecular weight of 10,000 or more from the viewpoint of flatness of the cured product. Further, from the viewpoint of dispersibility of the colorant and the inorganic filler and suppression of sedimentation of the composition, an acrylic copolymer having a glass transition point of 20 ° C. or less and a weight average molecular weight of 100,000 to 1,000,000 is preferable. An acrylic copolymer having a transition point of −5 to 15 ° C. and a weight average molecular weight of 200,000 to 500,000 is preferable.

The acrylic acid ester copolymer may have a functional group, and examples of the functional group include a carboxyl group, a hydroxyl group, an epoxy group, and an amide group.

The acrylic acid ester copolymer preferably has an epoxy group, and more preferably has an epoxy group and an amide group. By having an epoxy group, warpage of the cured product can be suppressed.

As the acrylic acid ester copolymer, Teisan resin SG-70L, SG-708-6, WS-023 EK30, SG-P3, SG-80H, SG-280 EK23, SG-600TEA, SG manufactured by Nagase ChemteX Corporation. -790 can be mentioned. The acrylic acid ester copolymer may be obtained by synthesizing, and examples of the synthesizing method include the synthesizing method described in JP-A-2016-102200.

One type of polymer resin can be used alone or in combination of two or more types. The blending amount of the polymer resin is preferably 1 to 35% by mass, more preferably 1 to 30% by mass, based on the total solid content of the composition. Within the above range, the dispersibility of the inorganic filler and the like and the long-term stability of the composition can be improved. In particular, when the compounding amount of the polymer resin is 5% by mass or more, a cured film having low transmittance and suppressing warpage of the substrate can be obtained.

In the present specification, the value of the weight average molecular weight (Mw) can be measured by the gel permeation chromatography (GPC) method (polystyrene standard), for example, with the measuring device and measuring conditions described below.
Measuring device: "Waters 2695" manufactured by Waters
Detector: Waters 2414, RI (Differential Refractometer)
Column: Waters "HSPgel Colon, HR MB-L, 3 μm, 6 mm x 150 mm" x 2 + Waters "HSPgel Colon, HR 1, 3 μm, 6 mm x 150 mm" x 2
Measurement condition:
Column temperature: 40 ° C
RI detector set temperature: 35 ° C
Developing solvent: tetrahydrofuran Flow rate: 0.5 mL / min Sample volume: 10 μL
Sample concentration: 0.7% by mass

[Colorant]
The colorant is not particularly limited as long as it can obtain a light-shielding curable resin composition, but a known and commonly used black colorant can be used. Specific examples thereof include carbon black, titanium black, iron oxide, cobalt oxide, and perylene-based black colorants, and these colorants can be used alone or in combination of two or more.
The colorant may be a combination of a perillene-based colorant and a colorant having a complementary color relationship with the perillene-based colorant, and the combination may provide light-shielding properties.
Some perylene-based colorants indicate colors such as green, yellow, orange, red, purple, and black, and have the following color index (CI; published by The Society of Dyers and Colorists) numbers. Can be mentioned.
-Green: Solvent Green 5
-Orange: Solvent Orange 55
-Red: Solvent Red 135, 179; Pigment Red 123, 149, 178, 179, 190, 194, 224
-Purple: Pigment Violet 29
-Black: Pigment Black 31, 32
Perylene-based colorants other than the above can also be used, for example, BASF's Lumogen® Black FK4280, Lumogen Black FK4281, collection, which is known as a near-infrared transmissive black organic pigment without a color index number. Lumogen F Yellow 083, Lumogen F Orange 240, Lumogen F Red305, Lumogen F Green 850, etc., which are known as light fluorescent dyes, are also suitable because they absorb less ultraviolet region and have high coloring power like other perylene compounds. Can be used.

The complementary colorant used in combination with the perillene colorant in the present invention will be described below. First, the complementary color relationship in the present invention will be described.
Since the colorant may not have the same color as the color index color, the appearance color tone of the cured coating film of the resin composition is measured and displayed by the method specified in JIS Z8729, and the L * a * b * table is used. Check the a * and b * values that indicate the colors in the color system on the coordinate axes (see Fig. 2), and check the (a * value, b * value) of the cured coating film obtained in combination with the perillene colorant. A colorant that is as close as possible to (0,0) is selected as a colorant that has a complementary color relationship. Here, the film thickness of the cured coating film is not particularly limited, but is, for example, 40 μm.
Further, as (a * value, b * value) as close as possible to (0,0), the a value and the b value are in the range of −5 to +5, respectively, and preferably in the range of −2 to +2. .. Further, the colorant having a complementary color relationship may be a perillene-based colorant or a colorant other than the perillene-based colorant.

As a colorant having a complementary color relationship with the perillene-based colorant, any colorant as long as the color-based a * value and b * value of each colorant approach 0 depending on the combination with the perillene-based colorant. It may be a colorant, and examples thereof include the following colorants.
A more preferable combination of the perylene-based colorant and the colorant having a complementary color relationship is a combination of Pigment Red 149, 178, 179 and a green anthraquinone-based colorant (Solvent Green 3, Solvent Green 20, Solvent Green 28, etc.). , If it is a color mixture (combination) of perylene-based colorants, a combination of a red perylene-based colorant (Pigment Red 149,178,179) and a black perylene-based colorant (Pigment Black 31, 32) and a black perylene-based colorant It is a combination with a black perylene-based colorant (Lumogen (registered trademark) BlackFK4280.4281) as well as a colorant (Pigment Black 31, 32).

The colorants include a combination of a yellow colorant and a purple colorant, a combination of a yellow colorant and a blue colorant and a red colorant, a combination of a green colorant and a purple colorant, and a combination of a green colorant and a red colorant. Any combination selected from the combination of the yellow colorant, the purple colorant and the blue colorant, and the combination of the green colorant, the red colorant and the blue colorant may be used, and the combination of the combination causes the resin composition to have a light-shielding property. You just have to have. In addition, a purple colorant, an orange colorant, a brown colorant, or the like may be combined.

Examples of the blue colorant include phthalocyanine-based and anthraquinone-based compounds, and compounds classified into Pigment and Solvent. In addition to this, metal-substituted or unsubstituted phthalocyanine compounds can also be used.
Examples of the red colorant include monoazo type, dizuazo type, azolake type, benzimidazolone type, perylene type, diketopyrrolopyrrole type, condensed azo type, anthraquinone type, and quinacridone type.
Examples of the yellow colorant include monoazo type, disazo type, condensed azo type, benzimidazolone type, isoindolinone type, anthraquinone type and the like.
Examples of the green colorant include phthalocyanine type and anthraquinone type. In addition to this, metal-substituted or unsubstituted phthalocyanine compounds can also be used.

Specific examples of the purple colorant, orange colorant, and brown colorant include Pigment Violet 19, 23, 29, 32, 36, 38, 42; Solvent Violet 13, 36; CI Pigment Orange 1, CI Pigment Orange 1. 5, CI Pigment Orange 13, CI Pigment Orange 14, CI Pigment Orange 16, CI Pigment Orange 17, CI Pigment Orange 24, CI Pigment Orange 34, CI Pigment Orange 36, CI Pigment Orange 38, CI Pigment Orange 40, CI Pigment Orange 43, CI Pigment Orange 46, CI Pigment Orange 49, CI Pigment Orange 51, CI Pigment Orange 61, CI Pigment Orange 63, CI Pigment Orange 64, CI Pigment Orange 71, CI Pigment Orange 73; CI Pigment Brown 23, CI Pigment Brown 25; CI Pigment Black 1, CI Pigment Black 7, and the like can be mentioned.
The blending amount of the colorant is not particularly limited, but is preferably 0.3 to 20 parts by mass with respect to the total solid content of the composition. By setting the blending amount to 0.3 parts by mass or more, the light-shielding property can be improved. On the other hand, when the blending amount is 20 parts by mass or less, a composition having excellent dispersibility can be obtained.

Light-shielding property can be obtained by dispersing carbon black in the resin. As the carbon black, carbon black that is generally used for black colorants can be used. As the carbon black, one or more of known carbon blacks such as channel black, furnace black, thermal black, and lamp black can be used. Moreover, you may use resin-coated carbon black. Further, carbon nanofibers and carbon nanotubes may be used.
When blending carbon black into the resin composition, carbon black powder may be added, or a carbon black dispersion may be added.
The average particle size of carbon black is preferably 10 nm or more and 500 nm or less, more preferably 10 nm or more and 300 nm or less, and particularly preferably 10 nm or more and 100 nm or less. The average particle size is an arithmetic mean diameter obtained by observing with an electron microscope.

The blending amount of carbon black is preferably 0.1 to 20% by mass based on the total solid content of the light-shielding curable resin composition. When the blending amount of carbon black is 0.1% by mass or more, sufficient light-shielding property can be obtained, and when 20% by mass or less, the occurrence of cracks can be suppressed.
Further, the larger the amount of carbon black blended, the easier it is for the carbon black to settle. However, since the above-mentioned polymer resin having a glass transition point of 20 ° C. or less and a weight average molecular weight of 10,000 or more is contained, the carbon black is settled. It is suppressed. Here, the blending amount of the polymer resin having a glass transition point of 20 ° C. or lower and the weight average molecular weight of 10,000 or more and the blending amount of carbon black are preferably 1: 1 to 100: 1 in mass ratio. ..

[Inorganic filler]
The curable resin layer contains an inorganic filler. By blending an inorganic filler, the curing shrinkage of the obtained cured product is suppressed, and thermal characteristics such as adhesion, hardness, and crack resistance by combining the CTE with a conductor layer such as copper around the insulating layer are improved. be able to. Conventionally known inorganic fillers can be used as the inorganic fillers and are not limited to specific ones. For example, barium sulfate, barium titanate, amorphous silica, crystalline silica, molten silica, spherical silica and the like, talc and clay. , Neuburg Silica particles, boehmite, magnesium carbonate, calcium carbonate, titanium oxide, aluminum oxide, aluminum hydroxide, silicon nitride, aluminum nitride, calcium zirconate, copper, tin, zinc, nickel, silver, palladium, aluminum, iron , Cobalt, gold, platinum and other metal powders. The inorganic filler is preferably spherical particles. Of these, silica is preferable, and it suppresses the curing shrinkage of the cured product of the curable composition, lowers the CTE, and improves properties such as adhesion and hardness.

The inorganic filler may be surface-treated. As the surface treatment, a surface treatment using a coupling agent or a surface treatment such as an alumina treatment that does not introduce an organic group may be performed. The surface treatment method of the inorganic filler is not particularly limited, and a known and commonly used method may be used. A surface treatment agent having a curable reactive group, for example, a coupling agent having a curable reactive group as an organic group, is used as an inorganic filler. The surface may be treated.

The surface treatment of the inorganic filler is preferably a surface treatment with a coupling agent. As the coupling agent, silane-based, titanate-based, aluminate-based, zircoaluminate-based coupling agents and the like can be used. Of these, a silane coupling agent is preferable. Examples of such silane coupling agents include vinyltrimethoxysilane, vinyltriethoxysilane, N- (2-aminomethyl) -3-aminopropylmethyldimethoxysilane, and N- (2-aminoethyl) -3-amino. Propyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-anilinopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxy) Cyclohexyl) ethyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane and the like can be mentioned, and these can be used alone or in combination. It is preferable that these silane-based coupling agents are previously immobilized on the surface of the inorganic filler by adsorption or reaction. Here, the treated amount of the coupling agent with respect to 100 parts by mass of the inorganic filler is, for example, 0.5 to 10 parts by mass.

The thermosetting reactive group is preferable as the curable reactive group. Examples of the thermosetting reactive group include a hydroxyl group, a carboxyl group, an isocyanate group, an amino group, an imino group, an epoxy group, an oxetanyl group, a mercapto group, a methoxymethyl group, a methoxyethyl group, an ethoxymethyl group, an ethoxyethyl group and an oxazoline group. Can be mentioned. Of these, at least one of an amino group and an epoxy group is preferable. The surface-treated inorganic filler may have a photocurable reactive group in addition to the thermosetting reactive group.

The surface-treated inorganic filler may be contained in the curable resin layer in the surface-treated state, and the inorganic filler and the surface treatment agent are added to the curable resin composition forming the curable resin layer. The inorganic filler may be surface-treated in the composition by blending separately, but it is preferable to blend the inorganic filler which has been surface-treated in advance. By blending the inorganic filler that has been surface-treated in advance, it is possible to prevent deterioration of crack resistance and the like due to the surface treatment agent that may remain when the inorganic filler is blended separately and is not consumed in the surface treatment. In the case of surface treatment in advance, it is preferable to mix a pre-dispersion solution in which an inorganic filler is pre-dispersed in a solvent or a curable resin. It is more preferable that the surface-untreated inorganic filler is sufficiently surface-treated when it is pre-dispersed in a solvent, and then the pre-dispersion solution is blended into the composition.
The inorganic filler may be blended with other components of the curable resin composition in a powder or solid state, or may be mixed with a solvent or a dispersant to form a slurry, and then blended with other components.

The maximum particle size of the aggregated particles of the inorganic filler is X / 2 (μm) or less, where X (μm) is the thickness of the curable resin layer. When the maximum particle size of the agglomerated particles is less than half the thickness of the curable resin layer, it is possible to suppress light scattering by the inorganic filler in the curable resin layer and obtain sufficient light-shielding property. In addition, the inclusion of the inorganic filler itself is advantageous in suppressing burrs during dicing, but if the maximum particle size of the aggregated grains is large, burrs are likely to occur, and chips are likely to occur during dicing. ..
The maximum particle size of the aggregated particles of the inorganic filler is preferably 10 μm or less after satisfying the relationship with the film thickness of the curable resin layer described above. When the maximum particle size of the aggregated particles of the inorganic filler is 10 μm or less, burrs and chips during dicing can be suppressed more effectively. The above-mentioned polymer resin having a glass transition point of 20 ° C. or less and a weight average molecular weight of 10,000 or more can improve the dispersibility of the inorganic filler. Therefore, the curable resin composition containing a polymer resin having a glass transition point of 20 ° C. or less and a weight average molecular weight of 10,000 or more has excellent dispersion stability in the state of ink and suppresses aggregation of inorganic fillers. Can be done. Therefore, the maximum particle size of the aggregated particles of the inorganic filler can be maintained at 10 μm or less even after the ink, that is, the curable resin composition is stored for a long period of time.

The inorganic filler may be used alone or as a mixture of two or more. The blending amount of the inorganic filler is preferably 0.1 to 70% by mass based on the total solid content of the curable resin layer of the dry film. When the blending amount of the inorganic filler is 0.1% by mass or more, thermal expansion is suppressed and the heat resistance is improved, while when it is 70% by mass or less, the occurrence of cracks can be suppressed. Further, it is preferable that the blending amount of the inorganic filler is 20% by mass or more because the dicing resistance is improved.

[Epoxy resin]
The light-shielding curable resin composition may contain an epoxy resin. The epoxy resin is a resin having an epoxy group, and any conventionally known resin can be used. Examples thereof include a bifunctional epoxy resin having two epoxy groups in the molecule, a polyfunctional epoxy resin having three or more epoxy groups in the molecule, and the like. It may be a hydrogenated epoxy resin. The epoxy resin includes a solid epoxy resin, a liquid epoxy resin, a semi-solid epoxy resin, and a crystallized epoxy resin, and among them, it is preferable to include at least a liquid epoxy resin. The solid epoxy resin and the liquid epoxy resin can be used individually by 1 type or in combination of 2 or more types. In the present specification, the solid epoxy resin refers to an epoxy resin that is solid at 40 ° C., and the semi-solid epoxy resin refers to an epoxy resin that is solid at 20 ° C. and liquid at 40 ° C., and is a liquid epoxy resin. Refers to an epoxy resin that is liquid at 20 ° C. Judgment of liquidity is carried out in accordance with the "Liquid confirmation method" of Attachment 2 of the Ministerial Ordinance on Dangerous Goods Testing and Properties (Ministerial Ordinance No. 1 of 1989). For example, the method described in paragraphs 23 to 25 of JP2016-079384A is used. Further, the crystalline epoxy resin means an epoxy resin having strong crystallinity, and at a temperature below the melting point, the polymer chains are regularly arranged, and although it is a solid resin, it has a low viscosity comparable to that of a liquid resin when melted. A thermosetting epoxy resin.

Examples of the liquid epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, phenol novolac type epoxy resin, tert-butyl-catechol type epoxy resin, glycidylamine type epoxy resin, and aminophenol type epoxy resin. , Alicyclic epoxy resin and the like. By containing a liquid epoxy resin, the flexibility of the dry film is excellent.

Examples of the solid epoxy resin include naphthalene type epoxy resins such as HP-4700 (naphthalene type epoxy resin) manufactured by DIC and NC-7000 (polyfunctional solid epoxy resin containing naphthalene skeleton) manufactured by Nippon Kayaku Co., Ltd .; EPPN manufactured by Nihon Kayaku Co., Ltd. Epoxy product (trisphenol type epoxy resin) of a condensate of phenols such as -502H (trisphenol epoxy resin) and aromatic aldehyde having a phenolic hydroxyl group; EPICLON HP-7200H (dicyclopentadiene skeleton content) manufactured by DIC. Dicyclopentadiene aralkyl type epoxy resin such as functional solid epoxy resin); Biphenyl aralkyl type epoxy resin such as NC-3000H (biphenyl skeleton-containing polyfunctional solid epoxy resin) manufactured by Nippon Kayaku Co., Ltd .; NC-3000L manufactured by Nihon Kayaku Co., Ltd. Biphenyl / phenol novolac type epoxy resin; novolak type epoxy resin such as EPICLON N660, EPICLON N690, N770 manufactured by DIC, EOCN-104S manufactured by Nippon Kayaku Co., Ltd .; phosphorus-containing epoxy resin such as TX0712 manufactured by Nittetsu Chemical & Materials Co., Ltd .; Examples thereof include tris (2,3-epoxypropyl) isocyanurate such as TEPIC manufactured by Nissan Chemical Co., Ltd. By containing the solid epoxy resin, the glass transition temperature of the cured product becomes high and the heat resistance is excellent.

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

As the crystalline epoxy resin, for example, a crystalline epoxy resin having a biphenyl structure, a sulfide structure, a phenylene structure, a naphthalene structure, or the like can be used. Examples of the biphenyl type epoxy resin are jER YX4000, jER YX4000H, jER YL6121H, jER YL6640, and jER YL6677 manufactured by Mitsubishi Chemical Corporation. The diphenyl sulfide type epoxy resin is, for example, Epototo YSLV-120TE manufactured by Nippon Steel Chemical & Materials Co., Ltd. The phenylene type epoxy resin is, for example, Epototo YDC-1312 manufactured by Nippon Steel Chemical & Materials Co., Ltd. The naphthalene type epoxy resin is, for example, EPICLON HP-4032, EPICLON HP-4032D, EPICLON HP-4700 manufactured by DIC Corporation. Further, as the crystalline epoxy resin, Epototo YSLV-90C manufactured by Nippon Steel Chemical Industries, Ltd. and TEPIC-S (triglycidyl isocyanurate) manufactured by Nissan Chemical Industries, Ltd. can also be used.

The total amount of the epoxy resin compounded is preferably 1 to 70% by mass based on the total solid content of the composition. Within the above range, the cured product is excellent in heat resistance, flexibility and crack resistance. The amount of the liquid epoxy resin to be blended is preferably 5 to 60% by mass based on the total solid content of the epoxy resin, the curing agent, the curing accelerator, and the polymer resin. When it is within the above range, the flexibility of the dry film is excellent.

The light-shielding curable resin composition may contain a curable resin component other than the epoxy resin as long as the effects of the present invention are not impaired. For example, an isocyanate compound, a blocked isocyanate compound, an amino resin, a benzoxazine resin, etc. Known and commonly used thermosetting resins such as carbodiimide resins, cyclocarbonate compounds, polyfunctional oxetane compounds, and episulfide resins can be used.

[Hardener]
The light-shielding curable resin composition preferably contains a curing agent. Examples of the curing agent include compounds having a phenolic hydroxyl group, polycarboxylic acids and their acid anhydrides, compounds having a cyanate ester group, compounds having an active ester group, compounds having a maleimide group, alicyclic olefin polymers and the like. Be done. As the curing agent, one type may be used alone or two or more types may be used in combination.

Resins having a phenolic hydroxyl group include phenol novolac resin, alkylphenol volac resin, bisphenol A novolak resin, dicyclopentadiene type phenol resin, Xylok type phenol resin, terpene-modified phenol resin, cresol / naphthol resin, polyvinylphenols, phenol. / Conventionally known substances such as naphthol resin, α-naphthol skeleton-containing phenolic resin, triazine skeleton-containing cresol novolak resin, biphenyl aralkyl type phenol resin, and zylock type phenol novolac resin can be used.
Examples of the resin having a phenolic hydroxyl group include a dicyclopentadiene skeleton phenol novolac resin (GDP series, manufactured by Gunei Chemical Co., Ltd.), a zylock type phenol novolac resin (MEH-7800, manufactured by Meiwa Kasei Co., Ltd.), and a biphenyl aralkyl type novolac resin. (MEH-7851, manufactured by Meiwa Kasei Co., Ltd.), naphthol aralkyl type curing agent (SN series, manufactured by Nittetsu Chemical & Materials Co., Ltd.), cresol novolac resin containing triazine skeleton (LA-3018-50P, manufactured by DIC), containing triazine skeleton Examples thereof include phenol novolac resin (LA-705N, manufactured by DIC).

The compound having a cyanate ester group is preferably a compound having two or more cyanate ester groups (-OCN) in one molecule. As the compound having a cyanate ester group, any conventionally known compound can be used. Examples of the compound having a cyanate ester group include phenol novolac type cyanate ester resin, alkylphenol novolac type cyanate ester resin, dicyclopentadiene type cyanate ester resin, bisphenol A type cyanate ester resin, bisphenol F type cyanate ester resin, and bisphenol S type. Cyanate ester resin can be mentioned. Further, it may be a prepolymer in which a part is triazine-ized.

Commercially available compounds having a cyanate ester group include phenol novolac type polyfunctional cyanate ester resin (manufactured by Lonza Japan, PT30S), and a prepolymer in which part or all of bisphenol A disicianate is triazined to form a trimer. (Lonza Japan Co., Ltd., BA230S75), dicyclopentadiene structure-containing cyanate ester resin (Lonza Japan Co., Ltd., DT-4000, DT-7000) and the like can be mentioned.

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

Commercially available compounds having an active ester group include dicyclopentadiene-type diphenol compounds, such as HPC8000-65T (manufactured by DIC), HPC8100-65T (manufactured by DIC), and HPC8150-65T (manufactured by DIC). Can be mentioned.

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

Commercially available compounds having a maleimide group include BMI-1000 (4,5'-diphenylmethanebismaleimide, manufactured by Daiwa Kasei Kogyo Co., Ltd.), BMI-2300 (phenylmethanebismaleimide, manufactured by Daiwa Kasei Kogyo Co., Ltd.), BMI- 3000 (m-phenylene bismaleimide, manufactured by Daiwa Kasei Kogyo Co., Ltd.), BMI-5100 (3,3'-dimethyl-5,5'-dimethyl-4,4'-diphenylmethane bismaleimide, manufactured by Daiwa Kasei Kogyo Co., Ltd.), BMI -7000 (4-methyl-1,3,-phenylene bismaleimide, manufactured by Daiwa Kasei Kogyo Co., Ltd.), BMI-TMH ((1,6-bismaleimide-2,2,4-trimethyl) hexane, manufactured by Daiwa Kasei Kogyo Co., Ltd.) ) And so on.

The blending amount of the curing agent is preferably 20 to 500 parts by mass, more preferably 25 to 500 parts by mass with respect to 100 parts by mass of the epoxy resin.

In the following, as an example, in the case of forming a light-shielding curable resin composition with a thermosetting resin composition that does not contain a photocurable component, components that can be contained in addition to the above components will be described.

The light-shielding curable resin composition can further contain a thermoplastic resin in order to improve the mechanical strength of the obtained cured film. The thermoplastic resin is preferably soluble in a solvent. When it is soluble in a solvent, the flexibility of the dry film is improved, and the generation of cracks and the falling of powder can be suppressed. As the thermoplastic resin, various acid anhydrides or acid chlorides are used for the thermoplastic polyhydroxypolyether resin, the phenoxy resin which is a condensate of epichlorohydrin and various bifunctional phenol compounds, or the hydroxyl group of the hydroxyether portion existing in the skeleton. Examples thereof include a phenoxy resin, a polyvinyl acetal resin, a polyamide resin, a polyamide-imide resin, and a block copolymer that have been esterified. The thermoplastic resin may be used alone or in combination of two or more.

The blending amount of the thermoplastic resin is preferably 0.5 to 20% by mass, more preferably 0.5 to 10% by mass, based on the total solid content of the light-shielding curable resin composition. When the blending amount of the thermoplastic resin is within the above range, a uniform roughened surface state can be easily obtained.

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

The average particle size of the rubber-like particles is preferably in the range of 0.005 to 1 μm, more preferably in the range of 0.2 to 1 μm. The average particle size of the rubber-like particles can be obtained by a laser diffraction type particle size distribution measuring device and a measuring device by a dynamic light scattering method. Examples of the measuring device by the laser diffraction method include Microtrac MT3300EXII manufactured by Microtrac Bell, and examples of the measuring device by the dynamic light scattering method include Nanotrac Wave II UT151 manufactured by Microtrac Bell.

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

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

The curing accelerator can be used alone or in combination of two or more. The use of a curing accelerator is not essential, but when it is particularly desired to accelerate curing, it can be preferably used in the range of 0.01 to 5 parts by mass with respect to 100 parts by mass of the epoxy resin. In the case of a metal catalyst, 10 to 550 ppm is preferable, and 25 to 200 ppm is more preferable in terms of metal with respect to 100 parts by mass of the compound having a cyanate ester group.

The organic solvent is not particularly limited, and examples thereof include ketones, aromatic hydrocarbons, glycol ethers, glycol ether acetates, esters, alcohols, aliphatic hydrocarbons, and petroleum-based solvents. it can. Specifically, ketones such as methyl ethyl ketone, cyclohexanone, methyl butyl ketone and methyl isobutyl ketone; aromatic hydrocarbons such as toluene, xylene and tetramethylbenzene; cellosolve, methyl cellosolve, butyl cellosolve, carbitol, methyl carbitol, etc. Glycol ethers such as butyl carbitol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, triethylene glycol monoethyl ether; acetic acid Esters such as ethyl, butyl acetate, isobutyl acetate, ethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol butyl ether acetate; ethanol, propanol, 2-methoxy Alcohols such as propanol, n-butanol, isobutyl alcohol, isopentyl alcohol, ethylene glycol, propylene glycol; aliphatic hydrocarbons such as octane and decane; petroleum-based such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, solvent naphtha, etc. In addition to solvents and the like, N, N-dimethylformamide (DMF), tetrachloroethylene, televisionne oil and the like can be mentioned. In addition, Maruzen Petrochemical Co., Ltd. Swazole 1000, Swazole 1500, Sankyo Chemical Co., Ltd. Solvent # 100, Solvent # 150, Shell Chemicals Japan Co., Ltd. Shellsol A100, Shellsol A150, Idemitsu Kosan Co., Ltd. Ipsol No. 100, Ipsol No. 150, etc. You may use the organic solvent of. The organic solvent may be used alone or as a mixture of two or more.

The amount of residual solvent in the light-shielding curable resin composition is preferably 0.5 to 7.0% by mass. When the residual solvent is 7.0% by mass or less, bumping during thermosetting is suppressed and the flatness of the surface becomes better. In addition, it is possible to prevent the resin from flowing due to the melt viscosity being lowered too much, and the flatness is improved. When the residual solvent is 0.5% by mass or more, the fluidity at the time of laminating is good, and the flatness and embedding property are more good.

The light-shielding curable resin composition further comprises conventionally known colorants such as phthalocyanine blue, phthalocyanine green, iodin green, disazo yellow, crystal violet, titanium oxide, naphthalene black, asbestos, orben, as required. Conventionally known thickeners such as Benton and fine powder silica, defoaming agents such as silicone-based, fluorine-based and polymer-based and / or adhesion-imparting agents such as leveling agents, thiazole-based, triazole-based and silane coupling agents. , Flame retardants, titanates, and aluminum-based conventionally known additives can be used.

The thickness of the curable resin layer of the dry fill made of the light-shielding curable resin composition may be, for example, 1 to 200 μm. Within these thickness ranges, the maximum diameter of the aggregated particles of the inorganic filler in the light-shielding curable resin composition is reduced to less than half the thickness of the curable resin layer. Since the curable resin layer is more excellent in flatness when the thickness is large, for example, a thickness of 30 μm or more, further 50 μm or more, and even 100 μm or more can be preferably used. A plurality of curable resin layers may be superposed to form a curable resin layer having a thickness of more than 200 μm. In that case, a roll laminator or a vacuum laminator may be used.

[Carrier film]
The carrier film supports the curable resin layer of the dry film, and is a film to which the light-shielding curable resin composition is applied when the curable resin layer is formed. Examples of the carrier film include polyester films such as polyethylene terephthalate and polyethylene naphthalate, polyimide films, polyamideimide films, polyethylene films, polytetrafluoroethylene films, polypropylene films, and films made of thermoplastic resins such as polystyrene films. Surface-treated paper or the like can be used. Among these, a polyester film can be preferably used from the viewpoint of heat resistance, mechanical strength, handleability and the like. The thickness of the carrier film is not particularly limited, but is appropriately selected in the range of approximately 10 to 150 μm according to the application. The surface of the carrier film on which the curable resin layer is provided may be subjected to a mold release treatment. Further, a sputtered or ultrathin copper foil may be formed on the surface of the carrier film on which the curable resin layer is provided.

[Protective film]
The protective film is provided on the surface opposite to the carrier film of the curable resin layer for the purpose of preventing dust and the like from adhering to the surface of the curable resin layer of the dry film and improving handleability. It is preferable to use a biaxially stretched polypropylene film (OPP) as the protective film. By using the biaxially stretched polypropylene film, it is possible to reduce the cooling shrinkage after laminating on the curable resin layer. However, the protective film is not limited to the biaxially stretched polypropylene film. The thickness of the protective film is not particularly limited, but is appropriately selected in the range of approximately 10 to 100 μm according to the application. It is preferable that the surface of the protective film on which the curable resin layer is provided is subjected to a treatment for improving adhesion such as embossing, corona treatment, or slight adhesion treatment, or a mold release treatment.

The dry film of the present invention is laminated on a semiconductor wafer or the like and the curable resin layer is cured to form a cured product, thereby forming a sealing material or permanent protection for electronic components, particularly semiconductor devices, printed wiring boards and optical sensor modules. It can be preferably used for forming a film. Above all, it is suitable as a sealing material for semiconductor chips. A wiring plate may be formed by bonding wirings using the dry film of the present invention.

Examples of electronic components using the cured product of the light-shielding curable resin composition of the present invention or the cured product of the dry film of the present invention include semiconductor devices, printed wiring boards, and optical sensor modules. As a method for manufacturing such an electronic component, a conventionally known method may be used.

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

<Preparation of light-shielding curable resin composition>
The solvent described in Examples and Comparative Examples was placed in a container, stirred while heating at 50 ° C. so that the solvent did not volatilize, and then a resin component and a coupling agent were added, respectively. After confirming that the resin component was dissolved, the inorganic filler and the colorant described in the examples were added, and the mixture was sufficiently stirred. Then, it was kneaded with a bead mill filled with zirconia zies to prepare a light-shielding curable resin composition. As a bead mill, a conical type K-8 (manufactured by Buhra) was used and kneaded under the conditions of a rotation speed of 1200 rpm, a discharge rate of 20%, a bead particle size of 0.65 mm, and a filling rate of 88%. The numerical values in the table indicate parts by mass unless otherwise specified, and indicate the amount of solids other than the solvent, polymer resin and nanosilica.

<Dispersibility>
The prepared light-shielding curable resin composition was checked for the degree of dispersion using a grind gauge of 0-50 μm according to the method of JIS K5600-2-5 degree of dispersion. The evaluation criteria are as follows. The maximum particle size of the agglomerated particles obtained by using the grind gauge is shown in the table.
〇: Dispersity judged by 5 grain value is 20 μm or less Δ: Dispersity judged by 5 grain value is more than 20 μm and less than 30 μm ×: Dispersity judged by 5 grain value is more than 30 μm

<Suppression of sedimentation of composition (ink)>
The prepared light-shielding curable resin composition was placed in a transparent glass screw tube and stored in a constant temperature bath set at 23 ° C. for 12 hours for aging treatment. The light-shielding curable resin composition was charged 50 mm from the bottom of the screw tube. After aging, the light-shielding curable resin composition was taken out and visually observed from the side surface to confirm the sedimentation state of the light-shielding curable resin composition. The judgment criteria are as follows.
〇: No sedimentation is observed.
Δ: A transparent supernatant of less than 1 mm was confirmed from the upper part of the composition.
X: A transparent supernatant of 20 mm or more was confirmed from the upper part of the composition.

<Making dry film>
Adjust the amount of the solvent so that the prepared light-shielding curable resin composition has a viscosity of 0.5 to 20 dPa · s (rotational viscometer 5 rpm, 25 ° C.), and use a bar coater to prepare the curable resin. The layer was applied to a carrier film (PET film; TN-200 manufactured by Toyobo Co., Ltd., thickness 38 μm, size 30 cm × 30 cm) so that the film thickness after drying was 40 μm. Next, the curable resin layer was dried in a hot air circulation type drying oven at 70 to 120 ° C. (average 100 ° C.) for 5 to 10 minutes so that the residual solvent of the curable resin layer was 0.5 to 2.5% by mass, and the carrier film was used. A curable resin layer was formed on the top. Next, a biaxially stretched polypropylene film (OPP, Alfan FG-201, Fish Aires, manufactured by Oji F-Tex Co., Ltd.) was laminated on the surface of the produced dry film using a roll laminator set at a temperature of 80 ° C. to form three layers. A dry film having a structure was produced.

<Transmittance>
The protective film of the obtained three-layer structure dry film was peeled off and laminated on a slide glass having a thickness of 1 mm using a vacuum laminator MVLP-500 (manufactured by Meiki Co., Ltd.). The conditions were a laminating temperature of 80 to 110 ° C. and a pressure of 0.5 MPa. Then, the carrier film was peeled off, and the resin layer was cured under the conditions of 100 ° C. × 30 min and 200 ° C. × 60 min in a hot air circulation type drying oven. The transmittance of the obtained cured product was measured at 380 nm to 780 nm using an ultraviolet-visible near-infrared spectrophotometer V-700 (manufactured by JASCO Corporation). The evaluation criteria are as follows.
⊚: Transmittance less than 0.1% in all wavelength regions ◯: Transmittance 0.1% or more and less than 0.5% in all wavelength regions ×: Transmittance 0.5% or more in all wavelength regions

<Dicing resistance>
The protective film of the obtained three-layer structure dry film was peeled off and laminated on an 8-inch silicon wafer having a thickness of 700 μm using a vacuum laminator MVLP-500 (manufactured by Meiki Co., Ltd.). The conditions were a laminating temperature of 80 to 110 ° C. and a pressure of 0.5 MPa. Then, the carrier film was peeled off, and the resin layer was cured under the conditions of 100 ° C. × 30 min and 200 ° C. × 60 min in a hot air circulation type drying oven. Then, a dicing machine DFD6240 (manufactured by Disco Corporation, equipped with a ceramic blade) was used to evaluate the dicing resistance of the cured film. The dicing conditions were a rotation speed of 10000 rpm and a feed rate of 1 mm / min. The evaluation criteria are as follows.
⊚: No burrs on the surface of the cured film or chipping of resin 〇: The length of burrs or resin chipping on the surface of the cured film is less than 1.0 mm ×: Length of burrs or resin chipping on the surface of the cured film Is 1.0 mm or more

<Curved board>
A copper-clad substrate (MCL-E-770G, manufactured by Hitachi Kasei Co., Ltd., size 10 x 10 cm) having a copper thickness of 12 μm and a plate thickness of 0.1 mm is treated with electrolytic copper plating (Atotech Co., Ltd., surface roughness after plating 100 nm or less). The total copper thickness was 20 μm. Then, CZ-8101 (1 μm etching, manufactured by MEC) was performed as a pretreatment. Then, the dry film from which the OPP was peeled off was laminated on one side of the substrate using a 2-chamber vacuum laminator CVP-600 (manufactured by Nichigo Morton). The conditions were a temperature of 80 to 110 ° C. and a pressure of 0.5 MPa for each of the laminate and the press. Then, the carrier film was peeled off, and the resin layer was cured under the conditions of 100 ° C. × 30 min and 200 ° C. × 60 min in a hot air circulation type drying oven.
Then, 5 cycles of reflow treatment were performed in which the exposure time was set to 10 seconds or more at a peak temperature of 280 ° C. and 275 ° C. or higher, and the warped state (warped shape is all smile) at the four corners of the substrate was measured with a caliper. The evaluation criteria are as follows.
⊚: No warpage 〇: The amount of warpage of the part with the largest warp is less than 10 mm among the four corners Δ: The amount of warpage of the part with the largest warp of the four corners is 10 mm or more and less than 30 mm ×: Of the four corners The amount of warpage of the part with the largest warp is 30 mm or more

Table 1 shows the mixing ratio of each component and the evaluation results.

Notes * 1 to 17 in Table 1 are as follows.
* 1: Mitsubishi Chemical's jER828, bisphenol A type epoxy resin, epoxy equivalent 189 g / eq, liquid * 2: Nippon Kayaku's NC-3000H, biphenyl novolac type epoxy compound, epoxy equivalent 290 g / eq,
* 3: Primasset PT-30 manufactured by Ronza Japan, novolak type cyanate resin, cyanate equivalent 124 g / eq, solid * 4: EPICLON HPC-8000 manufactured by DIC, active ester resin, active equivalent 223 g / eq, solid * 5: HF-1M manufactured by Meiwa Kasei Co., Ltd., phenol novolac resin * 6: 2E4MZ manufactured by Shikoku Kasei Co., Ltd., 2-ethyl-4-methylimidazole * 7: Cobalt (II) acetylacetonate manufactured by Tokyo Kasei Kogyo Co., Ltd. * 8: Glass transition point A polymer resin with a weight average molecular weight of 10,000 or more at 20 ° C. or less, Teisan Resin SG-80H MEK cut product manufactured by Nagase ChemteX, solid content 18% by mass, acrylic acid ester copolymer resin (functional group: epoxy group). , Amid group)
* 9: Mitsubishi Chemical Corporation carbon black powder MA77 (average particle size 23 nm)
* 10: Paliogen Red K 3580, Pigment Red 149, BASF, perylene colorant * 11: Solvent Green 3, Tokyo Kasei Kogyo, green anthraquinone colorant * 12: Firstgen Blue 5380, DIC, Phthalocyanine blue * 13: Cromophtal (registered trademark) Red A2BN, manufactured by BASF, red anthraquinone-based colorant * 14: silica fine particles FB-3SDC manufactured by Denka (D50 = 3.1 μm)
* 15: Silica fine particles SO-E1 (D50 = 0.2 μm) manufactured by Admatex Co., Ltd.
* 16: Nanosilica manufactured by Admatex (D50 = 50 nm), solid content 30% by mass
* 17: Shin-Etsu Chemical's epoxy silane coupling agent KBM-403

From the results shown in Table 1 above, the dry film provided with the curable resin layer made of the light-shielding curable resin composition shown in each example has dispersibility, ink settling inhibitory property, and light transmission inhibitory property (in other words, in other words). It can be seen that it is excellent in light-shielding property), dicing resistance, and substrate warpage suppression property.

11 Dry film 12 Curable resin layer 13 Carrier film 14 Protective film

Claims (8)

1. A curable resin layer composed of a light-shielding curable resin composition containing a polymer resin having a glass transition point of 20 ° C. or lower and a weight average molecular weight of 10,000 or more, a colorant, and an inorganic filler.
   When the thickness of the curable resin layer is X (μm), the dry film is characterized in that the maximum particle size of the aggregated particles of the inorganic filler is X / 2 (μm) or less.
2. The dry film according to claim 1, wherein the maximum particle size of the aggregated particles of the inorganic filler is 10 μm or less.
3. The dry film according to claim 1 or 2, wherein the blending amount of the inorganic filler is 0.1 to 70% by mass with respect to the solid content of the light-shielding curable resin composition.
4. The dry film according to any one of claims 1 to 3, wherein the amount of the colorant blended is 0.3 to 20% by mass with respect to the solid content of the light-shielding curable resin composition.
5. Claims 1 to 35, wherein the amount of the polymer resin having a glass transition point of 20 ° C. or less and a weight average molecular weight of 10,000 or more is 1 to 35% by mass with respect to the solid content of the light-shielding curable resin composition. The dry film according to any one of 4.
6. The dry film according to any one of claims 1 to 5, wherein the curable resin layer further contains a liquid epoxy resin.
7. A cured product obtained by curing the curable resin layer of the dry film according to any one of claims 1 to 6.
8. An electronic component having the cured product according to claim 7.

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