TWI700183B - Photosensitive resin laminate - Google Patents

Abstract

The present invention provides a photosensitive resin laminate that can avoid the occurrence of resist protrusions, form a good resist pattern shape, and is obtained with good productivity. In one aspect, the present invention provides a photosensitive resin laminate, which is provided with a support film and a photosensitive resin composition layer formed on the support film, and the support film contains fine particles and is included in the epi-type The area where the total area ratio of the optical anomaly area when observing the support film in an area of 13.5 mm ² with a laser microscope is less than 300 ppm.

Description

Photosensitive resin laminate

The present invention relates to a photosensitive resin laminate.

In electronic devices such as personal computers and mobile phones, printed wiring boards can be used for mounting parts and semiconductors. As a resist for the manufacture of printed wiring boards, etc., the industry previously used a photosensitive resin laminate layer formed by laminating a photosensitive resin composition layer on a support film, and then laminating a protective film on the photosensitive resin composition layer as necessary The so-called dry film photoresist (hereinafter, sometimes referred to as DF). As the photosensitive resin composition layer, at present, it is usually an alkaline developing type that uses a weakly alkaline aqueous solution as a developing solution. When using DF to make printed wiring boards, for example, go through the following steps. When DF has a protective film, first peel off the protective film. After that, DF is laminated on a substrate for permanent circuit production such as a copper foil laminated board or a flexible substrate using a laminator or the like, and is exposed through a wiring pattern mask or the like. Secondly, if necessary, the support film is peeled off, and the photosensitive resin composition layer of the uncured part (for example, the unexposed part if it is negative type) is dissolved or dispersed by a developer to form a cured resist pattern on the substrate (hereinafter, Sometimes referred to as a resist pattern for short).

After the resist pattern is formed, the circuit formation process is roughly divided into two methods. The first method is to etch and remove the substrate surface (such as the copper surface of a copper foil laminate) that is not covered by the resist pattern, and then use an alkaline aqueous solution stronger than the developer to remove the resist pattern part (etching method) ). The second method is to remove the part of the resist pattern in the same way as the first method after plating the above substrate surface with copper, solder, nickel, tin, etc., and then to the exposed substrate surface (such as copper foil The method of etching the copper surface of the laminate (plating method). Copper chloride, ferric chloride, copper ammonia complex solution, etc. can be used in etching. In recent years, with the miniaturization and weight reduction of electronic devices, the miniaturization and high-density of printed wiring boards continue to develop. In the manufacturing steps described above, it is required to provide high resolution, good line width reproducibility, etc. High performance DF.

Patent Document 1 describes a photosensitive element that includes a support film and a layer containing a photosensitive resin composition formed on the support film, and the support film has a haze of 0.01 to 2.0%. The total number of particles with a diameter of 5 μm or more and agglomerates with a diameter of 5 μm or more contained in the support film is 5 pieces/mm ² or less. The layer containing the photosensitive resin composition contains (A) a binder polymer, (B ) A photopolymerizable compound having an ethylenically unsaturated bond and (C) a photopolymerization initiator, and the thickness of the layer containing the photosensitive resin composition is 3-30 μm, and its purpose is to reduce the defect of the resist . [Prior Art Document] [Patent Document]

[Patent Document 1] International Publication No. 2008/093643

[The problem to be solved by the invention]

The aforementioned Patent Document 1 focuses on the number of fine particles with a diameter of 5 μm or more in order to reduce the defect of the resist. However, the inventor of this case conducted diligent research and found that, as the cause of the abnormal shape of the resist, in addition to the particles themselves, the optically abnormal regions (such as the abnormal refractive index regions) other than the particles in the support film are also considered. Although Patent Document 1 focuses on the number of particles with a diameter of 5 μm or more, it does not focus on the optically abnormal regions other than the particles in the support film. If there are many optically abnormal areas in the support film, the following exposure control failures will occur: light scattering, diffraction, etc., light is irradiated to parts that are not originally intended to be irradiated, or foreign objects block the exposure light, and the exposure light It is not irradiated to the place where the light originally intended to be exposed. Therefore, the exposure control is poor, and there are cases where resist protrusions are generated, and the desired resist pattern shape cannot be obtained. Patent Document 1 does not pay attention to the occurrence of such resist protrusions, and the current situation is that a photosensitive resin laminate that can avoid resist protrusions has not been obtained.

An object of one aspect of the present invention is to solve the above-mentioned problems and provide a photosensitive resin laminate that avoids resist protrusions and forms a good resist pattern shape. [Technical means to solve the problem]

In order to solve the above-mentioned problems, the inventors have conducted diligent research and repeated experiments. As a result, it was discovered that in one aspect, the problem can be solved by the following technical means.

That is, the present invention includes the following aspects. [1] A photosensitive resin laminate comprising a support film and a photosensitive resin composition layer formed on the support film, and the support film contains fine particles, and includes an epi-laser microscope at 13.5 mm ² The area where the total area ratio of the optically anomalous areas when the above-mentioned support film is observed is 300 ppm or less. [2] The photosensitive resin laminate as described in the above aspect 1, wherein the support film includes an epi-laser microscope. The total area ratio of the optically abnormal regions when the support film is observed in an area of 13.5 mm ² is The area below 200 ppm. [3] The photosensitive resin laminate as described in the above aspect 1, wherein the support film includes an epi-laser microscope. The total area ratio of the optically abnormal regions when the support film is observed in an area of 13.5 mm ² is The area below 100 ppm. [4] The photosensitive resin laminate as described in the above aspect 1, wherein the support film includes an epi-laser microscope. The total area ratio of the optically abnormal regions when the support film is observed in an area of 13.5 mm ² is The area below 50 ppm. [5] The photosensitive resin laminate as described in any one of the above aspects 1 to 4, wherein the support film contains 10 ppm or more of fine particles on a mass basis. [6] A photosensitive resin laminate comprising a support film and a photosensitive resin composition layer formed on the support film, the support film contains fine particles, and the support film has 13.5 mm ^{2 of} the support film Among the above-mentioned microparticles with a diameter of 0.5 μm or more contained in the area, the number of microparticles in contact with regions other than the microparticles in the optically anomalous region is an area of 1,200 or less on average. [7] The photosensitive resin laminate as described in the above aspect 6, wherein the support film has a diameter of 0.5 μm or more contained in an area of 13.5 mm ² of the support film, and the above-mentioned optically abnormal The number of microparticles in the area other than the microparticles in the area is an area of 1000 or less on average. [8] The photosensitive resin laminate as described in the above aspect 6, wherein the support film has a diameter of 0.5 μm or more contained in an area of 13.5 mm ² of the support film, and the above-mentioned optically abnormal The number of particles in the area other than the particles in the area is 900 or less. [9] The photosensitive resin laminate as described in the above aspect 6, wherein the support film has a diameter of 0.5 μm or more of the fine particles contained in the area of 13.5 mm ² of the support film, and the optically abnormal The number of particles in the area other than the particles in the area is 500 or less. [10] The photosensitive resin laminate as described in the above aspect 6, wherein the support film has a diameter of 0.5 μm or more of the fine particles contained in the area of 13.5 mm ² of the support film, and the optically abnormal The number of particles in the area other than the particles in the area is less than 200. [11] The photosensitive resin laminate according to any one of the above aspects 6 to 10, wherein the support film has among the fine particles with a diameter of 1.0 μm or more contained in an area of 13.5 mm ² of the support film , The number of microparticles in contact with the area other than the microparticles in the above-mentioned optically anomalous area becomes less than 500 areas. [12] The photosensitive resin laminate as described in the above aspect 11, wherein the support film has a diameter of 1.0 μm or more of the fine particles contained in the area of 13.5 mm ² of the support film, and the optically abnormal The number of particles in the area other than the particles in the area becomes less than 300 areas. [13] The photosensitive resin laminate as described in the above aspect 11, wherein the support film has a diameter of 1.0 μm or more contained in an area of 13.5 mm ² of the support film, and is optically abnormal The number of particles in the area other than the particles in the area is less than 100. [14] The photosensitive resin laminate as described in the above aspect 11, wherein the support film has a diameter of 1.0 μm or more contained in an area of 13.5 mm ² of the support film, and the above-mentioned optically abnormal The number of particles in the area other than the particles in the area is 50 or less. [15] The photosensitive resin laminate according to any one of the above aspects 6 to 14, wherein the support film has among the fine particles with a diameter of 2.0 μm or more contained in an area of 13.5 mm ² of the support film , The number of microparticles in contact with the area other than the microparticles in the above-mentioned optically anomalous area becomes less than 200 areas. [16] The photosensitive resin laminate as described in the above aspect 15, wherein the support film has a diameter of 2.0 μm or more contained in the support film in an area of 13.5 mm ² , and the above-mentioned optically abnormal The number of particles in the area other than the particles in the area is less than 100. [17] The photosensitive resin laminate as described in the above aspect 15, wherein the support film has a diameter of 2.0 μm or more contained in the support film in an area of 13.5 mm ² , and the above-mentioned optically abnormal The number of particles in the area other than the particles in the area is 50 or less. [18] The photosensitive resin laminate as described in the above aspect 15, wherein the support film has a diameter of 2.0 μm or more contained in the support film in an area of 13.5 mm ² , and the above-mentioned optically abnormal The number of microparticles in the area other than the microparticles in the area becomes less than 10 areas. [19] The photosensitive resin laminate according to any one of the above aspects 1 to 18, wherein the refractive index difference between the refractive index of the fine particles and the refractive index of the main region of the support film is 0.2 or less. [20] The photosensitive resin laminate as described in the above aspect 19, wherein the refractive index difference between the refractive index of the fine particles and the refractive index of the main region of the support film is 0.1 or less. [21] The photosensitive resin laminate as described in the above aspect 19, wherein the refractive index difference between the refractive index of the fine particles and the refractive index of the main region of the support film is 0.05 or less. [22] The photosensitive resin laminate as described in the above aspect 19, wherein the refractive index difference between the refractive index of the fine particles and the refractive index of the main region of the support film is 0.02 or less. [23] The photosensitive resin laminate according to any one of the above aspects 1 to 22, wherein the optically abnormal region includes a cavity. [24] The photosensitive resin laminate according to any one of the above aspects 1 to 23, wherein the optically abnormal region includes a region having an orientation different from that of the main region of the support film. [25] The photosensitive resin laminate according to any one of the above aspects 1 to 24, wherein the optically abnormal region includes a region having a crystallinity different from that of the main region of the support film. [26] The photosensitive resin laminate as described in any one of the above aspects 1 to 25, which is used for wiring formation with a line width/gap width of 20/20 (μm) or less. [27] The photosensitive resin laminate as described in the above aspect 26, which is used for wiring formation with a line width/gap width of less than 10/10 (μm). [28] A method of manufacturing a resist pattern in a printed wiring board using the photosensitive resin laminate as described in any one of the above aspects 1 to 27. [29] The method described in the above aspect 28 is performed by a semi-additive method. [30] The method as described in the above aspect 28 or 29, wherein the line width/gap width of the resist pattern is less than 10/10 (μm). [31] A photosensitive resin laminate comprising a support film and a photosensitive resin composition layer formed on the support film, and a line width/gap width of 8 is formed on the substrate directly using a graphics exposure machine In the case of a resist pattern of /8 (μm), the line width when focusing on the surface of the photosensitive resin composition layer side of the support film, and the line width when shifting from the surface to the inside of the 400 μm substrate in the thickness direction The difference is 1.8 μm or less. [Effects of Invention]

According to one aspect of the present invention, it is possible to provide a photosensitive resin laminate that avoids resist protrusions and forms a good resist pattern shape.

Hereinafter, an exemplary form (hereinafter, simply referred to as "embodiment") for implementing the present invention will be described in detail. In addition, the present invention is not limited to the following embodiments, and can be implemented with various changes within the scope of the gist.

[Photosensitive resin laminate] This embodiment provides a photosensitive resin laminate including a support film and a photosensitive resin composition layer formed on the support film. In this embodiment, the total area ratio of the optically abnormal regions when observing the support film in an area of 13.5 mm ² with an epi-laser microscope is 300 ppm or less.

As the support film, a transparent support film that transmits light emitted from a light source for exposure is preferred. Examples of such supporting films include polyethylene terephthalate films, polyvinyl alcohol films, polyvinyl chloride films, vinyl chloride copolymer films, polyvinylidene chloride films, vinylidene chloride copolymer films, Polymethyl methacrylate copolymer film, polystyrene film, polyacrylonitrile film, styrene copolymer film, polyamide film, cellulose derivative film, etc. These films can also be used for extension if necessary.

In addition, the support film may have a single-layer structure or a multilayer structure in which resin layers formed of a plurality of compositions are laminated. In the case of a multilayer structure, an antistatic layer may be present. In the case of a multilayer structure such as a two-layer structure or a three-layer structure, for example, a resin layer containing fine particles can be formed on one side A, and on the other side B, (1) the same as the side A containing fine particles, (2 ) Contains less fine particles than surface A, (3) Contains finer particles than surface A, (4) Contains no fine particles and other structures. In the case of the structures of (2), (3), and (4), it is preferable to form a photosensitive resin composition layer on the surface B side. At this time, if there is a resin layer containing fine particles on the surface A side, it is preferable from the viewpoint of the sliding properties of the film.

In the support film, the total area ratio of the optical anomaly area when observed in an area of 13.5 mm ² with an epi-laser microscope is 300 ppm or less, more preferably 250 ppm or less, more preferably 200 ppm or less, and more preferably 150 ppm or less, more preferably 100 ppm or less, more preferably 80 ppm or less, more preferably 70 ppm or less, more preferably 60 ppm or less, more preferably 50 ppm or less, more preferably 40 ppm or less, more preferably 20 ppm or less, more preferably 10 ppm or less. The smaller the above-mentioned total area ratio is, the more advantageous it is to avoid resist protrusions in order to reduce shading, abnormal refraction, or diffraction. Because the resist bumps (especially in the semi-additive method (SAP)) bring about the defects of the wiring, the specified resistance value of the wiring is deviated, and the reliability of the circuit is reduced (ie the signal (sine wave) is disturbed), so Avoiding the resist protrusion is advantageous in terms of obtaining good reliability of the circuit. The total area ratio of the optically anomalous regions when observing the support film in an area of 13.5 mm ² with an epi-laser microscope can be 1 ppm or more, 5 ppm or more, 10 ppm or more, or 20 ppm or more.

The area of the optically anomalous region and the number of fine particles in the present invention refer to the area of the optically anomalous region and the number of fine particles observed in a region of 2 μm in the center of the thickness of the support film. When the support film has a multilayer structure, it means The area of the optically anomalous region and the number of particles are measured in a region of 2 μm in the center of the thickness of the entire multilayer structure.

Hereinafter, the reason for measuring the area of the optically abnormal region and the number of fine particles in the region of 2 μm in the center of the thickness of the support film will be explained. The inventor of the present invention conducted diligent research and found that the main factors such as light scattering, diffraction, and shading are optically abnormal regions. In the present invention, the so-called anomalous optical region is a region having different optical properties from the main region of the support film (resin constituting the support film) (specifically, the reflectance or refractive index is different from the main region, or the optical properties such as scattering and diffraction) The area where the phenomenon occurs more strongly than the main area). The optically anomalous region may include both a light-shielding portion caused by fine particles and an optically anomalous region other than the fine particles (for example, an abnormal refractive index region having a refractive index different from that of the main region of the fine particles and the support film). Examples of the optically anomalous regions are regions in which the orientation and/or crystallinity are different from the main region of the support film, air regions, gas regions other than air, cavity regions where there is almost no gas, and the like. For example, in the case of stretching during the manufacturing process of the support film, due to the presence of fine particles in the support film, etc., the stretching conditions may be generated in regions where the vicinity of the fine particles is different from other regions. Since this region is different from other regions because of its orientation and/or crystallinity, the refractive index is different from other regions. In addition, in the manufacturing process of the support film, due to the presence of fine particles in the support film, etc., areas where air, gas other than air, and cavity areas may be generated. The refractive index of this area is different from other areas. Optically anomalous regions such as anomalous refractive index regions mostly exist in the vicinity of fine particles, but they do not necessarily exist in the vicinity of fine particles. Since the refractive index of the optically anomalous area is different from that of the surrounding main area, when visually recognized with an optical microscope, the light is scattered and refracted between the optically anomalous area and the main area, so it looks brighter, etc. area. Due to the generation of the optically abnormal area (especially the abnormal refractive index area), the optically abnormal area is not easy to be generated on the surface of the support film, but is easily generated inside the support film. Therefore, in the present invention, the thickness center of the support film is 2 μm Measure the area of the optical anomaly area and the number of particles in the area.

As a method of reducing the optically abnormal area, it is more useful to increase the affinity of the surface of the particles for the material constituting the support film (for example, when the support film is a PET (Polyethylene Terephthalate) film, The method of coating the surface of fine particles with aromatic polymers); after the biaxial stretching of the support film, the film is subjected to thermocompression bonding at a temperature above the glass transition temperature of the support film to make the optical abnormal area (especially abnormal refraction) Rate area) disappearing method, etc. When the support film is a PET film, the temperature of the thermocompression bonding treatment can be, for example, about 180 to 250°C.

The method of measuring the total area of the optically abnormal regions is as follows. Insert a polarizing filter (OLS4000-QWP) above the objective lens of an epi-laser microscope (OLS-4100 manufactured by Olympus). Secondly, a porous adsorption plate (65F-HG manufactured by Universal Giken) and a vacuum pump are used on the mounting table of the laser microscope to horizontally suck and fix the support film sample cut into 30 mm×30 mm. Using the objective lens 50 times the amount of laser light 60 (laser wavelength is 405 nm) to observe the support film for attracting and fixing. At this time, the area of 2 μm in the center of the thickness direction of the support film is defined as the measurement area, and the measurement area is 259 μm×260 μm, and the measurement area is measured at 200 points (therefore, the total measurement area becomes 0.259 mm×0.26 mm ×200=13.5 mm ² ).

The light quantity difference between the pixel with the maximum light quantity and the pixel with the minimum light quantity in the measured image is 4096 levels (the value of the maximum light quantity is 4095, and the value of the minimum light quantity becomes 0). Create a histogram (horizontal axis: light intensity level (minimum value 0, maximum value 4095), vertical axis: number of pixels) that graphs the light distribution of pixels in the image. Set the level obtained by adding 400 levels to the value of the lower pendulum that has two lower pendulums in the created histogram as the threshold value, and binarize the measured image to the pixels with light intensity greater than the threshold Sum up the areas, and set the total area as the total area of the optically abnormal area. Calculate the ratio of the total area of the optical anomaly area to the measured area.

Fig. 1 is a diagram explaining the method of measuring the total area of the optically abnormal regions. Figure 1 shows an exemplary histogram. The points of α and β in the histogram indicate that there are β pixels for measuring the amount of light α in the screen (the maximum amount of light is 4095, and the value of the minimum amount of light becomes 0, and the pixels are standardized using 4096 levels). The threshold value is the threshold value obtained by adding 400 levels to the lower swing part of the histogram that is larger (because the place where the light quantity is 0 is also counted as the lower swing part, so one of the two lower swing parts becomes the light quantity 0 place). If a threshold is used to binarize pixels with a light amount above the threshold (typically a few pixels and very few) (that is, pixels with a light amount below the threshold are set to black, and pixels with a light amount above the threshold are set to Is white), then there are a few pixels of white points in the black measurement screen. The white dot corresponds to the light-shielding part, that is, the part that reflects the laser of the epi-type laser microscope by the particles in the support film or other optically anomalous areas (for example, an abnormal refractive index area). Set the above measurement to the measurement using the laser microscope mode of OLS-4100 manufactured by Olympus.

Next, the method for measuring the number of fine particles is as follows. After measuring the total area of the optically abnormal area, switch the epi-laser microscope (OLS-4100 manufactured by Olympus) to the optical microscope mode. Thereafter, in the measurement area 259 μm×260 μm, the optically anomalous area (such as the abnormal refractive index area) other than the particles corresponding to the position of the light-shielding part (ie the position of the particles) confirmed by the laser microscope mode by visual inspection is measured. ) The number and diameter of the connected particles. That is, use the optical microscope mode to visually observe the parts of the white dots (shading parts) that are counted in the laser microscope mode to confirm whether the white dots are in contact with optically anomalous areas (such as abnormal refractive index areas) other than particles Further, the diameter of the fine particles was measured by visual observation. Perform the same measurement at 200 points of measurement (ie, within an area of 0.259 mm×0.26 mm×200=13.5 mm ² ), and calculate the total count for each diameter of the fine particles. When the particle is not a perfect sphere, the longest width of the particle is set as the diameter of the particle. Figure 2 is a diagram for explaining the measurement of the number of particles in the laser microscope mode. The white dots correspond to the light-shielding parts. In addition, FIG. 3 is a diagram for explaining the measurement of the number of fine particles in the optical microscope mode. Temporarily set the place in the white dashed area in Fig. 2 to correspond to the place in the white dashed area in Fig. 3. In this case, in the region corresponding to the white dotted line region in FIG. 2, there is one fine particle that is in contact with an optically abnormal region (for example, an abnormal refractive index region) other than the fine particle. Observe all parts of the white point (shading range) observed by the laser microscope mode using the optical microscope mode, and measure the number of particles in contact with the optically anomalous areas (such as the abnormal refractive index area) other than the particles. diameter. There are also cases where the white point (shielding area) observed by the laser microscope mode is not a fine particle that is in contact with an optically anomalous region (for example, an abnormal refractive index region) other than the particle.

If the support film does not contain fine particles at all, it will be difficult to obtain sufficient windability when the photosensitive resin laminate is wound on a roll. Therefore, in this embodiment, the support film contains fine particles. The content of the fine particles is not particularly limited, and relative to the support film, in terms of mass ratio, it is preferably 5 to 1,000 ppm, more preferably 10 to 800 ppm, and particularly preferably 20 to 500 ppm.

As the fine particles contained in the support film, there are, for example, inorganic fine particles or organic fine particles, agglomerates of lubricants and additives, foreign materials mixed in the raw materials, foreign materials mixed in the manufacturing process, and the like. Specific examples of fine particles include: calcium carbonate, calcium phosphate, silicon oxide (silica), kaolin, talc, titanium dioxide, aluminum oxide (alumina), barium sulfate, calcium fluoride, lithium fluoride, zeolite, and molybdenum sulfide Such as inorganic particles, cross-linked polymer particles, organic particles such as calcium oxalate, etc. These may be single or a combination of two or more.

The fine particles are blended into the support film according to a common method. When manufacturing the support film in which the total area of the light-shielding part is set to a specific range, for example, a method such as filtering the material resin with a filter (for example, a filter with a mesh of 2.0 μm or less) can be cited. The more the filter mesh is made finer, and the more the number of times the material resin passes through the filter is increased, the smaller the number of particles in the material resin, the smaller the size of the particles, the smaller the total area of the shading part.

From the viewpoint of suppressing the occurrence of resist protrusions, the refractive index difference between the refractive index of the fine particles and the refractive index of the main region of the support film is preferably 0.2 or less, more preferably 0.18 or less, more preferably 0.15 or less, and more preferably It is 0.12 or less, more preferably 0.1 or less, more preferably 0.08 or less, more preferably 0.05 or less, still more preferably 0.04 or less, still more preferably 0.03 or less, still more preferably 0.02 or less, and particularly preferably 0.01 or less. If the refractive index difference between the fine particles and the support film is small, the light scattering tends to decrease. In the present invention, the so-called "main area of the support film" refers to the area that occupies most of the support film in the area other than the optically abnormal area of the support film. Since the refractive index of the support film for the photosensitive resin laminate is typically about 1.4 to 1.7, as a method of reducing the refractive index difference between the fine particles and the support film, the use of the same refractive index as the fine particles can be mentioned. The refractive index of the support film is preferably 1.4 to 1.7, more preferably 1.5 to 1.7. Furthermore, the refractive index in the specification of this case refers to the refractive index at a wavelength of 589 nm.

As a method of reducing the number of fine particles in the supporting film, a method of manufacturing a supporting film using a membrane material that has passed a filter for removing particles can be exemplified. For example, when you want to reduce the number of particles with a diameter of 0.5 μm or more, you only need to use a filter that removes particles with a diameter of 0.5 μm or more. Furthermore, after using this filter, fine particles are added later to increase the number of fine particles to a desired range and adjust the number of fine particles.

Since the optically anomalous region is a region in which light scatters, diffracts, etc., in particular, if the microparticles and the optically anomalous region other than the microparticles are close to each other, the light scattering becomes significant and poor. Therefore, it is preferable to reduce the number of fine particles existing in the vicinity of an optically abnormal region (for example, an abnormal refractive index region) other than the fine particles.

From the viewpoint of reducing the influence of light-shielding caused by the particles in the support film, it is preferable to have particles with a diameter of 0.5 μm or more contained in an area of 13.5 mm ² of the support film, which is different from the support film The number of the optically anomalous area (e.g., the abnormal refractive index area) other than the microparticles of the main area of the optical properties (e.g., refractive index) is preferably 1500 or less, preferably 1200 or less, more preferably Be 1000 or less, preferably 900 or less, preferably 800 or less, preferably 700 or less, preferably 600 or less, preferably 500 or less, preferably 400 Less than, preferably less than 300, more preferably less than 200, more preferably less than 100, more preferably less than 80, more preferably less than 50, more preferably less than 30 or less, preferably less than 10 areas. Regarding the diameter of the particles with a diameter of 0.5 μm or more, there is no particular upper limit. It can be 10 μm or less, 8 μm or less, 5 μm or less, 4.5 μm or less, 4 μm or less, or 3.5 μm or less, but also 3 μm or less.

A preferred aspect provides a photosensitive resin laminate, which is provided with a support film and a photosensitive resin composition layer formed on the support film, and the support film contains fine particles and is included in the use of an epi-laser microscope When observing the support film in an area of 13.5 mm ² , the total area ratio of the optically anomalous area is less than 300 ppm, and the support film has particles with a diameter of 0.5 μm or more contained in the area of 13.5 mm ² of the support film Among them, the number of microparticles in contact with areas other than the microparticles in the optically anomalous area is an area of 1200 or less on average. In addition, in the photosensitive resin laminate that replaces the above-mentioned aspect or is a combination of the above-mentioned aspect, a resist pattern with a line width/gap width of 8/8 (μm) is formed directly on the substrate using a drawing exposure machine In this case, the difference between the line width when focusing on the surface of the photosensitive resin composition layer side of the support film and the line width when shifting from the surface to the inside of the 400 μm substrate in the thickness direction is 1.8 μm or less.

Furthermore, in the present invention, the so-called fine particles with a specific diameter refers to a primary particle agglomerate including primary particles with a specific diameter and an agglomerate of primary particles with a diameter of the specific value. Furthermore, when the primary particle is not a complete sphere, the longest width of the primary particle is set as the diameter of the primary particle. In addition, when the primary particle aggregate is not a complete sphere, the longest width of the primary particle aggregate is set as the diameter of the primary particle aggregate. For example, fine particles with a diameter of 0.5 μm or more include primary particles with a diameter of 0.5 μm or more, and agglomerates of primary particles with a diameter of 0.5 μm or less, and primary particle aggregates with a diameter of 0.5 μm or more.

When the optical anomaly area is observed in the optical microscope mode, since the presentation method (transmission and reflection of light) is different from the main area around it, the optical microscope can be used to visually observe whether the microparticles are related to the microparticles as shown in Figure 3. The abnormal regions (for example, the abnormal refractive index regions) meet.

Furthermore, when measuring the number of fine particles in the support film, if there is a part having the number of fine particles specified in the specific aspect of this embodiment, the photosensitive resin laminate is included in the photosensitive of the specific aspect In the resin laminate. That is, even if the number of fine particles is not met when the measurement is performed at a certain part, the number of fine particles is met when the measurement is performed at another part, the photosensitive resin laminate is included in the specific aspect of the photosensitive性resin laminate.

In a preferred aspect, the total area of the support film is preferably 5% or more, preferably 10% or more, preferably 20% or more, preferably 30% or more, preferably 50% or more, More preferably 60% or more, more preferably 70% or more, more preferably 80% or more, still more preferably 90% or more, and particularly preferably about 100% (ie, substantially the entire area) is a specific aspect of this embodiment Specified optical anomaly area or area with specific particles (shading area, diameter and number of particles) specified in the sample.

The support film contains fine particles from the viewpoint of obtaining good roll-windability of the photosensitive resin laminate. In addition, the support film may have an optically anomalous region (for example, among particles with a diameter of 0.5 μm or more contained in an area of 13.5 mm ² The number of microparticles in the abnormal refractive index region) is preferably one or more, more preferably three or more, and still more preferably five or more regions. Regarding the diameter of the particles with a diameter of 0.5 μm or more, there is no particular upper limit. It can be 10 μm or less, 8 μm or less, 5 μm or less, 4.5 μm or less, 4 μm or less, or 3.5 μm or less, but also 3 μm or less.

In this embodiment, the supporting film can have an optical property other than the fine particles having a diameter of 1.0 μm or more contained in the area of 13.5 mm ² and the optical properties (such as refractive index) different from the main area of the supporting film. The number of particles in contact with an abnormal region (e.g., an abnormal refractive index region) is preferably 500 or less, more preferably 400 or less, more preferably 300 or less, more preferably 200 or less, and more preferably To be 100 or less, more preferably 80 or less, more preferably 50 or less, still more preferably 30 or less, and particularly preferably 10 or less regions. Regarding the diameter of the particles with a diameter of 1.0 μm or more, there is no particular upper limit. It can be 10 μm or less, 8 μm or less, 5 μm or less, 4.5 μm or less, 4 μm or less, or 3.5 μm or less, but also 3 μm or less.

The support film contains fine particles from the viewpoint of obtaining good roll-windability of the photosensitive resin laminate. In addition, the support film may have an optically anomalous region (for example, among the particles with a diameter of 1.0 μm or more contained in an area of 13.5 mm ²⁾ that have different optical properties (such as refractive index) from the main region of the support film The number of microparticles in the abnormal refractive index region) is preferably one or more, more preferably three or more, and still more preferably five or more regions. Regarding the diameter of the particles with a diameter of 1.0 μm or more, there is no particular upper limit. It can be 10 μm or less, 8 μm or less, 5 μm or less, 4.5 μm or less, 4 μm or less, or 3.5 μm or less, but also 3 μm or less.

In this embodiment, the support film may have optical properties other than particles having a diameter of 2.0 μm or more contained in an area of 13.5 mm ² and having optical properties (such as refractive index) different from the main area of the support film. The number of particles in contact with an abnormal region (for example, an abnormal refractive index region) is an average of 10 locations, and is preferably 200 or less, more preferably 180 or less, more preferably 150 or less, more preferably Be 120 or less, more preferably 100 or less, more preferably 80 or less, more preferably 50 or less, more preferably 30 or less, particularly preferably 10 or less . Regarding the diameter of the particles with a diameter of 2.0 μm or more, there is no particular upper limit. It can be 10 μm or less, 8 μm or less, 5 μm or less, 4.5 μm or less, 4 μm or less, or 3.5 μm or less, but also 3 μm or less.

The support film contains fine particles from the viewpoint of obtaining good roll-windability of the photosensitive resin laminate. In addition, the support film may have an optically anomalous region (for example, among the particles with a diameter of 2.0 μm or more contained in the area of 13.5 mm ² The number of the microparticles in the abnormal refractive index region is preferably one or more, more preferably three or more, and still more preferably five or more regions. Regarding the diameter of the particles with a diameter of 2.0 μm or more, there is no particular upper limit. It can be 10 μm or less, 8 μm or less, 5 μm or less, 4.5 μm or less, 4 μm or less, or 3.5 μm or less, but also 3 μm or less.

In addition, this embodiment provides a photosensitive resin laminate having a support film and a photosensitive resin composition layer formed on the support film, the support film contains fine particles, and the support film has an area of 13.5 mm ² Among the contained fine particles with a diameter of 0.5 μm or more, the number of fine particles in contact with an optically anomalous region (such as an abnormal refractive index region) other than the fine particles having an optical property (such as refractive index) different from the main region of the support film is The average number of 10 parts becomes an area of 1500 or less. The number of particles in contact with the optically anomalous area can be 1200 or less, 1000 or less, 800 or less, 500 or less, 300 or less, or less than the average number of 10 locations. Less than 100. In the photosensitive resin laminate, the above-mentioned 13.5 mm ² area is in contact with the abnormal refractive index region which is the optically abnormal region other than the fine particles, and the refractive index difference with the main region of the support film is preferably 0.2 Below, preferably 0.15 or less, preferably 0.10 or less, more preferably 0.05 or less, more preferably 0.03 or less, more preferably 0.02 or less, more preferably 0.01 or less, and the number of fine particles with a diameter of 0.5 μm or more can be 1 The above may be 10 or more, or 50 or more. The number of microparticles in contact with the abnormal refractive index region is preferably small, but as long as the microparticles have a small refractive index difference with the main region of the support film, the problem of light scattering is small. In addition, the presence of fine particles can provide the advantage of improving the sliding properties of the photosensitive resin laminate, and contribute to the excellent windability when the photosensitive resin laminate is wound on a roll. Regarding the diameter of the particles with a diameter of 0.5 μm or more, there is no particular upper limit. It can be 10 μm or less, 8 μm or less, 5 μm or less, 4.5 μm or less, 4 μm or less, or 3.5 μm or less, but also 3 μm or less.

In addition, this embodiment provides a photosensitive resin laminate having a support film and a photosensitive resin composition layer formed on the support film, the support film contains fine particles, and the support film has an area of 13.5 mm ² Among the contained microparticles with a diameter of 1.0 μm or more, the number of microparticles in contact with optically anomalous areas (e.g., anomalous refractive index areas) other than those having optical properties (e.g., refractive index) different from the main area of the support film becomes Areas below 500. The number of microparticles in contact with the optical anomaly area can be 400 or less, 300 or less, 250 or less, 200 or less, 150 or less, 100 or less, or 80 Numbers or less, may be 50 or less, 30 or less, 10 or less, or 5 or less.

In the photosensitive resin laminate, the above-mentioned 13.5 mm ² area is in contact with the abnormal refractive index region which is the optically abnormal region other than the fine particles, and the refractive index difference with the main region of the support film is preferably 0.2 Below, preferably 0.15 or less, preferably 0.10 or less, more preferably 0.05 or less, more preferably 0.03 or less, more preferably 0.02 or less, more preferably 0.01 or less, and the number of particles with a diameter of 1.0 μm or more is 10 parts The average number may be 1 or more, 5 or more, or 10 or more. Regarding the diameter of the particles with a diameter of 1.0 μm or more, there is no particular upper limit. It can be 10 μm or less, 8 μm or less, 5 μm or less, 4.5 μm or less, 4 μm or less, or 3.5 μm or less, but also 3 μm or less.

In addition, this embodiment provides a photosensitive resin laminate having a support film and a photosensitive resin composition layer formed on the support film, the support film contains fine particles, and the support film has an area of 13.5 mm ² Among the contained microparticles with a diameter of 2.0 μm or more, the number of microparticles in contact with optically anomalous areas (e.g., anomalous refractive index areas) other than those having optical properties (e.g., refractive index) different from the main area of the support film becomes Areas less than 200. The number of fine particles in contact with the optically anomalous region is more preferably 180 or less, more preferably 150 or less, more preferably 120 or less, more preferably 100 or less, and more preferably 80 Numbers or less, more preferably 50 or less, more preferably 30 or less, and particularly preferably 10 or less.

In the photosensitive resin laminate, the above-mentioned 13.5 mm ² area is in contact with the abnormal refractive index region which is the optically abnormal region other than the fine particles, and the refractive index difference with the main region of the support film is preferably 0.2 Below, preferably 0.15 or less, preferably 0.10 or less, more preferably 0.05 or less, more preferably 0.03 or less, more preferably 0.02 or less, more preferably 0.01 or less, the number of particles with a diameter of 2.0 μm or more is 10 parts The average number may be 1 or more, 5 or more, or 10 or more. Regarding the diameter of the particles with a diameter of 2.0 μm or more, there is no particular upper limit. It can be 10 μm or less, 8 μm or less, 5 μm or less, 4.5 μm or less, 4 μm or less, or 3.5 μm or less, but also 3 μm or less.

From the viewpoint of suppressing light scattering during exposure, the supporting film is preferably one having a haze of 5% or less, more preferably 2% or less, still more preferably 1.5% or less, and particularly preferably 1.0% or less. From the same viewpoint, the surface roughness Ra of the surface in contact with the photosensitive layer is preferably 30 nm or less, more preferably 20 nm or less, and particularly preferably 10 nm or less.

The thinner the thickness of the support film is, the better the image formation and the economic efficiency are improved. However, in order to maintain the strength of the photosensitive resin laminate, a thickness of 10 μm to 30 μm can be preferably used.

An important characteristic of the protective layer used in the photosensitive resin laminate is that the adhesive force with the photosensitive resin composition layer is sufficiently smaller than that of the support layer and can be easily peeled off. For example, polyethylene film or polypropylene film can be preferably used as the protective layer. Moreover, the film with excellent peelability as shown in Japanese Patent Laid-Open No. 59-202457 can also be used. The thickness of the protective layer is preferably 10 μm to 100 μm, more preferably 10 μm to 50 μm.

There exists a gel called fish eye on the surface of the polyethylene film. When a polyethylene film with fish eyes is used as a protective layer, the fish eyes may be transferred to the photosensitive resin composition layer. If the fish eyes are transferred to the photosensitive resin composition layer, air may be entrained during lamination and become voids, which may cause defects in the resist pattern. From the viewpoint of preventing fish eyes, the material of the protective layer is preferably stretched polypropylene. As a specific example, ALPHAN E-200A manufactured by Oji Paper Co., Ltd. can be cited.

Although the thickness of the photosensitive resin composition layer in the photosensitive resin laminate varies in application, it is preferably 1 μm to 300 μm, more preferably 3 μm to 100 μm, and particularly preferably 5 μm to 60 μm , The best is 10 μm～30 μm. The thinner the thickness of the photosensitive resin composition layer, the better the resolution, and the thicker the thickness, the better the film strength.

Next, the manufacturing method of the photosensitive resin laminated body is demonstrated.

As a method of manufacturing a photosensitive resin laminate by sequentially laminating a support film, a photosensitive resin composition layer, and a protective layer as necessary, a known method can be adopted. For example, the photosensitive resin composition used in the photosensitive resin composition layer is mixed with a solvent that dissolves it to form a uniform solution, and then a bar coater or roll coater is used to coat the support film Then, drying is performed to remove the above-mentioned solvent, whereby a photosensitive resin composition layer containing a photosensitive resin composition can be laminated on the support film. Then, by laminating the protective layer on the photosensitive resin composition layer as necessary, a photosensitive resin laminate can be produced.

[Photosensitive resin composition] In this embodiment, the photosensitive resin composition preferably contains (A) an alkali-soluble polymer, (B) a compound having an ethylenically unsaturated double bond, and (C) a photopolymerization initiator. The photosensitive resin composition preferably contains (A) an alkali-soluble polymer: 10% to 90% by mass; (B) an ethylenically unsaturated polymer based on the mass of all solid components of the photosensitive resin composition. Bonding compound: 5 mass% to 70 mass%; and (C) photopolymerization initiator: 0.01 mass% to 20 mass%. Hereinafter, each component will be described in order.

＜(A) Alkali-soluble polymer＞ In the present invention, (A) alkali-soluble polymers include polymers that are easily soluble in alkaline substances. More specifically, (A) the amount of carboxyl groups contained in the alkali-soluble polymer is 100 to 600, preferably 250 to 450 in terms of acid equivalent. The so-called acid equivalent refers to the mass (unit: gram) of a polymer having 1 equivalent of carboxyl group in its molecule. (A) The carboxyl group in the alkali-soluble polymer is necessary for imparting developability and releasability to the alkaline aqueous solution to the photosensitive resin composition layer. From the viewpoint of improving development resistance, resolution, and adhesion, it is preferable to set the acid equivalent to 100 or more. Furthermore, it is more preferable to set the acid equivalent to 250 or more. On the other hand, from the viewpoint of improving developability and peelability, it is preferable to set the acid equivalent to 600 or less. Furthermore, it is more preferable to set the acid equivalent to 450 or less. In the present invention, the acid equivalent is a value measured by the potentiometric titration method using a potentiometric titration device and titrated in a 0.1 mol/L NaOH aqueous solution.

(A) The weight average molecular weight of the alkali-soluble polymer is preferably 5,000 to 500,000. From the viewpoint of improving resolution and developability, it is preferable to set the weight average molecular weight to 500,000 or less. The weight average molecular weight is more preferably 100,000 or less, still more preferably 60,000 or less, and particularly preferably 50,000 or less. On the other hand, from the viewpoint of controlling the properties of the developed agglomerates and the properties of the unexposed film such as edge meltability and chipping properties in the case of forming a photosensitive resin laminate, it is preferable to set the weight average molecular weight to Above 5,000. It is more preferable to set the weight average molecular weight to 10,000 or more, and still more preferably to be 20,000 or more. The so-called edge meltability refers to the ease of overflow of the photosensitive resin composition layer (ie, the layer containing the photosensitive resin composition) from the end surface of the wound when the photosensitive resin laminate is made and wound into a roll shape The degree. The so-called chipping property refers to the degree of easy scattering of chips when the unexposed film is cut by a cutter. If the cutting chips adhere to the upper surface of the photosensitive resin laminate, etc., they are transferred to the mask in the subsequent exposure step and the like, resulting in defective products. (A) The degree of dispersion of the alkali-soluble polymer is preferably 1.0 to 6.0, more preferably 1.0 to 5.0, still more preferably 1.0 to 4.0, and still more preferably 1.0 to 3.0.

In the present embodiment, regarding the photosensitive resin composition, it is preferable to include a monomer component having an aromatic hydrocarbon group as a monomer component from the viewpoint of suppressing a thickening of the line width or deterioration of resolution when the focal position shifts during exposure (A) Alkali-soluble polymers. Furthermore, as such an aromatic hydrocarbon group, for example, a substituted or unsubstituted phenyl group, or a substituted or unsubstituted aralkyl group can be cited. Regarding the content ratio of the monomer component having an aromatic hydrocarbon group in the (A) alkali-soluble polymer, based on the total mass of all the monomer components, it is preferably 20% by mass or more, more preferably 40% by mass or more, More preferably, it is 50% by mass or more, particularly preferably 55% by mass or more, and most preferably 60% by mass or more. The upper limit is not particularly limited, but it is preferably 95% by mass or less, and more preferably 80% by mass or less. In addition, the content ratio of the monomer component having an aromatic hydrocarbon group in the case of containing a plurality of (A) alkali-soluble polymers is calculated as a weight average value.

Examples of the monomer having an aromatic hydrocarbon group include: monomers having aralkyl groups, styrene, and polymerizable styrene derivatives (such as methylstyrene, vinyl toluene, tertiary butoxybenzene Ethylene, acetoxystyrene, 4-vinylbenzoic acid, styrene dimer, styrene trimer, etc.). Among them, a monomer having an aralkyl group or styrene is preferred.

Examples of the aralkyl group include substituted or unsubstituted phenylalkyl groups (except for benzyl groups), substituted or unsubstituted benzyl groups, and the like, and substituted or unsubstituted benzyl groups are preferred.

Examples of the comonomer having a phenylalkyl group include phenylethyl (meth)acrylate and the like.

Examples of comonomers having a benzyl group include: (meth)acrylates having a benzyl group, such as benzyl (meth)acrylate, chlorobenzyl (meth)acrylate, etc.; vinyl monomers having a benzyl group For example, vinyl benzyl chloride, vinyl benzyl alcohol and the like. Among them, benzyl (meth)acrylate is preferred.

The (A) alkali-soluble polymer containing a monomer component having an aromatic hydrocarbon group is preferably obtained by combining a monomer having an aromatic hydrocarbon group with at least one of the following first monomers and/or the following second It is obtained by polymerizing at least one of the monomers.

The (A) alkali-soluble polymer containing no monomer component having an aromatic hydrocarbon group is preferably obtained by polymerizing at least one of the following first monomers, more preferably by making the first monomer It is obtained by copolymerizing at least one type with at least one type of the following second monomer.

The first monomer has a carboxyl group in the molecule. Examples of the first monomer include (meth)acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, 4-vinylbenzoic acid, maleic anhydride, and maleic acid Half ester and so on. Among them, (meth)acrylic acid is preferred.

Furthermore, in this specification, the so-called "(meth)acrylic acid" refers to acrylic acid or methacrylic acid, the so-called "(meth)acrylic acid group" refers to acrylic acid group or methacrylic acid group, and the so-called "( "Meth)acrylate" means "acrylate" or "methacrylate".

Regarding the copolymerization ratio of the first monomer, based on the total mass of all monomer components, it is preferably 10 to 50% by mass. From the viewpoint of expressing good developability and controlling edge meltability, the copolymerization ratio is preferably 10% by mass or more, more preferably 15% by mass or more, and still more preferably 20% by mass or more. From the viewpoint of the high resolution of the resist pattern and the shape of the hem portion, and from the viewpoint of the chemical resistance of the resist pattern, it is preferable to set the copolymerization ratio to 50% by mass or less. From a viewpoint, it is more preferably 35% by mass or less, still more preferably 30% by mass or less, and particularly preferably 27% by mass or less.

The second monomer system is a non-acidic monomer with at least one polymerizable unsaturated group in the molecule. As the second monomer, for example, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-(meth)acrylate Butyl ester, isobutyl (meth)acrylate, tertiary butyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, (meth)acrylic acid ring (Meth)acrylates such as hexyl ester and 2-ethylhexyl (meth)acrylate; vinyl alcohol esters such as vinyl acetate; and (meth)acrylonitrile. Among them, methyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and n-butyl (meth)acrylate are preferred.

From the viewpoint of suppressing thickening of the line width or deterioration of the resolution when the focus position is shifted during exposure, it is preferable to contain a monomer having an aralkyl group and/or styrene as a monomer. For example, a copolymer containing methacrylic acid, benzyl methacrylate, and styrene, a copolymer containing methacrylic acid, methyl methacrylate, benzyl methacrylate, and styrene, etc. are preferred.

(A) Alkali-soluble polymers may be used alone or in combination of two or more. In the case of mixing two or more kinds, it is preferable to mix two alkali-soluble polymers containing monomer components with aromatic hydrocarbon groups for use, or to mix alkali-soluble polymers containing monomer components with aromatic hydrocarbon groups , Used with alkali-soluble polymers that do not contain monomer components with aromatic hydrocarbon groups. In the latter case, the use ratio of the alkali-soluble polymer containing monomer components having aromatic hydrocarbon groups relative to the total amount of (A) alkali-soluble polymer is preferably 50% by mass or more, more preferably 70% by mass or more , Preferably 80% by mass or more, more preferably 90% by mass or more.

(A) The synthesis of alkali-soluble polymers is preferably carried out by the following method: in a solution obtained by diluting the singular or plural monomers described above with a solvent such as acetone, methyl ethyl ketone, isopropanol, etc. , Add an appropriate amount of radical polymerization initiators such as benzoyl peroxide and azoisobutyronitrile, and heat and stir. There are also cases where a part of the mixture is added dropwise to the reaction solution while the synthesis is carried out. After the reaction is over, there are cases where a solvent is further added to adjust the concentration to the desired concentration. As a synthesis method, in addition to solution polymerization, bulk polymerization, suspension polymerization, or emulsion polymerization may also be used.

(A) The weight average Tg ^total of the glass transition temperature Tg of the alkali-soluble polymer is preferably 30°C or more and 135°C or less. Tg ^total is calculated by the method described in the following examples. In the photosensitive resin composition, by using (A) alkali-soluble polymer having a Tg ^total of 135°C or less, it is possible to prevent the line width from becoming coarse or the resolution deterioration when the focus position shifts during exposure. From this point of view, the Tg ^{total of} (A) alkali-soluble polymer is more preferably 120°C or less, more preferably 115°C or less, more preferably 110°C or less, still more preferably 105°C or less, and particularly preferably 110 Below ℃. In addition, from the viewpoint of improving edge melting resistance, it is preferable to use (A) alkali-soluble polymers having a Tg ^total of 30°C or higher. From this viewpoint, the Tg ^{total of the} (A) alkali-soluble polymer is more preferably 40°C or higher, more preferably 50°C or higher, and particularly preferably 60°C or higher.

(A) The ratio of the alkali-soluble polymer to the total solid component mass of the photosensitive resin composition is preferably in the range of 10% by mass to 90% by mass, more preferably 30% by mass to 70% by mass, and still more preferably 40% to 60% by mass. From the viewpoint of controlling the development time, it is preferable to set the ratio of the (A) alkali-soluble polymer to the photosensitive resin composition to be 90% by mass or less. On the other hand, from the viewpoint of improving edge melting resistance, it is preferable to set the ratio of the (A) alkali-soluble polymer to the photosensitive resin composition to 10% by mass or more.

＜(B) Compounds with ethylenically unsaturated double bonds＞ (B) The compound having an ethylenically unsaturated double bond is preferably contained in a compound having a (meth)acryloyl group in the molecule from the viewpoint of curability and compatibility with the (A) alkali-soluble polymer. (B) The number of (meth)acryloyl groups in the compound may be one or more.

As the (B) compound having one (meth)acryloyl group, for example, a compound obtained by adding (meth)acrylic acid to one end of polyalkylene oxide; or to one end of polyalkylene oxide A compound obtained by adding (meth)acrylic acid and etherifying the other end of the alkyl group or allyl group; phthalic acid-based compounds, etc., are preferred from the viewpoint of releasability and flexibility of the cured film .

Examples of such compounds include: Phenoxyhexaethylene glycol mono(meth)acrylate, which is a (meth)acrylate compound obtained by adding polyethylene glycol to a phenyl group, As a compound obtained by adding polypropylene glycol to which an average of 2 mol of propylene oxide is added and polyethylene glycol to which an average of 7 mol of ethylene oxide is added to nonylphenol (methyl ) 4-Nonylphenoxy heptaethylene glycol dipropylene glycol (meth)acrylate of acrylate, As a compound obtained by adding polypropylene glycol to which an average of 1 mol of propylene oxide is added and polyethylene glycol to which an average of 5 mol of ethylene oxide is added to nonylphenol (methyl ) 4-Nonylphenoxy pentaethylene glycol monopropylene glycol (meth)acrylate of acrylate, 4-n-nonylphenoxy octaethylene glycol (methyl) as an acrylate compound obtained by adding polyethylene glycol with an average of 8 mol of ethylene oxide added to nonylphenol Acrylate (for example, M-114 manufactured by Toagosei Co., Ltd.) and the like.

Furthermore, if γ-chloro-β-hydroxypropyl-β'-methacryloxyethyl-phthalate is included, in addition to the above-mentioned viewpoints, it is determined from the viewpoints of sensitivity, resolution, and adhesion The language is also better.

As a compound having two (meth)acrylic groups in the molecule, for example, compounds having (meth)acrylic groups at both ends of the alkylene oxide chain, or compounds having two (meth)acrylic acid groups in the ethylene oxide chain and epoxy The propane chain is a compound with (meth)acrylic acid groups at both ends of the alkylene oxide chain formed by random or block bonding.

As such compounds, for example, in addition to tetraethylene glycol di(meth)acrylate, pentaethylene glycol di(meth)acrylate, hexaethylene glycol di(meth)acrylate, heptaethylene glycol di(meth)acrylate, Base) acrylate, octaethylene glycol di(meth)acrylate, nonaethylene glycol di(meth)acrylate, decaethylene glycol di(meth)acrylate, ethylene oxide at 12 mol In addition to polyethylene glycol (meth)acrylates such as compounds having (meth)acrylic acid groups at both ends of the chain, polypropylene glycol di(meth)acrylate and polybutylene glycol di(meth)acrylic acid can be cited Ester etc. As the polyalkylene oxide di(meth)acrylate compound containing an ethylene oxide group and a propylene oxide group in the compound, for example, two types of polypropylene glycols to which an average of 12 moles of propylene oxide are added The two ends of the diol dimethacrylate obtained by adding an average of 3 mol of ethylene oxide to the ends, and the polypropylene glycol with an average of 18 mols of propylene oxide added to the two ends of the polypropylene glycol, respectively adding an average of 15 Dimethacrylate, FA-023M, FA-024M, FA-027M (product name, manufactured by Hitachi Chemical Co., Ltd.), etc., which are diols made from mol of ethylene oxide. These are preferable in terms of flexibility, resolution, and adhesion.

As another example of a compound having two (meth)acryloyl groups in the molecule, from the viewpoints of resolution and adhesion, it is preferable to modify bisphenol A with alkylene oxide. A compound having a (meth)acryloyl group at the end. Specifically, the following general formula (I) can be used:

{式中，R₁ 及R₂ 分別獨立地表示氫原子或甲基，A為C₂ H₄ ，B為C₃ H₆ ，n1及n3分別獨立地為1～39之整數，且n1＋n3為2～40之整數，n2及n4分別獨立地為0～29之整數，且n2＋n4為0～30之整數，-(A-O)-及-(B-O)-之重複單元之排列可為無規亦可為嵌段。並且，於嵌段之情形時，-(A-O)-與-(B-O)-中之任一者可為雙苯基側} 所表示之化合物。[化1]

{In the formula, R ₁ and R ₂ each independently represent a hydrogen atom or a methyl group, A is C ₂ H ₄ , B is C ₃ H ₆ , n1 and n3 are each independently an integer of 1 to 39, and n1+n3 is 2. An integer of ~40, n2 and n4 are each independently an integer of 0-29, and n2+n4 is an integer of 0-30, the arrangement of the repeating units of -(AO)- and -(BO)- can be random or Block. In addition, in the case of a block, any one of -(AO)- and -(BO)- may be a compound represented by a double phenyl side}.

For example, in terms of resolution and adhesion, it is preferable to add a polyethylene glycol dimethacrylate with an average of 5 moles of ethylene oxide to both ends of bisphenol A, Dimethacrylate of polyethylene glycol with an average of 2 mol of ethylene oxide is added to both ends of bisphenol A, and an average of 1 mol is added to both ends of bisphenol A. Dimethacrylate of polyethylene glycol of ethylene oxide.

In addition, compounds having heteroatoms and/or substituents can be used for the aromatic ring in the general formula (I).

Examples of heteroatoms include halogen atoms and the like. Examples of substituents include alkyl groups having 1 to 20 carbon atoms, cycloalkyl groups having 3 to 10 carbon atoms, aryl groups having 6 to 18 carbon atoms, and benzyl groups. Methyl, amino, alkylamino with 1 to 10 carbons, dialkylamino with 2 to 20 carbons, nitro, cyano, carbonyl, mercapto, alkyl mercapto with 1 to 10 carbons, aromatic Group, hydroxyl group, hydroxyalkyl group with 1 to 20 carbons, carboxyl group, carboxyalkyl group with 1 to 10 carbon atoms, alkyl group with 1 to 10 carbon atoms, alkyl group with 1 to 20 carbon atoms Oxy group, alkoxycarbonyl group with 1 to 20 carbons, alkylcarbonyl group with 2 to 10 carbons, alkenyl group with 2 to 10 carbons, N-alkylamine methanoyl group with 2 to 10 carbons or containing hetero Ring groups, or aryl groups substituted with these substituents, etc. These substituents may form a condensed ring, or the hydrogen atoms in these substituents may be substituted by heteroatoms such as halogen atoms. When the aromatic ring in the general formula (I) has plural substituents, the plural substituents may be the same or different.

As a compound having 3 or more (meth)acryloyl groups in the molecule, a group having 3 mol or more of an alkylene oxide group in the molecule can be added as the central skeleton and added to it Alcohols derived from ethyleneoxy groups, propyleneoxy groups, butoxyethylene groups, etc. are made into (meth)acrylates. In this case, as a compound that can become a central skeleton, for example, glycerin, trimethylolpropane, pentaerythritol, dipentaerythritol, isocyanurate ring, etc. can be cited. Examples of these compounds include: tri(meth)acrylates such as ethoxylated glycerol tri(meth)acrylate, ethoxylated isocyanuric acid tri(meth)acrylate, and pentaerythritol tri( Meth) acrylate, trimethylolpropane tri(meth)acrylate (for example, from the viewpoints of flexibility, adhesion, and exudation suppression, it is preferable to add an average of 21 moles to trimethylolpropane Trimethacrylate made from ethylene oxide of ears, trimethacrylate made by adding 30 moles of ethylene oxide to trimethylolpropane, etc.; Tetra(meth)acrylic acid Esters such as di-trimethylolpropane tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, etc.; five(meth)acrylates such as dipentaerythritol penta(meth)acrylate Yl)acrylate and the like; hexa(meth)acrylate such as dipentaerythritol hexa(meth)acrylate and the like. From the viewpoints of resolution, adhesion, and the shape of the resist bottom part, a compound having 3 or more (meth)acrylic groups is preferred, and if it is a compound having 3 or more methacrylic groups, Better.

As the tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate is preferred. The pentaerythritol tetra(meth)acrylate may be a tetra(meth)acrylate etc. in which a total of 1-40 mol of epoxy groups are added to the 4 ends of pentaerythritol.

As the hexa(meth)acrylate, it is preferable to add hexa(meth)acrylate with a total of 1-40 mol of ethylene oxide added to the 6 ends of dipentaerythritol, and add to the 6 ends of dipentaerythritol A total of 1-20 moles of ε-caprolactone hexa(meth)acrylate.

The (meth)acrylate compounds described above can be used independently or in combination. The photosensitive resin composition may contain other compounds as (B) the compound having an ethylenically unsaturated bond. Examples of other compounds include (meth)acrylates having urethane bonds, compounds obtained by reacting α,β-unsaturated carboxylic acids with polyhydric alcohols, and α,β-unsaturated carboxylic acids Compounds obtained by reacting with glycidyl-containing compounds, 1,6-hexanediol di(meth)acrylate, etc.

(B) The ratio of the compound having an ethylenically unsaturated double bond to the total solid component mass of the photosensitive resin composition is preferably 5 mass% to 70 mass%. From the viewpoint of sensitivity, resolution, and adhesion, it is preferable to set the ratio to 5% by mass or more. It is more preferable to set the ratio to 20% by mass or more, and still more preferably to be 30% by mass or more. On the other hand, from the viewpoint of suppressing edge melting and the delay in peeling of the cured resist, it is preferable to set the ratio to 70% by mass or less. More preferably, the ratio is 50% by mass or less.

＜(C) Photopolymerization initiator＞ (C) The photopolymerization initiator is a compound that uses light to polymerize monomers. The photosensitive resin composition contains a compound generally known in this technical field as (C) a photopolymerization initiator.

The total content of the (C) photopolymerization initiator in the photosensitive resin composition is preferably in the range of 0.01-20% by mass, more preferably in the range of 0.05-10% by mass, and still more preferably 0.1% by mass It is in the range of% to 7 mass%, and more preferably in the range of 0.1 to 6 mass%. Regarding (C) the total content of the photopolymerization initiator, from the viewpoint of obtaining sufficient sensitivity, it is preferably 0.01% by mass or more, so that light can be sufficiently transmitted to the bottom surface of the resist and good high resolution can be obtained From a standpoint, it is preferably 20% by mass or less.

類、二烷基胺基苯甲酸酯類、肟酯類、吖啶類(例如，就感度、解像性、密接性之觀點而言，較佳為9-苯基吖啶、雙吖啶基庚烷、9-(對甲基苯基)吖啶、9-(間甲基苯基)吖啶)，進而可列舉：六芳基聯咪唑、吡唑啉化合物、蒽化合物(例如，就感度、解像性、密接性之觀點而言，較佳為9,10-二丁氧基蒽、9,10-二乙氧基蒽)、香豆素化合物(例如，就感度、解像性、密接性之觀點而言，較佳為7-二乙基胺基-4-甲基香豆素)、N-芳基胺基酸或其酯化合物(例如，就感度、解像性、密接性之觀點而言，較佳為N-苯基甘胺酸)、及鹵素化合物(例如三溴甲基苯基碸)等。該等可單獨使用一種或組合兩種以上而使用。除此以外，亦可使用2,2-二甲氧基-1,2-二苯乙烷-1-酮、2-甲基-1-(4-甲基噻吩基)-2-嗎啉基丙烷-1-酮、2,4,6-三甲基苯甲醯基-二苯基氧化膦、三苯基氧化膦。(C) Photopolymerization initiators include quinones, aromatic ketones, acetophenones, phosphine oxides, benzoin or benzoin ethers, dialkyl ketals, and 9-oxysulfur

Type, dialkylaminobenzoic acid esters, oxime esters, acridines (for example, from the viewpoints of sensitivity, resolution, and adhesion, 9-phenylacridine, bisacridinyl Heptane, 9-(p-methylphenyl)acridine, 9-(m-methylphenyl)acridine), and further examples include: hexaarylbiimidazole, pyrazoline compounds, anthracene compounds (for example, the sensitivity From the viewpoints of resolution and adhesion, 9,10-dibutoxyanthracene, 9,10-diethoxyanthracene), coumarin compounds (for example, in terms of sensitivity, resolution, From the viewpoint of adhesion, 7-diethylamino-4-methylcoumarin), N-arylamino acid or its ester compound (for example, in terms of sensitivity, resolution, and adhesion From a standpoint, N-phenylglycine), halogen compounds (for example, tribromomethylphenylsulfonium), and the like are preferred. These can be used individually by 1 type or in combination of 2 or more types. In addition, 2,2-dimethoxy-1,2-diphenylethane-1-one, 2-methyl-1-(4-methylthienyl)-2-morpholinyl can also be used Propan-1-one, 2,4,6-trimethylbenzyl-diphenylphosphine oxide, triphenylphosphine oxide.

As aromatic ketones, for example, benzophenone, Michelone [4,4'-bis(dimethylamino)benzophenone], 4,4'-bis(diethylamine) Group) benzophenone, 4-methoxy-4'-dimethylaminobenzophenone. These can be used individually by 1 type or in combination of 2 or more types. Among them, 4,4'-bis(diethylamino)benzophenone is preferred from the viewpoint of adhesion. Furthermore, from the viewpoint of transmittance, the content of aromatic ketones in the photosensitive resin composition is preferably in the range of 0.01% by mass to 0.5% by mass, and more preferably in the range of 0.02% by mass to 0.3% by mass Inside.

Examples of hexaarylbiimidazole include: 2-(o-chlorophenyl)-4,5-diphenylbiimidazole, 2,2',5-tri-(o-chlorophenyl)-4-( 3,4-Dimethoxyphenyl)-4',5'-diphenylbiimidazole, 2,4-bis-(o-chlorophenyl)-5-(3,4-dimethoxyphenyl) )-Diphenylbiimidazole, 2,4,5-tris-(o-chlorophenyl)-diphenylbiimidazole, 2-(o-chlorophenyl)-bis-4,5-(3,4-di Methoxyphenyl)-biimidazole, 2,2'-bis-(2-fluorophenyl)-4,4',5,5'-tetra-(3-methoxyphenyl)-biimidazole, 2,2'-Bis-(2,3-Difluoromethylphenyl)-4,4',5,5'-Tetra-(3-methoxyphenyl)-biimidazole, 2,2'- Bis-(2,4-difluorophenyl)-4,4',5,5'-tetra-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,5- Difluorophenyl)-4,4',5,5'-tetra-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,6-difluorophenyl)-4 ,4',5,5'-tetra-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,3,4-trifluorophenyl)-4,4',5 ,5'-tetra-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,3,5-trifluorophenyl)-4,4',5,5'-tetra -(3-Methoxyphenyl)-biimidazole, 2,2'-bis-(2,3,6-trifluorophenyl)-4,4',5,5'-tetra-(3-methyl (Oxyphenyl)-biimidazole, 2,2'-bis-(2,4,5-trifluorophenyl)-4,4',5,5'-tetra-(3-methoxyphenyl) -Biimidazole, 2,2'-bis-(2,4,6-trifluorophenyl)-4,4',5,5'-tetra-(3-methoxyphenyl)-biimidazole, 2 ,2'-bis-(2,3,4,5-tetrafluorophenyl)-4,4',5,5'-tetra-(3-methoxyphenyl)-biimidazole, 2,2' -Bis-(2,3,4,6-tetrafluorophenyl)-4,4',5,5'-tetra-(3-methoxyphenyl)-biimidazole, and 2,2'-bis -(2,3,4,5,6-pentafluorophenyl)-4,4',5,5'-tetra-(3-methoxyphenyl)-biimidazole, etc., these can be used alone Or use a combination of two or more. From the viewpoints of high sensitivity, resolution, and adhesion, 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer is preferred.

In this embodiment, the content of the hexaarylbisimidazole compound in the photosensitive resin composition is preferably from 0.05% by mass to the viewpoint of improving the peeling characteristics and/or sensitivity of the photosensitive resin composition layer. It is within the range of 7 mass %, more preferably within the range of 0.1 mass% to 6 mass %, and still more preferably within the range of 1 mass% to 5 mass %.

From the viewpoints of the peeling characteristics, sensitivity, resolution, and adhesion of the photosensitive resin composition layer, the photosensitive resin composition preferably also contains a pyrazoline compound as a photosensitizer.

唑-2-基)苯基)-3-(4-第三丁基-苯乙烯基)-5-(4-第三丁基-苯基)-吡唑啉、1-苯基 -3-(4-聯苯基)-5-(4-第三丁基-苯基)-吡唑啉、1-苯基-3-(4-聯苯基)-5-(4-第三辛基-苯基)-吡唑啉、1-苯基-3-(4-異丙基苯乙烯基)-5-(4-異丙基苯基)-吡唑啉、1-苯基-3-(4-甲氧基苯乙烯基)-5-(4-甲氧基苯基)-吡唑啉、1-苯基-3-(3,5-二甲氧基苯乙烯基)-5-(3,5-二甲氧基苯基)-吡唑啉、1-苯基-3-(3,4-二甲氧基苯乙烯基)-5-(3,4-二甲氧基苯基)-吡唑啉、1-苯基-3-(2,6-二甲氧基苯乙烯基)-5-(2,6-二甲氧基苯基)-吡唑啉、1-苯基-3-(2,5-二甲氧基苯乙烯基)-5-(2,5-二甲氧基苯基)-吡唑啉、1-苯基-3-(2,3-二甲氧基苯乙烯基)-5-(2,3-二甲氧基苯基)-吡唑啉、1-苯基-3-(2,4-二甲氧基苯乙烯基)-5-(2,4-二甲氧基苯基)-吡唑啉等。該等之中，更佳為1-苯基-3-(4-聯苯基)-5-(4-第三丁基-苯基)-吡唑啉。As the pyrazoline compound, it is preferable from the above viewpoint, for example, 1-phenyl-3-(4-tert-butyl-styryl)-5-(4-tert-butyl-phenyl) )-Pyrazoline, 1-(4-(Benzo

(Azol-2-yl)phenyl)-3-(4-tert-butyl-styryl)-5-(4-tert-butyl-phenyl)-pyrazoline, 1-phenyl-3- (4-Biphenyl)-5-(4-tertiary butyl-phenyl)-pyrazoline, 1-phenyl-3-(4-biphenyl)-5-(4-tertiary octyl) -Phenyl)-pyrazoline, 1-phenyl-3-(4-isopropylstyryl)-5-(4-isopropylphenyl)-pyrazoline, 1-phenyl-3- (4-methoxystyryl)-5-(4-methoxyphenyl)-pyrazoline, 1-phenyl-3-(3,5-dimethoxystyryl)-5- (3,5-Dimethoxyphenyl)-pyrazoline, 1-phenyl-3-(3,4-dimethoxystyryl)-5-(3,4-dimethoxybenzene Yl)-pyrazoline, 1-phenyl-3-(2,6-dimethoxystyryl)-5-(2,6-dimethoxyphenyl)-pyrazoline, 1-benzene Group-3-(2,5-dimethoxystyryl)-5-(2,5-dimethoxyphenyl)-pyrazoline, 1-phenyl-3-(2,3-di Methoxystyryl)-5-(2,3-dimethoxyphenyl)-pyrazoline, 1-phenyl-3-(2,4-dimethoxystyryl)-5- (2,4-Dimethoxyphenyl)-pyrazoline and the like. Among these, 1-phenyl-3-(4-biphenyl)-5-(4-tert-butyl-phenyl)-pyrazoline is more preferred.

In this embodiment, the content of the photosensitizer in the photosensitive resin composition is preferably 0.05% by mass to 5% by mass from the viewpoint of improving the peeling characteristics and/or sensitivity of the photosensitive resin composition layer Within the range, it is more preferably within the range of 0.1% by mass to 3% by mass.

＜(D)Phenol derivatives＞ In this embodiment, the photosensitive resin composition preferably further contains (D) a phenol derivative. (D) Phenol derivatives include, for example, p-methoxyphenol, hydroquinone, pyrogallol, tertiary butylcatechol, 2,6-di-tert-butyl-p-methyl Phenol, 2,2'-methylene bis (4-methyl-6-tertiary butyl phenol), 2,2'-methylene bis (4-ethyl-6-tertiary butyl phenol), 2,6-Di-tert-butyl-4-methylphenol, 2,5-di-tert-pentylhydroquinone, 2,5-di-tert-butylhydroquinone, 2,2 '-Methylene bis(4-methyl-6-tert-butylphenol), bis(2-hydroxy-3-tert-butyl-5-ethylphenyl)methane, triethylene glycol-bis[ 3-(3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis[3-(3,5-di-tert-butyl- 4-hydroxyphenyl)propionate], pentaerythritol-tetra[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 2,2-thio-diethylene Base bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3-(3,5-di-tert-butyl-4-hydroxy Phenyl) propionate, N,N'-hexamethylene bis(3,5-di-tert-butyl-4-hydroxy-phenylpropanamide), 3,5-di-tert-butyl- Diethyl 4-hydroxybenzylphosphonate, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, tris- (3,5-Di-tert-butyl-4-hydroxybenzyl)-isocyanurate, 4,4'-thiobis(6-tert-butyl-m-cresol), 4,4' -Butylene bis(3-methyl-6-tert-butylphenol), 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, styrene Chemical phenol (for example, Kawaguchi Chemical Industry Co., Ltd., Antage SP), tribenzyl phenol (for example, Kawaguchi Chemical Industry Co., Ltd., TBP, phenol with 1 to 3 benzyl groups), biphenol, and the like. From the viewpoint of suppressing thickening of the line width or deterioration of the resolution when the focus position is shifted during exposure, it is preferable to contain (D) a phenol derivative, and from the same viewpoint, hindered phenol or biphenol is preferable . In addition, from the same viewpoint, (D) the phenol derivative preferably has two or more phenol nuclei.

(D) The ratio of the phenol derivative to the total solid content mass of the photosensitive resin composition is preferably 0.001% by mass to 10% by mass. The ratio is preferably 0.001% by mass or more, more preferably 0.005% by mass or more, and still more preferably 0.01% by mass from the viewpoint of suppressing thickening of the line width or deterioration of resolution when the focus position is shifted during exposure. Above, it is more preferably 0.05% by mass or more, and particularly preferably 0.1% by mass or more. On the other hand, the ratio is preferably 10% by mass or less, more preferably 5% by mass or less, and still more preferably 3% by mass or less in terms of less reduction in sensitivity and improvement in resolution, especially It is preferably 2% by mass or less, and most preferably 1.5% by mass or less.

＜Additives＞ The photosensitive resin composition may contain additives such as dyes, plasticizers, antioxidants, and stabilizers as necessary. For example, the additives listed in JP 2013-156369 A can be used.

(Dyes and coloring substances) In this embodiment, the photosensitive resin composition may further contain at least one selected from the group consisting of dyes (for example, leuco dyes, fluorescent yellow matrix dyes, etc.) and coloring substances as needed.

Examples of coloring substances include magenta, phthalocyanine green, aureaine, p-magenta, crystal violet, methyl orange, Nero blue 2B, Victoria blue, and malachite green (for example, Aizen manufactured by Hodogaya Chemical Co., Ltd.) (Registered trademark) MALACHITE GREEN), basic blue 20, diamond green (for example, Aizen (registered trademark) DIAMOND GREEN GH manufactured by Hodogaya Chemical Co., Ltd.). Regarding the content of the coloring substance in the photosensitive resin composition, when the mass of all solid components of the photosensitive resin composition is 100% by mass, it is preferably 0.001% by mass to 1% by mass. From the viewpoint of improving the handleability of the photosensitive resin composition, the content is preferably 0.001% by mass or more. On the other hand, from the viewpoint of the storage stability of the photosensitive resin composition, the content is preferably 1% by mass or less.

The photosensitive resin composition contains a dye to make the exposed part develop color, so it is better in terms of visibility. In addition, when an inspection machine or the like reads the alignment marker used for exposure, the exposed part and The larger contrast of the unexposed part is easier to recognize and is advantageous. From this point of view, preferred dyes include leuco dyes and fluorescent yellow matrix dyes.

Examples of leuco dyes include tris(4-dimethylaminophenyl)methane [leuco crystal violet], bis(4-dimethylaminophenyl)phenylmethane [leuco malachite green], and the like. In particular, from the viewpoint that the contrast becomes better, it is preferable to use leuco crystal violet as the leuco dye. The content of the leuco dye in the photosensitive resin composition is preferably 0.1% by mass to 10% by mass relative to the mass of the total solid content of the photosensitive resin composition. From the viewpoint of making the contrast between the exposed part and the unexposed part good, it is preferable to set the content to 0.1% by mass or more. The content is more preferably 0.2% by mass or more, and particularly preferably 0.4% by mass or more. On the other hand, from the viewpoint of maintaining storage stability, the content is preferably 10% by mass or less. The content is more preferably 5% by mass or less, and particularly preferably 2% by mass or less.

In addition, from the viewpoint of optimizing adhesion and contrast, it is preferable to use the photosensitive resin composition in combination with a leuco dye and the halogen compound described in (C) the photopolymerization initiator. When the leuco dye is used in combination with the halogen compound, the content of the halogen compound in the photosensitive resin composition is maintained when the total solid content of the photosensitive resin composition is set to 100% by mass From the viewpoint of the storage stability of the hue in the photosensitive layer, it is preferably 0.01% by mass to 3% by mass.

(Other additives) In order to improve thermal stability and storage stability, the photosensitive resin composition may further contain at least one compound selected from the group consisting of radical polymerization inhibitors, benzotriazoles, and carboxybenzotriazoles.

Examples of the radical polymerization inhibitor include naphthylamine, cuprous chloride, nitrosophenylhydroxylamine aluminum salt, and diphenylnitrosamine. In order not to impair the sensitivity of the photosensitive resin composition, nitrosophenylhydroxylamine aluminum salt is preferable.

As benzotriazoles, for example, 1,2,3-benzotriazole, 1-chloro-1,2,3-benzotriazole, bis(N-2-ethylhexyl)amino sub Methyl-1,2,3-benzotriazole, bis(N-2-ethylhexyl)aminomethylene-1,2,3-tolyltriazole, bis(N-2-hydroxyethyl) ) Aminomethylene-1,2,3-benzotriazole, etc.

As carboxybenzotriazoles, for example, 4-carboxy-1,2,3-benzotriazole, 5-carboxy-1,2,3-benzotriazole, N-(N,N-di -2-Ethylhexyl)aminomethylenecarboxybenzotriazole, N-(N,N-di-2-hydroxyethyl)aminomethylenecarboxybenzotriazole, N-(N,N -Di-2-ethylhexyl)amino ethylene carboxy benzotriazole and the like.

Regarding the total content of the radical polymerization inhibitor, benzotriazoles, and carboxybenzotriazoles, when the total solid content of the photosensitive resin composition is 100% by mass, it is preferably 0.01% by mass ~3% by mass, more preferably 0.05% by mass to 1% by mass. From the viewpoint of imparting storage stability to the photosensitive resin composition, the content is preferably 0.01% by mass or more. On the other hand, from the viewpoint of maintaining sensitivity and suppressing decolorization of the dye, the content is preferably 3% by mass or less.

In this embodiment, the photosensitive resin composition may further contain epoxy compounds of bisphenol A. As the epoxy compounds of bisphenol A, for example, compounds obtained by modifying bisphenol A with polypropylene glycol and epoxidizing the terminal can be cited.

In this embodiment, the photosensitive resin composition may further contain a plasticizer. Examples of plasticizers include phthalate esters (for example, diethyl phthalate, etc.), o-toluenesulfonamide, p-toluenesulfonamide, tributyl citrate, and triethyl citrate , Acetyl triethyl citrate, acetyl tri-n-propyl citrate, acetyl tri-n-butyl citrate, polyethylene glycol, polypropylene glycol, polyethylene glycol alkyl ether, polypropylene glycol alkyl ether, etc. In addition, ADEKA NOL SDX-1569, ADEKA NOL SDX-1570, ADEKA NOL SDX-1571, ADEKA NOL SDX-479 (the above are manufactured by Asahi Denka Co., Ltd.), Newpol BP-23P, Newpol BP-3P, Newpol BP-5P, Newpol BPE-20T, Newpol BPE-60, Newpol BPE-100, Newpol BPE-180 (the above are manufactured by Sanyo Chemical Co., Ltd.), Uniol DB-400, Uniol DAB-800, Uniol DA-350F, Uniol DA-400, Uniol DA-700 (manufactured by Nippon Oil & Fat Co., Ltd. above), BA-P4U Glycol, BA-P8 Glycol (manufactured by Nippon Emulsifier Co., Ltd. above) and other compounds having a bisphenol skeleton.

Regarding the content of the plasticizer in the photosensitive resin composition, it is preferably 1% by mass to 50% by mass, and more preferably 1% by mass to 30% by mass relative to the mass of all solid components of the photosensitive resin composition. From the viewpoint of suppressing the delay of the development time and imparting flexibility to the cured film, the content is preferably 1% by mass or more. On the other hand, from the viewpoint of suppressing insufficient hardening and cold flow, the content is preferably 50% by mass or less.

[Solvent] The photosensitive resin composition can be dissolved in a solvent and used in the production of a photosensitive resin laminate in the form of a photosensitive resin composition preparation liquid. As a solvent, ketones, alcohols, etc. are mentioned. The above-mentioned ketones are represented by methyl ethyl ketone (MEK) and acetone. The above-mentioned alcohols are represented by methanol, ethanol, and isopropanol. The solvent is preferably added to the photosensitive resin laminate in such an amount that the viscosity of the photosensitive resin composition blend liquid coated on the support layer at 25° C. becomes 500 mPa·s～4,000 mPa·s during the production of the photosensitive resin laminate In the photosensitive resin composition.

＜Formation method of resist pattern＞ Next, an example of the method of manufacturing a resist pattern using the photosensitive resin laminate of this embodiment is demonstrated. The method may include the following steps: a lamination step, which is a bulk layer of a photosensitive resin laminate on a substrate; an exposure step, which exposes the photosensitive resin composition of the photosensitive resin laminate; and a development step, which is The unexposed part of the photosensitive resin composition layer is developed and removed. Examples of the resist pattern include: printed wiring boards, semiconductor elements, printing plates, liquid crystal display panels, flexible substrates, lead frame substrates, COF (chip on film) substrates, semiconductor packaging substrates, transparent electrodes for liquid crystals , Wiring for TFT (Thin Film Transistor) for liquid crystal, and electrode for PDP (Plasma Display Panel). Since the photosensitive resin laminate of this embodiment has the advantage of avoiding resist protrusions, for example, the line width/gap width is 20/20 (μm) or less, or the line width/gap width is less than 10/10 (μm) and other high-definition wiring formation is particularly useful. The line width/gap width (μm) applicable to the photosensitive resin laminate of this embodiment is not particularly limited, and for example, it is 15/15 (μm) or less, preferably 10/10 (μm) or less, and more It is preferably 9.5/9.5 (μm) or less, and particularly preferably 9.0/9.0 (μm) or less. The lower limit of the line width/gap width (μm) is not particularly limited, and it may be 3/3 (μm) or more, 4/4 (μm) or more, or 5/5 (μm) or more. In addition, the photosensitive resin laminate of the present embodiment is particularly useful for wiring formation by the semi-additive method (SAP) due to the above-mentioned advantages. The SAP method can be implemented by a conventional method. For example, a laminate of an insulating resin layer and a copper layer (for example, an electroless copper plating layer containing palladium as a catalyst) can be used to form wiring by a known plating method. As an example, the manufacturing method of a printed wiring board is demonstrated as follows.

The printed wiring board is manufactured through the following steps. (1) Laminating step First, in the lamination step, a laminating machine is used to form a photosensitive resin composition layer on the substrate. Specifically, when the photosensitive resin laminate has a protective layer, after the protective layer is peeled off, the photosensitive resin composition layer is heated and pressure-bonded to the surface of the substrate with a laminator to laminate. Examples of the material of the substrate include copper, stainless steel (SUS), glass, indium tin oxide (ITO), and the like.

In this embodiment, the photosensitive resin composition layer may be laminated on only one side of the substrate surface, or laminated on both sides as necessary. The heating temperature during lamination is usually 40°C to 160°C. In addition, by performing heat and pressure bonding during lamination twice or more, the adhesion of the obtained resist pattern to the substrate can be improved. At the time of heating and pressure bonding, pressure bonding can be performed by using a two-stage laminator equipped with a twin roll, or by repeatedly passing the laminate of the substrate and the photosensitive resin composition layer through the roll several times.

(2) Exposure step In this step, the photosensitive resin composition layer is exposed by the following exposure method: the mask with the required wiring pattern is adhered to the support layer, and the exposure method using an active light source is used as the required wiring The exposure method of drawing the pattern directly; or the exposure method of projecting the image of the mask through the lens. The advantage of the photosensitive resin composition of this embodiment is more prominent in the exposure method using direct drawing of the drawing pattern, or the exposure method of projecting the image of the mask through the lens, and is more prominent in the direct drawing using the drawing pattern Especially notable in the exposure method.

(3) Development step In this step, after exposure, the support layer on the photosensitive resin composition layer is peeled off, and then the unexposed part is developed and removed using a developer of an alkaline aqueous solution, thereby forming a resist pattern on the substrate.

An aqueous solution of Na ₂ CO ₃ or K ₂ CO ₃ is used as the alkaline aqueous solution. The alkaline aqueous solution is appropriately selected according to the characteristics of the photosensitive resin composition layer, and is preferably a Na ₂ CO ₃ aqueous solution with a concentration of about 0.2% by mass to about 2% by mass and about 20°C to about 40°C.

The resist pattern can be obtained through the steps (1) to (3) above. After these steps, depending on the situation, a heating step of about 100°C to about 300°C may be further performed. By implementing this heating step, chemical resistance can be further improved. Heating furnace can be heated by hot air, infrared, or far infrared. Moreover, this heating step can be implemented after the exposure step.

(4) Etching step or plating step The surface of the substrate exposed by development (for example, the copper surface of a copper foil laminated board) is etched or plated to produce a conductive pattern.

(5) Peeling step Thereafter, the resist pattern is stripped from the substrate using an aqueous solution having an alkalinity stronger than that of the developer. The alkaline aqueous solution for peeling is not particularly limited, but preferably is an aqueous solution of NaOH or KOH with a concentration of about 2% by mass to about 5% by mass and a temperature of about 40 to about 70°C. A small amount of water-soluble solvent can also be added to the stripping liquid.

The photosensitive resin laminate system of this embodiment is suitable for printed wiring boards, flexible substrates, lead frame substrates, COF substrates, semiconductor packaging substrates, transparent electrodes for liquid crystals, wiring for TFTs for liquid crystals, electrodes for PDPs, etc. Photosensitive resin laminate for the manufacture of resist patterns or conductor patterns.

Furthermore, as for the various parameters described above, unless otherwise specified, they are measured in accordance with the measurement methods in the following examples or methods understood by those in the field as equivalent. [Example]

Next, the present embodiment will be explained more specifically with examples and comparative examples. However, this embodiment is not limited to the following embodiments as long as it does not deviate from the gist. The physical properties in the examples were measured by the following methods.

Shows the method of preparing evaluation samples of the examples and comparative examples, the evaluation method of the obtained samples, and the evaluation results.

<Examples 1 to 3 and Comparative Example 1> 1. Preparation of photosensitive resin composition By making (A) an alkali-soluble polymer of methacrylic acid/benzyl methacrylate copolymer (polymerization ratio 20/80 (mass ratio), acid equivalent 430, weight average molecular weight 50,000) 47 parts by mass, (B) 0.1 parts by mass of 4,4'-bis(diethylamino)benzophenone and 2-(o-chlorophenyl)-4,5-diphenylimidazole dimerization as a photopolymerization initiator 3 parts by mass, (C) 14 parts by mass of tetraacrylate obtained by adding an average of 15 mol of ethylene oxide to the 4 ends of pentaerythritol as a compound having an ethylenic double bond, and As a dye, 0.05 parts by mass of diamond green and 0.3 parts by mass of leuco crystal violet It is dissolved in a solvent to prepare a photosensitive resin composition.

2. Support film production Polyethylene terephthalate (PET) was produced as each supporting film of Examples 1 to 3 and Comparative Example 1. The total area ratio of the optically abnormal regions in each support film is as described in Table 1. The number of particles in the support film is adjusted by the thickness of the mesh of the filter, the number of times the material constituting the support film passes through the filter and the number of added particles. Furthermore, the adjustment of the area of the optically anomalous region (the part that generates reflection, scattering, etc.) is carried out by the following method: after the biaxial stretching of the PET film, the film is appropriately adjusted again at 180-250°C The thermal compression bonding process makes the optically anomalous area around the microparticles (ie, cavities, or areas with different alignment or crystallinity, etc.) disappear.

3. Manufacturing of photosensitive resin laminate On one side of a support film (thickness 12 μm) made of polyethylene terephthalate (PET), use a bar coater to coat the photosensitive resin composition prepared above, and heat it at 95°C. It dried for 2.5 minutes in a dryer to form a photosensitive resin composition layer, thereby obtaining a photosensitive resin laminate. The dry thickness of the photosensitive resin composition layer was 20 μm. Then, a 19 μm thick polyethylene film (manufactured by Tamapoly Co., Ltd., GF-818) was attached as a protective layer on the surface of the photosensitive resin composition layer on the side where the polyethylene terephthalate film was not laminated. , And a photosensitive resin laminate is obtained.

<The entire surface of the substrate> Use a soft etchant (manufactured by Ryoko Chemical Co., Ltd., CPE-900) to treat a 0.4 mm thick copper laminate laminate with 18 μm rolled copper foil as an image evaluation substrate, and The surface of the substrate was washed with 10% by mass H ₂ SO ₄ .

＜Laminating＞ Peel off the polyethylene film (protective layer) of the photosensitive resin laminate on one side, and use a heated roll laminator (manufactured by Asahi Kasei Co., Ltd., AL-700) on the copper foil laminated board preheated to 60°C at the temperature of the roll The photosensitive resin laminate was laminated at 105°C. The air pressure is set to 0.35 MPa, and the lamination speed is set to 1.5 m/min.

＜Exposure＞ Use a direct graphics exposure machine (FDi-3 manufactured by ORC MANUFACTURING, dominant wavelength 405±5 nm), use Stouffer 41-level stage exposure meter or specific direct imaging (DI) exposure mask pattern, Make an exposure. The exposure was performed using the above-mentioned Stouffer 41-step exposure meter as a mask for exposure, and the maximum remaining film step during development became 14 steps.

<Development> After peeling off the polyethylene terephthalate film (supporting film), use an alkaline developer (manufactured by FUJI KIKO, dry film developer) to spray 1% by mass Na ₂ CO at 30°C for a specific period of time ₃ Aqueous solution to dissolve and remove the unexposed part of the photosensitive resin composition layer in twice the minimum development time. At this time, the minimum time required for the photosensitive resin composition layer of the unexposed part to be completely dissolved is set as the minimum development time.

<Measurement of the total area of the optical abnormal region> Insert a polarizing filter (OLS4000-QWP) above the objective lens of an epi-laser microscope (OLS-4100 manufactured by Olympus). Secondly, a porous adsorption plate (65F-HG manufactured by Universal Giken) and a vacuum pump are used on the mounting table of the laser microscope to horizontally suck and fix the support film sample cut into 30 mm×30 mm. Using the objective lens 50 times the amount of laser light 60 (laser wavelength is 405 nm) to observe the support film for attracting and fixing. At this time, the area of 2 μm in the center of the thickness direction of the support film is defined as the measurement area, and the measurement area is 259 μm×260 μm, and the measurement area is measured at 200 points (therefore, the total measurement area becomes 0.259 mm×0.26 mm ×200=13.5 mm ² ).

The light quantity difference between the pixel with the maximum light quantity and the pixel with the minimum light quantity in the measured image is 4096 levels (the value of the maximum light quantity is 4095, and the value of the minimum light quantity becomes 0). Create a histogram (horizontal axis: light intensity level (minimum value 0, maximum value 4095), vertical axis: number of pixels) that graphs the light distribution of pixels in the image. Set the level obtained by adding 400 levels to the value of the lower pendulum that has two lower pendulums in the created histogram as the threshold value, and binarize the measured image to the pixels with light intensity greater than the threshold Sum up the areas, and set the total area as the total area of the optically abnormal area. Calculate the ratio of the total area of the optical anomaly area to the measured area.

<Number of particles with a diameter of 0.5 μm or more, particles with a diameter of 1.0 μm or more, and particles with a diameter of 2.0 μm that are in contact with the optical anomaly area> After measuring the total area of the optical anomaly area, use an epi-laser microscope (Olympus The manufactured OLS-4100) is switched to the optical microscope mode. After that, the number and diameter of the microparticles in the optical anomaly area corresponding to the position of the microparticles in the optical anomaly area confirmed by visual inspection using the laser microscope mode were measured in the measurement area 259 μm×260 μm. Perform the same measurement at 200 points of measurement (ie, within an area of 0.259 mm×0.26 mm×200=13.5 mm ² ), and calculate the total count for each diameter of the fine particles.

<Evaluation of resist protrusion> The entire surface of the evaluation substrate of 300 mm square was exposed so that L (line)/S (gap) = 8 μm/8 μm. At this time, the position of the focus during exposure is aligned with the surface of the polyethylene terephthalate film. Secondly, after peeling off the polyethylene terephthalate film (supporting film), the development time is twice the minimum development time. In addition, an optical microscope was used to focus on the surface of the resist to observe the resist pattern, and count the protrusions with a size of 2 μm or more. Furthermore, the observation area is set to 3 mm square (9 mm ² ). The results are shown in Table 1.

＜Evaluation of thicker line width＞ Expose the entire surface of the evaluation substrate of 300 mm square so that L (line)/S (gap) = 8 μm/8 μm. At this time, the position of the focus during exposure is aligned with the surface of the photosensitive layer resin side of the polyethylene terephthalate film. Secondly, after peeling off the polyethylene terephthalate film (supporting film), the development time is twice the minimum development time. Measure the line width and measure the line width of the thickest part (without focus shift). The measurement is performed on 30 lines in a range of 3 mm each, and the line width of the thickest part of each line is measured and set as an average value. Next, the position of the focal point during exposure was shifted from the surface of the photosensitive layer resin side of the polyethylene terephthalate film to the inside of the 400 μm substrate. Except for this, the measurement was carried out under the same conditions as above. Measure the line width of the thickest part of the root line, and obtain its average value.

<Examples 4-6 and Comparative Example 2> Polyethylene terephthalate (PET) was produced as each supporting film of Examples 4-6 and Comparative Example 2. The number of fine particles in each support film is shown in Table 2. The number of particles in the support film is adjusted by the thickness of the mesh of the filter, the number of times the material constituting the support film passes through the filter and the number of added particles. At this time, after the biaxial stretching of the PET film, the film is again subjected to thermocompression bonding treatment under the condition of 180-250°C, so that the optically abnormal area (ie, cavity, or alignment or crystallinity) around the particles Different areas, etc.) disappear. In addition, the refractive index difference between the main area of the support film and the fine particles is adjusted by changing the refractive index of the fine particles. The preparation of the photosensitive resin laminate and the measurement of the resist protrusion were performed in the same procedure as in Example 1, except that the support film was prepared by the method described above.

[Table 1] Table 1

[Table 2] Table 2

From the results shown in Tables 1 and 2, it can be seen that in Examples 1 to 3 in which the total area of the optically anomalous regions is reduced, the resist protrusions are reduced compared to Comparative Example 1 where the total area of the optically anomaly regions is larger. In Examples 4 to 6, where the number of particles in contact with the abnormal refractive index region other than the optically anomalous region was reduced, compared with Comparative Example 2 where there were more particles in contact with the abnormal refractive index region, the resist The protrusions are reduced. [Industrial availability]

The photosensitive resin laminate of the present invention avoids defects (protrusions) of the resist pattern caused by foreign matter in the support film and forms a good resist pattern shape, so it can be suitably used for printed wiring boards, flexible substrates, and leads Manufacture of conductor patterns such as frame substrates, COF (chip on film) substrates, semiconductor packaging substrates, transparent electrodes for liquid crystals, wiring for TFTs for liquid crystals, and electrodes for PDP (plasma display panels).

Fig. 1 is a diagram explaining the method of measuring the total area of the optically abnormal regions. Fig. 2 is a diagram explaining the measurement of the number of particles in the laser microscope mode. Fig. 3 is a diagram explaining the measurement of the number of fine particles in the optical microscope mode.

Claims (31)

A photosensitive resin laminate comprising a support film and a photosensitive resin composition layer formed on the support film, and the support film contains fine particles, including an epi-laser microscope in an area of 13.5 mm ² The area where the total area ratio of the optically abnormal areas when observing the support film is 300 ppm or less. The photosensitive resin laminate of claim 1, wherein the support film includes an area where the total area ratio of the optically abnormal regions when the support film is observed in an area of 13.5 mm ² by an epi-laser microscope is 200 ppm or less. The photosensitive resin laminate of claim 1, wherein the support film includes a region where the total area ratio of the optically abnormal regions when the support film is observed in an area of 13.5 mm ² by an epi-laser microscope is 100 ppm or less. The photosensitive resin laminate of claim 1, wherein the support film includes a region where the total area ratio of the optically abnormal regions when the support film is observed in an area of 13.5 mm ² by an epi-laser microscope is 50 ppm or less. The photosensitive resin laminate according to any one of claims 1 to 4, wherein the support film contains 10 ppm or more of fine particles on a mass basis. A photosensitive resin laminate having a support film and a photosensitive resin composition layer formed on the support film, the support film includes fine particles, and the support film has an area of 13.5 mm ² of the support film Among the contained fine particles with a diameter of 0.5 μm or more, the number of fine particles in contact with regions other than the fine particles in the optically anomalous region becomes a region of 1200 or less on average. The photosensitive resin laminate of claim 6, wherein the support film has a region of the above-mentioned particles having a diameter of 0.5 μm or more contained in an area of 13.5 mm ² of the above-mentioned support film, which corresponds to a region other than the particles in the optically abnormal region The number of connected particles is an area of 1000 or less on average. The photosensitive resin laminate of claim 6, wherein the support film has a region of the above-mentioned particles having a diameter of 0.5 μm or more contained in an area of 13.5 mm ² of the above-mentioned support film, which corresponds to a region other than the particles in the optically abnormal region The number of connected particles becomes an area of 900 or less. The photosensitive resin laminate of claim 6, wherein the support film has a region of the above-mentioned particles having a diameter of 0.5 μm or more contained in an area of 13.5 mm ² of the above-mentioned support film, which corresponds to a region other than the particles in the optically abnormal region The number of connected particles becomes an area of 500 or less. The photosensitive resin laminate of claim 6, wherein the support film has a region of the above-mentioned particles having a diameter of 0.5 μm or more contained in an area of 13.5 mm ² of the above-mentioned support film, which corresponds to a region other than the particles in the optically abnormal region The number of connected particles becomes an area of 200 or less. The photosensitive resin laminate according to any one of claims 6 to 10, wherein the support film has the above-mentioned optically abnormal region among the above-mentioned fine particles with a diameter of 1.0 μm or more contained in an area of 13.5 mm ² of the above-mentioned support film The number of particles in the area other than the particles is 500 or less. The photosensitive resin laminate of claim 11, wherein the support film has an area of the support film having a diameter of 1.0 μm or more contained in the area of 13.5 mm ² of the support film, and the area other than the particles in the optical anomaly area The number of particles connected becomes an area of 300 or less. The photosensitive resin laminate of claim 11, wherein the support film has an area of the support film having a diameter of 1.0 μm or more contained in the area of 13.5 mm ² of the support film, and the area other than the particles in the optical anomaly area The number of connected particles becomes an area of 100 or less. The photosensitive resin laminate of claim 11, wherein the support film has an area of the support film having a diameter of 1.0 μm or more contained in the area of 13.5 mm ² of the support film, and the area other than the particles in the optical anomaly area The number of connected particles becomes less than 50 areas. The photosensitive resin laminate according to any one of claims 6 to 10, wherein the support film has the optically abnormal region among the fine particles with a diameter of 2.0 μm or more contained in an area of 13.5 mm ² of the support film The number of particles in the area other than the particles is less than 200. The photosensitive resin laminate of claim 15, wherein the support film has a region of the above-mentioned particles having a diameter of 2.0 μm or more contained in an area of 13.5 mm ² of the above-mentioned support film, which corresponds to a region other than the particles in the above-mentioned optically abnormal region The number of connected particles becomes an area of 100 or less. The photosensitive resin laminate of claim 15, wherein the support film has a region of the above-mentioned particles having a diameter of 2.0 μm or more contained in an area of 13.5 mm ² of the above-mentioned support film, which corresponds to a region other than the particles in the above-mentioned optically abnormal region The number of connected particles becomes less than 50 areas. The photosensitive resin laminate of claim 15, wherein the support film has a region of the above-mentioned particles having a diameter of 2.0 μm or more contained in an area of 13.5 mm ² of the above-mentioned support film, which corresponds to a region other than the particles in the above-mentioned optically abnormal region The number of connected particles becomes an area of 10 or less. The photosensitive resin laminate according to any one of claims 1 to 4 and 6 to 10, wherein the refractive index difference between the refractive index of the fine particles and the refractive index of the main region of the support film is 0.2 or less. The photosensitive resin laminate according to claim 19, wherein the refractive index difference between the refractive index of the fine particles and the refractive index of the main region of the support film is 0.1 or less. The photosensitive resin laminate according to claim 19, wherein the refractive index difference between the refractive index of the fine particles and the refractive index of the main region of the support film is 0.05 or less. The photosensitive resin laminate according to claim 19, wherein the refractive index difference between the refractive index of the fine particles and the refractive index of the main region of the support film is 0.02 or less. The photosensitive resin laminate according to any one of claims 1 to 4 and 6 to 10, wherein the optically abnormal region includes a cavity. The photosensitive resin laminate according to any one of claims 1 to 4 and 6 to 10, wherein the optically abnormal region includes a region having an orientation different from that of the main region of the support film. The photosensitive resin laminate according to any one of claims 1 to 4 and 6 to 10, wherein the optically abnormal region includes a region having a different crystallinity from the main region of the support film. The photosensitive resin laminate according to any one of claims 1 to 4 and 6 to 10 is used for wiring formation with a line width/gap width of 20/20 (μm) or less. For example, the photosensitive resin laminate of claim 26, whose line width/gap width is less than 10/10 (μm) Used for wiring formation. A method for manufacturing a resist pattern in a printed wiring board, which uses the photosensitive resin laminate according to any one of claims 1 to 27. Such as the method of claim 28, which is carried out by the semi-additive method. The method of claim 28 or 29, wherein the line width/gap width of the above-mentioned resist pattern is less than 10/10 (μm). A photosensitive resin laminate is provided with a support film and a photosensitive resin composition layer formed on the support film, and the line width/gap width is 8/8 ( In the case of the resist pattern of μm), the difference between the line width when focusing on the surface of the photosensitive resin composition layer side of the support film and the line width when shifting from the surface in the thickness direction to the inside of the 400 μm substrate is 1.8 Below μm.

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