WO2019124452A1 - 感光性樹脂積層体 - Google Patents

感光性樹脂積層体 Download PDF

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Publication number
WO2019124452A1
WO2019124452A1 PCT/JP2018/046833 JP2018046833W WO2019124452A1 WO 2019124452 A1 WO2019124452 A1 WO 2019124452A1 JP 2018046833 W JP2018046833 W JP 2018046833W WO 2019124452 A1 WO2019124452 A1 WO 2019124452A1
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WIPO (PCT)
Prior art keywords
area
support film
fine particles
photosensitive resin
less
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PCT/JP2018/046833
Other languages
English (en)
French (fr)
Japanese (ja)
Inventor
純 宮崎
Original Assignee
旭化成株式会社
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Publication date
Application filed by 旭化成株式会社 filed Critical 旭化成株式会社
Priority to KR1020207014783A priority Critical patent/KR102471794B1/ko
Priority to JP2019560540A priority patent/JP7068340B2/ja
Priority to MYPI2020002762A priority patent/MY192613A/en
Priority to CN201880081747.0A priority patent/CN111492309B/zh
Publication of WO2019124452A1 publication Critical patent/WO2019124452A1/ja

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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/20—Exposure; Apparatus therefor
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
    • H05K3/06—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding the conductive material being removed chemically or electrolytically, e.g. by photo-etch process

Definitions

  • the present invention relates to a photosensitive resin laminate.
  • a printed wiring board or the like is used in electronic devices such as personal computers and mobile phones in order to mount components, semiconductors and the like.
  • a photosensitive resin composition layer is laminated on a support film, and a protective film is laminated on the photosensitive resin composition layer as required, as a resist for manufacturing printed wiring boards and the like.
  • Resin laminates so-called dry film photoresists (hereinafter sometimes referred to as DF) are used.
  • DF dry film photoresists
  • an alkali developing type using a weak alkaline aqueous solution as a developer is generally used. In order to manufacture a printed wiring board etc. using DF, it goes through the following processes, for example.
  • the protective film is first peeled off. Thereafter, DF is laminated on a substrate for producing a permanent circuit such as a copper-clad laminate or a flexible substrate using a laminator or the like, and exposure is performed through a wiring pattern mask film or the like. Next, the support film is peeled if necessary, and the photosensitive resin composition layer of the uncured portion (for example, the unexposed portion in the case of a negative type) is dissolved or dispersed and removed by a developer, and a cured resist pattern (described below) , Sometimes referred to as a resist pattern).
  • a photosensitive resin composition layer of the uncured portion for example, the unexposed portion in the case of a negative type
  • the process of forming a circuit can be roughly divided into two methods.
  • the first method is a method of etching away the substrate surface not covered by the resist pattern (for example, the copper surface of a copper clad laminate) and then removing the resist pattern portion with an alkaline aqueous solution stronger than the developer (etching method) It is.
  • the substrate surface is plated with copper, solder, nickel, tin or the like, and then the resist pattern portion is removed in the same manner as in the first method, and the substrate surface (for example, It is a method (plating method) of etching the copper surface of a copper clad laminate.
  • Cupric chloride, ferric chloride, a copper ammonia complex solution or the like is used for the etching.
  • miniaturization and weight reduction of electronic devices miniaturization and densification of printed wiring boards have progressed, and high resolution, good line width reproducibility, etc. are given in the above manufacturing steps.
  • High performance DF is required.
  • Patent Document 1 discloses a photosensitive element including a support film and a layer made of a photosensitive resin composition formed on the support film, wherein the haze of the support film is 0.01 to 2.0. % And the total number of particles having a diameter of 5 ⁇ m or more and aggregates having a diameter of 5 ⁇ m or more contained in the support film is 5 pieces / mm 2 or less, and the layer comprising the photosensitive resin composition is (A) Photosensitivity comprising a binder polymer, (B) a photopolymerizable compound having an ethylenically unsaturated bond, and (C) a photopolymerization initiator, and having a layer thickness of 3 to 30 ⁇ m consisting of the photosensitive resin composition. Sex elements have been described and are aimed at reducing defects in the resist.
  • Patent Document 1 focuses on the number of fine particles having a diameter of 5 ⁇ m or more in order to reduce defects in the resist.
  • optically abnormal regions for example, abnormal refractive index regions
  • Patent Document 1 focuses on the number of fine particles having a diameter of 5 ⁇ m or more, but does not focus on optically abnormal regions other than the fine particles in the support film. If there is a large number of optically abnormal areas in the support film, light scattering, diffraction, etc.
  • Patent Document 1 does not pay attention to the occurrence of such resist protrusions, and at present, no photosensitive resin laminate capable of avoiding the resist protrusions has been obtained.
  • One aspect of the present invention aims to solve the above-mentioned problems, to provide a photosensitive resin laminate that avoids resist protrusions and gives a good resist pattern shape.
  • 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 photosensitive resin laminate includes a region in which the total area ratio of the optically abnormal region is 300 ppm or less when the support film is observed at an area of 13.5 mm 2 with an epi-illumination laser microscope .
  • 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, In the support film, among the fine particles having a diameter of 0.5 ⁇ m or more included in the area of 13.5 mm 2 of the support film, the number of fine particles in contact with the area other than the fine particles in the optically abnormal area is 1,200 in number average
  • the photosensitive resin laminated body which has the area
  • the number of fine particles in contact with the area other than the fine particles of the optically abnormal area among the fine particles having a diameter of 0.5 ⁇ m or more included in the area of 13.5 mm 2 of the support film is a number average
  • the number of fine particles in contact with the area other than the fine particles in the optically abnormal area among the fine particles having a diameter of 0.5 ⁇ m or more included in the area of 13.5 mm 2 of the support film is 900
  • the photosensitive resin laminated body of the said aspect 6 which has the area
  • the number of fine particles in contact with the area other than the fine particles in the optically abnormal area among the fine particles having a diameter of 0.5 ⁇ m or more included in the area of 13.5 mm 2 of the support film is 500
  • the number of fine particles in contact with the area other than the fine particles in the optically abnormal area among the fine particles having a diameter of 0.5 ⁇ m or more included in the area of 13.5 mm 2 of the support film is 200
  • the number of fine particles in contact with the area other than the fine particles in the optically abnormal area among the fine particles having a diameter of 1.0 ⁇ m or more included in the area of 13.5 mm 2 of the support film is 500
  • the number of fine particles in contact with the area other than the fine particles in the optically abnormal area among the fine particles having a diameter of 1.0 ⁇ m or more included in the area of 13.5 mm 2 of the support film is 300
  • the photosensitive resin laminated body of the said aspect 11 which has the area
  • the number of fine particles in contact with the area other than the fine particles in the optically abnormal area among the fine particles having a diameter of 1.0 ⁇ m or more included in the area of 13.5 mm 2 of the support film is 100
  • the number of fine particles in contact with the area other than the fine particles in the optically abnormal area among the fine particles having a diameter of 1.0 ⁇ m or more included in the area of 13.5 mm 2 of the support film is 50
  • the number of fine particles in contact with the area other than the fine particles in the optically abnormal area among the fine particles having a diameter of 2.0 ⁇ m or more included in the area of 13.5 mm 2 of the support film is 200
  • the number of fine particles in contact with the area other than the fine particles in the optically abnormal area among the fine particles having a diameter of 2.0 ⁇ m or more included in the area of 13.5 mm 2 of the support film is 100
  • the photosensitive resin laminated body of the said aspect 15 which has the area
  • the number of fine particles in contact with the area other than the fine particles in the optically abnormal area among the fine particles having a diameter of 2.0 ⁇ m or more included in the area of 13.5 mm 2 of the support film is 50
  • the number of the fine particles in contact with the area other than the fine particles in the optically abnormal area among the fine particles having a diameter of 2.0 ⁇ m or more included in the area of 13.5 mm 2 of the support film is 10
  • the optically abnormal area includes an area different in orientation from the main area of the support film.
  • a photosensitive resin laminate comprising: a support film; and a photosensitive resin composition layer formed on the support film,
  • a resist pattern with a line width / space width of 8/8 ( ⁇ m) is formed on a substrate using a direct writing exposure machine, the surface on the photosensitive resin composition layer side of the support film is focused
  • the photosensitive resin laminated body whose difference of the line width and the line width at the time of shifting to the board
  • a photosensitive resin laminate can be provided which avoids resist protrusions and gives a good resist pattern shape.
  • FIG. 1 is a diagram for explaining a method of measuring the total area of the optical abnormality area.
  • FIG. 2 is a diagram for explaining measurement of the number of microparticles in the laser microscope mode.
  • FIG. 3 is a view for explaining measurement of the number of microparticles in the optical microscope mode.
  • the present embodiment provides a photosensitive resin laminate including a support film and a photosensitive resin composition layer formed on the support film.
  • the total area ratio of the optically abnormal area is 300 ppm or less when the support film is observed with an area of 13.5 mm 2 with an incident-type laser microscope.
  • emitted from an exposure light source is preferable.
  • a support film for example, polyethylene terephthalate film, polyvinyl alcohol film, polyvinyl chloride film, vinyl chloride copolymer film, polyvinylidene chloride film, vinylidene chloride copolymer film, polymethyl methacrylate copolymer film, A polystyrene film, a polyacrylonitrile film, a styrene copolymer film, a polyamide film, a cellulose derivative film etc. are mentioned. These films may be stretched if necessary.
  • the support film may have a single layer structure, or may have a multilayer structure in which resin layers formed of a plurality of compositions are laminated.
  • an antistatic layer may be present.
  • a resin layer containing fine particles is formed on one side A, and on the other side B
  • (2) contains a smaller amount of particles than surface A
  • (3) contains particles smaller than surface A
  • (4) does not contain particles.
  • the total area ratio of the optically abnormal area when observed in an area of 13.5 mm 2 with an incident type laser microscope is 300 ppm or less, more preferably 250 ppm or less, more preferably 200 ppm or less, more preferably Is 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 It is below.
  • the resist projection causes a chipping of the wiring (especially in the semi-additive method (SAP)), and causes a deviation from the specified resistance value of the wiring and thus a reduction in the reliability of the circuit (that is, a disturbance of the signal (sinusoidal wave)). Avoiding resist protrusions is advantageous in obtaining good circuit reliability.
  • 1 ppm or more may be sufficient as the total area ratio of an optical abnormal area at the time of observing a support film by the incident type laser microscope in the area of 13.5 mm 2 , 5 ppm or more, 10 ppm or more, 20 ppm or more may be sufficient. .
  • the area of the optically abnormal area and the number of fine particles of the present disclosure mean the area of the optically abnormal area and the number of fine particles observed in the center 2 ⁇ m area of the thickness of the support film. It means the area of the optical anomaly area and the number of particles measured in the center 2 ⁇ m area of the thickness of the entire structure.
  • the optically abnormal region is a region having a different optical property from the main region of the support film (the resin constituting the support film) (specifically, the reflectance or the refractive index is different from the main region, or An area where optical phenomena such as scattering and diffraction occur more strongly than the main area.
  • the optically abnormal area may include both a light shielding portion by the fine particles and an optically abnormal area other than the fine particles (for example, an abnormal refractive index area having a refractive index different from that of the fine area and the main area of the support film).
  • an optically abnormal area are an area different in orientation and / or crystallinity from the main area of the support film, an area of air, an area of gas other than air, a hollow area where gas is substantially absent, and the like.
  • regions having stretching conditions different from other regions may occur in the vicinity of the particles because of the presence of the particles in the support film.
  • this region is different in orientation and / or crystallinity from other regions, it has a different refractive index from the other regions.
  • An optically abnormal region such as an abnormal refractive index region is often present in the vicinity of the fine particle, but is not necessarily present in the vicinity of the fine particle.
  • the optically abnormal area is different from the main area, for example, it looks bright because light is scattered and refracted between the optically abnormal area and the main area when viewed with an optical microscope etc. Show it.
  • the thickness center of the support film is 2 ⁇ m because in the present disclosure, the optical abnormality region is hard to be generated on the surface of the support film and is easily generated inside the support film due to the generation of the optical abnormality region (in particular, abnormal refractive index region). Measure the area of the optically abnormal area and the number of fine particles in the area.
  • thermocompression bonding As a method of reducing the optically abnormal area, a method of improving the affinity of the surface of the fine particle for the support film constituting material (for example, when the support film is a PET film, a method of coating the fine particle surface with an aromatic polymer), support After biaxial stretching of the film, a method of subjecting the film to thermocompression bonding at a temperature higher than the glass transition temperature of the support film again to eliminate the optically abnormal area (particularly, the abnormal refractive index area) is useful.
  • the temperature of the thermocompression bonding process may be, for example, about 180 to 250.degree.
  • the measurement method of the total area of the optically abnormal area is as follows.
  • a polarizing filter (OLS4000-QWP) is inserted above the objective lens of the incident type laser microscope (OLS-4100 manufactured by Olympus).
  • a support film sample cut to 30 mm ⁇ 30 mm is suctioned and fixed horizontally on a stage of a laser microscope using a porous adsorption plate (65F-HG manufactured by Universal Giken) and a vacuum pump.
  • the suction-fixed support film is observed with a laser light amount 60 (laser wavelength is 405 nm) of 50 times the objective lens.
  • the light amount difference between the pixel of the maximum light amount and the pixel of the minimum light amount in the measured image is divided into 4096 gradations (the maximum light amount is 4095 and the minimum light amount is 0).
  • a histogram horizontal axis: gradation of light quantity (minimum value 0, maximum value 4095), vertical axis: number of pixels) graphing the light quantity distribution of pixels in the image is created.
  • the measured image is binarized using the gradation obtained by adding 400 gradations from the value of the larger one of the two base values in the created histogram as the threshold value, and the areas of the pixels whose light amounts are larger than the threshold are summed.
  • the total area thereof is the total area of the optical anomaly region.
  • the ratio of the total area of the optical abnormality area to the measurement area is calculated.
  • FIG. 1 is a diagram for explaining a method of measuring the total area of the optical abnormality area.
  • An exemplary histogram is shown in FIG.
  • the points of ⁇ and ⁇ of the histogram are ⁇ pixels of the light amount ⁇ (normalized with 4096 gradations so that the value of the maximum light amount is 4095 and the value of the minimum light amount is 0) in the measurement screen Indicates that it exists.
  • a gray scale obtained by adding 400 gradations from the large bottom of the histogram (since one of the two bottoms is at the light quantity 0 because the light quantity 0 is also counted as the foot) is used as a threshold.
  • This white point corresponds to the light shielding portion, that is, the portion where the laser of the incident type laser microscope is reflected by the fine particles in the support film and other optically abnormal regions (for example, abnormal refractive index regions).
  • the above measurement is taken as a measurement by OLS-4100 made by Olympus in a laser microscope mode.
  • the method of measuring the number of microparticles is as follows. After measuring the total area of the optically abnormal area, the incident type laser microscope (OLS-4100 manufactured by Olympus) is switched to the optical microscope mode. Thereafter, the number of particles in contact with an optically abnormal area (for example, an abnormal refractive index area) other than the microparticles corresponding to the position of the light shielding portion (that is, the position of the microparticles) visually confirmed in the laser microscope mode in the measurement area 259 ⁇ m ⁇ 260 ⁇ m Measure the diameter.
  • OLS-4100 manufactured by Olympus
  • a portion counted as a white point (light shielding portion) in the laser microscope mode is visually observed in the optical microscope mode, and it is determined whether the white point is a particle in contact with an optical abnormality area (for example, an abnormal refractive index area) other than the microparticles.
  • an optical abnormality area for example, an abnormal refractive index area
  • Check and also measure the diameter visually. The same measurement is carried out at 200 measurement points (that is, carried out with an area of 0.259 mm ⁇ 0.26 mm ⁇ 200 13.5 mm 2 ), and the total number is calculated for each particle diameter. If the particle is not a perfect sphere, the longest width of the particle is taken as the particle diameter.
  • FIG. 2 is a diagram for explaining measurement of the number of particles in the laser microscope mode, and a white point corresponds to a light shielding portion.
  • FIG. 3 is a figure explaining the measurement by the optical microscope mode of the number of microparticles
  • the location of the white dotted area in FIG. 2 corresponds to the location of the white dotted area in FIG.
  • fine particles in contact with an optical abnormal area (for example, an abnormal refractive index area) other than one fine particle are present.
  • an optical abnormal area for example, an abnormal refractive index area
  • the white point (light-shielded area) observed in the laser microscope mode is not a fine particle in contact with an optical abnormal area (for example, an abnormal refractive index area) other than the fine particles.
  • the support film does not contain any particulates, it is difficult to obtain sufficient windability when the photosensitive resin laminate is wound on a roll, and in the present embodiment, the support film contains particulates.
  • the content of the fine particles is not particularly limited, but is preferably 5 to 1,000 ppm, more preferably 10 to 800 ppm, particularly preferably 20 to 500 ppm by mass ratio to the support film.
  • the fine particles contained in the support film include, for example, inorganic fine particles or organic fine particles, such as lubricants, aggregates of additives, foreign matter mixed in the raw material, foreign matter mixed in the manufacturing process, and the like.
  • specific examples of fine particles include inorganic particles such as calcium carbonate, calcium phosphate, silica (silicon dioxide), kaolin, talc, titanium dioxide, alumina (aluminum oxide), barium sulfate, calcium fluoride, lithium fluoride, zeolite, molybdenum sulfide and the like
  • cross-linked polymer particles organic particles such as calcium oxalate, and the like. These may be alone or in combination of two or more.
  • the fine particles are blended into the support film according to a conventional method.
  • a method of filtering the material resin with a filter for example, an eye filter of 2.0 ⁇ m or less
  • the finer the filter eyes, and the greater the number of passes of the material resin through the filter the smaller the number of fine particles in the material resin, the smaller the fine particles, and the smaller the total area of the light shielding portion.
  • 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, and more preferably 0 from the viewpoint of suppressing the generation of resist protrusions. .15 or less, more preferably 0.12 or less, more preferably 0.1 or less, more preferably 0.08 or less, more preferably 0.05 or less, more preferably 0.04 or less, more preferably 0. It is at most 03, more preferably at most 0.02, particularly preferably at most 0.01. When the difference in refractive index between the fine particles and the support film is small, light scattering tends to be reduced.
  • main region of support film means a region that occupies most of the support film in the region other than the optical abnormality region 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 means for reducing the difference in refractive index between the fine particles and the support film, the fine particles may be used as fine particles. And using the same refractive index.
  • the refractive index of the support film is preferably 1.4 to 1.7, more preferably 1.5 to 1.7.
  • the refractive index in the present specification means the refractive index at a wavelength of 589 nm.
  • a method of producing a support film using a film material passing through a filter for removing fine particles can be exemplified.
  • a filter that removes particles having a diameter of 0.5 ⁇ m or more may be used.
  • the number of particles may be adjusted by increasing the number of particles to a desired range by post-adding the particles after using such a filter.
  • the optically abnormal region is a region that particularly scatters or diffracts light, if the fine particles and the optically abnormal region other than the fine particles are close to each other, the light scattering becomes remarkable, which is not preferable. Therefore, it is preferable that the number of fine particles present in the vicinity of an optically abnormal area (for example, an abnormal refractive index area) other than the fine particles be reduced.
  • an optically abnormal area for example, an abnormal refractive index area
  • optical properties different from the main region of the support film is preferably 1500 or less, preferably 1200 or less, preferably 1000 or less, preferably 900 or less, preferably There are 800 or less, preferably 700 or less, preferably 600 or less, preferably 500 or less, preferably 400 or less, preferably 300 or less, more preferably 200 or less, more preferably 100 or less, more preferably Preferably not more than 80, more preferably not more than 50, still more preferably not more than 30, particularly preferably It is preferable to have a region of 10 or less.
  • the diameter of the fine particles having a diameter of 0.5 ⁇ m or more, but it may be 10 ⁇ m or less, 8 ⁇ m or less, 5 ⁇ m or less, or 4.5 ⁇ m or less It may be 4 ⁇ m or less, 3.5 ⁇ m or less, or 3 ⁇ m or less.
  • a preferred embodiment is 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 includes a region in which the total area ratio of the optically abnormal region is 300 ppm or less when the support film is observed at an area of 13.5 mm 2 with an incident-type laser microscope, Among the fine particles having a diameter of 0.5 ⁇ m or more included in the area of 13.5 mm 2 of the support film, the number of fine particles in contact with the area other than the fine particles in the optically abnormal area is 1200 or less in the support film.
  • a photosensitive resin laminate having a region.
  • the line width / space width formed the resist pattern of 8/8 (micrometer) on the board
  • the difference between the line width when focusing on the surface of the support film on the photosensitive resin composition layer side and the line width when shifted from the surface toward the inner side of the 400 ⁇ m substrate in the thickness direction is 1.8 ⁇ m or less is there.
  • fine particles having a specific value of diameter mean that primary particles having a specific value of the diameter and primary particle aggregates having a specific value of the aggregate of primary particles are included.
  • the longest width of the primary particles is taken as the diameter of the primary particles.
  • the primary particle aggregate is not a complete sphere, the longest width of the primary particle aggregate is taken as the diameter of the primary particle aggregate.
  • the fine particles having a diameter of 0.5 ⁇ m or more include primary particles having a diameter of 0.5 ⁇ m or more, and aggregates of primary particles having a diameter of 0.5 ⁇ m or less and include primary particle aggregates having a diameter of 0.5 ⁇ m or more.
  • the appearance (transmission and reflection) of the main area around it is different from that of the surrounding area. As shown in FIG. It can be observed visually with an optical microscope whether it is in contact with the region.
  • the photosensitive resin laminate is photosensitive according to the specific aspect. It is included in a resin laminate. That is, even if the specified number of fine particles is not satisfied when measured at a certain place, when the specified number of fine particles is satisfied when measured at another place, the photosensitive resin laminate is exposed to the light according to the specific aspect. Is included in the conductive resin laminate.
  • 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.
  • the support film contains fine particles.
  • the support film is an optically abnormal area other than the fine particles having optical properties (for example, refractive index) different from the main area of the support film
  • the number of fine particles in contact with the extraordinary refractive index region may be preferably 1 or more, more preferably 3 or more, and still more preferably 5 or more.
  • the diameter of the fine particles having a diameter of 0.5 ⁇ m or more, but it may be 10 ⁇ m or less, 8 ⁇ m or less, 5 ⁇ m or less, or 4.5 ⁇ m or less It may be 4 ⁇ m or less, 3.5 ⁇ m or less, or 3 ⁇ m or less.
  • the support film is an optical component other than the fine particles having optical properties (for example, refractive index) different from the main region of the support film.
  • the number of fine particles in contact with the abnormal area is preferably 500 or less, more preferably 400 or less, more preferably 300 or less, more preferably 200 or less, still more preferably 100 or less. It is possible to have a region which is more preferably 80 or less, more preferably 50 or less, still more preferably 30 or less, particularly preferably 10 or less.
  • the diameter of the fine particles having a diameter of 1.0 ⁇ m or more, but may be 10 ⁇ m or less, 8 ⁇ m or less, 5 ⁇ m or less, or 4.5 ⁇ m or less It may be 4 ⁇ m or less, 3.5 ⁇ m or less, or 3 ⁇ m or less.
  • the support film contains fine particles. Further, among the fine particles having a diameter of 1.0 ⁇ m or more included in the area of 13.5 mm 2 , the support film is an optical abnormal area (for example, a fine particle other than the fine particles having optical properties (for example, refractive index) different from the main area of the support film)
  • the number of fine particles in contact with the extraordinary refractive index region may be preferably 1 or more, more preferably 3 or more, and still more preferably 5 or more.
  • the diameter of the fine particles having a diameter of 1.0 ⁇ m or more, but may be 10 ⁇ m or less, 8 ⁇ m or less, 5 ⁇ m or less, or 4.5 ⁇ m or less It may be 4 ⁇ m or less, 3.5 ⁇ m or less, or 3 ⁇ m or less.
  • the support film is an optical component other than fine particles having optical properties (for example, refractive index) different from the main region of the support film.
  • the number of fine particles in contact with the abnormal region is preferably 200 or less, more preferably 180 or less, more preferably 150 or less, more preferably 120 or less, at a number average of 10 locations. It is possible to have a region of 100 or less, more preferably 80 or less, still more preferably 50 or less, still more preferably 30 or less, particularly preferably 10 or less.
  • the diameter of the particles having a diameter of 2.0 ⁇ m or more there is no particular upper limit to the diameter of the particles having a diameter of 2.0 ⁇ m or more, but it may be 10 ⁇ m or less, 8 ⁇ m or less, 5 ⁇ m or less, or 4.5 ⁇ m or less It may be 4 ⁇ m or less, 3.5 ⁇ m or less, or 3 ⁇ m or less.
  • the support film contains fine particles. Further, among the fine particles having a diameter of 2.0 ⁇ m or more included in the area of 13.5 mm 2 , the support film is an optically abnormal area other than the fine particles having optical properties (for example, refractive index) different from the main area of the support film
  • the number of fine particles in contact with the extraordinary refractive index region may be preferably 1 or more, more preferably 3 or more, and still more preferably 5 or more.
  • the diameter of the particles having a diameter of 2.0 ⁇ m or more there is no particular upper limit to the diameter of the particles having a diameter of 2.0 ⁇ m or more, but it may be 10 ⁇ m or less, 8 ⁇ m or less, 5 ⁇ m or less, or 4.5 ⁇ m or less It may be 4 ⁇ m or less, 3.5 ⁇ m or less, or 3 ⁇ m or less.
  • the present embodiment is also a photosensitive resin laminate including a support film and a photosensitive resin composition layer formed on the support film,
  • the support film contains fine particles, Among the fine particles having a diameter of 0.5 ⁇ m or more included in the area of 13.5 mm 2 , the support film is an optical abnormal area (for example, anomalous refraction) other than the fine particles having optical properties (for example, refractive index) different from the main area of the support film.
  • a photosensitive resin laminate is provided which has an area in which the number of fine particles in contact with the ratio area is 1,500 or less on a number average of ten.
  • the number of fine particles in contact with the optically abnormal area may be 1200 or less, 1000 or less, 800 or less, 500 or less, 300 or less, or 100 or less in number average at 10 locations. May be.
  • the abnormal refractive index area as an optical abnormal area other than the fine particles, which is included in the area of 13.5 mm 2 , and the difference in refractive index with the main area of the support film is preferable.
  • the number of fine particles having a diameter of 0.5 ⁇ m or more may be one or more, ten or more, or fifty or more. The smaller the number of fine particles in contact with the abnormal refractive index region, the better. However, if the fine particles have a small difference in refractive index from the main region of the support film, the problem of light scattering is small. Further, the presence of the fine particles provides the advantage of improving the slipperiness of the photosensitive resin laminate, and can contribute to the excellent winding property when the photosensitive resin laminate is wound on a roll.
  • the diameter of the fine particles having a diameter of 0.5 ⁇ m or more, but it may be 10 ⁇ m or less, 8 ⁇ m or less, 5 ⁇ m or less, or 4.5 ⁇ m or less It may be 4 ⁇ m or less, 3.5 ⁇ m or less, or 3 ⁇ m or less.
  • the present embodiment is also a photosensitive resin laminate including a support film and a photosensitive resin composition layer formed on the support film,
  • the support film contains fine particles, Among the fine particles having a diameter of 1.0 ⁇ m or more included in the area of 13.5 mm 2 , the support film is an optical abnormal area (for example, anomalous refraction) other than the fine particles having optical properties (for example, refractive index) different from the main area of the support film.
  • the photosensitive resin laminate has a region in which the number of fine particles in contact with the ratio region is 500 or less.
  • the number of particles in contact with the optically abnormal area may be 400 or less, 300 or less, 250 or less, 200 or less, 150 or less, 100 or less, or 80 or less. It may be 50 or less, 30 or less, 10 or less, or 5 or less.
  • the abnormal refractive index area as an optical abnormal area other than the fine particles, which is included in the area of 13.5 mm 2 , and the difference in refractive index with the main area of the support film is preferable.
  • the number of fine particles having a diameter of 1.0 ⁇ m or more which is the following, may be one or more, five or more, or ten or more in a number average of ten places.
  • the diameter of the fine particles having a diameter of 1.0 ⁇ m or more, but may be 10 ⁇ m or less, 8 ⁇ m or less, 5 ⁇ m or less, or 4.5 ⁇ m or less It may be 4 ⁇ m or less, 3.5 ⁇ m or less, or 3 ⁇ m or less.
  • the present embodiment is also a photosensitive resin laminate including a support film and a photosensitive resin composition layer formed on the support film,
  • the support film contains fine particles, Among the fine particles having a diameter of 2.0 ⁇ m or more included in the area of 13.5 mm 2 , the support film is an optical abnormal area (for example, anomalous refraction) other than the fine particles having optical properties (for example, refractive index) different from the main area of the support film.
  • the photosensitive resin laminate has a region in which the number of fine particles in contact with the ratio region is 200 or less.
  • the number of fine particles in contact with the optically abnormal region is more preferably 180 or less, more preferably 150 or less, more preferably 120 or less, still more preferably 100 or less, still more preferably 80 or less, still more preferably 50 Or less, more preferably 30 or less, particularly preferably 10 or less.
  • the abnormal refractive index area as an optical abnormal area other than the fine particles, which is included in the area of 13.5 mm 2 , and the difference in refractive index with the main area of the support film is preferable.
  • the number of fine particles having a diameter of 2.0 ⁇ m or more, which is the following, may be one or more, five or more, or ten or more in a number average of ten places.
  • the diameter of the particles having a diameter of 2.0 ⁇ m or more there is no particular upper limit to the diameter of the particles having a diameter of 2.0 ⁇ m or more, but it may be 10 ⁇ m or less, 8 ⁇ m or less, 5 ⁇ m or less, or 4.5 ⁇ m or less It may be 4 ⁇ m or less, 3.5 ⁇ m or less, or 3 ⁇ m or less.
  • the support film preferably has 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 viewpoint of suppressing light scattering during exposure.
  • 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 protective layer used in the photosensitive resin laminate is that the adhesion to the photosensitive resin composition layer is sufficiently smaller than that of the carrier layer, and the layer can be easily peeled off.
  • polyethylene film or polypropylene film can be preferably used as a protective layer. Further, it is also possible to use a film with excellent releasability disclosed in JP-A-59-202457.
  • the thickness of the protective layer is preferably 10 ⁇ m to 100 ⁇ m, and more preferably 10 ⁇ m to 50 ⁇ m.
  • a gel called a fish eye may be present on the polyethylene film surface.
  • the fish eye may be transferred to the photosensitive resin composition layer.
  • the fish eye is transferred to the photosensitive resin composition layer, air may be taken in during lamination to form a void, which leads to a defect in the resist pattern.
  • stretched polypropylene is preferable as a material of the protective layer.
  • Alphan E-200A manufactured by Oji Paper Co., Ltd. can be mentioned.
  • the thickness of the photosensitive resin composition layer in the photosensitive resin laminate varies depending on the application, but is preferably 1 ⁇ m to 300 ⁇ m, more preferably 3 ⁇ m to 100 ⁇ m, particularly preferably 5 ⁇ m to 60 ⁇ m, and most preferably 10 ⁇ m to 30 ⁇ m. The thinner the thickness of the photosensitive resin composition layer, the higher the resolution, and the thicker the layer, the higher the film strength.
  • a known method can be adopted as a method of producing a photosensitive resin laminate by sequentially laminating a support film and a photosensitive resin composition layer, and, if necessary, a protective layer.
  • the photosensitive resin composition used for the photosensitive resin composition layer is mixed with a solvent that dissolves the photosensitive resin composition layer to form a uniform solution, first coated on a support film using a bar coater or a roll coater, and then dried By removing the solvent, a photosensitive resin composition layer composed of the photosensitive resin composition can be laminated on the support film. Subsequently, the photosensitive resin laminated body can be produced by laminating a protective layer on the photosensitive resin composition layer as needed.
  • 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 comprises (A) an alkali-soluble polymer: 10% by mass to 90% by mass, based on the total solid content mass of the photosensitive resin composition; and (B) a compound having an ethylenically unsaturated double bond.
  • C a photopolymerization initiator: 0.01% by mass to 20% by mass.
  • the (A) alkali-soluble polymer includes a polymer that is easily soluble in an alkaline substance. More specifically, the amount of carboxyl groups contained in the (A) alkali-soluble polymer is 100 to 600, preferably 250 to 450 in acid equivalent.
  • the acid equivalent refers to the mass (unit: gram) of a polymer having one equivalent of carboxyl group in the molecule.
  • the carboxyl group in the (A) alkali-soluble polymer is required to give the photosensitive resin composition layer developability and releasability to an aqueous alkali solution. Increasing the acid equivalent to 100 or more is preferable from the viewpoint of improving the development resistance, the resolution and the adhesion.
  • the acid equivalent is a value measured by potentiometric titration with a 0.1 mol / L aqueous solution of NaOH using a potentiometric titrator.
  • the weight average molecular weight of the (A) alkali-soluble polymer is preferably 5,000 to 500,000. It is preferable from the viewpoint of improving resolution and developability to make the weight average molecular weight 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.
  • setting the weight average molecular weight to 5,000 or more is a viewpoint of controlling the properties of development aggregate and the properties of unexposed film such as edge fuse property and cut tip property in the case of forming a photosensitive resin laminate. It is preferable from The weight average molecular weight is more preferably 10,000 or more, and still more preferably 20,000 or more.
  • the cut tip property refers to the degree of the chip's flyability when the unexposed film is cut by a cutter. When this chip adheres to the upper surface or the like of the photosensitive resin laminate, it is transferred to a mask in a later exposure process or the like to cause defective products.
  • the dispersion degree of the alkali soluble polymer (A) is preferably 1.0 to 6.0, more preferably 1.0 to 5.0, and 1.0 to 4.0. More preferably, it is more preferably 1.0 to 3.0.
  • the photosensitive resin composition contains an aromatic hydrocarbon group as the (A) alkali-soluble polymer. It is preferable to contain the monomer component which it has.
  • an aromatic hydrocarbon group a substituted or unsubstituted phenyl group and a substituted or unsubstituted aralkyl group are mentioned, for example.
  • the content ratio of the monomer component having an aromatic hydrocarbon group in the (A) alkali-soluble polymer is preferably 20% by mass or more based on the total mass of all the monomer components, and 40% by mass
  • the content is more preferably 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 is preferably 95% by mass or less, more preferably 80% by mass or less.
  • the content rate of the monomer component which has an aromatic hydrocarbon group in, when containing multiple types of (A) alkali-soluble polymer was calculated
  • the monomer having an aromatic hydrocarbon group for example, a monomer having an aralkyl group, styrene, and a polymerizable styrene derivative (for example, methylstyrene, vinyltoluene, tert-butoxystyrene, acetoxystyrene, 4-vinyl Benzoic acid, styrene dimer, styrene trimer etc. may be mentioned.
  • monomers having an aralkyl group or styrene are preferable.
  • a substituted or unsubstituted phenylalkyl group except for a benzyl group
  • a substituted or unsubstituted benzyl group and the like can be mentioned, and a substituted or unsubstituted benzyl group is preferable.
  • Examples of the comonomer having a phenylalkyl group include phenylethyl (meth) acrylate and the like.
  • (meth) acrylates having a benzyl group such as benzyl (meth) acrylate, chlorobenzyl (meth) acrylate etc .
  • vinyl monomers having a benzyl group such as vinyl benzyl chloride, vinyl benzyl alcohol etc
  • benzyl (meth) acrylate is preferred.
  • the (A) alkali-soluble polymer containing a monomer component having an aromatic hydrocarbon group is a monomer having an aromatic hydrocarbon group and / or at least one of a first monomer described later and / or It is preferably obtained by polymerizing with at least one of the second monomers described later.
  • the (A) alkali-soluble polymer which does not contain a monomer component having an aromatic hydrocarbon group is preferably obtained by polymerizing at least one of the first monomers described later, and It is more preferable to be obtained by copolymerizing at least one of the monomers and at least one of the second monomers described later.
  • the first monomer is a monomer having a carboxyl group in the molecule.
  • the first monomer include (meth) acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, 4-vinylbenzoic acid, maleic anhydride, maleic acid half ester and the like.
  • (meth) acrylic acid is preferable.
  • (meth) acrylic acid means acrylic acid or methacrylic acid
  • (meth) acryloyl group means acryloyl group or methacryloyl group
  • (meth) acrylate” means “acrylate” or “methacrylate”.
  • the copolymerization ratio of the first monomer is preferably 10 to 50% by mass based on the total mass of all the monomer components. Making the copolymerization ratio 10% by mass or more is preferable from the viewpoint of expressing good developability, controlling edge fuse property, etc., preferably 15% by mass or more, and more preferably 20% by mass or more. . Setting the copolymerization ratio to 50% by mass or less is preferable from the viewpoints of high resolution and shape of the resist pattern, and further from the viewpoint of chemical resistance of the resist pattern, and in these aspects, 35% by mass The following is more preferable, 30 mass% or less is further preferable, and 27 mass% or less is particularly preferable.
  • the second monomer is a non-acidic monomer having at least one polymerizable unsaturated group in the molecule.
  • the second monomer for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate , (Meth) acrylates such as tert-butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate; vinyl acetate And esters of vinyl alcohol, and (meth) acrylonitrile and the like.
  • methyl (meth) acrylate, 2-ethylhexyl (meth) acrylate 2-
  • a monomer having an aralkyl group and / or styrene as a monomer from the viewpoint of suppressing the line width thickening and resolution deterioration when the focal position at the time of exposure shifts.
  • a copolymer containing methacrylic acid, benzyl methacrylate and styrene, a copolymer containing methacrylic acid, methyl methacrylate, benzyl methacrylate and styrene, and the like are preferable.
  • the (A) alkali-soluble polymer can be used singly or in combination of two or more.
  • two kinds of alkali-soluble polymers containing a monomer component having an aromatic hydrocarbon group may be mixedly used, or a monomer component having an aromatic hydrocarbon group It is preferable to use a mixture of an alkali-soluble polymer containing at least one alkali-soluble polymer and an alkali-soluble polymer not containing a monomer component having an aromatic hydrocarbon group.
  • the proportion of the alkali-soluble polymer containing the monomer component having an aromatic hydrocarbon group is preferably 50% by mass or more based on the total of (A) the alkali-soluble polymer, and 70 It is more preferable that it is mass% or more, It is preferable that it is 80 mass% or more, It is more preferable that it is 90 mass% or more.
  • the synthesis of the alkali-soluble polymer can be carried out by using benzoyl peroxide, azoisobutyronitrile or the like in a solution obtained by diluting one or more of the monomers described above with a solvent such as acetone, methyl ethyl ketone or isopropanol. It is preferable to be carried out by adding a suitable amount of a radical polymerization initiator and heating and stirring. In some cases, synthesis is performed while a portion of the mixture is dropped into the reaction solution. After completion of the reaction, a solvent may be further added to adjust to a desired concentration. As a synthesis means, bulk polymerization, suspension polymerization, or emulsion polymerization may be used other than solution polymerization.
  • Weight average Tg total glass transition temperature Tg of the (A) alkali-soluble polymer is preferably at 30 ° C. or higher 135 ° C. or less. Tg total is calculated by the method described in the examples described later.
  • the Tg total of the (A) alkali-soluble polymer is more preferably 120 ° C. or less, still more preferably 115 ° C. or less, still more preferably 110 ° C. or less, and 105 ° C.
  • the Tg total of the (A) alkali-soluble polymer is more preferably 40 ° C. or more, still more preferably 50 ° C. or more, and particularly preferably 60 ° C. or more.
  • the ratio of the (A) alkali-soluble polymer to the total solid content mass of the photosensitive resin composition is preferably in the range of 10% by mass to 90% by mass, and more preferably 30% by mass to 70% by mass. More preferably, it is 40% by mass to 60% by mass. It is preferable from the viewpoint of controlling the development time that the ratio of the (A) alkali-soluble polymer to the photosensitive resin composition is 90% by mass or less. On the other hand, it is preferable from the viewpoint of improving the edge fuse resistance that the ratio of the (A) alkali-soluble polymer to the photosensitive resin composition is 10% by mass or more.
  • the compound which has (B) an ethylenically unsaturated double bond contains the compound which has a (meth) acryloyl group in a molecule
  • the number of (meth) acryloyl groups in the compound (B) may be one or more.
  • the (B) compound having one (meth) acryloyl group for example, a compound obtained by adding (meth) acrylic acid to one end of a polyalkylene oxide, or (meth) acrylic at one end of a polyalkylene oxide
  • examples thereof include compounds obtained by adding an acid and alkyl etherifying or allyl etherifying the other end, phthalic acid compounds and the like, which are preferable from the viewpoint of peelability and flexibility of a cured film.
  • Phenoxyhexaethylene glycol mono (meth) acrylate which is a (meth) acrylate of a compound in which polyethylene glycol is added to a phenyl group
  • 4-normalnonylphenoxyheptaethylene glycol dipropylene glycol which is a (meth) acrylate of a compound obtained by adding polypropylene glycol to which 2 mol of propylene oxide is added and polyethylene glycol to which 7 mol of ethylene oxide is added to nonylphenol on average (Meth) acrylate
  • 4-normalnonylphenoxypentaethylene glycol monopropylene glycol which is a (meth) acrylate of a compound obtained by adding polypropylene glycol to which 1 mol of propylene oxide is added and polyethylene glycol to which 5 mol of ethylene oxide is added to nonylphenol on average (Meth) acrylate
  • 4-normalnonylphenoxyoctaethylene glycol (meth) acrylate e
  • a compound having two (meth) acryloyl groups in the molecule for example, a compound having a (meth) acryloyl group at both ends of the alkylene oxide chain, or an alkylene in which an ethylene oxide chain and a propylene oxide chain are bound by random or block
  • the compound etc. which have a (meth) acryloyl group in the both ends of an oxide chain can be mentioned.
  • tetraethylene glycol di (meth) acrylate pentaethylene glycol di (meth) acrylate, hexaethylene glycol di (meth) acrylate, heptaethylene glycol di (meth) acrylate, octaethylene glycol di
  • Polyethylene glycol (meth) acrylates such as (meth) acrylates, nonaethylene glycol di (meth) acrylates, decaethylene glycol di (meth) acrylates, and compounds having (meth) acryloyl groups at both ends of a 12 mol ethylene oxide chain
  • Polypropylene glycol di (meth) acrylate, polybutylene glycol di (meth) acrylate and the like can be mentioned.
  • polyalkylene oxide di (meth) acrylate compound containing an ethylene oxide group and a propylene oxide group in the compound for example, an average of 3 moles of ethylene oxide is further added to both ends of polypropylene glycol to which an average of 12 moles of propylene oxide is added.
  • diethylene glycol, and dimethacrylate of glycol in which 15 mol of ethylene oxide is further added on average to both ends of polypropylene glycol added with 18 mol of propylene oxide on average FA-023 M, FA-024 M, FA-027 M (product name) And Hitachi Chemical Co., Ltd.). These are preferable in terms of flexibility, resolution, adhesion and the like.
  • 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
  • n 1 and n 3 are each independently 1 to -(AO)-is an integer of 39
  • n1 + n3 is an integer of 2 to 40
  • n2 and n4 are each independently an integer of 0 to 29
  • n2 + n4 is an integer of 0 to 30,
  • the arrangement of repeating units of and-(BO)- may be random or block. And in the case of a block, either-(A-O)-or-(B-O)-may be on the side of the bisphenyl group.
  • the compounds represented by can be used.
  • polyethylene glycol dimethacrylate of polyethylene glycol in which ethylene oxide is added in an average of 5 moles at each end of bisphenol A polyethylene glycol in which ethylene oxide is added at an average of 2 moles in each end of bisphenol A
  • Polyethylene glycol dimethacrylate in which ethylene oxide is added on average at 1 mole each to both ends of dimethacrylate and bisphenol A is preferable in view of resolution and adhesion.
  • hetero atom examples include a halogen atom and the like, and examples of the substituent include an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an aryl group having 6 to 18 carbon atoms, and a phenacyl group Amino group, alkylamino group having 1 to 10 carbon atoms, dialkylamino group having 2 to 20 carbon atoms, nitro group, cyano group, cyano group, carbonyl group, mercapto group, alkyl mercapto group having 1 to 10 carbon atoms, aryl group, hydroxyl group A hydroxyalkyl group having 1 to 20 carbon atoms, a carboxyl group, a carboxyalkyl group having 1 to 10 carbon atoms, an acyl group having 1 to 10 carbon atoms for the alkyl group, an alkoxy group having 1 to 20 carbon atoms, Alkoxycarbonyl group having 1 to 20 carbon atoms,
  • substituents may form a condensed ring, or hydrogen atoms in these substituents may be substituted with a heteroatom such as a halogen atom.
  • the aromatic ring in the general formula (I) has a plurality of substituents, the plurality of substituents may be the same or different.
  • the compound having three or more (meth) acryloyl groups in the molecule has, as a central skeleton, three or more moles of a group to which an alkylene oxide group can be added in the molecule, and ethyleneoxy group, propyleneoxy group, etc. It can be obtained by converting an alcohol obtained by adding an alkyleneoxy group such as a butyleneoxy group to (meth) acrylate.
  • examples of the compound capable of becoming a central skeleton include glycerin, trimethylolpropane, pentaerythritol, dipentaerythritol, isocyanurate ring and the like.
  • tri (meth) acrylates such as ethoxylated glycerin tri (meth) acrylate, ethoxylated isocyanuric acid tri (meth) acrylate, pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate (for example, Trimethacrylate obtained by adding an average of 21 moles of ethylene oxide to trimethylolpropane, and trimethacrylate obtained by adding an average of 30 moles of ethylene oxide to trimethylolpropane are preferable from the viewpoint of flexibility, adhesion and suppression of bleed out), etc .; (Meth) acrylates, such as ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate ; Penta (meth) acrylate, for
  • pentaerythritol tetra (meth) acrylate is preferable.
  • the pentaerythritol tetra (meth) acrylate may be tetra (meth) acrylate or the like in which a total of 1 to 40 moles of alkylene oxide is added to the four terminals of pentaerythritol.
  • hexa (meth) acrylate in which a total of 1 to 40 moles of ethylene oxide is added to the six ends of dipentaerythritol, and a total of 1 to 20 moles of ⁇ at the six ends of dipentaerythritol Hexa (meth) acrylates to which caprolactone is added are preferred.
  • the (meth) acrylate compounds described above can be used independently or in combination.
  • the photosensitive resin composition may also contain other compounds as a compound having (B) an ethylenically unsaturated bond.
  • Other compounds include (meth) acrylate having a urethane bond, a compound obtained by reacting a polyhydric alcohol with an ⁇ , ⁇ -unsaturated carboxylic acid, and a glycidyl group-containing compound with an ⁇ , ⁇ -unsaturated carboxylic acid And compounds obtained by reaction, 1,6-hexanediol di (meth) acrylate and the like.
  • the ratio of the compound (B) having an ethylenically unsaturated double bond to the total solid content mass of the photosensitive resin composition is preferably 5% by mass to 70% by mass. It is preferable to make this proportion 5% by mass or more from the viewpoint of sensitivity, resolution and adhesion. The proportion is more preferably 20% by mass or more, and still more preferably 30% by mass or more. On the other hand, it is preferable to make this ratio 70% by mass or less from the viewpoint of suppressing the peeling delay of the edge fuse and the cured resist. It is more preferable to make this ratio 50 mass% or less.
  • a photoinitiator is a compound which polymerizes a monomer by light.
  • the photosensitive resin composition contains a compound generally known in the art as a (C) photopolymerization initiator.
  • the total content of the photopolymerization initiator (C) in the photosensitive resin composition is preferably 0.01 to 20% by mass, more preferably 0.05% to 10% by mass, and still more preferably 0.1% by mass. % To 7% by mass, particularly preferably 0.1% to 6% by mass.
  • the total content of the photopolymerization initiator (C) is preferably 0.01% by mass or more from the viewpoint of obtaining sufficient sensitivity, and light is sufficiently transmitted to the bottom of the resist to obtain good high resolution. It is preferable that it is 20 mass% or less from a viewpoint of obtaining.
  • quinones, aromatic ketones, acetophenones, acyl phosphine oxides, benzoin or benzoin ethers, dialkyl ketals, thioxanthones, dialkyl aminobenzoic acid esters, oxime esters And acridines eg, 9-phenylacridine, bisacridinylheptane, 9- (p-methylphenyl) acridine, 9- (m-methylphenyl) acridine are preferred in terms of sensitivity, resolution and adhesion
  • coumarin compounds eg, 7-diethylamino-4-methyl Coumarins are preferred in terms of
  • aromatic ketones examples include benzophenone, Michler's ketone [4,4'-bis (dimethylamino) benzophenone], 4,4'-bis (diethylamino) benzophenone, 4-methoxy-4'-dimethylaminobenzophenone Can. These can be used singly or in combination of two or more. Among these, from the viewpoint of adhesion, 4,4'-bis (diethylamino) benzophenone is preferable. Furthermore, from the viewpoint of transmittance, the content of the aromatic ketone in the photosensitive resin composition is preferably 0.01% by mass to 0.5% by mass, and more preferably 0.02% by mass to 0.3%. It is in the range of mass%.
  • hexaarylbiimidazole examples include 2- (o-chlorophenyl) -4,5-diphenylbiimidazole and 2,2 ', 5-tris- (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-dimethoxyphenyl) -biimidazole, 2,2'-bis- (2-fluorophenyl) -4,4 ' 5,5'-tetrakis- (3-methoxyphenyl) -biimidazo
  • the content of the hexaarylbisimidazole compound in the photosensitive resin composition is preferably 0.05% by mass or more from the viewpoint of improving the peeling characteristics and / or the sensitivity of the photosensitive resin composition layer. It is in the range of 7% by mass, more preferably 0.1% by mass to 6% by mass, and still more preferably 1% by mass to 5% by mass.
  • the photosensitive resin composition also contains a pyrazoline compound as a photosensitizer from the viewpoints of peeling characteristics or sensitivity, resolution, and adhesiveness of the photosensitive resin composition layer.
  • a pyrazoline compound for example, 1-phenyl-3- (4-tert-butyl-styryl) -5- (4-tert-butyl-phenyl) -pyrazoline, 1- (4- (benzoxazol-2-yl) Phenyl) -3- (4-tert-butyl-styryl) -5- (4-tert-butyl-phenyl) -pyrazoline, 1-phenyl-3- (4-biphenyl) -5- (4-tert-butyl- Phenyl) -pyrazoline, 1-phenyl-3- (4-biphenyl) -5- (4-tert-octyl-phenyl) -pyrazoline, 1-phenyl-3- (4-isopropylstyryl) -5- (4-isopropyl) Phenyl) -pyrazoline, 1-phenyl-3- (4-methoxystyryl) -5- (4-methoxyphenyl)
  • the content of the photosensitizer in the photosensitive resin composition is preferably 0.05% by mass to 5% from the viewpoint of improving the peeling characteristics and / or the sensitivity of the photosensitive resin composition layer.
  • the content is preferably in the range of 0.1% by mass to 3% by mass.
  • the photosensitive resin composition preferably further includes (D) a phenol derivative.
  • (D) phenol derivatives include p-methoxyphenol, hydroquinone, pyrogallol, tert-butyl catechol, 2,6-di-tert-butyl-p-cresol, and 2,2'-methylenebis (4-methyl-6-) tert-Butylphenol), 2,2'-methylenebis (4-ethyl-6-tert-butylphenol), 2,6-di-tert-butyl-4-methylphenol, 2,5-di-tert-amylhydroquinone, 2 , 5-Di-tert-butylhydroquinone, 2,2'-methylenebis (4-methyl-6-tert-butylphenol), bis (2-hydroxy-3-t-butyl-5-ethylphenyl) methane, triethylene glycol -Bis [3- (3-t-butyl-5-
  • the inclusion of the (D) phenol derivative is preferable from the viewpoint of suppressing the line width thickening and the deterioration of resolution when the focal position at the time of exposure shifts, and from the same viewpoint, a hindered phenol or biphenol is preferable. Further, from the same viewpoint, it is preferable that the (D) phenol derivative has two or more phenol nuclei.
  • the ratio of the (D) phenol derivative to the total solid content mass of the photosensitive resin composition is preferably 0.001 mass% to 10 mass%. This ratio is preferably 0.001% by mass or more, and 0.005% by mass or more from the viewpoint of suppressing the line width thickening and the deterioration of resolution when the focal position at the time of exposure shifts. Is more preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and particularly preferably 0.1% by mass or more. On the other hand, this ratio is preferably 10% by mass or less, more preferably 5% by mass or less, and 3% by mass or less, from the viewpoint of little decrease in sensitivity and improvement in resolution. Is more preferable, 2% by mass or less is particularly preferable, and 1.5% by mass or less is most preferable.
  • the photosensitive resin composition may optionally contain additives such as a dye, a plasticizer, an antioxidant, and a stabilizer.
  • additives listed in Japanese Patent Application Laid-Open No. 2013-156369 may be used.
  • the photosensitive resin composition may further optionally contain at least one selected from the group consisting of dyes (for example, leuco dyes, fluoran dyes and the like) and coloring substances.
  • coloring substances examples include fuchsin, phthalocyanine green, auramine base, paramagienta, crystal violet, methyl orange, Nile blue 2B, Victoria blue, malachite green (for example, Hoedagaya Chemical Co., Ltd. Eisen (registered trademark) MALACITE GREEN), Basic Blue 20, diamond green (for example, Eiden (registered trademark) DIAMOND GREEN GH manufactured by Hodogaya Chemical Co., Ltd.) can be mentioned.
  • the content of the coloring substance in the photosensitive resin composition is preferably 0.001% by mass to 1% by mass, based on 100% by mass of the total solid content of the photosensitive resin composition. Setting the content to 0.001% by mass or more is preferable from the viewpoint of improving the handleability of the photosensitive resin composition. On the other hand, making the content 1% by mass or less is preferable from the viewpoint of maintaining the storage stability of the photosensitive resin composition.
  • the photosensitive resin composition is preferable from the viewpoint of visibility because the exposed portion is colored by containing the dye, and when the inspection machine or the like reads the alignment marker for exposure, the exposed portion and the unexposed portion The larger the contrast of the image, the easier it is to recognize.
  • Preferred dyes in this regard include leuco dyes and fluoran dyes.
  • leuco dyes examples include tris (4-dimethylaminophenyl) methane [leuco crystal violet], bis (4-dimethylaminophenyl) phenylmethane [leucomalachite green] and the like.
  • leuco crystal violet is preferably used as the leuco dye, from the viewpoint of achieving good contrast.
  • the content of the leuco dye in the photosensitive resin composition is preferably 0.1% by mass to 10% by mass with respect to the total solid content mass of the photosensitive resin composition. Making this content 0.1% by mass or more is preferable from the viewpoint of improving the contrast between the exposed part and the unexposed part.
  • the content is more preferably 0.2% by mass or more, and particularly preferably 0.4% by mass or more.
  • the content is more preferably 5% by mass or less, and particularly preferably 2% by mass or less.
  • the content of the halogen compound in the photosensitive resin composition is 0.01 mass based on 100% by mass of the total solid content of the photosensitive resin composition. % To 3% by mass is preferable from the viewpoint of maintaining the storage stability of the hue in the photosensitive layer.
  • the photosensitive resin composition further contains at least one compound selected from the group consisting of radical polymerization inhibitors, benzotriazoles, and carboxybenzotriazoles in order to improve thermal stability and storage stability. It is also good.
  • radical polymerization inhibitor examples include naphthylamine, cuprous chloride, nitrosophenylhydroxyamine aluminum salt, diphenylnitrosamine and the like. In order not to impair the sensitivity of the photosensitive resin composition, nitrosophenylhydroxyamine aluminum salt is preferred.
  • benzotriazoles include 1,2,3-benzotriazole, 1-chloro-1,2,3-benzotriazole, bis (N-2-ethylhexyl) aminomethylene-1,2,3-benzotriazole, Bis (N-2-ethylhexyl) aminomethylene-1,2,3-tolyltriazole, bis (N-2-hydroxyethyl) aminomethylene-1,2,3-benzotriazole and the like can be mentioned.
  • carboxybenzotriazoles for example, 4-carboxy-1,2,3-benzotriazole, 5-carboxy-1,2,3-benzotriazole, N- (N, N-di-2-ethylhexyl) aminomethylene
  • carboxybenzotriazole N- (N, N-di-2-hydroxyethyl) aminomethylene carboxybenzotriazole, N- (N, N-di-2-ethylhexyl) aminoethylene carboxybenzotriazole and the like.
  • the total content of the radical polymerization inhibitor, benzotriazoles, and carboxybenzotriazoles is preferably 0.01% by mass or less, based on 100% by mass of the total solid content of the photosensitive resin composition. It is 3% by mass, more preferably 0.05% by mass to 1% by mass. The content of 0.01% by mass or more is preferable from the viewpoint of imparting storage stability to the photosensitive resin composition. On the other hand, setting the content to 3% by mass or less is preferable from the viewpoint of maintaining the sensitivity and suppressing the decolorization of the dye.
  • the photosensitive resin composition may further contain epoxy compounds of bisphenol A.
  • epoxy compounds of bisphenol A include, for example, compounds obtained by modifying bisphenol A with polypropylene glycol and epoxidizing the end.
  • the photosensitive resin composition may further contain a plasticizer.
  • a plasticizer for example, phthalic acid esters (eg, diethylflate etc.), o-toluenesulfonic acid amide, p-toluenesulfonic acid amide, tributyl citrate, triethyl citrate, triethyl acetyl citrate, triethyl acetyl citrate And n-propyl, acetyl tri-n-butyl acetyl citrate, polyethylene glycol, polypropylene glycol, polyethylene glycol alkyl ether, polypropylene glycol alkyl ether and the like.
  • adecanol SDX-1569, adecanol SDX-1570, adecanol SDX-1571, adecanol SDX-479 (manufactured by Asahi Denka Co., Ltd.), Newpol BP-23P, Newpol BP-3P, Newpol BP-5P, New Paul BPE-20T, New Paul BPE-60, New Paul BPE-100, New Paul BPE-180 (manufactured by Sanyo Chemical Industries, Ltd.), Uniol DB-400, Uniol DAB-800, Uniol DA-350F, Uniol DA- And compounds having a bisphenol skeleton, such as 400, Uniol DA-700 (manufactured by Nippon Oil and Fats Co., Ltd.), BA-P4U glycol, BA-P8 glycol (manufactured by Nippon Emulsifier Co., Ltd.), and the like.
  • the content of the plasticizer in the photosensitive resin composition is preferably 1% by mass to 50% by mass, more preferably 1% by mass to 30% by mass, with respect to the total solid content mass of the photosensitive resin composition. It is. It is preferable to make the content 1% by mass or more from the viewpoint of suppressing the delay of development time and imparting flexibility to the cured film. On the other hand, making the content 50% by mass or less is preferable from the viewpoint of suppressing insufficient curing and cold flow.
  • the photosensitive resin composition can be dissolved in a solvent and used in the form of a photosensitive resin composition preparation liquid for producing a photosensitive resin laminate.
  • the solvent include ketones and alcohols.
  • the ketones are represented by methyl ethyl ketone (MEK) and acetone.
  • the alcohols are represented by methanol, ethanol and isopropanol.
  • the solvent is used in an amount such that the viscosity at 25 ° C. of the photosensitive resin composition preparation liquid applied onto the support layer is 500 mPa ⁇ s to 4,000 mPa ⁇ s during the production of the photosensitive resin laminate. Preferably, it is added to the resin composition.
  • the method comprises a laminating step of laminating a photosensitive resin laminate on a substrate, an exposing step of exposing a photosensitive resin composition layer of the photosensitive resin laminate, and developing an unexposed portion of the photosensitive resin composition layer. It can include a developing step to be removed.
  • the resist pattern for example, printed wiring board, semiconductor element, printing plate, liquid crystal display panel, flexible substrate, lead frame substrate, substrate for COF (chip on film), substrate for semiconductor package, transparent electrode for liquid crystal, TFT for liquid crystal And wiring patterns, electrodes for PDP (plasma display panel) and the like.
  • the photosensitive resin laminate of the present embodiment has an advantage of avoiding the resist protrusions well, and for example, the line width / space width is 20/20 ( ⁇ m or less) or the line width / space width is 10 /. It is particularly useful for the formation of fine wiring of less than 10 ( ⁇ m).
  • the line width / space width ( ⁇ m) to which the photosensitive resin laminate of the present embodiment can be applied is not particularly limited, and for example, 15/15 ( ⁇ m) or less, preferably 10/10 ( ⁇ m) or less, and further Preferably it is 9.5 / 9.5 ( ⁇ m) or less, particularly preferably 9.0 / 9.0 ( ⁇ m) or less.
  • the lower limit value of the line width / space width ( ⁇ m) is not particularly limited, but may be 3/3 ( ⁇ m) or more, 4/4 ( ⁇ m) or more, or 5/5 ( ⁇ m) or more.
  • the photosensitive resin laminate of the present embodiment is particularly useful for wiring formation by the semi-additive method (SAP) from the above advantages.
  • SAP method can be carried out by a conventional method, and for example, wiring can be formed by a known plating method using a laminate of an insulating resin layer and a copper layer (for example, an electroless copper plating layer containing palladium as a catalyst).
  • a method of manufacturing a printed wiring board will be described as follows.
  • the printed wiring board is manufactured through the following steps.
  • the material of the substrate include copper, stainless steel (SUS), glass, indium tin oxide (ITO) and the like.
  • the photosensitive resin composition layer may be laminated only on one side of the substrate surface, or may be laminated on both sides as needed.
  • the heating temperature during lamination is generally 40.degree. C. to 160.degree.
  • the adhesion of the obtained resist pattern to the substrate can be improved by performing the thermocompression bonding twice or more at the time of lamination.
  • a two-stage laminator provided with dual rolls may be used, or the laminate of the substrate and the photosensitive resin composition layer may be crimped by being repeatedly passed through the roll several times.
  • Exposure step In this step, a mask film having a desired wiring pattern is brought into close contact with the support layer and an exposure method is performed using an active light source, an exposure method by direct drawing of a drawing pattern which is a desired wiring pattern, The photosensitive resin composition layer is exposed by an exposure method by projecting an image of a photomask through a lens.
  • the advantage of the photosensitive resin composition according to the present embodiment is more remarkable in an exposure method by direct drawing of a drawing pattern or an exposure method in which an image of a photomask is projected through a lens, and exposure by direct drawing of a drawing pattern It is particularly remarkable in the method.
  • 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 in accordance with the characteristics of the photosensitive resin composition layer, and an aqueous Na 2 CO 3 solution having a concentration of about 0.2% by mass to about 2% by mass and a temperature of about 20 ° C to about 40 ° C is used. preferable.
  • a resist pattern can be obtained through the above steps (1) to (3). After these steps, optionally, a heating step of about 100 ° C. to about 300 ° C. can also be performed. By performing this heating step, it is possible to further improve the chemical resistance. For heating, a heating furnace of a hot air, infrared or far infrared type can be used. Also, this heating process may be performed after the exposure process.
  • a substrate surface for example, a copper surface of a copper clad laminate exposed by development is etched or plated to manufacture a conductor pattern.
  • the resist pattern is peeled from the substrate by an aqueous solution having a stronger alkalinity than the developer.
  • the aqueous alkaline solution for peeling is not particularly limited, but an aqueous solution of NaOH or KOH having a concentration of about 2% by mass to about 5% by mass and a temperature of about 40 to about 70 ° C. is preferable.
  • a small amount of water-soluble solvent can also be added to the stripping solution.
  • the photosensitive resin laminate of the present embodiment is a resist pattern of a printed wiring board, a flexible substrate, a lead frame substrate, a substrate for COF, a substrate for semiconductor package, a transparent electrode for liquid crystal, a wiring for TFT for liquid crystal, an electrode for PDP, etc. Or it is a photosensitive resin laminated body suitable for manufacture of a conductor pattern.
  • Examples 1 to 3 and Comparative Example 1 Preparation of photosensitive resin composition
  • A 47 parts by mass of methacrylic acid / benzyl methacrylate copolymer (polymerization ratio 20/80 (mass ratio), acid equivalent 430, weight average molecular weight 50,000) as an alkali soluble polymer
  • B 0.1 parts by mass of 4,4′-bis (diethylamino) benzophenone and 3 parts by mass of 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer as a photopolymerization initiator
  • C 14 parts by mass of tetraacrylate in which an average of 15 moles of ethylene oxide is added to four ends of pentaerythritol as a compound having an ethylenic double bond, and 0.05 parts by mass of diamond green and leuco as a dye
  • a photosensitive resin composition was prepared by dissolving 0.3 parts by mass of crystal violet in a solvent.
  • PET polyethylene terephthalate
  • the total area ratio of the optically abnormal area in each support film is as described in Table 1.
  • the number of particulates in the support film was adjusted by the fineness of the filter and the number of times the material constituting the support film was passed through the filter and the number of particulates added.
  • the adjustment of the area of the optically abnormal area is carried out by thermocompression bonding of the film under the conditions of 180 to 250 ° C. as appropriate after biaxial stretching of the PET film. It was carried out by eliminating the region (that is, the cavity or the region having different orientation or crystallinity).
  • the photosensitive resin composition prepared above is coated on one surface of a polyethylene terephthalate (PET) support film (12 ⁇ m in thickness) with a bar coater, and it is 2.5 in a dryer at 95 ° C.
  • a photosensitive resin laminate was obtained by drying for a minute to form a photosensitive resin composition layer.
  • the dry thickness of the photosensitive resin composition layer was 20 ⁇ m.
  • a 19 ⁇ m thick polyethylene film (manufactured by Tamapoly Co., Ltd., GF-818) is laminated as a protective layer to form a photosensitive resin laminate. I got a body.
  • a 0.4 mm thick copper-clad laminate obtained by laminating 18 ⁇ m rolled copper foil is treated with a soft etching agent (CPE-900, manufactured by Hishie Kagaku Co., Ltd.), and 10 mass% H 2 SO The substrate surface was washed with 4 .
  • a soft etching agent CPE-900, manufactured by Hishie Kagaku Co., Ltd.
  • the photosensitive resin laminate While peeling off the polyethylene film (protective layer) of the photosensitive resin laminate, the photosensitive resin laminate is rolled with a hot roll laminator (AL-700 manufactured by Asahi Kasei Co., Ltd.) on a copper-clad laminate preheated to 60 ° C. It laminated at the temperature of 105 degreeC. The air pressure was 0.35 MPa, and the laminating speed was 1.5 m / min.
  • a hot roll laminator AL-700 manufactured by Asahi Kasei Co., Ltd.
  • Exposure was carried out with a direct drawing exposure apparatus (FDi-3 manufactured by Oak Manufacturing Co., Ltd., main wavelength 405 ⁇ 5 nm) using a stofer 41-step tablet or a mask pattern for predetermined direct imaging (DI) exposure.
  • the exposure was performed with an exposure amount such that the maximum number of remaining film steps was 14 when exposed and developed using the Stoffer 41-step tablet as a mask.
  • a polarizing filter (OLS4000-QWP) was inserted above the objective lens of the incident-type laser microscope (OLS-4100 manufactured by Olympus).
  • OLS-4100 manufactured by Olympus
  • a support film sample cut to 30 mm ⁇ 30 mm was suctioned and fixed horizontally on a stage of a laser microscope using a porous adsorption plate (65F-HG manufactured by Universal Giken) and a vacuum pump.
  • the suction-fixed support film was observed with a 50 ⁇ laser light amount 60 (laser wavelength is 405 nm) of an objective lens.
  • the difference in light amount between the pixel of the maximum light amount and the pixel of the minimum light amount in the measured image was divided into 4096 gradations (the maximum light amount is 4095 and the minimum light amount is 0).
  • a histogram horizontal axis: gradation of light quantity (minimum value 0, maximum value 4095), vertical axis: number of pixels) graphing the light quantity distribution of the pixels in the image was created.
  • the measured image is binarized using the gradation obtained by adding 400 gradations from the value of the larger one of the two base values in the created histogram as the threshold value, and the areas of the pixels whose light amounts are larger than the threshold are summed.
  • the total area thereof is the total area of the optical anomaly region.
  • the ratio of the total area of the optically abnormal area portion to the measurement area is calculated.
  • Examples 4 to 6 and Comparative Example 2 Polyethylene terephthalate (PET) was produced as a support film of each of Examples 4 to 6 and Comparative Example 2.
  • the number of microparticles in each support film is as described in Table 2.
  • the number of particulates in the support film was adjusted by the fineness of the filter and the number of times the material constituting the support film was passed through the filter and the number of particulates added.
  • the film is subjected to thermocompression bonding treatment again under the conditions of 180 to 250 ° C. after biaxial stretching of the PET film, so that an optically abnormal area around the fine particles (that is, a cavity or an area having different orientation or crystallinity) Disappeared.
  • fine-particles was adjusted by changing the refractive index of microparticles
  • the photosensitive resin laminate of the present invention avoids resist pattern defects (protrusions) caused by foreign matter on the support film, and gives a good resist pattern shape. Therefore, a printed wiring board, a flexible substrate, a lead frame substrate, COF (COF It can be suitably used for manufacturing conductor patterns such as a substrate for chip on film, a substrate for semiconductor package, a transparent electrode for liquid crystal, a wiring for TFT for liquid crystal, and an electrode for PDP (plasma display panel).
  • conductor patterns such as a substrate for chip on film, a substrate for semiconductor package, a transparent electrode for liquid crystal, a wiring for TFT for liquid crystal, and an electrode for PDP (plasma display panel).

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PCT/JP2018/046833 2017-12-20 2018-12-19 感光性樹脂積層体 WO2019124452A1 (ja)

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WO2021220981A1 (ja) * 2020-05-01 2021-11-04 富士フイルム株式会社 感光性転写材料、樹脂パターンの製造方法、回路配線の製造方法及びタッチパネルの製造方法、並びに、ポリエチレンテレフタレートフィルム

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