WO2022019046A1 - 感光性エレメント、レジストパターンの形成方法及びプリント配線板の製造方法 - Google Patents

感光性エレメント、レジストパターンの形成方法及びプリント配線板の製造方法 Download PDF

Info

Publication number
WO2022019046A1
WO2022019046A1 PCT/JP2021/024156 JP2021024156W WO2022019046A1 WO 2022019046 A1 WO2022019046 A1 WO 2022019046A1 JP 2021024156 W JP2021024156 W JP 2021024156W WO 2022019046 A1 WO2022019046 A1 WO 2022019046A1
Authority
WO
WIPO (PCT)
Prior art keywords
barrier layer
mass
layer
photosensitive
meth
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2021/024156
Other languages
English (en)
French (fr)
Japanese (ja)
Inventor
陽介 賀口
博史 小野
壮和 粂
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Resonac Corp
Original Assignee
Showa Denko Materials Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Showa Denko Materials Co Ltd filed Critical Showa Denko Materials Co Ltd
Priority to CN202180047105.0A priority Critical patent/CN115867864A/zh
Priority to KR1020227045886A priority patent/KR102870994B1/ko
Priority to JP2022538654A priority patent/JPWO2022019046A1/ja
Publication of WO2022019046A1 publication Critical patent/WO2022019046A1/ja
Anticipated expiration legal-status Critical
Priority to JP2026009778A priority patent/JP2026063359A/ja
Ceased legal-status Critical Current

Links

Images

Classifications

    • 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
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/11—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having cover layers or intermediate layers, e.g. subbing layers
    • 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 disclosure relates to a method for forming a photosensitive element, a resist pattern, and a method for manufacturing a printed wiring board.
  • a photosensitive resin composition and a layer formed by using a photosensitive resin composition on a support film as a resist material used for etching treatment, plating treatment, etc. (hereinafter referred to as , Also referred to as a "photosensitive layer”) is widely used.
  • the printed wiring board is manufactured by the following procedure, for example, using the above-mentioned photosensitive element. That is, first, the photosensitive layer of the photosensitive element is laminated on a circuit-forming substrate such as a copper-clad laminate. At this time, the surface of the photosensitive layer opposite to the surface in contact with the support film is laminated so as to be in close contact with the surface of the circuit forming substrate that forms the circuit. Further, laminating is performed, for example, by heat-pressing a photosensitive layer on a circuit-forming substrate (normal pressure laminating method).
  • a desired region of the photosensitive layer is exposed via the support film to generate radicals.
  • the generated radicals pass through several reaction pathways and contribute to the cross-linking reaction (photo-curing reaction) of the photopolymerizable compound.
  • the uncured portion of the photosensitive layer is dissolved or dispersed and removed with a developing solution to form a resist pattern.
  • an etching treatment or a plating treatment is performed to form a conductor pattern, and finally the photocured portion (resist pattern) of the photosensitive layer is peeled off (removed).
  • the coating stability of the barrier layer is not always sufficient, and cissing is likely to occur when the barrier layer is formed on the support film, and the surface of the obtained barrier layer is defective (for example, a part of the barrier layer has a dent in the coating film).
  • the base is exposed due to the occurrence, etc.).
  • Defects on the surface of the barrier layer cause exposure defects, which causes resist defects.
  • the barrier layer has strong adhesion to the support film, and when the support film is peeled off, a part of the barrier layer may be peeled off together with the support film while being attached to the support film, and the barrier layer may be damaged.
  • the present disclosure has been made in view of the above-mentioned problems of the prior art, and is a photosensitive element and a resist that can reduce the number of defects on the surface of the barrier layer and suppress the defect of the barrier layer when the support film is peeled off. It is an object of the present invention to provide a method for forming a pattern and a method for manufacturing a printed wiring board.
  • the present disclosure provides a photosensitive element comprising a support film, a barrier layer, and a photosensitive layer in this order, wherein the barrier layer contains a leveling agent. offer.
  • the barrier layer contains a leveling agent, repelling can be suppressed due to a decrease in surface tension, the number of defects on the surface can be reduced, and the adhesion between the barrier layer and the support film can be reduced. It is possible to prevent the barrier layer from being damaged when the support film is peeled off.
  • the leveling agent has a copolymer weight derived from at least one selected from the group consisting of butyl (meth) acrylate, isobutyl (meth) acrylate, and terminal methoxy group EO-modified (meth) acrylate. May include coalescence.
  • the leveling agent contains the above-mentioned copolymer, the number of surface defects of the barrier layer can be further reduced, and the defect of the barrier layer when the support film is peeled off can be more sufficiently suppressed.
  • the barrier layer may contain polyvinyl alcohol.
  • the gas barrier property of the barrier layer can be further improved, and the deactivation of radicals generated by the active light rays used for exposure can be further suppressed.
  • the thickness of the barrier layer may be 2 to 12 ⁇ m.
  • the photosensitive layer may contain a bisphenol A type di (meth) acrylate compound.
  • the photosensitive layer is composed of 2,2-bis (4-((meth) acryloxipentethoxy) phenyl) propane and / or 2,2-bis (4-((meth) acryloxidiethoxy) phenyl) propane. May include.
  • the present disclosure also includes a step of arranging a photosensitive layer, a barrier layer, and a supporting film on a substrate in this order from the substrate side using the photosensitive element of the present disclosure, and removing the supporting film.
  • a method for forming a resist pattern which comprises a step of exposing the photosensitive layer with an active light via a barrier layer and a step of removing the uncured portion of the photosensitive layer and the barrier layer from the substrate. According to such a resist pattern forming method, since the resist pattern is formed by using the photosensitive element of the present disclosure, it is possible to form a resist pattern having few defects.
  • the present disclosure further provides a method for manufacturing a printed wiring board, which comprises a step of forming a conductor pattern by etching or plating a substrate on which a resist pattern is formed by the method for forming a resist pattern of the present disclosure.
  • a method for manufacturing a printed wiring board since the resist pattern is formed by the resist pattern forming method of the present disclosure, a resist pattern with few defects can be formed, which is suitable for increasing the density of the printed wiring board.
  • a method for manufacturing a printed wiring board can be provided.
  • a photosensitive element capable of reducing the number of defects on the surface of the barrier layer and suppressing the defect of the barrier layer when the support film is peeled off, a method for forming a resist pattern, and a method for manufacturing a printed wiring board. can do.
  • (meth) acrylic acid means at least one of acrylic acid and methacrylic acid corresponding thereto.
  • the materials exemplified below may be used alone or in combination of two or more.
  • the content of each component in the composition means the total amount of the plurality of substances present in the composition when a plurality of substances corresponding to each component are present in the composition, unless otherwise specified.
  • process is used not only as an independent process but also as long as the intended action of the process is achieved even if it cannot be clearly distinguished from other processes. included.
  • the numerical range indicated by using "-" in the present specification indicates a range including the numerical values before and after "-" as the minimum value and the maximum value, respectively.
  • the upper limit value or the lower limit value of the numerical range of one step may be replaced with the upper limit value or the lower limit value of the numerical range of another step.
  • the upper limit value or the lower limit value of the numerical range may be replaced with the value shown in the examples.
  • the term "layer” includes not only a structure having a shape formed on the entire surface but also a structure having a shape partially formed when observed as a plan view.
  • the photosensitive element 1 of the present embodiment includes a support film 2, a barrier layer 3, and a photosensitive layer 4 in this order, and may further include other layers such as a protective layer 5. good. Further, the barrier layer 3 contains a leveling agent.
  • each layer of the photosensitive element according to the present embodiment will be described in detail.
  • the support film of the present embodiment can be used without particular limitation.
  • the support film include polyester films such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT) and polyethylene-2,6-naphthalate (PEN), and polyolefin films such as polypropylene and polyethylene.
  • PET polyethylene terephthalate
  • PBT polybutylene terephthalate
  • PEN polyethylene-2,6-naphthalate
  • polyolefin films such as polypropylene and polyethylene.
  • a polyester film may be used.
  • the mechanical strength and heat resistance of the support film can be improved.
  • defects such as wrinkles of the barrier layer generated when the barrier layer is formed on the support film can be suppressed, and workability tends to be improved.
  • a polyester film containing particles (lubricant or the like) may be used from the viewpoint of suppressing the occurrence of minute omission of the resist pattern.
  • a barrier layer may be formed on the surface having the particles (lubricant or the like).
  • examples of such a polyester film include a polyester film in which particles (lubricant, etc.) are kneaded, a polyester film having a layer containing particles (lubricant, etc.) on both sides, or particles (lubricant, etc.) on one side. ) May be used to form a layer containing the polyester film.
  • the support film may be a single layer or a multilayer.
  • a method of adding particles such as lubricant to the support film for example, a method of kneading particles (lubricant, etc.) into the support film, a layer containing particles (lubricant, etc.) on the support film, roll coating, and flow.
  • a method of forming by using a known method such as a coat, a spray coat, a curtain flow coat, a dip coat, and a slit die coat.
  • haze means the degree of cloudiness.
  • the haze in the present disclosure refers to a value measured using a commercially available turbidity meter (turbidity meter) in accordance with the method specified in JIS K7105. The haze can be measured with a commercially available turbidity meter such as NDH-5000 (manufactured by Nippon Denshoku Kogyo Co., Ltd., trade name).
  • the support film a commercially available general industrial film that can be used as a support film for the photosensitive element may be obtained and appropriately processed and used.
  • PET films "FB-40", “QS69", “FS-31” (manufactured by Toray Industries, Inc., product name), "A4100", “A1517” (manufactured by Toyobo Co., Ltd., Product name), "G2H” (manufactured by Teijin DuPont Film Co., Ltd., product name), "R-705G” (manufactured by Mitsubishi Chemical Co., Ltd., product name) and the like.
  • the thickness of the support film may be 1 to 200 ⁇ m, 1 to 100 ⁇ m, 1 to 60 ⁇ m, 5 to 60 ⁇ m, 10 to 60 ⁇ m, 10 to 50 ⁇ m, 10 to 40 ⁇ m, 10 to 30 ⁇ m, or 10 to 25 ⁇ m.
  • the thickness of the support film is 1 ⁇ m or more, it tends to be possible to prevent the support film from being torn when the support film is peeled off. Further, when the thickness of the support film is 200 ⁇ m or less, it tends to be easy to obtain economic benefits.
  • the photosensitive element of the present embodiment includes a barrier layer between the support film and the photosensitive layer.
  • the barrier layer also contains a leveling agent.
  • the barrier layer may be a layer formed by using the resin composition for forming the barrier layer.
  • the resin composition for forming a barrier layer of the present embodiment contains a leveling agent, and may further contain a water-soluble resin and water. Further, the barrier layer may have water solubility or solubility in a developing solution. From the viewpoint of further improving the gas barrier property of the barrier layer, the adhesive force between the support film and the barrier layer may be smaller than the adhesive force between the barrier layer and the photosensitive layer. In this case, when the support film is peeled from the photosensitive element, unintentional peeling between the barrier layer and the photosensitive layer can be suppressed.
  • the leveling agent is oriented on the surface of the coating film and equalizes the tension on the surface of the coating film.
  • the leveling agent include acrylic polymers, vinyl-based, silicone-based, and fluorine-based agents.
  • the leveling agent is preferably an acrylic polymer from the viewpoint of transferability to a photosensitive element and solubility in a developing solution. The acrylic polymer keeps the adhesion between the barrier layer and the support film in an appropriate range, and makes the adhesive force between the support film and the barrier layer smaller than the adhesive force between the barrier layer and the photosensitive layer, while unintentional between the layers.
  • a polymer having a structural unit derived from and a polymer having a structural unit derived from butyl (meth) acrylate, isobutyl (meth) acrylate, and terminal methoxy group EO-modified (meth) acrylate. It is more preferable to include it.
  • the content of each structural unit constituting the acrylic polymer may be, for example, in the following range based on the total amount of the structural units.
  • the content of the structural unit derived from butyl (meth) acrylate is 2 from the viewpoint of further reducing the number of defects on the surface of the barrier layer and further suppressing the defect of the barrier layer when the support film is peeled off. It may be up to 20% by mass, 5 to 15% by mass, or 5 to 10% by mass.
  • the content of the structural unit derived from isobutyl (meth) acrylate is 40 from the viewpoint of further reducing the number of defects on the surface of the barrier layer and further suppressing the defect of the barrier layer when the support film is peeled off.
  • the content of the structural unit derived from the terminal methoxy group EO-modified (meth) acrylate further reduces the number of defects on the surface of the barrier layer and further suppresses the defect of the barrier layer when the support film is peeled off. From the viewpoint, it may be 15 to 45% by mass, 20 to 40% by mass, or 25 to 35% by mass.
  • the weight average molecular weight of the acrylic polymer is 10,000 to 40 from the viewpoint of further reducing the number of defects on the surface of the barrier layer and further suppressing the defect of the barrier layer when the support film is peeled off. It may be 000 or 10,000 to 20,000.
  • the content of the leveling agent in the barrier layer is based on the total solid content of the barrier layer from the viewpoint of further reducing the number of defects on the surface of the barrier layer and further suppressing the defect of the barrier layer when the support film is peeled off. , 0.05 to 1.0% by mass, 0.1 to 0.7% by mass, or 0.2 to 0.5% by mass.
  • the barrier layer may contain a water-soluble resin.
  • water soluble resin means a resin solubility is less than 5g / 100mL-C 6 H 14 against hexanes 100mL of 25 ° C.. This solubility can be calculated by mixing hexane at 25 ° C. with a dried water-soluble resin and examining the presence or absence of cloudiness. Specifically, sample 1 obtained by putting a mixed solution of dried water-soluble resin A (g) and 100 mL of hexane in a colorless and transparent glass container with a ground glass stopper, and 100 mL of hexane only are put. Prepare each of the obtained samples 2.
  • water-soluble resin examples include polyvinyl alcohol, polyvinylpyrrolidone, and water-soluble polyimides.
  • the water-soluble resin may contain polyvinyl alcohol from the viewpoint of further improving the gas barrier property of the barrier layer and further suppressing the deactivation of radicals generated by the active light rays used for exposure.
  • Polyvinyl alcohol can be obtained, for example, by saponifying polyvinyl acetate obtained by polymerizing vinyl acetate.
  • the saponification degree of polyvinyl alcohol used in this embodiment may be 50 mol% or more, 70 mol% or more, or 80 mol% or more. The upper limit of the saponification degree is 100 mol%.
  • the "saponification degree" in the present specification means a value measured in accordance with JIS K 6726 (1994) (polyvinyl alcohol test method) specified in Japanese Industrial Standards.
  • polyvinyl alcohol two or more kinds having different saponification degree, viscosity, degree of polymerization, modified kind and the like may be used in combination.
  • the average degree of polymerization of polyvinyl alcohol may be 300 to 5000, 300 to 3500, or 300 to 2000.
  • the water-soluble resin may be used alone or in combination of two or more.
  • the water-soluble resin may contain, for example, polyvinyl alcohol and polyvinylpyrrolidone.
  • the mass ratio of polyvinyl alcohol to polyvinylpyrrolidone (PVA: PVP) may be 40:60 to 90:10, 50:50 to 90:10, or 60:40 to 90:10.
  • the content of the water-soluble resin in the resin composition for forming the barrier layer of the present embodiment is 50 to 300 parts by mass, 60 to 250 parts by mass, and 70 to 200 parts by mass with respect to 500 parts by mass of water from the viewpoint of improving the gas barrier property. It may be parts by mass, 80 to 150 parts by mass, or 80 to 125 parts by mass.
  • the content of the water-soluble resin in the barrier layer is 99 based on the total solid content of the barrier layer from the viewpoint of improving the gas barrier property, the peelability between the support film and the barrier layer, and the solubility in the developing solution. It may be 0.0 to 99.95% by mass, 99.3 to 99.9% by mass, or 99.5 to 99.8% by mass.
  • the barrier layer may contain an ultraviolet absorber.
  • the ultraviolet absorber (UV absorber) is a compound having a light absorption band in the wavelength range of 300 nm to 400 nm.
  • the ultraviolet absorber may be water-soluble.
  • the ultraviolet absorber may have a maximum absorption wavelength in the wavelength range of 250 nm to 500 nm from the viewpoint of further improving the resolution. By containing these ultraviolet absorbers, the resolution can be improved.
  • the i-ray absorption rate of the ultraviolet absorber may be 5 to 95%, 10 to 90%, or 15 to 75%.
  • the i-ray absorption rate can be measured by an ultraviolet-visible spectrophotometer.
  • the above-mentioned ultraviolet absorber may be used alone or in combination of two or more. Further, the solubility of the ultraviolet absorber in water at 20 ° C. is 0.01 g / 100 mL-H 2 O or more and 0.1 g / 100 mL-H 2 from the viewpoint of suppressing aggregation and precipitation of the ultraviolet absorber in the barrier layer. It may be O or more, or 1 g / 100 mL-H 2 O or more.
  • Examples of the ultraviolet absorber include oxybenzophenone compounds, triazole compounds, benzotriazole compounds, salicylic acid ester compounds, benzophenone compounds, diphenyl acrylate compounds, cyanoacrylate compounds, diphenyl cyanoacrylate compounds, iron or nickel complex salt compounds and the like.
  • an oxybenzophenone compound and a benzophenone compound are preferable, a benzophenone sulfonic acid compound is more preferable, and an oxybenzophenone sulfonic acid compound is further preferable, from the viewpoint of further improving the resolution.
  • the "benzophenone sulfonic acid compound” is a compound having a sulfo group in the benzophenone compound, and the benzophenone sulfonic acid compound may be a hydrate. These compounds have a hydrophilic sulfo group in the benzophenone skeleton, which makes the benzophenone skeleton more compatible with the resist, while the sulfo group has a higher affinity with the barrier layer, resulting in resolution and removal of the barrier layer. I presume that it is possible to achieve both sex. Further, among the oxybenzophenone compounds, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid hydrate represented by the following formula (1) is preferable.
  • the barrier layer of the present embodiment may have an absorbance of 0.01 to 2.0 or 0.1 to 1.0 for light having a wavelength of 365 nm.
  • the absorbance of the barrier layer can be measured using, for example, a UV spectrophotometer (Spectrophotometer U-3310, manufactured by Hitachi, Ltd.).
  • a laminated film having a barrier layer of an arbitrary thickness formed on the support film is placed on the measurement side, the support film is placed on the reference side, and the wavelength of 300 to 700 nm is continuously measured by the absorbance mode, and the value at the wavelength of 365 nm is measured. It is done by reading.
  • the resin composition for forming a barrier layer of the present embodiment may contain alcohols having 3 or more carbon atoms.
  • the alcohols having 3 or more carbon atoms may be monohydric alcohols or polyhydric alcohols (excluding the plasticizer of the polyhydric alcohol compound described later).
  • Alcohols having 3 or more carbon atoms may contain at least one selected from the group consisting of the compounds represented by the following chemical formulas (2) to (4) and the compounds represented by the following general formula (5). good.
  • R 11 represents an alkyl group and R 12 represents an alkylene group.
  • the sum of the carbon atoms of the group of R 11 and the group of R 12 is 3 or more.
  • the sum of the carbon atoms of the group of R 11 and the group of R 12 may be 10 or less, 8 or less, 7 or less, or 5 or less from the viewpoint of further improving the affinity with water.
  • the alkyl group represented by R 11 may be an alkyl group having 1 to 4 carbon atoms
  • the alkylene group represented by R 12 may be an alkylene group having 1 to 3 carbon atoms.
  • the alcohol having 3 or more carbon atoms represented by the general formula (5) may be 2-butoxy-ethanol or 1-methoxy-2-propanol.
  • the alcohols having 3 or more carbon atoms may be used alone or in combination of two or more. Further, the solubility of alcohols having 3 or more carbon atoms in water at 20 ° C. is 300 mL / 100 mL-H 2 O or more, 500 mL / 100 mL-H 2 O or more, or 500 mL / 100 mL-H 2 O or more, from the viewpoint of further suppressing the layer separation of the barrier layer. It may be 1000 mL / 100 mL-H 2 O or more.
  • the "solubility of alcohols having 3 or more carbon atoms in water at 20 ° C.” in the present specification can be calculated by mixing the alcohols with water at 20 ° C. and examining the presence or absence of cloudiness. Specifically, it was obtained by putting Sample 3 obtained by putting a mixed solution of the alcohols AmL and 100 mL of water into a colorless and transparent glass container with a rubbed glass stopper, and putting only water (100 mL) into it. Prepare each sample 4. Next, after sufficiently shaking each of the sample 3 and the sample 4 in the glass container, it is confirmed that the bubbles have disappeared.
  • both containers are arranged side by side under diffuse daylight or equivalent light, and the state of the liquid in the sample 3 and the state of the liquid in the sample 4 are compared.
  • the sample 3 and the sample 4 are compared, and the addition amount AmL of the alcohols when the sample 3 is observed to be more cloudy is defined as the solubility of the alcohols in water at 20 ° C.
  • the content of alcohols having 3 or more carbon atoms in the resin composition for forming a barrier layer of the present embodiment may be 100 to 500 parts by mass or 125 to 450 parts by mass with respect to 500 parts by mass of water. ..
  • this content is 100 parts by mass or more, the peelability between the formed barrier layer and the support film tends to be improved, and when it is 500 parts by mass or less, the solubility of the water-soluble resin is improved and the barrier. Layers tend to be easier to form.
  • the content of alcohols having 3 or more carbon atoms in the barrier layer of the present embodiment is more than 0% by mass and 2 based on the total amount of the barrier layer (total solid content of the resin composition for forming the barrier layer forming the barrier layer). It may be 0.0% by mass or less, 0.001 to 2.0% by mass, or 0.005 to 1.0% by mass. When this content is 2.0% by mass or less, the diffusion of alcohols in a later step tends to be suppressed, and when it is 0.001% by mass or more, the barrier layer and the support film are peeled off. There is a tendency for sex to improve.
  • the resin composition for forming a barrier layer of the present embodiment may contain alcohols having less than 3 carbon atoms.
  • the content thereof may be 125 to 375 parts by mass or 150 to 325 parts by mass with respect to 500 parts by mass of water.
  • this content is 125 parts by mass or more, the solubility of the water-soluble resin is improved and the barrier layer tends to be easily formed, and when it is 375 parts by mass or less, it supports the formed barrier layer. The peelability from the film tends to be improved.
  • the content of alcohols having less than 3 carbon atoms in the barrier layer of the present embodiment is based on the total amount of alcohols having 3 or more carbon atoms in the barrier layer from the viewpoint of improving the peelability between the barrier layer and the support film. Even if it is 0.1 to 10% by mass (that is, the amount of alcohols having less than 3 carbon atoms is 0.1 to 10 parts by mass with respect to 100 parts by mass of the total amount of alcohols having 3 or more carbon atoms). good.
  • the barrier layer and the resin composition for forming the barrier layer of the present embodiment may contain known additives such as a plasticizer and a surfactant as long as the effects of the present disclosure are not impaired. Further, a peeling accelerator may be contained as long as the effect of the present disclosure is not impaired.
  • the barrier layer in the photosensitive element of the present embodiment can be formed, for example, by applying the resin composition for forming the barrier layer of the present embodiment on a support film and drying it.
  • the resin composition for forming a barrier layer of the present embodiment is applied on the support film, the leveling agent tends to be unevenly distributed on the surface side of the support film in the coating film.
  • the surface tension of the resin composition for forming the barrier layer is likely to decrease, and repelling is likely to be suppressed.
  • the leveling agent is unevenly distributed on the surface side of the support film, so that the adhesive force between the support film and the barrier layer tends to decrease.
  • the thickness of the barrier layer is not particularly limited.
  • the thickness of the barrier layer may be 12 ⁇ m or less, 10 ⁇ m or less, 8 ⁇ m or less, 7 ⁇ m or less, or 6 ⁇ m or less from the viewpoint of easy removal of the barrier layer.
  • the thickness of the barrier layer may be 1.0 ⁇ m or more, 1.5 ⁇ m or more, 2 ⁇ m or more, 3 ⁇ m or more, or 4 ⁇ m or more from the viewpoint of ease of forming the barrier layer and resolution. Further, from the viewpoint of suppressing migration of the barrier layer, the thickness of the barrier layer may be 2 ⁇ m or more, 3 ⁇ m or more, or 4 ⁇ m or more.
  • the photosensitive layer of this embodiment is a layer formed by using a photosensitive resin composition described later.
  • the photosensitive resin composition can be used according to a desired purpose as long as the properties change (for example, photocuring) when irradiated with light, and the photosensitive resin composition may be a negative type or a positive type. May be good.
  • the photosensitive resin composition may contain (A) a binder polymer, (B) a photopolymerizable compound, and (C) a photopolymerization initiator. Further, if necessary, (D) a photosensitizer, (E) a polymerization inhibitor or other components may be contained.
  • each component used in the photosensitive resin composition in the present embodiment will be described in more detail.
  • the (A) binder polymer (hereinafter, also referred to as “component (A)”) can be produced, for example, by radically polymerizing a polymerizable monomer.
  • the polymerizable monomer include a polymerizable styrene derivative substituted with an ⁇ -position or an aromatic ring such as styrene, vinyltoluene and ⁇ -methylstyrene, acrylamide such as diacetoneacrylamide, acrylic nitrile, and vinyl.
  • Vinyl alcohol ethers such as -n-butyl ether, (meth) acrylic acid alkyl ester, (meth) acrylic acid benzyl ester such as benzyl methacrylate, (meth) acrylic acid tetrahydrofurfuryl ester, (meth) acrylic acid dimethylaminoethyl Estel, (meth) acrylic acid diethylaminoethyl ester, (meth) acrylic acid glycidyl ester, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, ( Meta) Acrylic acid, ⁇ -bromoacrylic acid, ⁇ -chloracrylic acid, ⁇ -frill (meth) acrylic acid, ⁇ -styryl (meth) acrylic acid, maleic acid, maleic acid anhydride, monomethyl maleate, monoethyl maleate , Maleic acid monoester such as monoisopropy
  • a (meth) acrylic acid alkyl ester may be contained from the viewpoint of improving plasticity.
  • examples of the (meth) acrylic acid alkyl ester include compounds represented by the following general formula (II) and compounds in which the alkyl group of these compounds is replaced with a hydroxyl group, an epoxy group, a halogen group or the like.
  • H 2 C C (R 6 ) -COOR 7 (II)
  • R 6 represents a hydrogen atom or a methyl group
  • R 7 represents an alkyl group having 1 to 12 carbon atoms.
  • the alkyl group having 1 to 12 carbon atoms represented by R 7 include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group and an undecyl group. Examples include groups, dodecyl groups and structural isomers of these groups.
  • Examples of the (meth) acrylic acid alkyl ester represented by the general formula (II) include (meth) acrylic acid methyl ester, (meth) acrylic acid ethyl ester, (meth) acrylic acid propyl ester, and (meth) acrylic.
  • Acid butyl ester (meth) acrylic acid pentyl ester, (meth) acrylic acid hexyl ester, (meth) acrylic acid heptyl ester, (meth) acrylic acid octyl ester, (meth) acrylic acid 2-ethylhexyl ester, (meth) acrylic
  • acrylic examples thereof include acid nonyl ester, (meth) acrylic acid decyl ester, (meth) acrylic acid undecyl ester, and (meth) acrylic acid dodecyl ester. These can be used alone or in combination of two or more.
  • the component (A) may contain a carboxyl group from the viewpoint of alkali developability.
  • the component (A) containing a carboxyl group can be produced, for example, by radically polymerizing a polymerizable monomer having a carboxyl group and another polymerizable monomer.
  • the polymerizable monomer having a carboxyl group may be (meth) acrylic acid or methacrylic acid.
  • the acid value of the component (A) containing a carboxyl group may be 50 to 250 mgKOH / g, 50 to 200 mgKOH / g, or 100 to 200 mgKOH / g.
  • the carboxyl group content of the component (A) is from the viewpoint of improving the alkali developability and the alkali resistance in a well-balanced manner. Therefore, it may be 12 to 50% by mass, 12 to 40% by mass, 15 to 35% by mass, 15 to 30% by mass, or 20 to 30% by mass.
  • the carboxyl group content is 12% by mass or more, the alkali developability tends to be improved, and when the carboxyl group content is 50% by mass or less, the alkali resistance tends to be excellent.
  • the content of the structural unit derived from the polymerizable monomer having a carboxyl group in the component (A) correlates with the compounding ratio of the polymerizable monomer having a carboxyl group, and thus is 12 to 50% by mass. , 12-40% by mass, 15-35% by mass, 15-30% by mass, or 20-30% by mass.
  • styrene or a styrene derivative may be used as the polymerizable monomer from the viewpoint of adhesion and chemical resistance.
  • its content the mixing ratio of styrene or styrene derivative with respect to the total amount of the polymerizable monomer used for the component (A) determines the adhesion and chemical resistance. From the viewpoint of further improvement, it may be 10 to 60% by mass, 15 to 50% by mass, 30 to 50% by mass, 35 to 50% by mass, or 40 to 50% by mass.
  • this content is 10% by mass or more, the adhesion tends to be improved, and when it is 60% by mass or less, it is possible to suppress the size of the peeled pieces during development, and the time required for peeling tends to be long. be.
  • the content of the structural unit derived from styrene or the styrene derivative in the component (A) correlates with the blending ratio of the styrene or the styrene derivative, it is 10 to 60% by mass, 15 to 50% by mass, and 30 to 50. It may be% by mass, 35 to 50% by mass, or 40 to 50% by mass.
  • (meth) acrylic acid benzyl ester may be used as the polymerizable monomer from the viewpoint of resolution and aspect ratio.
  • the content of the structural unit derived from the (meth) acrylic acid benzyl ester in the component (A) is 15 to 50% by mass, 15 to 45% by mass, and 15 to 40% by mass from the viewpoint of further improving the resolution and the aspect ratio. %, 15 to 35% by mass, or 20 to 30% by mass.
  • binder polymers can be used alone or in combination of two or more.
  • the component (A) includes, for example, two or more kinds of binder polymers composed of different polymerizable monomers, two or more kinds of binder polymers having different weight average molecular weights, and different dispersions. Two or more kinds of binder polymers can be mentioned.
  • the component (A) can be produced by a usual method. Specifically, for example, it can be produced by radical polymerization of (meth) acrylic acid alkyl ester, (meth) acrylic acid, styrene and the like.
  • the weight average molecular weight of the component (A) is 20,000 to 300,000, 40,000 to 150,000, 40,000 to 120,000, or from the viewpoint of improving mechanical strength and alkali developability in a well-balanced manner. It may be 50,000 to 80,000.
  • the weight average molecular weight in the present specification is a value measured by gel permeation chromatography (GPC) and converted by a calibration curve prepared using standard polystyrene.
  • the content of the component (A) is 30 to 80 parts by mass, 40 to 75 parts by mass, and 50 to 70 parts by mass with respect to 100 parts by mass of the total solid content of the component (A) and the component (B) described later. Alternatively, it may be 50 to 60 parts by mass. When the content of the component (A) is within this range, the coating film property and the strength of the photocurable portion of the photosensitive resin composition become better.
  • the photosensitive resin composition according to the present embodiment may contain (B) a photopolymerizable compound (hereinafter, also referred to as “(B) component”).
  • the component (B) can be used without particular limitation as long as it is a photopolymerizable compound or a photocrosslinkable compound, and for example, a compound having at least one ethylenically unsaturated bond in the molecule may be used. can.
  • a bisphenol type (meth) acrylate compound may be contained.
  • the bisphenol type (meth) acrylate compound include 2,2-bis (4-((meth) acryloxypolyethoxy) phenyl) propane and 2,2-bis (4-((meth) acryloxypolypropoxy)).
  • Phenyl) propane, 2,2-bis (4-((meth) acryloxypolyethoxypolypropoxy) phenyl) propane and the like can be mentioned. These can be used alone or in combination of two or more.
  • bisphenol type (meth) acrylate compound 2,2-bis (4- (methacryloxypentethoxy) phenyl) propane and 2,2-bis (4- (methacryloxydiethoxy) phenyl) propane are contained. May be good.
  • bisphenol-type (meth) acrylate compounds include, for example, 2,2-bis (4- (methacryloxydiethoxy) phenyl) propane (“BPE-200” manufactured by Shin-Nakamura Chemical Industry Co., Ltd. " ), 2,2-Bis (4- (methacryloxypentethoxy) phenyl) propane (“BPE-500” manufactured by Shin Nakamura Chemical Industry Co., Ltd.
  • the content of the bisphenol type (meth) acrylate compound is 1 to 50% by mass and 3 to 40% by mass with respect to the total solid content of the components (A) and (B) from the viewpoint of further improving the chemical resistance. It may be 10 to 40% by mass, 20 to 40% by mass, or 30 to 40% by mass.
  • the content of the bisphenol type (meth) acrylate compound is 30 to 99% by mass, 50 to 97% by mass, 60 to 60 to the total solid content of the component (B) from the viewpoint of further improving the chemical resistance. It may be 95% by mass, 70 to 95% by mass, or 80 to 90% by mass.
  • the content of the component (B) may be 20 to 70 parts by mass, 25 to 60 parts by mass, or 30 to 50 parts by mass with respect to 100 parts by mass of the total solid content of the component (A) and the component (B). good.
  • the content of the component (B) is within this range, the light sensitivity and the coating film property are further improved in addition to the resolution, the adhesion and the suppressive property of resist skirt generation of the photosensitive resin composition.
  • the photosensitive resin composition according to the present embodiment may contain at least one (C) photopolymerization initiator (hereinafter, also referred to as “(C) component”).
  • the component (C) is not particularly limited as long as it can polymerize the component (B), and can be appropriately selected from commonly used photopolymerization initiators.
  • Examples of the component (C) include 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-.
  • Aromatic ketones such as propanone-1, quinones such as alkylanthraquinone, benzoin ether compounds such as benzoin alkyl ethers, benzoin compounds such as benzoin and alkylbenzoin, benzyl derivatives such as benzyldimethylketal, 2- (o-chlorophenyl)- 2,4,5-Triarylimidazole dimer such as 4,5-diphenylimidazole dimer, 2- (o-fluorophenyl) -4,5-diphenylimidazole dimer, 9-phenylacridin, 1, Examples thereof include an acridin derivative such as 7- (9,9'-acrydinyl) heptane. These can be used
  • 2,4,5-triarylimidazole dimer may be contained from the viewpoint of improving the resolution.
  • Examples of the 2,4,5-triarylimidazole dimer include 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer and 2- (o-chlorophenyl) -4,5-bis-. Examples thereof include (m-methoxyphenyl) imidazole dimer and 2- (p-methoxyphenyl) -4,5-diphenylimidazole dimer.
  • 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer may be contained from the viewpoint of improving the photosensitivity stability.
  • 2,4,5-triarylimidazole dimer for example, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetraphenylbiimidazole is B-CIM (hodogaya). It is commercially available as (product name) manufactured by Hodogaya Chemical Co., Ltd.
  • the component (C) contains at least one of 2,4,5-triarylimidazole dimer from the viewpoint of further improving the light sensitivity and adhesion and further suppressing the light absorption of the component (C).
  • it may contain 2- (2-chlorophenyl) -4,5-diphenylimidazole dimer.
  • the structure of the 2,4,5-triarylimidazole dimer may be symmetric or asymmetric.
  • the content of the component (C) is 0.01 to 30 parts by mass, 0.1 to 10 parts by mass, and 1 to 7 parts by mass with respect to 100 parts by mass of the total solid content of the components (A) and (B). It may be 1 to 6 parts by mass, 1 to 5 parts by mass, or 2 to 5 parts by mass.
  • the content of the component (C) is 0.01 parts by mass or more, the light sensitivity, resolution and adhesion tend to be improved, and when the content is 30 parts by mass or less, the resist pattern shape tends to be excellent.
  • the photosensitive resin composition according to the present embodiment may contain (D) a photosensitizer (hereinafter, also referred to as “(D) component”).
  • a photosensitizer hereinafter, also referred to as “(D) component.
  • the component (D) examples include pyrazolines, dialkylaminobenzophenones, anthracenes, coumarins, acridines, xanthones, oxazoles, benzoxazoles, thiazoles, benzothiazoles, triazoles, stelvenes, and triazines. Species, thiophenes, naphthalimides and triarylamines. These can be used alone or in combination of two or more. From the viewpoint that the absorption wavelength of the active light used for exposure can be used more effectively, the component (D) may contain pyrazolines, anthracenes, coumarins, acridines or dialkylaminobenzophenones, among others, coumarins.
  • dialkylaminobenzophenones may be included, and dialkylaminobenzophenones may be included.
  • dialkylaminobenzophenones examples include "EAB” manufactured by Hodogaya Chemical Co., Ltd.
  • the content thereof is 1.0 part by mass or less, 0.5 part by mass or less, and 0. It may be 15 parts by mass or less, 0.12 parts by mass or less, or 0.10 parts by mass or less.
  • the content of the component (D) is 1.0 part by mass or less with respect to 100 parts by mass of the total solid content of the component (A) and the component (B)
  • deterioration of the resist pattern shape and the resist hem generation property is suppressed. It can and tends to have better resolution.
  • the content of the component (D) is 0.01 part by mass or more with respect to 100 parts by mass of the total solid content of the components (A) and (B) from the viewpoint that high light sensitivity and good resolution can be easily obtained. There may be.
  • the photosensitive resin composition according to the present embodiment may contain (E) a polymerization inhibitor (hereinafter, also referred to as “(E) component”).
  • (E) component a polymerization inhibitor
  • the exposure amount required for photocuring the photosensitive resin composition tends to be adjusted to the optimum exposure amount for exposure with a projection exposure machine.
  • the component (E) include catechol, resorcinol (resorcin), 1,4-hydroquinone, 2-methylcatechol, 3-methylcatechol, 4-methylcatechol, 2-ethylcatechol, 3-ethylcatechol, 4-ethyl.
  • Resorcinol 2-propyl catechol, 3-propyl catechol, 4-propyl catechol, 2-n-butyl catechol, 3-n-butyl catechol, 4-n-butyl catechol, 2-tert-butyl catechol, 3-tert-butyl Alkyl catechols such as catechol, 4-tert-butyl catechol, 3,5-di-tert-butyl catechol, 2-methylresorcinol, 4-methylresorcinol, 5-methylresorcinol (orcin), 2-ethylresorcinol, 4-ethyl Alkyl resorcinols such as resorcinol, 2-propylresorcinol, 4-propylresorcinol, 2-n-butylresorcinol, 4-n-butylresorcinol, 2-tert-butylresorcinol, 4-tert-butylresorcinol, methylhydroquinone, ethylhydroquinon
  • the photosensitive resin composition according to the present embodiment includes dyes such as malakite green, Victoria pure blue, brilliant green and methyl violet, tribromophenyl sulfone, leuco crystal violet, diphenylamine, benzylamine and triphenyl, if necessary.
  • Photocoloring agents such as amines, diethylaniline, and o-chloroaniline, heat coloring inhibitors, plasticizers such as p-toluenesulfonamide, pigments, fillers, defoaming agents, flame retardant agents, adhesion imparting agents, leveling agents.
  • the photosensitive resin composition according to the present embodiment contains at least one organic solvent, if necessary, in order to improve the handleability of the photosensitive composition and to adjust the viscosity and storage stability.
  • the organic solvent a commonly used organic solvent can be used without particular limitation. Specific examples thereof include organic solvents such as methanol, ethanol, acetone, methyl ethyl ketone, methyl cellosolve, ethyl cellosolve, toluene, N, N-dimethylformamide, propylene glycol monomethyl ether, and mixed solvents thereof. These can be used alone or in combination of two or more.
  • a protective layer may be laminated on the surface of the photosensitive layer opposite to the surface in contact with the barrier layer.
  • a protective layer for example, a polymer film such as polyethylene or polypropylene may be used. Further, the same polymer film as the above-mentioned support film may be used, or a different polymer film may be used.
  • a water-soluble resin containing polyvinyl alcohol is mixed with water heated to 70 to 90 ° C. and an organic solvent used as necessary so that the solid content is 10 to 20% by mass. It is gradually added to a solvent and stirred for about 1 hour, and then the leveling agent is mixed and uniformly dissolved to obtain a resin composition for forming a barrier layer containing polyvinyl alcohol and the leveling agent.
  • the term "solid content” refers to the non-volatile content of the resin composition excluding volatile substances such as water and organic solvents. That is, it refers to components other than solvents such as water and organic solvents that remain without volatilization in the drying step, and includes liquid, starch syrup-like and wax-like components at room temperature around 25 ° C.
  • the resin composition for forming the barrier layer is applied onto the support film and dried to form the barrier layer.
  • the resin composition for forming a barrier layer can be applied onto a support film by a known method such as a roll coat, a comma coat, a gravure coat, an air knife coat, a die coat, a bar coat, or a spray coat.
  • the drying of the applied resin composition for forming a barrier layer is not particularly limited as long as at least a part of the solvent such as water can be removed, but it may be dried at 70 to 150 ° C. for 5 to 30 minutes. After drying, the amount of residual solvent in the barrier layer may be 2% by mass or less from the viewpoint of preventing the diffusion of the solvent in a later step.
  • the photosensitive resin composition is applied onto the barrier layer of the support film on which the barrier layer is formed in the same manner as the application of the resin composition for forming the barrier layer and dried to form the photosensitive layer on the barrier layer.
  • a photosensitive element including a support film, a barrier layer, a photosensitive layer, and a protective layer in this order is produced. Can be done.
  • the support film, the barrier layer, the photosensitive layer, and the protective layer can be attached to each other. Photosensitive elements provided in order may be obtained.
  • the thickness of the photosensitive layer in the photosensitive element can be appropriately selected depending on the intended use, but the thickness after drying may be 1 ⁇ m or more, 5 ⁇ m or more, or 10 ⁇ m or more, and is 200 ⁇ m or less, 100 ⁇ m or less, 50 ⁇ m or less. , Or it may be less than 20 ⁇ m.
  • the thickness of the photosensitive layer is 1 ⁇ m or more, 5 ⁇ m or more, or 10 ⁇ m or more, industrial coating is facilitated and productivity tends to be improved.
  • the thickness of the photosensitive layer is 200 ⁇ m or less, 100 ⁇ m or less, 50 ⁇ m or less, or less than 20 ⁇ m, the light sensitivity is high and the photocurability of the resist bottom is excellent, so that a resist pattern having excellent resolution and aspect ratio is formed. There is a tendency to be able to do it.
  • the melt viscosity of the photosensitive layer in the photosensitive element at 110 ° C. can be appropriately selected depending on the type of the substrate (base) in contact with the photosensitive layer, but after drying, at 110 ° C., 50 to 10000 Pa ⁇ s, 100 to 5000 Pa. It may be s or 200 to 1000 Pa ⁇ s.
  • the melt viscosity at 110 ° C. is 50 Pa ⁇ s or more, wrinkles and voids do not occur in the laminating step, and the productivity tends to be improved.
  • the melt viscosity at 110 ° C. is 10,000 Pa ⁇ s or less, the adhesiveness with the substrate is improved in the laminating step, and there is a tendency to reduce the adhesive defect.
  • the form of the photosensitive element according to this embodiment is not particularly limited.
  • it may be in the form of a sheet, or may be in the form of a roll wound around a winding core.
  • the support film When winding in a roll shape, the support film may be wound so as to be on the outside.
  • the material of the winding core include plastics such as polyethylene resin, polypropylene resin, polystyrene resin, polyvinyl chloride resin or ABS resin (acrylonitrile-butadiene-styrene copolymer).
  • An end face separator may be installed on the end face of the roll-shaped photosensitive element roll thus obtained from the viewpoint of end face protection, and a moisture-proof end face separator may be installed from the viewpoint of edge fusion resistance. May be good.
  • As a packing method it may be wrapped in a black sheet having low moisture permeability.
  • the photosensitive element according to this embodiment can be suitably used, for example, in a method for forming a resist pattern and a method for manufacturing a printed wiring board, which will be described later.
  • the method for forming a resist pattern is as follows: (i) Using the photosensitive element, a step of arranging a photosensitive layer, a barrier layer, and a support film on a substrate in this order from the substrate side (hereinafter, "(I) Photosensitive layer and barrier layer forming step”) and (ii) A step of removing the support film and exposing the photosensitive layer with active light through the barrier layer (hereinafter, "(ii)”. Also referred to as “exposure step”) and (iii) a step of removing the uncured portion of the barrier layer and the photosensitive layer from the substrate (hereinafter, also referred to as "(iii) developing step”), and necessary.
  • the resist pattern can be said to be a photocured product pattern of the photosensitive resin composition and also a relief pattern. Further, depending on the purpose, the resist pattern in the present embodiment may be used as a resist or may be used for other purposes such as a protective film.
  • the photosensitive layer and the barrier layer are formed on the substrate by using the photosensitive element.
  • the substrate is not particularly limited, but usually, a circuit forming substrate provided with an insulating layer and a conductor layer formed on the insulating layer, or a die pad (lead frame substrate) such as an alloy substrate may be used. Used.
  • the photosensitive layer and the barrier layer As a method of forming the photosensitive layer and the barrier layer on the substrate, for example, in the case of using a photosensitive element having a protective layer, after removing the protective layer, the photosensitive layer of the photosensitive element is heated. By crimping to the substrate, the photosensitive layer and the barrier layer can be formed on the substrate. As a result, a laminated body including the substrate, the photosensitive layer, the barrier layer, and the support film in this order can be obtained.
  • the photosensitive layer and the barrier layer forming step When the photosensitive layer and the barrier layer forming step is performed using the photosensitive element, it may be performed under reduced pressure from the viewpoint of adhesion and followability.
  • the heating at the time of crimping may be performed at a temperature of 70 to 130 ° C., and the crimping may be performed at a pressure of 0.1 to 1.0 MPa (1 to 10 kgf / cm 2 ), but these conditions are necessary. It can be selected as appropriate. If the photosensitive layer of the photosensitive element is heated to 70 to 130 ° C., it is not necessary to preheat the substrate in advance, but the substrate is preheated in order to further improve the adhesion and the followability. You can also.
  • (Ii) exposure step In the exposure step, the support film is removed and the photosensitive layer is exposed to the active light through the barrier layer. As a result, the exposed portion irradiated with the active light may be photo-cured to form a photo-cured portion (latent image), or the unexposed portion not irradiated with the active light may be photo-cured. A photo-curing portion may be formed.
  • the photosensitive layer and the barrier layer are formed by using the photosensitive element, the support film existing on the photosensitive layer is peeled off and then exposed. By exposing the photosensitive layer through the barrier layer, a resist pattern having excellent resolution and resist pattern shape can be formed.
  • a known exposure method can be applied.
  • a method of irradiating an image through a lens using an active light beam on which an image of a photomask is projected (projection exposure method) and the like can be mentioned.
  • the projection exposure method may be used from the viewpoint of excellent resolution. That is, the photosensitive element or the like according to the present embodiment is applied to the projection exposure method.
  • the projection exposure method can also be said to be an exposure method using activated light rays having an attenuated amount of energy.
  • the light source of the active light is not particularly limited as long as it is a known light source that is usually used.
  • Such as solid-state lasers, semiconductor lasers such as gallium nitride blue-violet lasers, etc. that effectively radiate ultraviolet rays are used.
  • a photographic flood bulb, a solar lamp, or the like that effectively radiates visible light may be used.
  • a light source capable of emitting i-line monochromatic light having an exposure wavelength of 365 nm a light source capable of emitting h-line monochromatic light having an exposure wavelength of 405 nm, or an exposure wavelength of ihg mixed lines.
  • a light source capable of radiating the active light of the above may be used, and among them, a light source capable of radiating i-line monochromatic light having an exposure wavelength of 365 nm may be used.
  • Examples of the light source capable of emitting i-line monochromatic light having an exposure wavelength of 365 nm include an ultrahigh voltage mercury lamp and the like.
  • the uncured portion of the barrier layer and the photosensitive layer is removed from the substrate.
  • a resist pattern composed of a photo-cured portion in which the photosensitive layer is photo-cured is formed on the substrate.
  • the barrier layer is water-soluble, the barrier layer may be removed by washing with water, and then the uncured portion other than the photocured portion may be removed with a developing solution, and the barrier layer is dissolved in the developing solution. If it has a property, the barrier layer may be removed with a developing solution together with the uncured portion other than the photocured portion. Examples of the developing method include wet development.
  • wet development it can be developed by a known wet development method using a developer corresponding to the photosensitive resin composition.
  • the wet development method include a method using a dip method, a paddle method, a high-pressure spray method, brushing, slapping, scraping, rocking immersion, etc. From the viewpoint of improving resolution, the high-pressure spray method is the most suitable. Is suitable.
  • These wet development methods may be developed individually by one type or in combination of two or more types.
  • the developer is appropriately selected according to the composition of the photosensitive resin composition.
  • an alkaline aqueous solution and an organic solvent developer can be mentioned.
  • an alkaline aqueous solution may be used as the developer.
  • the base of the alkaline aqueous solution include alkali hydroxides such as lithium, sodium or potassium hydroxides, alkali carbonates such as lithium, sodium, potassium or ammonium carbonates or bicarbonates, potassium phosphates and sodium phosphates.
  • Alkaline metal phosphates such as, sodium pyrophosphate, alkali metal pyrophosphates such as potassium pyrophosphate, sodium borate, sodium metasilicate, tetramethylammonium hydroxide, ethanolamine, ethylenediamine, diethylenetriamine, 2-amino-2- Hydroxymethyl-1,3-propanediol, 1,3-diamino-2-propanol and morpholin are used.
  • Examples of the alkaline aqueous solution used for development include a dilute solution of 0.1 to 5% by mass sodium carbonate, a dilute solution of 0.1 to 5% by mass of potassium carbonate, and a dilute solution of 0.1 to 5% by mass of sodium hydroxide.
  • a dilute solution of 0.1 to 5% by mass sodium tetraborate or the like can be used.
  • the pH of the alkaline aqueous solution used for development may be in the range of 9 to 11, and the temperature of the alkaline aqueous solution can be adjusted according to the developability of the photosensitive layer.
  • a surface active agent, a defoaming agent, a small amount of an organic solvent for accelerating development, or the like may be mixed in the alkaline aqueous solution.
  • the organic solvent used in the alkaline aqueous solution include 3-acetone alcohol, acetone, ethyl acetate, alkoxyethanol having an alkoxy group having 1 to 4 carbon atoms, ethyl alcohol, isopropyl alcohol, butyl alcohol, diethylene glycol monomethyl ether, and the like. Examples thereof include diethylene glycol monoethyl ether and diethylene glycol monobutyl ether.
  • organic solvent used in the organic solvent developer examples include 1,1,1-trichloroethane, N-methylpyrrolidone, N, N-dimethylformamide, cyclohexanone, methyl isobutyl ketone and ⁇ -butyrolactone. From the viewpoint of preventing ignition, these organic solvents may be prepared as an organic solvent developer by adding water so as to be in the range of 1 to 20% by mass.
  • the method for manufacturing a printed wiring board according to the present embodiment includes a step of etching or plating a substrate on which a resist pattern is formed by the above resist pattern forming method to form a conductor pattern, and if necessary, a resist pattern. Other steps such as a removal step may be included.
  • the method for manufacturing a printed wiring board according to the present embodiment can be suitably used for forming a conductor pattern by using the method for forming a resist pattern using the above-mentioned photosensitive element. Among them, the conductor pattern is formed by plating.
  • the application to the method is more suitable.
  • the conductor pattern can also be said to be a circuit.
  • the conductor layer of the substrate not covered with the resist is removed by etching using the resist pattern formed on the substrate provided with the conductor layer as a mask to form the conductor pattern.
  • the etching treatment method is appropriately selected according to the conductor layer to be removed.
  • the etching solution include a ferric chloride solution, a ferric chloride solution, an alkaline etching solution, a hydrogen peroxide-based etching solution, and the like, and the ferric chloride solution is used because the etch factor is good. It is also good.
  • the plating process copper or solder is plated on the conductor layer of the substrate not covered with the resist by using the resist pattern formed on the substrate provided with the conductor layer as a mask. After the plating treatment, the resist is removed by removing the resist pattern described later, and the conductor layer covered with this resist is further etched to form a conductor pattern.
  • the plating treatment method may be electrolytic plating treatment or electroless plating treatment, and may be electroless plating treatment.
  • electroless plating treatment include copper plating such as copper sulfate plating and copper pyrophosphate plating, solder plating such as high-slow solder plating, watt bath (nickel sulfate-nickel chloride) plating, and nickel plating such as nickel sulfamate plating.
  • Gold plating such as hard gold plating and soft gold plating can be mentioned.
  • the resist pattern on the substrate is removed.
  • the resist pattern can be removed, for example, with a stronger alkaline aqueous solution than the alkaline aqueous solution used in the development step.
  • a stronger alkaline aqueous solution for example, a 1 to 10% by mass sodium hydroxide aqueous solution, a 1 to 10% by mass potassium hydroxide aqueous solution, or the like is used. Among these, 1 to 5% by mass sodium hydroxide aqueous solution or potassium hydroxide aqueous solution may be used.
  • Examples of the resist pattern removing method include a dipping method and a spraying method, which may be used alone or in combination.
  • a desired printed wiring board can be manufactured by further etching the conductor layer covered with the resist by the etching treatment to form the conductor pattern.
  • the etching treatment method at this time is appropriately selected according to the conductor layer to be removed. For example, the above-mentioned etching solution can be applied.
  • the method for manufacturing a printed wiring board according to the present embodiment can be applied not only to the manufacture of a single-layer printed wiring board but also to the manufacture of a multilayer printed wiring board, and also to the manufacture of a printed wiring board having a small-diameter through hole. It is possible.
  • the method for manufacturing a printed wiring board according to the present embodiment can be suitably used for manufacturing a high-density package substrate, particularly for manufacturing a wiring board by a semi-additive method.
  • FIG. 2 shows an example of the manufacturing process of the wiring board by the semi-additive method.
  • FIG. 2A a substrate (circuit forming substrate) in which the conductor layer 40 is formed on the insulating layer 50 is prepared.
  • the conductor layer 40 is, for example, a copper layer.
  • FIG. 2B the photosensitive layer 30 and the barrier layer 20 are formed on the conductor layer 40 of the substrate by the photosensitive layer and barrier layer forming step.
  • the exposure step irradiates the photosensitive layer 30 with the active light rays 80 obtained by projecting an image of a photomask onto the photosensitive layer 30 to form a photocurable portion on the photosensitive layer 30.
  • the resist pattern 32 which is a photocurable portion on the substrate, is formed by removing the region (including the barrier layer) other than the photocurable portion formed by the exposure step from the substrate by the developing step.
  • the plating layer 60 is formed on the conductor layer 40 of the substrate which is not covered with the resist by the plating treatment using the resist pattern 32 which is the photo-curing portion as a mask.
  • the resist pattern 32 which is a photocurable portion, is peeled off with an aqueous solution of a strong alkali, and then the conductor layer 40 masked by the resist pattern 32 is removed by a flash etching process, and the plating after the etching process is performed.
  • a conductor pattern 70 including the layer 62 and the conductor layer 42 after the etching treatment is formed.
  • the material of the conductor layer 40 and the plating layer 60 may be the same or different.
  • the conductor layer 40 and the plating layer 60 may be integrated.
  • the resist pattern 32 may be formed by using the mask exposure method and the LDI exposure method in combination.
  • the binder polymer (A-1) was synthesized according to Synthesis Example 1.
  • ⁇ Synthesis example 1> As a polymerizable monomer, 125 g of methacrylic acid, 25 g of methyl methacrylate, 125 g of benzyl methacrylate and 225 g of styrene were mixed with 1.5 g of azobisisobutyronitrile to prepare a solution a.
  • a solution b 1.2 g of azobisisobutyronitrile was dissolved in 100 g of a mixed solution (mass ratio 3: 2) of 60 g of methyl cellosolve and 40 g of toluene to prepare a solution b.
  • a mixed solution of methyl cellosolve and toluene having a mass ratio of 3: 2 in a flask equipped with a stirrer, a reflux condenser, a thermometer, a dropping funnel and a nitrogen gas introduction tube (hereinafter, also referred to as “mixed solution x”). 400 g was added, and the mixture was stirred while blowing nitrogen gas and heated to 80 ° C.
  • the above solution a was added dropwise to the mixed solution x in the flask over 4 hours at a constant dropping rate, and then the mixture was stirred at 80 ° C. for 2 hours. Then, the solution b was added dropwise to the solution in the flask over 10 minutes at a constant dropping rate, and then the solution in the flask was stirred at 80 ° C. for 3 hours. Further, the solution in the flask was heated to 90 ° C. over 30 minutes, kept warm at 90 ° C. for 2 hours, and then cooled to room temperature to obtain a solution of the binder polymer (A-1).
  • the solution of the binder polymer (A-1) was prepared by adding the mixed solution x so that the non-volatile component (solid content) was 50% by mass.
  • the weight average molecular weight of the binder polymer (A-1) was 50,000, and the acid value was 163 mgKOH / g.
  • the acid value was measured by the neutralization titration method. Specifically, 30 g of acetone is added to 1 g of the solution of the binder polymer, and the mixture is further uniformly dissolved. Then, an appropriate amount of phenolphthalein, which is an indicator, is added to the solution of the binder polymer, and a 0.1 N KOH aqueous solution is added. It was measured by performing titration using.
  • the weight average molecular weight was measured by gel permeation chromatography (GPC) and derived by conversion using a standard polystyrene calibration curve. The conditions of GPC are shown below.
  • each component shown in Table 1 below was mixed in an amount (unit: parts by mass) shown in the same table to obtain a resin composition for forming a barrier layer.
  • the water-soluble resin was slowly added to water and alcohols at room temperature, and after the total amount was added, the mixture was heated to 90 ° C. After reaching 90 ° C., the mixture was stirred for 1 hour, then the leveling agent was mixed and uniformly dissolved, and the mixture was cooled to room temperature to obtain a resin composition for forming a barrier layer.
  • the blending amounts other than the solvent in Table 1 are the blending amounts in terms of solid content.
  • R-705G Biaxially oriented polyester film having a two-layer structure (manufactured by Mitsubishi Chemical Corporation, product name, thickness: 16 ⁇ m) having an antistatic layer on the opposite surface on the side to which the photosensitive resin composition is applied.
  • the resin composition for forming a barrier layer was applied onto the PET film (supporting film) so that the thickness was uniform, and dried in a hot air convection dryer at 95 ° C. for 10 minutes, and the thickness after drying was 5 ⁇ m. A barrier layer was formed. When the lubricant densities were different on both sides of the PET film, a barrier layer was formed on the surface of the PET film having less lubricant.
  • the photosensitive resin composition was applied onto the barrier layer of the support film so that the thickness was uniform, and dried in a hot air convection dryer at 100 ° C. for 10 minutes, and the thickness after drying was 15 ⁇ m. A photosensitive layer was formed.
  • a polyethylene protective film (protective layer) (manufactured by Tamapoli Co., Ltd., product name "NF-15A") is bonded onto this photosensitive layer, and the PET film (supporting film), the barrier layer, and the photosensitive layer are formed. , A photosensitive element in which the protective layer was laminated in this order was obtained.
  • ⁇ Manufacturing of laminated body> After the copper surface of a copper-clad laminate (board, manufactured by Hitachi Kasei Co., Ltd., product name "MCL-E-67"), which is a glass epoxy material in which copper foil with a thickness of 12 ⁇ m is laminated on both sides, is treated with acid and washed with water. , Dry with air flow.
  • the copper-clad laminate was heated to 80 ° C., and while the protective layer was peeled off, the photosensitive elements were pressure-bonded to the copper-clad laminate so that the photosensitive layer was in contact with the copper surface.
  • the crimping was performed using a heat roll at 110 ° C. at a pressure of 0.40 MPa and a roll speed of 1.0 m / min.
  • the measurement temperature was 23 ° C.
  • the peel strength the average value of the values measured for the five samples was obtained. The lower the peel strength, the easier it is to peel between the support film and the barrier layer when the support film is peeled off, and it is possible to prevent a part of the barrier layer from adhering to the support film and being damaged.
  • Photosensitive element 1 ... Photosensitive element, 2 ... Support film, 3, 20 ... Barrier layer, 4, 30 ... Photosensitive layer, 5 ... Protective layer, 32 ... Resist pattern, 40 ... Conductor layer, 42 ... Conductor layer after etching treatment, 50 ... Insulation layer, 60 ... Plating layer, 62 ... Plating layer after etching treatment, 70 ... Conductor pattern, 80 ... Active light.

Landscapes

  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Structural Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Architecture (AREA)
  • Materials For Photolithography (AREA)
  • Chemical & Material Sciences (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
PCT/JP2021/024156 2020-07-20 2021-06-25 感光性エレメント、レジストパターンの形成方法及びプリント配線板の製造方法 Ceased WO2022019046A1 (ja)

Priority Applications (4)

Application Number Priority Date Filing Date Title
CN202180047105.0A CN115867864A (zh) 2020-07-20 2021-06-25 感光性元件、抗蚀剂图案的形成方法及印刷线路板的制造方法
KR1020227045886A KR102870994B1 (ko) 2020-07-20 2021-06-25 감광성 엘리먼트, 레지스트 패턴의 형성 방법 및 프린트 배선판의 제조 방법
JP2022538654A JPWO2022019046A1 (https=) 2020-07-20 2021-06-25
JP2026009778A JP2026063359A (ja) 2020-07-20 2026-01-23 感光性エレメント

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2020-123768 2020-07-20
JP2020123768 2020-07-20

Publications (1)

Publication Number Publication Date
WO2022019046A1 true WO2022019046A1 (ja) 2022-01-27

Family

ID=79729437

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2021/024156 Ceased WO2022019046A1 (ja) 2020-07-20 2021-06-25 感光性エレメント、レジストパターンの形成方法及びプリント配線板の製造方法

Country Status (5)

Country Link
JP (2) JPWO2022019046A1 (https=)
KR (1) KR102870994B1 (https=)
CN (1) CN115867864A (https=)
TW (1) TWI902842B (https=)
WO (1) WO2022019046A1 (https=)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2025047730A1 (ja) * 2023-08-30 2025-03-06 富士フイルム株式会社 転写フィルム、パターン形成方法、積層体、半導体パッケージ

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017007001A1 (ja) * 2015-07-08 2017-01-12 日立化成株式会社 感光性エレメント、積層体、レジストパターンの形成方法及びプリント配線板の製造方法
WO2020054075A1 (ja) * 2018-09-14 2020-03-19 日立化成株式会社 転写型感光性フィルム、樹脂硬化膜の形成方法及び樹脂硬化膜付センサ基板の製造方法
WO2020105457A1 (ja) * 2018-11-20 2020-05-28 富士フイルム株式会社 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

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019215848A1 (ja) 2018-05-09 2019-11-14 日立化成株式会社 感光性エレメント、バリア層形成用樹脂組成物、レジストパターンの形成方法及びプリント配線板の製造方法
JP2022120464A (ja) * 2021-02-05 2022-08-18 昭和電工マテリアルズ株式会社 メタルマスクの製造方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017007001A1 (ja) * 2015-07-08 2017-01-12 日立化成株式会社 感光性エレメント、積層体、レジストパターンの形成方法及びプリント配線板の製造方法
WO2020054075A1 (ja) * 2018-09-14 2020-03-19 日立化成株式会社 転写型感光性フィルム、樹脂硬化膜の形成方法及び樹脂硬化膜付センサ基板の製造方法
WO2020105457A1 (ja) * 2018-11-20 2020-05-28 富士フイルム株式会社 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

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2025047730A1 (ja) * 2023-08-30 2025-03-06 富士フイルム株式会社 転写フィルム、パターン形成方法、積層体、半導体パッケージ

Also Published As

Publication number Publication date
TWI902842B (zh) 2025-11-01
KR20230041976A (ko) 2023-03-27
KR102870994B1 (ko) 2025-10-16
JPWO2022019046A1 (https=) 2022-01-27
JP2026063359A (ja) 2026-04-10
TW202206944A (zh) 2022-02-16
CN115867864A (zh) 2023-03-28

Similar Documents

Publication Publication Date Title
JP6870612B2 (ja) 感光性エレメント、バリア層形成用樹脂組成物、レジストパターンの形成方法及びプリント配線板の製造方法
JP2019109543A (ja) レジストパターンの形成方法、プリント配線板の製造方法、投影露光用感光性樹脂組成物及び感光性エレメント
KR20180027541A (ko) 감광성 엘리먼트, 적층체, 레지스터 패턴의 형성 방법 및 프린트 배선판의 제조 방법
WO2016104585A1 (ja) 感光性樹脂組成物、並びにこれを用いた感光性エレメント、レジストパターンの形成方法、及びプリント配線板の製造方法
JP7306382B2 (ja) 感光性エレメント、レジストパターンの形成方法及びプリント配線板の製造方法
JP2022120464A (ja) メタルマスクの製造方法
JP2026063359A (ja) 感光性エレメント
JP2025067970A (ja) 感光性エレメント
EP4685561A1 (en) Photosensitive element, method for forming resist pattern, and method for manufacturing printed wiring board
WO2025046694A1 (ja) 感光性エレメントの製造方法、感光性エレメント、レジストパターンの形成方法及びプリント配線板の製造方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 21845184

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2022538654

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 21845184

Country of ref document: EP

Kind code of ref document: A1