WO2021010058A1 - Film de transfert, procédé de fabrication de stratifié et procédé de fabrication de panneau tactile - Google Patents

Film de transfert, procédé de fabrication de stratifié et procédé de fabrication de panneau tactile Download PDF

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Publication number
WO2021010058A1
WO2021010058A1 PCT/JP2020/022684 JP2020022684W WO2021010058A1 WO 2021010058 A1 WO2021010058 A1 WO 2021010058A1 JP 2020022684 W JP2020022684 W JP 2020022684W WO 2021010058 A1 WO2021010058 A1 WO 2021010058A1
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Prior art keywords
resin layer
photosensitive resin
film
mass
group
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PCT/JP2020/022684
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English (en)
Japanese (ja)
Inventor
豊岡　健太郎
陽平 有年
達也 霜山
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富士フイルム株式会社
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Priority to JP2021532726A priority Critical patent/JP7213981B2/ja
Priority to CN202080045617.9A priority patent/CN114026498A/zh
Publication of WO2021010058A1 publication Critical patent/WO2021010058A1/fr

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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
    • G03F7/16—Coating processes; Apparatus therefor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/06—Interconnection of layers permitting easy separation
    • 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
    • G03F7/004—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
    • G—PHYSICS
    • G06—COMPUTING; CALCULATING OR COUNTING
    • G06F—ELECTRIC DIGITAL DATA PROCESSING
    • G06F3/00—Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
    • G06F3/01—Input arrangements or combined input and output arrangements for interaction between user and computer
    • G06F3/03—Arrangements for converting the position or the displacement of a member into a coded form
    • G06F3/041—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means

Definitions

  • the present invention relates to a method for manufacturing a transfer film, a laminate, and a method for manufacturing a touch panel.
  • a touch panel is often used as an input device in a display device of an electronic device (for example, a mobile phone, a car navigation system, a personal computer, a ticket vending machine, a bank terminal, etc.). It is known that such a touch panel is provided with a protective film for protecting electrodes including metal wiring.
  • Patent Document 1 includes a compound represented by the formula 1 as component A, a binder polymer as component B, and a photopolymerization initiator as component C.
  • Touch panel electrode protection A film-forming composition is described ([Claim 1]), and a transfer film having a temporary support and a photosensitive resin layer made of the touch panel electrode protective film-forming composition is used for a touch panel.
  • a method of providing a photosensitive resin layer on a substrate having an electrode is described ([Claim 6] [Claim 10]).
  • Q 1 and Q 2 independently represent a (meth) acryloyloxy group or a (meth) acryloyloxyalkyl group, and R 1 represents a divalent hydrocarbon group.
  • Patent Document 2 describes a compound represented by the formula 1 as a component A, a binder polymer as a component B, a photopolymerization initiator as a component C, and a monomer having a carboxy group as a component D.
  • a composition for forming a touch panel electrode protective film which is contained and the content of the component A is 5% by mass or more and less than 50% by mass with respect to the total mass of the monomer components ([claimed]. Item 1])
  • a photosensitive resin layer is formed on a base material having a touch panel electrode by using a transfer film having a temporary support and a photosensitive resin layer made of a composition for forming a touch panel electrode protective film. The method of providing is described ([Claim 6] [Claim 10]).
  • the present invention provides a method for manufacturing a transfer film, a laminate, and a touch panel, which are excellent in peelability of a temporary support and a protective film and excellent in punching processability of a cured film obtained by curing a photosensitive resin layer after transfer.
  • the challenge is to provide.
  • the present inventors have determined a temporary support having a predetermined surface roughness, a photosensitive resin layer having a break elongation at 120 ° C. after curing at a predetermined value, and a predetermined value.
  • the transfer film having the protective film having the surface roughness of the above in this order is excellent in the peelability of the temporary support and the protective film, and also excellent in the punching processability of the cured film obtained by curing the photosensitive resin layer after transfer.
  • the elongation at break at 120 ° C. of the cured film obtained by curing the photosensitive resin layer is 15% or more.
  • the arithmetic mean roughness Ra of the surface of the temporary support on the photosensitive resin layer side is 50 nm or less.
  • Y represents the surface of the temporary support on the photosensitive resin layer side. It represents the value (nm) of the arithmetic mean roughness Ra.
  • the transfer film according to claim 1 or 2 which satisfies the following formula (2).
  • Y represents the arithmetic mean roughness Ra value (nm) of the surface of the temporary support on the photosensitive resin layer side
  • Z represents the surface of the protective film on the photosensitive resin layer side. Represents the value (nm) of the arithmetic mean roughness Ra of.
  • the moisture permeability of a film thickness 40 ⁇ m of the cured film formed by curing a photosensitive resin layer is not more than 500g / m 2 / 24hr, the transfer film according to any one of [1] to [3].
  • the photosensitive resin layer contains a binder polymer, a polymerizable monomer, and a photopolymerization initiator.
  • Manufacturing method is a method for manufacturing method.
  • a transfer film, a method for manufacturing a laminate, and a method for manufacturing a touch panel which are excellent in peelability of a temporary support and a protective film and excellent in punching processability of a cured film obtained by curing a photosensitive resin layer after transfer. Can be provided.
  • FIG. 1 is a schematic cross-sectional view showing an example of the transfer film of the present invention.
  • FIG. 2 is a schematic cross-sectional view showing a first specific example of a touch panel having a photosensitive resin layer transferred using the transfer film of the present invention.
  • FIG. 3 is a schematic cross-sectional view showing a second specific example of a touch panel having a photosensitive resin layer transferred using the transfer film of the present invention.
  • FIG. 4 is a schematic view of a sample used for measuring the elongation at break.
  • the notation that does not describe substitution or non-substitution includes those having no substituent as well as those having a substituent.
  • the "alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
  • “% by mass” and “% by weight” are synonymous, and “parts by mass” and “parts by weight” are synonymous.
  • a combination of two or more preferred embodiments is a more preferred embodiment.
  • the amount 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.
  • the term “process” is included in the term not only in an independent process but also in the case where the intended purpose of the process is achieved even when it cannot be clearly distinguished from other processes.
  • "(meth) acrylic acid” is a concept that includes both acrylic acid and methacrylic acid
  • (meth) acrylate” is a concept that includes both acrylate and methacrylate
  • (meth) acrylate” is a concept that includes both acrylate and methacrylate.
  • Acryloyl group is a concept that includes both an acryloyl group and a methacrylic acid group.
  • the weight average molecular weight (Mw) and the number average molecular weight (Mn) in the present disclosure use columns of TSKgel GMHxL, TSKgel G4000HxL, and TSKgel G2000HxL (all trade names manufactured by Toso Co., Ltd.). It is a molecular weight converted by detecting with a solvent THF (tetrahydrofuran) and a differential refractometer by a gel permeation chromatography (GPC) analyzer and using polystyrene as a standard substance.
  • THF tetrahydrofuran
  • the molecular weight of a compound having a molecular weight distribution is the weight average molecular weight.
  • the ratio of the constituent units of the polymer is the molar ratio.
  • the refractive index is a value at a wavelength of 550 nm measured at 25 ° C. with an ellipsometer.
  • the transfer film of the present invention is a transfer film having a temporary support, a photosensitive resin layer, and a protective film in this order. Further, in the transfer film of the present invention, the breaking elongation of the cured film obtained by curing the photosensitive resin layer at 120 ° C. is 15% or more. Further, in the transfer film of the present invention, the arithmetic average roughness Ra of the surface of the temporary support on the photosensitive resin layer side is 50 nm or less, and the arithmetic average roughness Ra of the surface of the protective film on the photosensitive resin layer side is It is 150 nm or less.
  • a temporary support having an arithmetic average roughness Ra of the surface on the photosensitive resin layer side of 50 nm or less and a photosensitive resin layer having a breaking elongation at 120 ° C. after curing of 15% or more.
  • a transfer film having a protective film having an arithmetic average roughness Ra of the surface on the photosensitive resin layer side of 150 nm or less in this order has excellent peelability of the temporary support and the protective film, and is photosensitive after transfer.
  • the punching processability of the cured film obtained by curing the resin layer is also improved. This is not clear in detail, but the present inventors speculate as follows.
  • the transfer film of the present invention since the transfer film of the present invention has a photosensitive resin layer having a breaking elongation at 120 ° C. after curing of 15% or more, the cured film obtained by curing the photosensitive resin layer after transfer has toughness. As a result, it is considered that the punching workability is improved.
  • the arithmetic mean roughness on the surface of the temporary support and the protective film on the photosensitive resin layer side is taken into consideration in consideration of the timing of peeling the temporary support and the protective film and the timing of curing the photosensitive resin layer after transfer. It is considered that by adjusting the Ra to the above-mentioned range, the peelability could be improved while maintaining good punching workability.
  • the transfer film of the present invention has a temporary support.
  • the temporary support is preferably a film, more preferably a resin film.
  • a film that is flexible and does not cause significant deformation, shrinkage, or elongation under pressure, or under pressure and heating can be used.
  • Examples of such a film include a polyethylene terephthalate film (for example, a biaxially stretched polyethylene terephthalate film), a cellulose triacetate film, a polystyrene film, a polyimide film, and a polycarbonate film.
  • a biaxially stretched polyethylene terephthalate film is particularly preferable as the temporary support.
  • the film used as the temporary support has no deformation such as wrinkles or scratches.
  • the temporary support is preferably highly transparent, and the transmittance at 365 nm is preferably 60% or more, more preferably 70% or more.
  • the haze of the temporary support is small. Specifically, the haze value of the temporary support is preferably 2% or less, more preferably 0.5% or less, and particularly preferably 0.1% or less.
  • the number of fine particles, foreign substances, and defects contained in the temporary support is small.
  • the number of the above fine particles and foreign matter and defect diameter 1 ⁇ m is preferably 50/10 mm 2 or less, more preferably 10/10 mm 2 or less, further preferably 3/10 mm 2 or less , 0 pieces / 10 mm 2 is particularly preferable.
  • the temporary support of the transfer film of the present invention has an arithmetic average roughness Ra of the surface on the photosensitive resin layer side of 50 nm or less, preferably 1 to 20 nm, and more preferably 1 to 12 nm.
  • the arithmetic mean roughness Ra is an arithmetic mean roughness according to JIS B0601: 2001 measured using an optical surface texture measuring instrument.
  • the temporary support may contain particles from the viewpoint of adjusting the arithmetic mean roughness Ra of the surface of the temporary support on the photosensitive resin layer side to the above range, and the temporary support may contain particles.
  • a particle-containing layer constituting the surface on the photosensitive resin layer side may be provided.
  • the particles contained in the temporary support may be organic particles or inorganic particles.
  • the organic particles include polyimide resins, olefin or modified olefin resins, crosslinked polystyrene resins, and silicone resins.
  • Specific examples of the inorganic particles include silicon oxide, calcium carbonate, aggregated alumina, aluminum silicate, mica, clay, talc, and barium sulfate.
  • the arithmetic mean roughness Ra of the surface of the temporary support on the photosensitive resin layer side can be adjusted within the above range.
  • the thickness of the temporary support is not particularly limited, but is preferably 5 ⁇ m to 200 ⁇ m, more preferably 10 ⁇ m to 150 ⁇ m, and further preferably 10 to 50 ⁇ m from the viewpoint of ease of handling and versatility. preferable.
  • Preferred embodiments of the temporary support include, for example, paragraphs 0017 to 0018 of JP2014-85643), paragraphs 0019 to 0026 of JP2016-27363, paragraphs 0041 to 0057, WO2018 of WO2012 / 08168A1 / 179370A1 Publications are described in paragraphs 0029 to 0040, and the contents of these publications are incorporated herein by reference.
  • Preferred commercially available products of the temporary support include Lumirror 16KS40, Lumirror 16FB40 (all manufactured by Toray Industries, Inc.), Cosmoshine A4100, Cosmoshine A4300, and Cosmoshine A8300 (all manufactured by Toyobo Co., Ltd.).
  • the transfer film of the present invention has a photosensitive resin layer.
  • the photosensitive resin layer of the transfer film of the present invention is a photosensitive resin layer in which the cured film has a breaking elongation at 120 ° C. of 15% or more.
  • it is a photosensitive resin layer having a property that the elongation at break at 120 ° C. after curing is 15% or more.
  • the breaking elongation of the cured film at 120 ° C. the value measured by the method shown below is adopted.
  • the solid content concentration of the material for forming the photosensitive resin layer (hereinafter, also abbreviated as "photosensitive resin composition”) is appropriately adjusted, and the therapy (manufactured by Toray Industries, Inc.) so that the thickness after drying becomes 20 ⁇ m. It is applied on top and dried to form a coating film for evaluation of elongation at break.
  • the coating film formed on the surface of the therapy was exposed to 120 mJ / cm 2 with an ultra-high pressure mercury lamp to cure it, and then further exposed to 400 mJ / cm 2 with a high pressure mercury lamp and heated at 145 ° C. for 30 minutes. Cut into a size of 3 cm x 5 mm. After that, the coating film is peeled off from the therapy.
  • the obtained coating film is subjected to a tensile test using a tensile tester (Tensilon RTG-1210: manufactured by A & D Co., Ltd.) at a speed of 50 mm / min in an environment of 120 ° C.
  • a tensile tester Teensilon RTG-1210: manufactured by A & D Co., Ltd.
  • the tensile tester is set in the chuck portion 2 so that the measurement length of the sample 1 is 20 mm.
  • the sample width is 5 mm.
  • the elongation rate at the point where the coating film breaks is measured five times, and the average value is calculated as the breaking elongation.
  • the fracture elongation of the cured film obtained by curing the photosensitive resin layer at 23 ° C. is 120 ° C. It is preferable that the elongation at break is twice or more large.
  • the breaking elongation of the cured film at 23 ° C. a value measured by the same method as described above is adopted except that the environment of the tensile test is changed from 120 ° C. to 23 ° C.
  • the following formula (1) is satisfied because the peelability of the temporary support and the protective film and the punching processability of the cured film obtained by curing the photosensitive resin layer after transfer can be compatible at a higher level. Is preferable.
  • X represents the value (%) of the elongation at break at 120 ° C. of the cured film obtained by curing the photosensitive resin layer
  • Y represents the surface of the temporary support on the photosensitive resin layer side. It represents the value (nm) of the arithmetic mean roughness Ra.
  • the value of X ⁇ Y is obtained because the peelability of the temporary support and the protective film and the punching processability of the cured film obtained by curing the photosensitive resin layer after transfer can be compatible at a higher level. Is more preferably less than 400 and more preferably greater than 70.
  • moisture permeability of a film thickness 40 ⁇ m of the cured film formed by curing a photosensitive resin layer is not more than 500g / m 2 / 24hr preferably, more preferably 10 ⁇ 400g / m 2 / 24hr , further preferably 10 ⁇ 300g / m 2 / 24hr .
  • the moisture permeability of the cured film at a film thickness of 40 ⁇ m the value measured by the following procedure is adopted.
  • a photosensitive resin composition having a thickness of 8 ⁇ m is formed by applying a photosensitive resin composition on a polyethylene terephthalate (PET) film having a thickness of 75 ⁇ m as a temporary support using a slit-shaped nozzle and then drying the film. , Obtain a transfer film for sample preparation. Next, the transfer film for sample preparation was laminated on a PTFE (tetrafluoroethylene resin) membrane filter FP-100-100 manufactured by Sumitomo Electric Co., Ltd., and a temporary support / a photosensitive resin layer having a thickness of 8 ⁇ m / a membrane filter layer. A laminated body A having a structure is formed.
  • PET polyethylene terephthalate
  • the conditions for laminating are a membrane filter temperature of 40 ° C., a lamilol temperature of 110 ° C., a linear pressure of 3 N / cm, and a transport speed of 2 m / min.
  • the temporary support is peeled off from the laminated body A.
  • a laminated body B having a laminated structure of a photosensitive resin layer / membrane filter having a total film thickness of 40 ⁇ m is formed.
  • the photosensitive resin layer of the obtained laminate B was exposed to an exposure amount of 300 mJ / cm 2 by i-ray, and then post-baked at 145 ° C. for 30 minutes to cure and cure the photosensitive resin layer. Form a film. From the above, a sample for moisture permeability measurement having a laminated structure of a cured film / membrane filter having a total film thickness of 40 ⁇ m is obtained.
  • ⁇ Measurement of moisture permeability> Using a sample for measuring moisture permeability, the moisture permeability is measured by the cup method with reference to JIS-Z-0208 (1976). First, a circular sample having a diameter of 70 mm is cut out from the sample for measuring moisture permeability. Next, a measuring cup with a lid is prepared by putting 20 g of dried calcium chloride in the measuring cup and then covering with the circular sample. The measuring cup with a lid is left in a constant temperature and humidity chamber at 65 ° C. and 90% relative humidity (RH) for 24 hours. Standing from the mass change of the lid measuring cups before and after, the water vapor permeability of round sample: calculating the (unit g / m 2 / 24hr). The above measurement is performed three times, and the average value of water vapor permeability is calculated as the moisture permeability.
  • the photosensitive resin layer of the transfer film of the present invention preferably contains a binder polymer, a polymerizable monomer and a photopolymerization initiator, and is a photosensitive resin containing a binder polymer, a polymerizable monomer and a photopolymerization initiator. It is more preferably formed using the composition.
  • the binder polymer is preferably an alkali-soluble resin.
  • the binder polymer is preferably a binder polymer having an acid value of 30 to 160 mgKOH / g, and more preferably an alkali-soluble resin having an acid value of 30 to 160 mgKOH / g.
  • alkali-soluble means that the solubility of sodium carbonate in a 1% by mass aqueous solution at 22 ° C. is 0.1% by mass or more.
  • the acid value of the binder polymer is a value measured according to the method described in JIS K0070: 1992.
  • the binder polymer is, for example, a resin having a carboxy group having an acid value of 30 to 160 mgKOH / g (so-called carboxy group-containing resin) from the viewpoint that it is easily crosslinked with a crosslinked component by heating to form a strong film.
  • a resin having a carboxy group having an acid value of 30 to 160 mgKOH / g is particularly preferable.
  • the acrylic resin refers to a resin having a structural unit derived from a (meth) acrylic compound, and the content of the structural unit is preferably 30% by mass or more with respect to the total mass of the resin. , 50% by mass or more is more preferable.
  • the binder polymer is preferably an acrylic resin or a styrene-acrylic copolymer from the viewpoint of moisture permeability and bending resistance of the obtained cured film and the adhesiveness of the obtained uncured film, and is preferably a styrene-acrylic copolymer. It is more preferably a polymer.
  • the styrene-acrylic copolymer refers to a resin having a structural unit derived from a styrene compound and a structural unit derived from a (meth) acrylic compound, and the structural unit derived from the styrene compound and the (meth) compound.
  • the total content of the constituent units derived from the acrylic compound is preferably 30% by mass or more, more preferably 50% by mass or more, based on the total mass of the copolymer.
  • the content of the structural unit derived from the styrene compound is preferably 1% by mass or more, more preferably 5% by mass or more, and 5% by mass or more and 80% by mass with respect to the total mass of the copolymer. It is particularly preferable that it is% or less.
  • the content of the structural unit derived from the (meth) acrylic compound is preferably 5% by mass or more, more preferably 10% by mass or more, and 20% by mass, based on the total mass of the copolymer. It is particularly preferable that it is% or more and 95% by mass or less.
  • examples of the (meth) acrylic compound include (meth) acrylate compound, (meth) acrylic acid, (meth) acrylamide compound, and (meth) acrylonitrile. Of these, at least one compound selected from the group consisting of (meth) acrylate compounds and (meth) acrylic acid is preferable.
  • the binder polymer preferably has a structural unit having an aromatic ring from the viewpoint of moisture permeability and strength of the obtained cured film.
  • the monomer forming a structural unit having an aromatic ring include styrene, tert-butoxystyrene, methylstyrene, ⁇ -methylstyrene, benzyl (meth) acrylate and the like. Of these, styrene compounds are preferable, and styrene is particularly preferable.
  • the binder polymer more preferably has a structural unit (constituent unit derived from styrene) represented by the following formula (S) from the viewpoint of moisture permeability and strength of the obtained cured film.
  • the content of the structural unit having an aromatic ring is 5% by mass to 90% by mass with respect to the total mass of the binder polymer from the viewpoint of moisture permeability and strength of the obtained cured film. It is preferably by mass%, more preferably 10% by mass to 70% by mass, and particularly preferably 20% by mass to 50% by mass. Further, the content of the structural unit having an aromatic ring in the binder polymer is preferably 5 mol% to 70 mol% with respect to the total amount of the binder polymer from the viewpoint of the moisture permeability and strength of the obtained cured film. It is more preferably mol% to 60 mol%, and particularly preferably 20 mol% to 50 mol%.
  • the content of the structural unit represented by the above formula (S) in the binder polymer is 5 mol% to 70 mol% with respect to the total amount of the binder polymer from the viewpoint of the moisture permeability and strength of the obtained cured film. It is preferable, it is more preferably 10 mol% to 60 mol%, and particularly preferably 20 mol% to 50 mol%.
  • the above “constituent unit” is synonymous with the "monomer unit”.
  • the above-mentioned "monomer unit” may be modified after polymerization by a polymer reaction or the like. The same applies to the following.
  • the binder polymer preferably has a structural unit having an aliphatic hydrocarbon ring from the viewpoint of the strength of the obtained cured film and the adhesiveness of the obtained uncured film.
  • Examples of the aliphatic hydrocarbon ring in the constituent unit having an aliphatic hydrocarbon ring include a tricyclodecane ring, a cyclohexane ring, a cyclopentane ring, a norbornane ring, and an isoborone ring.
  • the ring is a condensed ring of two or more aliphatic hydrocarbon rings, and is a tetrahydrodicyclopentadiene ring.
  • Tricyclo [5.2.1.0 2,6 ] decane ring is particularly preferable.
  • the monomer forming a structural unit having an aliphatic hydrocarbon ring include dicyclopentanyl (meth) acrylate, cyclohexyl (meth) acrylate, and isobornyl (meth) acrylate.
  • the binder polymer more preferably has a structural unit represented by the following formula (Cy) from the viewpoint of the strength of the obtained cured film and the adhesiveness of the obtained uncured film, and the above formula (S). It is particularly preferable to have a structural unit represented by and a structural unit represented by the following formula (Cy).
  • R M represents a hydrogen atom or a methyl group
  • R Cy represents a monovalent group having an aliphatic hydrocarbon ring structure
  • R M in the formula (Cy) is preferably a methyl group.
  • R Cy in the formula (Cy) is a monovalent group having an aliphatic hydrocarbon ring structure having 5 to 20 carbon atoms from the viewpoint of the strength of the obtained cured film and the adhesiveness of the obtained uncured film. It is preferable that it is a monovalent group having an aliphatic hydrocarbon ring structure having 6 to 16 carbon atoms, and more preferably it is a monovalent group having an aliphatic hydrocarbon ring structure having 8 to 14 carbon atoms. Is particularly preferable.
  • aliphatic hydrocarbon cyclic structure in the R Cy of formula (Cy), the strength of the cured film obtained, and, from the viewpoint of the tackiness of the uncured film obtained, two or more rings aliphatic hydrocarbon ring condensed It is preferably a ring structure, and more preferably a ring in which 2 or more and 4 or less aliphatic hydrocarbon rings are fused.
  • R Cy in the formula (Cy), the strength of the cured film obtained, and, from the viewpoint of the tackiness of the uncured film obtained, and -C ( O) O- oxygen atom in the formula (Cy)
  • the binder polymer may have one type of structural unit having an aliphatic hydrocarbon ring alone, or may have two or more types.
  • the content of the structural unit having an aliphatic hydrocarbon ring is based on the total mass of the binder polymer in terms of the moisture permeability and strength of the obtained cured film. It is preferably 5% by mass to 90% by mass, more preferably 10% by mass to 80% by mass, and particularly preferably 20% by mass to 70% by mass.
  • the content of the structural unit having an aliphatic hydrocarbon ring in the binder polymer may be 5 mol% to 70 mol% with respect to the total amount of the binder polymer from the viewpoint of moisture permeability and strength of the obtained cured film. It is preferably 10 mol% to 60 mol%, more preferably 20 mol% to 50 mol%. Further, the content of the structural unit represented by the above formula (Cy) in the binder polymer is 5 mol% to 70 mol% with respect to the total amount of the binder polymer from the viewpoint of the moisture permeability and strength of the obtained cured film. It is preferable, it is more preferably 10 mol% to 60 mol%, and particularly preferably 20 mol% to 50 mol%.
  • the binder polymer contains a structural unit having an aromatic ring and a structural unit having an aliphatic hydrocarbon ring
  • the total content of the structural unit having an aromatic ring and the structural unit having an aliphatic hydrocarbon ring is the total content of the obtained cured film.
  • it is preferably 10% by mass to 90% by mass, more preferably 20% by mass to 80% by mass, and 40% by mass to the total mass of the binder polymer. It is particularly preferably 75% by mass.
  • the total content of the structural unit having an aromatic ring and the structural unit having an aliphatic hydrocarbon ring in the binder polymer is based on the total amount of the binder polymer from the viewpoint of moisture permeability, bending resistance and strength of the obtained cured film. It is preferably 10 mol% to 80 mol%, more preferably 20 mol% to 70 mol%, and particularly preferably 40 mol% to 60 mol%. Further, the total content of the structural unit represented by the above formula (S) and the structural unit represented by the above formula (Cy) in the binder polymer is determined from the viewpoint of moisture permeability, bending resistance and strength of the obtained cured film.
  • the molar amount nS of the structural unit represented by the above formula (S) and the molar amount nCy of the structural unit represented by the above formula (Cy) in the binder polymer are the moisture permeability, bending resistance and strength of the obtained cured film. From the viewpoint of, it is preferable to satisfy the relationship shown in the following formula (SCy), more preferably to satisfy the following formula (SCy-1), and particularly preferably to satisfy the following formula (SCy-2).
  • the binder polymer preferably has a structural unit having an acid group from the viewpoint of the strength of the obtained cured film and the developability.
  • the acid group include a carboxy group, a sulfo group, a phosphonic acid group, a phosphoric acid group and the like, but a carboxy group is preferable.
  • the structural unit having the acid group the structural unit derived from (meth) acrylic acid shown below is preferably mentioned, and the structural unit derived from methacrylic acid is more preferably mentioned.
  • the binder polymer may have one type of structural unit having an acid group alone or two or more types.
  • the content of the structural unit having an acid group is 5% by mass with respect to the total mass of the binder polymer from the viewpoint of the strength of the obtained cured film and the developability. It is preferably ⁇ 50% by mass, more preferably 5% by mass to 40% by mass, and particularly preferably 10% by mass to 30% by mass.
  • the content of the structural unit having an acid group in the binder polymer is preferably 5 mol% to 70 mol% with respect to the total amount of the binder polymer from the viewpoint of the strength of the obtained cured film and the developability.
  • the content of the (meth) acrylic acid-derived structural unit in the binder polymer is 5 mol% to 70 mol% with respect to the total amount of the binder polymer from the viewpoint of the strength of the obtained cured film and the developability. It is preferable, it is more preferably 10 mol% to 50 mol%, and particularly preferably 20 mol% to 40 mol%.
  • the binder polymer preferably has a reactive group, and more preferably has a structural unit having a reactive group, from the viewpoint of the strength of the obtained cured film and the adhesiveness of the obtained uncured film. ..
  • a reactive group a radically polymerizable group is preferable, and an ethylenically unsaturated group is more preferable.
  • the binder polymer preferably has a structural unit having an ethylenically unsaturated group in the side chain.
  • the "main chain” represents a relatively longest binding chain among the molecules of the polymer compound constituting the resin, and the “side chain” represents an atomic group branched from the main chain. ..
  • the ethylenically unsaturated group a (meth) acrylic group is preferable, and a (meth) acryloyl group is more preferable.
  • the structural unit having a reactive group include those shown below, but it goes without saying that the unit is not limited thereto.
  • the binder polymer may have one type of structural unit having a reactive group alone or two or more types.
  • the content of the structural unit having a reactive group of the binder polymer is determined from the viewpoint of the strength of the obtained cured film and the adhesiveness of the obtained uncured film. It is preferably 5% by mass to 70% by mass, more preferably 10% by mass to 50% by mass, and particularly preferably 20% by mass to 40% by mass with respect to the total mass.
  • the content of the structural unit having a reactive group in the binder polymer is 5 mol% to 70 with respect to the total amount of the binder polymer from the viewpoint of the strength of the obtained cured film and the adhesiveness of the obtained uncured film. It is preferably mol%, more preferably 10 mol% to 60 mol%, and particularly preferably 20 mol% to 50 mol%.
  • a reactive group into a binder polymer a hydroxy group, a carboxy group, a primary amino group, a secondary amino group, an acetoacetyl group, a sulfo group, etc., an epoxy compound, a blocked isocyanate compound, an isocyanate compound, etc.
  • examples thereof include a method of reacting a vinyl sulfone compound, an aldehyde compound, a methylol compound, a carboxylic acid anhydride and the like.
  • a preferred example of a means for introducing a reactive group into a binder polymer is that a polymer having a carboxy group is synthesized by a polymerization reaction and then glycidyl (meth) acrylate is added to a part of the carboxy groups of the obtained polymer by the polymer reaction.
  • a means for introducing a (meth) acryloxy group into a polymer by reacting By this means, a binder polymer having a (meth) acryloxy group in the side chain can be obtained.
  • the polymerization reaction is preferably carried out under a temperature condition of 70 ° C. to 100 ° C., and more preferably carried out under a temperature condition of 80 ° C. to 90 ° C.
  • an azo-based initiator is preferable, and for example, V-601 (trade name) or V-65 (trade name) manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. is more preferable.
  • the polymer reaction is preferably carried out under temperature conditions of 80 ° C. to 110 ° C.
  • a catalyst such as an ammonium salt.
  • the content of the residual monomer in each structural unit of the binder polymer is preferably 5,000 mass ppm or less, more preferably 2,000 mass ppm or less, based on the total mass of the binder polymer from the viewpoint of patterning property and reliability. It is preferable, and more preferably 500 mass ppm or less.
  • the lower limit is not particularly limited, but is preferably 1 mass ppm or more, and more preferably 10 mass ppm or more.
  • the residual monomer of each structural unit of the binder polymer is preferably 3,000 mass ppm or less, more preferably 600 mass ppm or less, based on the total mass of the photosensitive composition layer from the viewpoint of patterning property and reliability. More preferably, it is 100 mass ppm or less.
  • the lower limit is not particularly limited, but is preferably 0.1 mass ppm or more, and more preferably 1 mass ppm or more.
  • the amount of residual monomer of the monomer when synthesizing the binder polymer by the polymer reaction is also preferably in the above range.
  • the content of glycidyl acrylate is preferably in the above range.
  • the amount of residual monomer can be measured by a known method such as liquid chromatography or gas chromatography.
  • the binder polymer the following polymers are preferably mentioned.
  • the content ratios (a to d) and the weight average molecular weight Mw of each structural unit shown below can be appropriately changed according to the purpose.
  • the weight average molecular weight (Mw) of the binder polymer is preferably 5,000 or more, and preferably 10,000 or more, from the viewpoint of the strength of the obtained cured film and the adhesiveness of the obtained uncured film. More preferably, it is more preferably 10,000 to 50,000, and particularly preferably 20,000 to 30,000.
  • the photosensitive resin layer or the photosensitive resin composition may contain only one kind of binder polymer, or may contain two or more kinds of binder polymers.
  • the content of the binder polymer is, for example, 10% by mass to 90% by mass with respect to the total solid content of the photosensitive resin layer or the photosensitive resin composition from the viewpoint of the strength of the cured film and the handleability in the transfer film. It is preferably 20% by mass to 80% by mass, and even more preferably 30% by mass to 70% by mass.
  • the polymerizable monomer is preferably a radically polymerizable compound having an ethylenically unsaturated group (hereinafter, also simply abbreviated as “ethylenically unsaturated compound”).
  • the radically polymerizable compound having an ethylenically unsaturated group is a component that contributes to the photosensitivity (that is, photocurability) of the photosensitive resin layer and the strength of the cured film.
  • the ethylenically unsaturated compound is a compound having one or more ethylenically unsaturated groups.
  • the photosensitive resin layer preferably contains a bifunctional or higher functional ethylenically unsaturated compound as the ethylenically unsaturated compound.
  • the bifunctional or higher functional ethylenically unsaturated compound means a compound having two or more ethylenically unsaturated groups in one molecule.
  • a (meth) acryloyl group is more preferable.
  • a (meth) acrylate compound is preferable.
  • the photosensitive resin layer is composed of a bifunctional ethylenically unsaturated compound (preferably a bifunctional (meth) acrylate compound) and a trifunctional or higher functional ethylenically unsaturated compound (preferably). It is particularly preferable to contain (3 or more functional (meth) acrylate compounds).
  • the bifunctional ethylenically unsaturated compound is not particularly limited and may be appropriately selected from known compounds.
  • Examples of the bifunctional ethylenically unsaturated compound include tricyclodecanedimethanol di (meth) acrylate, tricyclodecanedimethanol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, and 1,6-hexane. Examples thereof include diol di (meth) acrylate.
  • the bifunctional ethylenically unsaturated compound includes tricyclodecanedimethanol diacrylate (A-DCP, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) and tricyclodecanedimethanol dimethacrylate (DCP, Shin Nakamura Chemical Industry Co., Ltd.).
  • A-DCP tricyclodecanedimethanol diacrylate
  • DCP tricyclodecanedimethanol dimethacrylate
  • Nakamura Chemical Industry Co., Ltd. 1,9-Nonandiol diacrylate
  • A-NOD-N 1,9-Nonandiol diacrylate
  • A-HD-N new Nakamura Chemical Industry Co., Ltd.
  • the trifunctional or higher functional ethylenically unsaturated compound is not particularly limited and may be appropriately selected from known compounds.
  • Examples of the trifunctional or higher functional ethylenically unsaturated compound include dipentaerythritol (tri / tetra / penta / hexa) (meth) acrylate, pentaerythritol (tri / tetra) (meth) acrylate, and trimethylolpropane tri (meth).
  • Examples thereof include acrylates, ditrimethylolpropane tetra (meth) acrylates, isocyanuric acid (meth) acrylates, and (meth) acrylate compounds having a glycerintri (meth) acrylate skeleton.
  • (tri / tetra / penta / hexa) (meth) acrylate) is a concept including tri (meth) acrylate, tetra (meth) acrylate, penta (meth) acrylate, and hexa (meth) acrylate.
  • (Tri / tetra) (meth) acrylate” is a concept that includes tri (meth) acrylate and tetra (meth) acrylate.
  • Examples of the ethylenically unsaturated compound include caprolactone-modified compounds of (meth) acrylate compounds (KAYARAD (registered trademark) DPCA-20 manufactured by Nippon Kayaku Co., Ltd., A-9300-1CL manufactured by Shin Nakamura Chemical Industry Co., Ltd., etc.).
  • (Meta) acrylate compound alkylene oxide-modified compound (KAYARAD RP-1040 manufactured by Nippon Kayaku Co., Ltd., ATM-35E, A-9300 manufactured by Shin Nakamura Chemical Industry Co., Ltd., EBECRYL (registered trademark) manufactured by Daicel Ornex Co., Ltd. Etc.), ethoxylated glycerin triacrylate (A-GLY-9E manufactured by Shin Nakamura Chemical Industry Co., Ltd., etc.) and the like.
  • Examples of the ethylenically unsaturated compound include urethane (meth) acrylate compounds (preferably trifunctional or higher functional urethane (meth) acrylate compounds).
  • the upper limit of the number of functional groups can be, for example, 20 functional or less.
  • Examples of trifunctional or higher functional urethane (meth) acrylate compounds include 8UX-015A (manufactured by Taisei Fine Chemical Co., Ltd.), UA-32P (manufactured by Shin Nakamura Chemical Industry Co., Ltd.), and UA-1100H (manufactured by Shin Nakamura Chemical Industry Co., Ltd.).
  • the ethylenically unsaturated compound preferably contains an ethylenically unsaturated compound having an acid group from the viewpoint of improving developability.
  • the acid group include a phosphoric acid group, a sulfonic acid group, and a carboxy group, and a carboxy group is preferable.
  • the ethylenically unsaturated compound having an acid group at least one selected from the group consisting of a bifunctional or higher functional ethylenically unsaturated compound containing a carboxy group and a carboxylic acid anhydride thereof is preferable. This enhances the developability and the strength of the cured film.
  • the bifunctional or higher functional ethylenically unsaturated compound containing a carboxy group is not particularly limited and can be appropriately selected from known compounds.
  • Examples of the bifunctional or higher functional ethylenically unsaturated compound containing a carboxy group include Aronix (registered trademark) TO-2349 (manufactured by Toa Synthetic Co., Ltd.), Aronix M-520 (manufactured by Toa Synthetic Co., Ltd.), or , Aronix M-510 (manufactured by Toa Synthetic Co., Ltd.) can be preferably used.
  • the ethylenically unsaturated compound having an acid group is also preferably a polymerizable compound having an acid group described in paragraphs 0025 to 0030 of JP-A-2004-239942. The contents of this publication are incorporated herein by reference.
  • the ethylenically unsaturated compound is preferably compound A represented by the following formula (I) (simply also referred to as “compound A”).
  • Q 2 -R 1 -Q 1 Formula (I) Q 1 and Q 2 each independently represent a (meth) acryloyloxy group, and R 1 represents a divalent linking group having a chain structure.
  • Q 1 and Q 2 in formula (I) from the viewpoint of ease of synthesis, it is preferred that Q 1 and Q 2 are the same group. Further, Q 1 and Q 2 in the formula (I) are preferably acryloyloxy groups from the viewpoint of reactivity.
  • R 1 in (I) from the viewpoint of bending resistance of the obtained cured film, an alkylene group, an alkylene oxyalkylene group (-L 1 -O-L 1 - ), or, polyalkylene oxyalkylene group (- (L 1- O) p- L 1- ) is preferable, and a hydrocarbon group having 2 to 20 carbon atoms or a polyalkyleneoxyalkylene group is more preferable, and an alkylene group having 4 to 20 carbon atoms.
  • the hydrocarbon group may have a chain structure at least in part, and may be, for example, linear, branched, cyclic, or a combination thereof, and the obtained cured film may be obtained.
  • it is preferably an alkylene group or a group in which two or more alkylene groups and one or more arylene groups are combined, more preferably an alkylene group, and a linear alkylene group. Is particularly preferable.
  • the L 1 independently represents an alkylene group, preferably an ethylene group, a propylene group, or a butylene group, and more preferably an ethylene group or a 1,2-propylene group.
  • p represents an integer of 2 or more, and is preferably an integer of 2 to 10.
  • the atomic number of the connecting chain of the shortest for connecting the Q 1, Q 2 in the compound A, from the viewpoint of moisture permeability and bending resistance of the obtained cured film is preferably from 3 to 50, The number is more preferably 4 to 40, further preferably 6 to 20, and particularly preferably 8 to 12.
  • the term "Q 1, Q atoms linking chain shortest connecting between two" shortest connecting the atom in R 1 be linked to Q 1 to atom in R 1 be linked to Q 2 Is the number of atoms in.
  • Compound A examples include 1,3-butanediol di (meth) acrylate, tetramethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, and 1,6-hexanediol di (meth) acrylate.
  • the ester monomer can also be used as a mixture.
  • 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, and 1,10-decanediol di (meth) acrylate from the viewpoint of bending resistance of the obtained cured film. It is preferably at least one compound selected from the group consisting of acrylates and neopentyl glycol di (meth) acrylates, preferably 1,6-hexanediol di (meth) acrylates, 1,9-nonanediol di ().
  • it is at least one compound selected from the group consisting of meta) acrylates and 1,10-decanediol di (meth) acrylates, with 1,9-nonanediol di (meth) acrylates and Particularly preferred is at least one compound selected from the group consisting of 1,10-decanediol di (meth) acrylates.
  • the weight average molecular weight (Mw) of the ethylenically unsaturated compound is preferably 200 to 3,000, more preferably 250 to 2,600, further preferably 280 to 2,200, and particularly preferably 300 to 2,200.
  • the proportion of the ethylenically unsaturated compound having a molecular weight of 300 or less among the ethylenically unsaturated compounds used in the photosensitive resin layer is higher than that of all the ethylenically unsaturated compounds contained in the photosensitive resin layer. 30% by mass or less is preferable, 25% by mass or less is more preferable, and 20% by mass or less is further preferable.
  • the ethylenically unsaturated compound may be used alone or in combination of two or more.
  • the content of the ethylenically unsaturated compound in the photosensitive resin layer is preferably 1% by mass to 70% by mass, more preferably 5% by mass to 70% by mass, and 10% by mass to the total mass of the photosensitive resin layer. 70% by mass is more preferable, 20% by mass to 60% by mass is particularly preferable, and 20% by mass to 50% by mass is most preferable.
  • the content of the bifunctional ethylenically unsaturated compound is contained in the photosensitive resin layer. It is preferably 10% by mass to 90% by mass, more preferably 20% by mass to 85% by mass, still more preferably 30% by mass to 80% by mass, based on all the ethylenically unsaturated compounds. Further, in this case, the content of the trifunctional or higher functional ethylenically unsaturated compound is preferably 10% by mass to 90% by mass, preferably 15% by mass or more, based on all the ethylenically unsaturated compounds contained in the photosensitive resin layer.
  • the content of the bifunctional or higher functional ethylenically unsaturated compound is 40% by mass or more 100 with respect to the total content of the bifunctional ethylenically unsaturated compound and the trifunctional or higher functional ethylenically unsaturated compound. It is preferably less than mass%, more preferably 40% by mass to 90% by mass, further preferably 50% by mass to 80% by mass, and particularly preferably 50% by mass to 70% by mass. ..
  • the photosensitive resin layer may further contain a monofunctional ethylenically unsaturated compound.
  • the photosensitive resin layer contains a bifunctional or higher functional ethylenically unsaturated compound
  • the ethylenically unsaturated compound contained in the photosensitive resin layer contains a bifunctional or higher functional ethylenically unsaturated compound as a main component. Is preferable.
  • the content of the bifunctional or higher ethylenically unsaturated compound is the ethylenically unsaturated compound contained in the photosensitive resin layer.
  • 60% by mass to 100% by mass is preferable, 80% by mass to 100% by mass is more preferable, and 90% by mass to 100% by mass is particularly preferable with respect to the total content of the saturated compound.
  • the photosensitive resin layer contains an ethylenically unsaturated compound having an acid group (preferably a bifunctional or higher functional ethylenically unsaturated compound containing a carboxy group or a carboxylic acid anhydride thereof), the acid group is used.
  • the content of the ethylenically unsaturated compound is preferably 1% by mass to 50% by mass, more preferably 1% by mass to 20% by mass, still more preferably 1% by mass to 10% by mass, based on the photosensitive resin layer.
  • the photopolymerization initiator is not particularly limited, and a known photopolymerization initiator can be used.
  • the photopolymerization initiator include a photopolymerization initiator having an oxime ester structure (hereinafter, also referred to as “oxym-based photopolymerization initiator”) and a photopolymerization initiator having an ⁇ -aminoalkylphenone structure (hereinafter, “ ⁇ -”).
  • Photopolymerization initiator hereinafter, also referred to as “acylphosphine oxide-based photopolymerization initiator”
  • photopolymerization initiator having an N-phenylglycine structure hereinafter, “N-phenylglycine-based photopolymerization initiator” Also called.
  • Etc. can be mentioned.
  • the photopolymerization initiator is selected from the group consisting of an oxime-based photopolymerization initiator, an ⁇ -aminoalkylphenone-based photopolymerization initiator, an ⁇ -hydroxyalkylphenone-based polymerization initiator, and an N-phenylglycine-based photopolymerization initiator. It preferably contains at least one, and preferably contains at least one selected from the group consisting of an oxime-based photopolymerization initiator, an ⁇ -aminoalkylphenone-based photopolymerization initiator, and an N-phenylglycine-based photopolymerization initiator. More preferred.
  • the photopolymerization initiator for example, the polymerization initiators described in paragraphs 0031 to 0042 of JP2011-95716A and paragraphs 0064 to 0081 of JP2015-014783 may be used. ..
  • photopolymerization initiators include 1- [4- (phenylthio) phenyl] -1,2-octanedione-2- (O-benzoyloxime) [trade name: IRGACURE (registered trademark) OXE-01, BASF.
  • Oxime ester-based [trade name: Lunar (trade name: Lunar) Registered trademark) 6, DKSH Japan Co., Ltd.], 1- [4- (phenylthio) phenyl] -3-cyclopentylpropane-1,2-dione-2- (O-benzoyloxime) (trade name: TR-PBG) -305, manufactured by Changshu Powerful Electronics New Materials Co., Ltd.), 1,2-propanedione, 3-cyclohexyl-1- [9-ethyl-6- (2-furanylcarbonyl) -9H-carbazole-3-yl]-, 2- (O-Acetyloxime) (trade name: TR-PBG-326, manufactured by Joshu Strong Electronics New Materials Co., Ltd.), 3-Cyclohexyl-1- (6- (2- (benzo Iloxyimino) Hexanoyl) -9-Ethyl-9H-Carbazole-3-yl) -Propane-1,2-dione-2
  • the photosensitive resin layer or the photosensitive resin composition may contain only one type of photopolymerization initiator, or may contain two or more types of photopolymerization initiators.
  • the content of the photopolymerization initiator is not particularly limited, but is preferably 0.1% by mass or more, preferably 0.5% by mass or more, based on the total solid content of the photosensitive resin layer or the photosensitive resin composition. It is more preferable that the amount is 1.0% by mass or more.
  • the content of the photopolymerization initiator is preferably 10% by mass or less, and more preferably 5% by mass or less, based on the total solid content of the photosensitive resin layer or the photosensitive resin composition.
  • the photosensitive resin composition for forming the photosensitive resin layer or the photosensitive resin layer of the transfer film of the present invention has a reason that the punching processability of the cured film obtained by curing the photosensitive resin layer after transfer becomes better. It preferably contains a compound (hereinafter, also abbreviated as "thermocrosslinkable compound”) that is generated by heating a group that can react with an acid group or a hydroxy group.
  • thermocrosslinkable compound examples include epoxy compounds, oxetane compounds, methylol compounds, blocked isocyanate compounds and the like. Among them, the blocked isocyanate compounds shown below are preferable from the viewpoint of the strength of the obtained cured film and the adhesiveness of the obtained uncured film.
  • the blocked isocyanate compound refers to "a compound having a structure in which the isocyanate group of isocyanate is protected (so-called masked) with a blocking agent".
  • the dissociation temperature of the blocked isocyanate compound is not particularly limited, but is preferably 100 ° C. to 160 ° C., more preferably 130 ° C. to 150 ° C.
  • the dissociation temperature of the blocked isocyanate means "the temperature of the endothermic peak associated with the deprotection reaction of the blocked isocyanate when measured by DSC (Differential scanning calorimetry) analysis using a differential scanning calorimetry". ..
  • a differential scanning calorimeter for example, a differential scanning calorimeter (model: DSC6200) manufactured by Seiko Instruments, Inc. can be preferably used. However, the differential scanning calorimeter is not limited to this.
  • the blocking agent having a dissociation temperature of 100 ° C. to 160 ° C. for example, at least one selected from oxime compounds is preferable from the viewpoint of storage stability.
  • the blocked isocyanate compound preferably has an isocyanurate structure, for example, from the viewpoint of improving the brittleness of the membrane and improving the adhesion to the transferred material.
  • the blocked isocyanate compound having an isocyanurate structure can be obtained, for example, by isocyanurate-forming and protecting hexamethylene diisocyanate.
  • a compound having an oxime structure using an oxime compound as a blocking agent is easier to set the dissociation temperature in a preferable range than a compound having no oxime structure, and reduces the development residue. It is preferable from the viewpoint of ease.
  • the blocked isocyanate compound preferably has a polymerizable group, and more preferably has a radically polymerizable group, for example, from the viewpoint of the strength of the cured film.
  • the polymerizable group is not particularly limited, and a known polymerizable group can be used.
  • Examples of the polymerizable group include an ethylenically unsaturated group such as a (meth) acryloxy group, a (meth) acrylamide group and a styryl group, and a group having an epoxy group such as a glycidyl group.
  • an ethylenically unsaturated group is preferable, a (meth) acryloxy group is more preferable, and an acryloxy group is particularly preferable, from the viewpoint of surface surface condition, development speed and reactivity of the obtained cured film. preferable.
  • blocked isocyanate compound a commercially available product can be used.
  • examples of commercially available blocked isocyanate compounds include Karenz (registered trademark) AOI-BM, Karenz (registered trademark) MOI-BM, Karenz (registered trademark) MOI-BP (all manufactured by Showa Denko KK), and block.
  • Examples include the Duranate series (for example, Duranate (registered trademark) TPA-B80E, manufactured by Asahi Kasei Chemicals Co., Ltd.).
  • the photosensitive resin layer or the photosensitive resin composition may contain only one type of the heat-crosslinkable compound, or may contain two or more types.
  • the content of the heat-crosslinkable compound is preferably 1% by mass to 50% by mass, preferably 5% by mass, based on the total solid content of the photosensitive resin layer or the photosensitive resin composition. It is more preferably about 30% by mass.
  • the photosensitive resin composition for forming the photosensitive resin layer or the photosensitive resin layer of the transfer film of the present invention has a reason that the punching processability of the cured film obtained by curing the photosensitive resin layer after transfer becomes better. It is preferable to contain a compound capable of Michael addition reaction, and more specifically, it is more preferable to contain a thiol compound shown below.
  • thiol compound a monofunctional thiol compound or a polyfunctional thiol compound is preferably used. Above all, from the viewpoint of hardness after curing, it is preferable to contain a bifunctional or higher functional thiol compound (polyfunctional thiol compound), and more preferably a polyfunctional thiol compound.
  • the polyfunctional thiol compound means a compound having two or more mercapto groups (thiol groups) in the molecule.
  • a low molecular weight compound having a molecular weight of 100 or more is preferable, specifically, a molecular weight of 100 to 1,500 is more preferable, and 150 to 1,000 is further preferable.
  • the number of functional groups of the polyfunctional thiol compound is preferably bifunctional to 10 functional, more preferably bifunctional to 8 functional, and even more preferably bifunctional to 6 functional, from the viewpoint of hardness after curing.
  • the polyfunctional thiol compound is preferably an aliphatic polyfunctional thiol compound from the viewpoint of tackiness, bending resistance after curing and hardness.
  • a secondary thiol compound is more preferable from the viewpoint of storage stability of the photosensitive transfer material.
  • polyfunctional thiol compound trimethylpropanthris (3-mercaptobutyrate), 1,4-bis (3-mercaptobutyryloxy) butane, pentaerythritol tetrakis (3-mercaptobutyrate), 1, 3,5-Tris (3-mercaptobutyryloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, trimethylolethanetris (3-mercaptobutyrate), Tris [(3-mercaptopropionyloxy) ethyl] isocyanurate, trimethylopropanthris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), tetraethylene glycol bis (3-mercaptopropionate) ), Dipentaerythritol hexakis (3-mercaptopropionate), ethylene glycol bisthiopropionate
  • trimethylolpropane tris (3-mercaptobutyrate), 1,4-bis (3-mercaptobutylyloxy) butane, pentaerythritol tetrakis (3-mercaptobutyrate), 1,3,5-tris (3-mercaptobutyrate) 3-Mercaptobutylyloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, trimethylolethanetris (3-mercaptobutyrate), tris [(3-mercapto) Propionyloxy) Ethyl] isocyanurate, trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), tetraethylene glycol bis (3-mercaptopropionate), and dipenta. Ellisritol hexakis (3-mercaptopropionate) is preferred.
  • both an aliphatic thiol compound and an aromatic thiol compound can be used.
  • Specific examples of the monofunctional aliphatic thiol compound include 1-octanethiol, 1-dodecanethiol, ⁇ -mercaptopropionic acid, methyl-3-mercaptopropionate, 2-ethylhexyl-3-mercaptopropionate, and the like. Examples thereof include n-octyl-3-mercaptopropionate, methoxybutyl-3-mercaptopropionate, and stearyl-3-mercaptopropionate.
  • Examples of the monofunctional aromatic thiol compound include benzenethiol, toluenethiol, xylenethiol and the like.
  • the thiol compound is preferably a thiol compound having an ester bond from the viewpoint of tackiness, bending resistance after curing, and hardness, and more preferably contains a compound represented by the following formula 1.
  • n represents an integer of 1 to 6
  • A represents an n-valent organic group having 1 to 15 carbon atoms, or a group represented by the following formula 2, and R1 represents the number of carbon atoms independently.
  • R 2 to R 4 independently represent a divalent organic group having 1 to 15 carbon atoms, and the wavy line portion represents a bond position with an oxygen atom adjacent to A in the above formula 1.
  • A represents a group represented by the following formula 2
  • n represents 3.
  • N in the formula 1 is preferably an integer of 2 to 6 from the viewpoint of hardness after curing.
  • a in the formula 1 is preferably an n-valent aliphatic group having 1 to 15 carbon atoms or a group represented by the above formula 2.
  • An n-valent aliphatic group having 4 to 15 carbon atoms, or a group represented by the above formula 2 more preferably an n-valent aliphatic group having 4 to 10 carbon atoms, or the above formula 2. It is more preferably a group represented by the above formula 2, and particularly preferably a group represented by the above formula 2.
  • a in the formula 1 is derived from an n-valent group consisting of a hydrogen atom and a carbon atom, or a hydrogen atom, a carbon atom and an oxygen atom from the viewpoint of tackiness, bending resistance after curing, hardness and moisture permeability. It is preferably an n-valent group, more preferably an n-valent group consisting of a hydrogen atom and a carbon atom, and particularly preferably an n-valent aliphatic hydrocarbon group.
  • Each R 1 in Formula 1 independently tackiness, as well, from the viewpoint of bending resistance and hardness after curing, it is preferably an alkylene group having 2 to 4 carbon atoms is an alkylene group having 1 to 15 carbon atoms More preferably, it is more preferably an alkylene group having 3 carbon atoms, and particularly preferably a 1,2-propylene group.
  • the alkylene group may be linear or may have a branch.
  • Each of R 2 to R 4 in the formula 2 is preferably an aliphatic group having 2 to 15 carbon atoms, and has 2 to 15 carbon atoms, from the viewpoint of tackiness, bending resistance after curing, and hardness. It is more preferably an alkylene group or a polyalkyleneoxyalkyl group having 3 to 15 carbon atoms, further preferably an alkylene group having 2 to 15 carbon atoms, and particularly preferably an ethylene group.
  • polyfunctional thiol compound a compound having two or more groups represented by the following formula S-1 is preferable.
  • R 1S represents a hydrogen atom or an alkyl group
  • a 1S represents -CO- or CH 2-
  • the wavy line portion represents a bonding position with another structure.
  • the alkyl group in R 1S in the formula S-1 is a linear, branched or cyclic alkyl group, and the carbon number range is preferably 1 to 16 and more preferably 1 to 10.
  • Specific examples of the alkyl group include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, s-butyl group, t-butyl group, pentyl group, hexyl group, 2-ethylhexyl group and the like.
  • a methyl group, an ethyl group, a propyl group or an isopropyl group is preferable.
  • R 1S a hydrogen atom, a methyl group, an ethyl group, a propyl group, or an isopropyl group is particularly preferable, and a methyl group or an ethyl group is most preferable.
  • polyfunctional thiol compound is particularly preferably a compound represented by the following formula S-2 having a plurality of groups represented by the above formula S-1.
  • R 1S independently represents a hydrogen atom or an alkyl group
  • a 1S independently represents -CO- or CH 2-
  • L 1S represents an nS-valent linking group
  • R 1S in Formula S-2 has the same meaning as R 1S in the formula S-1, the preferable range is also the same.
  • nS is preferably an integer of 2 to 6.
  • L 1S which is a linking group of nS valence in the formula S-2 include-(CH 2 ) mS- (mS represents an integer of 2 to 6),-(CH 2 ) mS ⁇ (CH 2 ).
  • Divalent linking groups such as mSO ⁇ mT (CH 2 ) mS- (mS and mT each independently represent an integer of 2 to 6), trimethyl propane residue,-(CH 2 ) pS- (pS is It represents an integer of 2 to 6), a trivalent linking group such as an isocyanul ring, a tetravalent linking group such as a pentaerythritol residue, and a pentavalent or hexavalent linking group such as a dipentaerythritol residue. Can be mentioned.
  • thiol compound examples include the following compounds, but it goes without saying that the thiol compound is not limited to these.
  • the photosensitive resin composition for forming the photosensitive resin layer or the photosensitive resin layer of the transfer film of the present invention preferably contains a heterocyclic compound.
  • the heterocyclic compound contributes to the improvement of the adhesion to the substrate (particularly the copper substrate) and the corrosion inhibitory property of the metal (particularly copper).
  • the heterocycle contained in the heterocyclic compound may be either a monocyclic or polycyclic heterocycle. Examples of the hetero atom contained in the heterocyclic compound include a nitrogen atom, an oxygen atom, and a sulfur atom.
  • the heterocyclic compound preferably has at least one atom selected from the group consisting of a nitrogen atom, an oxygen atom and a sulfur atom, and more preferably has a nitrogen atom.
  • heterocyclic compound for example, a triazole compound, a benzotriazole compound, a tetrazole compound, a thiazazole compound, a triazine compound, a rhonin compound, a thiazole compound, a benzothiazole compound, a benzoimidazole compound, a benzoxazole compound, or a pyrimidine compound is preferable. ..
  • the heterocyclic compound is at least one compound selected from the group consisting of a triazole compound, a benzotriazole compound, a tetrazole compound, a thiadiazol compound, a triazine compound, a rhonin compound, a thiazole compound, a benzoimidazole compound and a benzoxazole compound. It is preferable that the compound is at least one selected from the group consisting of a triazole compound, a benzotriazole compound, a tetrazole compound, a thiadiazol compound, a thiazole compound, a benzothiazole compound, a benzoimidazole compound and a benzoxazole compound. preferable.
  • heterocyclic compound Preferred specific examples of the heterocyclic compound are shown below.
  • examples of the triazole compound and the benzotriazole compound include the following compounds.
  • Examples of the tetrazole compound include the following compounds.
  • Examples of the thiadiazole compound include the following compounds.
  • Examples of the triazine compound include the following compounds.
  • Examples of the loadonine compound include the following compounds.
  • Examples of the thiazole compound include the following compounds.
  • benzothiazole compound examples include the following compounds.
  • Examples of the benzimidazole compound include the following compounds.
  • benzoxazole compound examples include the following compounds.
  • the photosensitive resin layer or the photosensitive resin composition may contain only one type of heterocyclic compound, or may contain two or more types.
  • the content of the heterocyclic compound is preferably 0.01% by mass to 20% by mass with respect to the total solid content of the photosensitive resin layer or the photosensitive resin composition. It is more preferably 1% by mass to 10% by mass, further preferably 0.3% by mass to 8% by mass, and particularly preferably 0.5% by mass to 5% by mass.
  • the content of the heterocyclic compound is within the above range, the adhesion to the base material (particularly copper substrate) and the corrosion inhibitory property of the metal (particularly copper) can be improved.
  • the photosensitive resin composition for forming the photosensitive resin layer or the photosensitive resin layer of the transfer film of the present invention may contain a surfactant.
  • the surfactant is not particularly limited, and a known surfactant can be used. Examples of the surfactant include the surfactants described in paragraphs 0017 of Japanese Patent No. 4502784 and paragraphs 0060 to 0071 of JP2009-237362A.
  • a fluorine-based surfactant or a silicon-based surfactant is preferable.
  • fluorine-based surfactants include Megafuck (registered trademark) F551A (manufactured by DIC Corporation).
  • commercially available products of fluorine-based surfactants include, for example, Megafuck F-171, F-172, F-173, F-176, F-177, F-141, F-142, F-143, F-144.
  • the fluorine-based surfactant has a molecular structure having a functional group containing a fluorine atom, and an acrylic compound in which a portion of the functional group containing a fluorine atom is cut off and the fluorine atom volatilizes when heat is applied.
  • fluorine-based surfactants include Megafuck DS series manufactured by DIC Corporation (The Chemical Daily (February 22, 2016), Nikkei Sangyo Shimbun (February 23, 2016)), for example, Megafuck. DS-21 can be mentioned.
  • the fluorine-based surfactant it is also preferable to use a polymer of a fluorine atom-containing vinyl ether compound having a fluorinated alkyl group or a fluorinated alkylene ether group and a hydrophilic vinyl ether compound.
  • a block polymer can also be used.
  • the fluorine-based surfactant has a repeating unit derived from a (meth) acrylate compound having a fluorine atom and 2 or more (preferably 5 or more) alkyleneoxy groups (preferably ethyleneoxy groups and propyleneoxy groups) (meth).
  • a fluorine-containing polymer compound containing a repeating unit derived from an acrylate compound can also be preferably used.
  • a fluorine-based surfactant a fluorine-containing polymer having an ethylenically unsaturated bond-containing group in the side chain can also be used. Megafvck RS-101, RS-102, RS-718K, RS-72-K (all manufactured by DIC Corporation) and the like can be mentioned.
  • Nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane, and their ethoxylates and propoxylates (eg, glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, etc.
  • Polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester, Pluronic L10, L31, L61, L62, 10R5, 17R2, 25R2 (or more) , BASF), Tetronic 304, 701, 704, 901, 904, 150R1 (above, BASF), Solsparse 20000 (above, Nippon Lubrizol Co., Ltd.), NCW-101, NCW-1001, NCW -1002 (above, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), Pionin D-6112, D-6112-W, D-6315 (above, manufactured by Takemoto Yushi Co., Ltd.), Orfin E1010, Surfinol 104, 400, 440 (above, manufactured by Nissin Chemical Industry Co., Ltd.) and the like can
  • silicon-based surfactant examples include a linear polymer composed of a siloxane bond and a modified siloxane polymer having an organic group introduced into a side chain or a terminal.
  • examples of commercially available silicon-based surfactants include DOWNSIL 8032 ADDITIVE, Torre Silicone DC3PA, Torre Silicone SH7PA, Torre Silicone DC11PA, Torre Silicone SH21PA, Torre Silicone SH28PA, Torre Silicone SH29PA, Torre Silicone SH30PA, Torre Silicone SH8400 (or more).
  • DOWNSIL registered trademark 8032 (manufactured by Dow Toray Co., Ltd.) can be mentioned.
  • a silicon-based surfactant is preferable because the protective film described later is easily pressure-bonded and peeled off from the photosensitive resin layer.
  • the photosensitive resin layer or the photosensitive resin composition may contain only one type of surfactant, or may contain two or more types of surfactants.
  • the content of the surfactant is preferably 0.01% by mass to 3% by mass, preferably 0.05% by mass, based on the total solid content of the photosensitive resin layer or the photosensitive resin composition. It is more preferably from mass% to 1% by mass, and even more preferably from 0.1% by mass to 0.8% by mass.
  • the photosensitive resin composition for forming the photosensitive resin layer or the photosensitive resin layer of the transfer film of the present invention preferably contains a hydrogen donating compound.
  • the hydrogen-donating compound has actions such as further improving the sensitivity of the photopolymerization initiator to active rays and suppressing inhibition of polymerization of the polymerizable compound by oxygen.
  • the hydrogen donating compound include amines, for example, M.I. R. "Journal of Polymer Society" by Sander et al., Vol. 10, p. 3173 (1972), JP-A-44-20189, JP-A-51-82102, JP-A-52-134692, JP-A-59-138205.
  • Examples thereof include compounds described in Japanese Patent Application Laid-Open No. 60-84305, Japanese Patent Application Laid-Open No. 62-18537, Japanese Patent Application Laid-Open No. 64-33104, Research Disclosure No. 33825, and the like.
  • Specific examples of the hydrogen donating compound include triethanolamine, p-dimethylaminobenzoic acid ethyl ester, p-formyldimethylaniline, p-methylthiodimethylaniline and the like.
  • Examples of the hydrogen donating compound include an amino acid compound (N-phenylglycine, etc.), an organometallic compound (tributyltin acetate, etc.) described in Japanese Patent Publication No. 48-42965, and hydrogen described in Japanese Patent Publication No. 55-344414. Donors, sulfur compounds (Tritian, etc.) described in JP-A-6-308727, and the like can also be mentioned.
  • the photosensitive resin layer or the photosensitive resin composition may contain only one kind of hydrogen donating compound, or may contain two or more kinds of hydrogen donating compounds.
  • the content of the hydrogen donating compound is, for example, the total solid of the photosensitive resin layer or the photosensitive resin composition from the viewpoint of improving the curing rate by balancing the polymerization growth rate and the chain transfer. It is preferably 0.01% by mass to 10% by mass, more preferably 0.03% by mass to 5% by mass, and further preferably 0.05% by mass to 3% by mass with respect to the amount. ..
  • the photosensitive resin composition forming the photosensitive resin layer of the transfer film of the present invention preferably contains a solvent.
  • the photosensitive resin composition contains a solvent, the formation of the photosensitive resin layer by coating tends to be easier.
  • the solvent a commonly used solvent can be used without particular limitation.
  • an organic solvent is preferable.
  • the organic solvent include methyl ethyl ketone, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate (also known as 1-methoxy-2-propyl acetate), diethylene glycol ethyl methyl ether, cyclohexanone, methyl isobutyl ketone, ethyl lactate, methyl lactate, caprolactam, n. -Propanol, 2-propanol and the like can be mentioned.
  • a mixed solvent of methyl ethyl ketone and propylene glycol monomethyl ether acetate, or a mixed solvent of diethylene glycol ethyl methyl ether and propylene glycol monomethyl ether acetate is preferable.
  • solvent Solvent described in paragraphs 0054 and 0055 of US Patent Application Publication No. 2005/282073 can also be used, the contents of which are incorporated herein by reference. Further, as the solvent, an organic solvent (high boiling point solvent) having a boiling point of 180 ° C. to 250 ° C. can be used, if necessary.
  • organic solvent high boiling point solvent
  • the photosensitive resin composition may contain only one type of solvent, or may contain two or more types of solvent.
  • the solid content of the photosensitive resin composition is preferably 5% by mass to 80% by mass, preferably 5% by mass to 40% by mass, based on the total mass of the photosensitive resin composition. More preferably, it is particularly preferably 5% by mass to 30% by mass.
  • the viscosity of the photosensitive resin composition at 25 ° C. is preferably 1 mPa ⁇ s to 50 mPa ⁇ s, for example, from the viewpoint of coatability, 2 mPa ⁇ s to 40 mPa ⁇ . It is more preferably s, and further preferably 3 mPa ⁇ s to 30 mPa ⁇ s.
  • Viscosity is measured using a viscometer.
  • a viscometer (trade name: VISCOMETER TV-22) manufactured by Toki Sangyo Co., Ltd. can be preferably used. However, the viscometer is not limited to this.
  • the surface tension of the photosensitive resin composition at 25 ° C. is preferably 5 mN / m to 100 mN / m, for example, from the viewpoint of coatability, and is preferably 10 mN / m to 80 mN. It is more preferably / m, and further preferably 15 mN / m to 40 mN / m.
  • Surface tension is measured using a surface tension meter.
  • a surface tension meter (trade name: Automatic Surface Tensiometer CBVP-Z) manufactured by Kyowa Interface Science Co., Ltd. can be preferably used.
  • the surface tension meter is not limited thereto.
  • the photosensitive resin layer or the photosensitive resin composition forming the photosensitive resin layer of the transfer film of the present invention may contain components other than the above-mentioned components (so-called other components).
  • other components include particles (for example, metal oxide particles), a colorant, and the like.
  • examples of other components include the thermal polymerization inhibitor described in paragraph 0018 of Japanese Patent No. 4502784, and other additives described in paragraphs 0058 to 0071 of Japanese Patent Application Laid-Open No. 2000-310706.
  • the photosensitive resin layer or the photosensitive resin composition may contain particles (for example, metal oxide particles; hereinafter the same) for the purpose of adjusting the refractive index, light transmission and the like.
  • the metal in the metal oxide particles also includes metalloids such as B, Si, Ge, As, Sb, and Te.
  • the average primary particle size of the particles is, for example, preferably 1 nm to 200 nm, more preferably 3 nm to 80 nm, from the viewpoint of transparency of the cured film.
  • the average primary particle size of the particles is calculated by measuring the particle size of 200 arbitrary particles using an electron microscope and arithmetically averaging the measurement results. When the shape of the particle is not spherical, the longest side is the particle diameter.
  • the photosensitive resin layer or the photosensitive resin composition When the photosensitive resin layer or the photosensitive resin composition contains particles, it may contain only one kind of particles having different metal types, sizes, etc., or may contain two or more kinds of particles.
  • the photosensitive resin layer or the photosensitive resin composition does not contain particles, or the content of the particles exceeds 0% by mass and 35% by mass with respect to the total solid content of the photosensitive resin layer or the photosensitive resin composition. It is preferably less than or equal to, and the particles are not contained, or the content of the particles is more than 0% by mass and 10% by mass or less with respect to the total solid content of the photosensitive resin layer or the photosensitive resin composition.
  • the content of the particles is more than 0% by mass and 5% by mass or less based on the total solid content of the photosensitive resin layer or the photosensitive resin composition. It is more preferable that the content of the particles is more than 0% by mass and 1% by mass or less based on the total solid content of the photosensitive resin layer or the photosensitive resin composition, and the particles are not contained. Is particularly preferable.
  • the photosensitive resin layer or the photosensitive resin composition may contain a trace amount of a colorant (pigment, dye, etc.), but for example, from the viewpoint of transparency, it is preferable that the photosensitive resin layer or the photosensitive resin composition contains substantially no colorant. ..
  • a colorant is contained, the content of the colorant is preferably less than 1% by mass, more preferably less than 0.1% by mass, based on the total solid content of the photosensitive resin layer or the photosensitive resin composition.
  • the thickness of the photosensitive resin layer is not particularly limited, but is preferably 20 ⁇ m or less, more preferably 15 ⁇ m or less, and further preferably 12 ⁇ m or less.
  • the thickness of the photosensitive resin layer is 20 ⁇ m or less, the entire transfer film is thinned, the transmittance of the photosensitive resin layer or the obtained cured film is improved, and the yellowing of the photosensitive resin layer or the obtained cured film is suppressed. It is advantageous in terms of such things.
  • the thickness of the photosensitive resin layer is, for example, preferably 1 ⁇ m or more, more preferably 2 ⁇ m or more, and particularly preferably 3 ⁇ m or more, from the viewpoint of manufacturing suitability.
  • the thickness of the photosensitive resin layer is calculated as an average value of 5 arbitrary points measured by cross-sectional observation with a scanning electron microscope (SEM).
  • the refractive index of the photosensitive resin layer is not particularly limited, but is preferably 1.47 to 1.56, more preferably 1.50 to 1.53, and 1.50 to 1.52. It is more preferable, and it is particularly preferable that it is 1.51 to 1.52.
  • the photosensitive resin layer is preferably achromatic. Specifically, the total reflection (incident angle 8 °, light source: D-65 (2 ° field of view)) has an L * value of 10 to 90 in the CIE1976 (L *, a *, b *) color space.
  • the a * value is preferably ⁇ 1.0 to 1.0
  • the b * value is preferably ⁇ 1.0 to 1.0.
  • the method for forming the photosensitive resin layer is not particularly limited, and a known method can be used.
  • An example of a method for forming a photosensitive resin layer is a method in which a photosensitive resin composition containing a solvent is applied onto a temporary support and, if necessary, dried to form the photosensitive resin layer. ..
  • a coating method a known method can be used.
  • the coating method include a printing method, a spray method, a roll coating method, a bar coating method, a curtain coating method, a spin coating method, a die coating method (that is, a slit coating method) and the like.
  • the die coating method is preferable as the coating method.
  • known methods such as natural drying, heat drying, and vacuum drying can be used, and these methods can be applied alone or in combination of two or more. In the present disclosure, "drying" means removing at least a portion of the solvent contained in the composition.
  • the transfer film of the present invention has a protective film.
  • the protective film include polyethylene terephthalate film, polypropylene film, polystyrene film, polycarbonate film and the like.
  • the protective film for example, the films described in paragraphs 0083 to 0087 and 093 of JP-A-2006-259138 may be used.
  • the protective film of the transfer film of the present invention has an arithmetic average roughness Ra of the surface on the photosensitive resin layer side of 150 nm or less, preferably 1 to 80 nm, and more preferably 1 to 30 nm.
  • the protective film may contain particles, and the layer contained in the temporary support.
  • a particle-containing layer constituting the surface on the photosensitive resin layer side may be provided.
  • the particles contained in the protective film (particularly the particle-containing layer) include those similar to those exemplified as the particles contained in the temporary support.
  • the following formula (2) is satisfied because the peelability of the temporary support and the protective film and the punching processability of the cured film obtained by curing the photosensitive resin layer after transfer can be compatible at a higher level. Is preferable.
  • Y represents the arithmetic mean roughness Ra value (nm) of the surface of the temporary support on the photosensitive resin layer side
  • Z represents the surface of the protective film on the photosensitive resin layer side. Represents the value (nm) of the arithmetic mean roughness Ra of.
  • the transfer film of the present invention may further have a refractive index adjusting layer having a higher refractive index than the photosensitive resin layer between the photosensitive resin layer and the protective film.
  • the refractive index of the refractive index adjusting layer is preferably 1.50 or more, more preferably 1.55 or more, further preferably 1.60 or more, and particularly preferably 1.70 or more. preferable.
  • the upper limit of the refractive index of the refractive index adjusting layer is not particularly limited, but is preferably 2.10 or less, more preferably 1.85 or less, still more preferably 1.78 or less. It is particularly preferably 74 or less.
  • the refractive index adjusting layer may have photocurability (that is, photosensitive), may have thermosetting property, and may have both photocurability and thermosetting property. However, from the viewpoint of forming a cured film having excellent strength, it is preferable to have photocurability.
  • the refractive index adjusting layer preferably has alkali solubility (for example, solubility in a weak alkaline aqueous solution).
  • the thickness of the refractive index adjusting layer is not particularly limited.
  • the thickness of the refractive index adjusting layer is preferably 50 nm or more and 500 nm or less, more preferably 55 nm or more and 110 nm or less, and further preferably 60 nm or more and 100 nm or less.
  • the thickness of the refractive index adjusting layer is calculated as an average value of 5 arbitrary points measured by cross-sectional observation with a scanning electron microscope (SEM).
  • the method of controlling the refractive index of the refractive index adjusting layer is not particularly limited, and for example, a method of using a resin having a predetermined refractive index alone, a method of using a resin and metal oxide particles or metal particles, a metal salt and a resin. A method using a complex with and the like can be mentioned.
  • the type of the metal oxide particles is not particularly limited, and known metal oxide particles can be used.
  • the metal oxide particles are specifically selected from the group consisting of zirconium oxide particles (ZrO 2 particles), Nb 2 O 5 particles, titanium oxide particles (TiO 2 particles), and silicon dioxide particles (SiO 2 particles). At least one of them is preferable.
  • the metal oxide particles for example, at least one selected from the group consisting of zirconium oxide particles and titanium oxide particles is selected from the viewpoint that the refractive index of the refractive index adjusting layer can be easily adjusted to 1.6 or more. More preferred.
  • the average primary particle size of the particles is, for example, preferably 1 nm to 200 nm, more preferably 3 nm to 80 nm, from the viewpoint of transparency of the cured film.
  • the average primary particle size of the particles is calculated by measuring the particle size of 200 arbitrary particles using an electron microscope and arithmetically averaging the measurement results. When the shape of the particle is not spherical, the longest side is the particle diameter.
  • the refractive index adjusting layer may contain only one kind of metal oxide particles, or may contain two or more kinds of metal oxide particles.
  • the refractive index adjusting layer may contain only one kind of metal oxide particles, or may contain two or more kinds of metal oxide particles.
  • a commercial product of metal oxide particles Calcined zirconium oxide particles (manufactured by CIK Nanotech Co., Ltd., product name: ZRPGM15WT% -F04), calcined zirconium oxide particles (manufactured by CIK Nanotech Co., Ltd., product name: ZRPGM15WT% -F74), calcined zirconium oxide particles (manufactured by CIK Nanotech Co., Ltd.) , Product name: ZRPGM15WT% -F75), calcined zirconium oxide particles (manufactured by CIK Nanotech Co., Ltd., product name: ZRPGM15WT% -F76), Zirconium oxide particles (Nan
  • the content of the metal oxide particles is the total mass of the refractive index adjusting layer from the viewpoint that the concealing property of the concealed object such as the electrode pattern is improved and the visibility of the concealed object can be effectively improved. On the other hand, it is preferably 1% by mass to 95% by mass, more preferably 20% by mass to 90% by mass, and further preferably 40% by mass to 85% by mass.
  • the content of the titanium oxide particles is preferably 1% by mass to 95% by mass, preferably 20% by mass to 90% by mass, based on the total mass of the refractive index adjusting layer. It is more preferably 40% by mass to 85% by mass.
  • the refractive index adjusting layer preferably contains a binder polymer and an ethylenically unsaturated compound.
  • the components of the refractive index adjusting layer the components of the curable second resin layer described in paragraphs 0019 to 0040 and 0144 to 0150 of JP-A-2014-108541, paragraphs 0024 of JP-A-2014-10814. You can refer to the components of the transparent layer described in 0035 and 0110 to 0112, the components of the composition having an ammonium salt, and the like described in paragraphs 0034 to 0056 of International Publication No. 2016/099980.
  • the binder polymer contained in the refractive index adjusting layer the same binder polymer as that contained in the photosensitive resin layer can be used, and the preferred range is also the same.
  • the ethylenically unsaturated compound contained in the refractive index adjusting layer the same radically polymerizable compound having an ethylenically unsaturated group contained in the photosensitive resin layer can be used, and the preferred range is also the same. ..
  • the refractive index adjusting layer preferably contains at least one kind of metal oxidation inhibitor from the viewpoint of the oxidation inhibitory property of the metal in contact with the refractive index adjusting layer.
  • the metal oxidation inhibitor for example, a compound having an aromatic ring containing a nitrogen atom in the molecule is preferably mentioned.
  • the metal oxidation inhibitor include imidazole, benzimidazole, tetrazole, mercaptothiadiazole, benzotriazole and the like.
  • the refractive index adjusting layer may contain other components other than the above-mentioned components. Examples of other components that can be contained in the refractive index adjusting layer include the same components as those contained in the photosensitive resin layer described above.
  • the refractive index adjusting layer preferably contains a surfactant as another component.
  • the folding ratio adjusting layer is preferably achromatic. Specifically, the total reflection (incident angle 8 °, light source: D-65 (2 ° field of view)) has an L * value of 10 to 90 in the CIE1976 (L *, a *, b *) color space.
  • the a * value is preferably ⁇ 1.0 to 1.0
  • the b * value is preferably ⁇ 1.0 to 1.0.
  • the method for forming the refractive index adjusting layer is not particularly limited. As an example of a method for forming the refractive index adjusting layer, a composition for forming a refractive index adjusting layer containing an aqueous solvent is applied onto the above-mentioned photosensitive resin layer formed on the temporary support, and if necessary.
  • a method of forming a refractive index adjusting layer by drying the mixture can be mentioned.
  • Specific examples of the coating and drying methods in the method for forming the refractive index adjusting layer are the same as the specific examples of coating and drying in the method for forming the photosensitive resin layer, respectively.
  • the transfer film of the present invention may further have a thermoplastic resin layer between the temporary support and the photosensitive resin layer.
  • a thermoplastic resin layer when the transfer film further has a thermoplastic resin layer, when the transfer film is transferred to a substrate to form a laminate, bubbles due to the lamination are less likely to be generated.
  • image unevenness and the like are less likely to occur, and excellent display characteristics can be obtained.
  • the thermoplastic resin layer preferably has alkali solubility.
  • the thermoplastic resin layer functions as a cushioning material that absorbs irregularities on the surface of the substrate during transfer. The irregularities on the surface of the substrate include images, electrodes, wiring, and the like that have already been formed.
  • the thermoplastic resin layer preferably has a property of being deformable according to the unevenness.
  • the thermoplastic resin layer preferably contains the organic polymer substance described in JP-A-5-72724, and the polymer softening point according to the Vicat method (specifically, the American material test method ASTMD 1235). It is more preferable to contain an organic polymer substance having a softening point of about 80 ° C. or lower according to the measurement method).
  • the thickness of the thermoplastic resin layer is, for example, preferably 3 ⁇ m to 30 ⁇ m, more preferably 4 ⁇ m to 25 ⁇ m, and even more preferably 5 ⁇ m to 20 ⁇ m.
  • the thickness of the thermoplastic resin layer is 3 ⁇ m or more, the followability to the unevenness of the substrate surface is further improved, so that the unevenness of the substrate surface can be absorbed more effectively.
  • the thickness of the thermoplastic resin layer is 30 ⁇ m or less, the manufacturing suitability is further improved. Therefore, for example, drying when the thermoplastic resin layer is applied and formed on the temporary support (so-called drying for solvent removal) The load is further reduced, and the development time of the thermoplastic resin layer after transfer is further shortened.
  • the thickness of the thermoplastic resin layer is calculated as an average value of 5 arbitrary points measured by cross-sectional observation with a scanning electron microscope (SEM).
  • the thermoplastic resin layer can be formed by applying a composition for forming a thermoplastic resin layer containing a solvent and a thermoplastic organic polymer to a temporary support and, if necessary, drying it.
  • Specific examples of the coating and drying methods in the method for forming the thermoplastic resin layer are the same as the specific examples of coating and drying in the method for forming the photosensitive resin layer, respectively.
  • the solvent is not particularly limited as long as it dissolves the polymer component forming the thermoplastic resin layer. Solvents include organic solvents (eg, methyl ethyl ketone, cyclohexanone, propylene glycol monomethyl ether acetate, n-propanol, and 2-propanol).
  • the thermoplastic resin layer preferably has a viscosity measured at 100 ° C. of 1,000 Pa ⁇ s to 10,000 Pa ⁇ s. Further, it is preferable that the viscosity of the thermoplastic resin layer measured at 100 ° C. is lower than the viscosity of the photosensitive resin layer measured at 100 ° C.
  • the transfer film of the present invention may further have an intermediate layer between the temporary support and the photosensitive resin layer.
  • the transfer film of the present invention has a thermoplastic resin layer
  • the component contained in the intermediate layer include at least one polymer selected from the group consisting of polyvinyl alcohol, polyvinylpyrrolidone and cellulose.
  • a layer described as a "separation layer" in JP-A-5-72724 can also be used as the intermediate layer.
  • the intermediate layer is, for example, a solvent that does not dissolve the thermoplastic resin layer.
  • an intermediate layer forming composition containing the above polymer as a component of the intermediate layer can be applied and, if necessary, dried. Specifically, first, the composition for forming a thermoplastic resin layer is applied onto the temporary support and, if necessary, dried to form the thermoplastic resin layer. Next, the composition for forming an intermediate layer is applied onto the formed thermoplastic resin layer and dried if necessary to form an intermediate layer.
  • a photosensitive resin composition (so-called composition for forming a photosensitive resin layer) containing an organic solvent is applied onto the formed intermediate layer and dried to form a photosensitive resin layer.
  • the organic solvent contained in the composition for forming the photosensitive resin layer is preferably an organic solvent that does not dissolve the intermediate layer.
  • Specific examples of the coating and drying methods in the method for forming the intermediate layer are the same as the specific examples of coating and drying in the method for forming the photosensitive resin layer, respectively.
  • the content of impurities in the photosensitive resin layer and the refractive index adjusting layer is small from the viewpoint of improving reliability and patterning property.
  • impurities include sodium, potassium, magnesium, calcium, iron, manganese, copper, aluminum, titanium, chromium, cobalt, nickel, zinc, tin, these ions, and halide ions (chloride ions, Bromide ion, iodide ion, etc.) and the like.
  • sodium ion, potassium ion, and chloride ion are easily mixed as impurities, so the following content is particularly preferable.
  • the content of impurities in each layer is preferably 1,000 ppm or less, more preferably 200 ppm or less, and particularly preferably 40 ppm or less on a mass basis.
  • the lower limit is not particularly defined, it can be set to 10 ppb or more and 100 ppb or more on a mass basis from the viewpoint of the limit that can be reduced realistically and the measurement limit.
  • Examples of the method for reducing impurities to the above range include selecting a raw material containing no impurities from the raw material of each layer, preventing impurities from being mixed in when forming the layer, and cleaning and removing the impurities. By such a method, the amount of impurities can be kept within the above range. Impurities can be quantified by known methods such as ICP (Inductively Coupled Plasma) emission spectroscopy, atomic absorption spectroscopy, and ion chromatography.
  • ICP Inductively Coupled Plasma
  • the content of compounds such as benzene, formaldehyde, trichlorethylene, 1,3-butadiene, carbon tetrachloride, chloroform, N, N-dimethylformamide, N, N-dimethylacetamide and hexane is low in each layer.
  • the content of these compounds in each layer is preferably 1,000 ppm or less, more preferably 200 ppm or less, and particularly preferably 40 ppm or less on a mass basis.
  • the lower limit is not particularly defined, it can be set to 10 ppb or more and 100 ppb or more on a mass basis from the viewpoint of the limit that can be reduced realistically and the measurement limit.
  • the content of impurities in the compound can be suppressed in the same manner as the above-mentioned impurities in the metal. Moreover, it can be quantified by a known measurement method.
  • FIG. 1 is a schematic cross-sectional view showing an example of the transfer film of the present invention.
  • the transfer film 10 has a laminated structure of a protective film 16 / refractive index adjusting layer 20A / photosensitive resin layer 18A / temporary support 12 (that is, the temporary support 12 and the photosensitive resin layer 18A. , The refractive index adjusting layer 20A and the protective film 16 are arranged in this order).
  • the transfer film of the present invention is not limited to the transfer film 10, and for example, the refractive index adjusting layer 20A may be omitted. Further, at least one of the above-mentioned thermoplastic resin layer and intermediate layer may be provided between the temporary support 12 and the photosensitive resin layer 18A.
  • the refractive index adjusting layer 20A is a layer arranged on the side opposite to the side where the temporary support 12 exists as viewed from the photosensitive resin layer 18A, and has a refractive index of 1.50 or more at a wavelength of 550 nm.
  • the transfer film 10 is a negative type material (so-called negative type film).
  • the method for producing the transfer film 10 is not particularly limited.
  • the method for producing the transfer film 10 includes, for example, a step of forming a photosensitive resin layer 18A on the temporary support 12, a step of forming a refractive index adjusting layer 20A on the photosensitive resin layer 18A, and a refractive index adjusting layer 20A.
  • the step of forming the protective film 16 on the top is included in this order.
  • the method for producing the transfer film 10 volatilizes ammonia, which is described in paragraph 0056 of International Publication No. 2016/09980, between the step of forming the refractive index adjusting layer 20A and the step of forming the protective film 16. The process may be included.
  • the use of the transfer film of the present invention is not particularly limited, but it is excellent in peelability of the temporary support and the protective film, and excellent in punching processability of the cured film obtained by curing the photosensitive resin layer after transfer, so that it is used for a touch panel. It can be suitably used as a transfer film, can be more preferably used as a transfer film for forming a protective film on a touch panel, and can be particularly preferably used as a transfer film for forming an electrode protective film on a touch panel.
  • the method for producing a laminate of the present invention is The first peeling step of peeling the protective film from the transfer film of the present invention described above, A transfer step of transferring a transfer film from which the protective film has been peeled off from the photosensitive resin layer side onto a substrate having electrodes, A curing step of curing at least a part of the transferred photosensitive resin layer to form a cured film, It has a second peeling step of peeling the temporary support after the curing step to obtain a laminated body in which a cured film is laminated on a substrate having electrodes.
  • first peeling step, the transfer step and the second peeling step of the laminated body manufacturing method of the present invention are the first peeling step, the transfer step and the transfer step of the touch panel manufacturing method of the present invention described later.
  • the same method as described in the second peeling step can be mentioned.
  • the laminate produced by the method for producing a laminate of the present invention is a laminate in which the photosensitive resin layer of the transfer film of the present invention is transferred onto a substrate having electrodes, and a cured cured film is laminated. ..
  • the substrate having the electrodes is preferably a substrate including the electrodes of the capacitance type input device. Further, the electrode of the capacitance type input device may have a transparent electrode pattern or may be a routing wiring.
  • a touch panel is preferably used as the capacitance type input device.
  • the touch panel electrode include a transparent electrode pattern arranged in at least an image display area of the touch panel.
  • the touch panel electrode may extend from the image display area to the frame portion of the touch panel.
  • the wiring for the touch panel include routing wiring (so-called take-out wiring) arranged in the frame portion of the touch panel.
  • the transparent electrode pattern and the routing wiring are electrically connected by laminating a part of the routing wiring on the portion extending to the frame portion of the touch panel of the transparent electrode pattern. Is preferable.
  • a metal oxide film such as ITO (indium tin oxide) or IZO (indium zinc oxide), or a fine metal wire such as a metal mesh or silver nanowire is preferable.
  • the thin metal wire include thin wires such as silver and copper. Of these, silver conductive materials such as silver mesh and silver nanowires are preferable.
  • Metal is preferable as the material of the routing wiring.
  • the metal used as the material of the routing wiring include gold, silver, copper, molybdenum, aluminum, titanium, chromium, zinc and manganese, and alloys composed of two or more of these metal elements.
  • copper, molybdenum, aluminum or titanium is preferable, and copper is particularly preferable.
  • FIG. 2 is a schematic cross-sectional view showing a first specific example of a touch panel having a photosensitive resin layer transferred using the transfer film of the present invention. More specifically, FIG. 2 is a schematic cross-sectional view of an image display area of the touch panel 30.
  • the touch panel 30 includes a substrate 32, a second refractive index adjusting layer 36, a transparent electrode pattern 34 as a touch panel electrode, a first refractive index adjusting layer 20, and a touch panel electrode protective film 18. And have a structure arranged in this order.
  • the touch panel electrode protective film 18 and the first refractive index adjusting layer 20 cover the entire transparent electrode pattern 34.
  • the second refractive index adjusting layer 36 and the first refractive index adjusting layer 20 directly or other layers the first region 40 in which the transparent electrode pattern 34 is present and the second region 42 in which the transparent electrode pattern 34 is not present, respectively. It is preferable to coat continuously through. According to such an aspect, the transparent electrode pattern 34 becomes less visible. It is preferable that the second refractive index adjusting layer 36 and the first refractive index adjusting layer 20 directly cover both the first region 40 and the second region 42 rather than covering them through other layers. Examples of the "other layer” include an insulating layer, an electrode pattern other than the transparent electrode pattern 34, and the like.
  • the first refractive index adjusting layer 20 is laminated over both the first region 40 and the second region 42.
  • the first refractive index adjusting layer 20 is adjacent to the second refractive index adjusting layer 36, and is also adjacent to the transparent electrode pattern 34.
  • the shape of the end portion of the transparent electrode pattern 34 at the point of contact with the second refractive index adjusting layer 36 is a tapered shape as shown in FIG. 2, the shape is along the tapered shape (that is, at the same inclination as the taper angle). ), It is preferable that the first refractive index adjusting layer 20 is laminated.
  • the ITO transparent electrode pattern is suitable.
  • the transparent electrode pattern 34 can be formed by, for example, the following method.
  • An electrode thin film (for example, an ITO film) is formed by sputtering on the substrate 32 on which the second refractive index adjusting layer 36 is formed.
  • an etching protective layer is formed by applying an etching photosensitive resist on the formed electrode thin film or by transferring an etching photosensitive film.
  • the formed etching protective layer is patterned into a desired pattern shape by exposure and development.
  • the portion of the electrode thin film that is not covered by the patterned etching protective layer is removed by etching, and the electrode thin film is formed into a pattern having a desired shape (that is, a transparent electrode pattern 34).
  • the etching protective layer patterned by the stripping solution is removed.
  • FIG. 3 is a schematic cross-sectional view showing a second specific example of a touch panel having a photosensitive resin layer transferred using the transfer film of the present invention.
  • the touch panel 90 has an image display area 74 and an image non-display area 75 (that is, a frame portion). Further, the touch panel 90 is provided with touch panel electrodes on both sides of the substrate 32. Specifically, the touch panel 90 includes a first transparent electrode pattern 70 on one surface of the substrate 32 and a second transparent electrode pattern 72 on the other surface.
  • the routing wiring 56 is connected to each of the first transparent electrode pattern 70 and the second transparent electrode pattern 72.
  • the routing wiring 56 is, for example, a copper wiring.
  • a touch panel electrode protective film 18 is formed on one surface of the substrate 32 so as to cover the first transparent electrode pattern 70 and the routing wiring 56, and the second transparent electrode protective film 18 is formed on the other surface of the substrate 32.
  • a touch panel electrode protective film 18 is formed so as to cover the electrode pattern 72 and the routing wiring 56.
  • the first refractive index adjusting layer and the second refractive index adjusting layer in the first specific example may be formed on one surface and the other surface of the substrate 32, respectively.
  • the method for manufacturing a touch panel of the present invention The first peeling step of peeling the protective film from the transfer film of the present invention described above, A transfer step of transferring a transfer film from which the protective film has been peeled off from the photosensitive resin layer side onto a touch panel substrate having a structure in which at least one of a touch panel electrode and a touch panel wiring is arranged on the substrate. An exposure process for pattern exposure of the transferred photosensitive resin layer, The second peeling step of peeling the temporary support after the exposure step and After the second peeling step, the pattern-exposed photosensitive resin layer is developed to obtain a touch panel protective film that protects at least one of the touch panel electrodes and the touch panel wiring.
  • the first peeling step is a step of peeling the protective film from the transfer film of the present invention described above, and the peeling method is not particularly limited, and a known method can be appropriately adopted.
  • the transfer step is a step of transferring the transfer film from which the protective film has been peeled off from the photosensitive resin layer side onto the touch panel substrate having a structure in which at least one of the touch panel electrode and the touch panel wiring is arranged on the substrate.
  • the transfer film of the present invention described above is laminated on a surface on which at least one of the touch panel electrode and the touch panel wiring of the touch panel substrate is arranged, and the photosensitive resin layer in the transfer film is laminated on the surface.
  • a method of forming a photosensitive resin layer on the above-mentioned surface by transferring onto the above-mentioned surface can be mentioned.
  • Lamination (so-called transfer of the photosensitive resin layer) can be performed using a known laminator such as a vacuum laminator or an auto-cut laminator.
  • the laminating temperature is preferably 80 ° C. to 150 ° C., more preferably 90 ° C. to 150 ° C., and even more preferably 100 ° C. to 150 ° C.
  • the laminating temperature refers to the temperature of the rubber rollers.
  • the substrate temperature at the time of laminating is not particularly limited.
  • the substrate temperature at the time of laminating is preferably 10 ° C. to 150 ° C., more preferably 20 ° C. to 150 ° C., and even more preferably 30 ° C. to 150 ° C.
  • the substrate temperature at the time of laminating is preferably 10 ° C to 80 ° C, more preferably 20 ° C to 60 ° C, and even more preferably 30 ° C to 50 ° C.
  • the linear pressure at the time of laminating is preferably 0.5 N / cm to 20 N / cm, more preferably 1 N / cm to 10 N / cm, and even more preferably 1 N / cm to 5 N / cm.
  • the transport speed (lamination speed) at the time of laminating is preferably 0.5 m / min to 5 m / min, more preferably 1.5 m / min to 3 m / min.
  • the photosensitive resin layer of the transfer film is transferred onto the surface of the touch panel substrate on the side where the electrodes and the like are arranged, and the temporary support / thermoplastic resin layer / photosensitive resin layer / electrodes and the like / substrate.
  • a laminated body having a laminated structure is formed.
  • the portion of "electrodes and the like / substrate” is a touch panel substrate.
  • the exposure step is a step of pattern-exposing the transferred photosensitive resin layer.
  • the “pattern exposure” refers to an exposure in which a pattern is exposed, that is, an exposure in which an exposed portion and a non-exposed portion are present.
  • the exposed portion in pattern exposure is cured to finally become a cured film.
  • the non-exposed portion in the pattern exposure is not cured and is dissolved and removed by the developing solution in the next developing step.
  • the non-exposed portion may form an opening of the cured film after the developing step.
  • the pattern exposure may be an exposure through a mask or a digital exposure using a laser or the like.
  • any light source in a wavelength range capable of curing the photosensitive resin layer (for example, 365 nm or 405 nm) can be appropriately selected and used.
  • the light source include various lasers, light emitting diodes (LEDs), ultra-high pressure mercury lamps, high pressure mercury lamps, metal halide lamps, and the like.
  • Exposure is preferably 5mJ / cm 2 ⁇ 200mJ / cm 2, more preferably 10mJ / cm 2 ⁇ 200mJ / cm 2.
  • the second peeling step is a step of peeling the temporary support after the exposure step, and the peeling method is not particularly limited, and a known method can be appropriately adopted.
  • the developing step is a step of obtaining a touch panel protective film that protects at least one of a touch panel electrode and a touch panel wiring by developing a pattern-exposed photosensitive resin layer after the second peeling step. ..
  • the developer used for development is not particularly limited, and a known developer such as the developer described in JP-A-5-72724 can be used. It is preferable to use an alkaline aqueous solution as the developing solution.
  • the alkaline compound that can be contained in the alkaline aqueous solution include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, and the like. Examples thereof include tetrabutylammonium hydroxide and choline (2-hydroxyethyltrimethylammonium hydroxide).
  • the pH of the alkaline aqueous solution at 25 ° C. is preferably 8 to 13, more preferably 9 to 12, and particularly preferably 10 to 12.
  • the content of the alkaline compound in the alkaline aqueous solution is preferably 0.1% by mass to 5% by mass, more preferably 0.1% by mass to 3% by mass, based on the total mass of the alkaline aqueous solution.
  • the developer may contain an organic solvent that is miscible with water.
  • Organic solvents include methanol, ethanol, 2-propanol, 1-propanol, butanol, diacetone alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-butyl ether, benzyl alcohol, acetone, methyl ethyl ketone, cyclohexanone. , ⁇ -caprolactone, ⁇ -butyrolactone, dimethylformamide, dimethylacetamide, hexamethylphosphoramide, ethyl lactate, methyl lactate, ⁇ -caprolactam, N-methylpyrrolidone and the like.
  • the concentration of the organic solvent is preferably 0.1% by mass to 30% by mass.
  • the developer may contain a known surfactant.
  • the concentration of the surfactant is preferably 0.01% by mass to 10% by mass.
  • the liquid temperature of the developing solution is preferably 20 ° C to 40 ° C.
  • Examples of the development method include paddle development, shower development, shower and spin development, dip development and the like.
  • shower development When shower development is performed, the non-exposed portion of the photosensitive resin layer is removed by spraying the developing solution on the photosensitive resin layer after pattern exposure in a shower shape.
  • a transfer film including a photosensitive resin layer and at least one of a thermoplastic resin layer and an intermediate layer is used, after the transfer of these layers onto the substrate and before the development of the photosensitive resin layer, An alkaline liquid having low solubility in the photosensitive resin layer may be sprayed in a shower manner to remove at least one of the thermoplastic resin layer and the intermediate layer (both if both are present) in advance. Further, after the development, it is preferable to remove the development residue by rubbing with a brush or the like while spraying a cleaning agent or the like with a shower.
  • the liquid temperature of the developing solution is preferably 20 ° C to 40 ° C.
  • the developing step may include a step of performing the above-mentioned development and a step of heat-treating the cured film obtained by the above-mentioned development (hereinafter, also referred to as "post-baking").
  • the post-baking temperature is preferably 100 ° C. to 160 ° C., more preferably 130 ° C. to 160 ° C.
  • the resistance value of the transparent electrode pattern can also be adjusted.
  • the photosensitive resin layer contains a carboxy group-containing (meth) acrylic resin, at least a part of the carboxy group-containing (meth) acrylic resin can be changed to a carboxylic acid anhydride by post-baking. When changed in this way, the developability and the strength of the cured film are excellent.
  • the developing step may include a step of performing the above-mentioned development and a step of exposing the cured film obtained by the above-mentioned development (hereinafter, also referred to as “post-exposure”). If the developing process includes both post-exposure and post-baking steps, it is preferable to perform post-baking after post-exposure.
  • the pattern (cured film of the photosensitive resin layer) formed by the above procedure is preferably achromatic.
  • the total reflection (incident angle 8 °, light source: D-65 (2 ° field of view)) has a pattern L * value of 10 to 90 in the CIE1976 (L *, a *, b *) color space.
  • the a * value of the pattern is preferably ⁇ 1.0 to 1.0
  • the b * value of the pattern is preferably ⁇ 1.0 to 1.0.
  • the touch panel manufacturing method according to the present disclosure may include steps (so-called other steps) other than the steps described above.
  • Other steps include known steps (eg, cleaning steps) that may be provided in a normal photolithography step.
  • the present disclosure will be described in more detail with reference to Examples below.
  • the materials, amounts used, proportions, treatment contents, treatment procedures, etc. shown in the following examples can be appropriately changed as long as they do not deviate from the gist of the present disclosure. Therefore, the scope of the present disclosure is not limited to the specific examples shown below.
  • "parts" and "%" are based on mass.
  • the weight average molecular weight of the resin is the weight average molecular weight determined in terms of polystyrene by gel permeation chromatography (GPC).
  • GPC gel permeation chromatography
  • the theoretical acid value was used as the acid value.
  • MAA-GMA A structural unit in which glycidyl methacrylate is added to a structural unit derived from methacrylic acid.
  • Material B-1 which is a coating liquid for forming a refractive index adjusting layer, was prepared so as to have the composition shown in Table 2 below.
  • a material A-1 for forming a photosensitive resin layer was applied onto a terephthalate film (temporary support) using a slit-shaped nozzle to form a photosensitive resin layer. The coating amount was adjusted so that the film thickness after drying would be the thickness shown in Table 3 below.
  • a polypropylene layer having a thickness of 1 ⁇ m containing 0.05% by mass of calcium carbonate (average particle size: 1.0 ⁇ m) on the photosensitive resin layer.
  • Examples 2 to 4, Example 8 and Comparative Example 1 A transfer film was produced in the same manner as in Example 1 except that the material A-1 for forming the photosensitive resin layer was changed to the material shown in Table 3 below.
  • Example 5 The material A-1 for forming the photosensitive resin layer was changed to the material shown in Table 3 below, and the particle-containing layer in the temporary support and the protective film was used so as to satisfy the arithmetic mean roughness Ra shown in Table 3 below.
  • a transfer film was prepared in the same manner as in Example 1 except that the concentration of calcium carbonate to be contained was changed.
  • Example 6 The material B-1 for forming the refractive index adjusting layer is applied onto the photosensitive resin layer formed by the same method as in Example 1 using a slit-shaped nozzle, dried at a drying temperature of 80 ° C., and has a refractive index. A regulating layer was formed. The coating amount was adjusted so that the film thickness after drying was 70 nm. Next, a polyethylene terephthalate film (protective film) having a thickness of 16 ⁇ m was pressure-bonded onto the refractive index adjusting layer to prepare a transfer film of Example 6. The refractive index of the refractive index adjusting layer was 1.68.
  • Example 7 A transfer film was prepared in the same manner as in Example 5 except that the concentration of calcium carbonate contained in the particle-containing layer in the temporary support and the protective film was changed so as to satisfy the arithmetic mean roughness Ra shown in Table 3 below. did.
  • Example 2 A transfer film was prepared in the same manner as in Example 1 except that the concentration of calcium carbonate contained in the particle-containing layer in the temporary support was changed so as to satisfy the arithmetic mean roughness Ra shown in Table 3 below.
  • Example 3 A transfer film was prepared in the same manner as in Example 1 except that the concentration of calcium carbonate contained in the particle-containing layer of the protective film was changed so as to satisfy the arithmetic mean roughness Ra shown in Table 3 below.
  • Moisture permeability (average value) was measured by the method described above. Based on the measured average value of moisture permeability, the water vapor permeability was evaluated according to the following evaluation criteria. In the following evaluation criteria, A and B are suitable for practical use. The results are described in the item of the photosensitive resin layer in 3 below.
  • the moisture permeability of the circular sample having the laminated structure of the cured film / membrane filter was measured. However, since the moisture permeability of the membrane filter is extremely higher than that of the cured film, the above measurement substantially measures the moisture permeability of the cured film itself of the photosensitive resin layer.
  • a cycloolefin resin film having a thickness of 38 ⁇ m and a refractive index of 1.53 is used as a wire electrode having an output voltage of 100%, an output of 250 W, a diameter of 1.2 mm, an electrode length of 240 mm, and a work electrode spacing using a high-frequency oscillator. Corona discharge treatment was performed for 3 seconds under the condition of 5 mm to modify the surface. The obtained film was used as a transparent film substrate.
  • the material of Material-C shown in Table 4 below is coated on a transparent film substrate using a slit-shaped nozzle, irradiated with ultraviolet rays (integrated light amount of 300 mJ / cm 2 ), and dried at about 110 ° C. By doing so, a transparent film having a refractive index of 1.60 and a film thickness of 80 nm was formed.
  • DC direct DC
  • magnetron sputtering conditions: transparent film substrate temperature 150 ° C., argon partial pressure 0.13 Pa, oxygen partial pressure 0.01 Pa
  • an ITO thin film with a thickness of 40 nm and a refractive index of 1.82. was formed, and a film in which a transparent film and a transparent electrode layer were formed on a transparent film substrate was obtained.
  • the surface resistance of the ITO thin film was 80 ⁇ / ⁇ (square per ⁇ ).
  • thermoplastic resin layer having the following formulation H1 was applied and dried on a 75 ⁇ m-thick polyethylene terephthalate film temporary support using a slit-shaped nozzle.
  • a coating liquid for an intermediate layer consisting of the following formulation P1 was applied and dried.
  • a coating liquid for an etching photocurable resin layer consisting of the following formulation E1 was applied and dried.
  • a laminated body made of the above was prepared, and finally a protective film (thickness 12 ⁇ m polypropylene film) was pressure-bonded.
  • a photosensitive film E1 for etching which is a transfer material in which a temporary support, a thermoplastic resin layer, an intermediate layer (oxygen blocking film), and a photocurable resin layer for etching are integrated, was produced.
  • ⁇ Formation of transparent electrode pattern> The film in which the transparent film and the transparent electrode layer were formed on the transparent film substrate was washed, and the photosensitive film E1 for etching from which the protective film was removed was laminated.
  • the laminating conditions were a transparent film substrate temperature: 130 ° C., a rubber roller temperature of 120 ° C., a linear pressure of 100 N / cm, and a transport speed of 2.2 m / min.
  • the distance between the surface of the exposure mask (quartz exposure mask having a transparent electrode pattern) and the photocurable resin layer for etching described above was set to 200 ⁇ m, and the exposure amount was 50 mJ / cm 2 ( The pattern was exposed with i-line).
  • a triethanolamine-based developer (containing 30% by mass of triethanolamine, trade name: T-PD2 (manufactured by FUJIFILM Corporation) diluted 10-fold with pure water) was added at 25 ° C. for 100 seconds.
  • Treat with a surfactant-containing developer (trade name: T-SD3 (manufactured by FUJIFILM Corporation) 10-fold diluted with pure water) at 33 ° C. for 20 seconds, and use a rotating brush and an ultra-high pressure cleaning nozzle.
  • the residue was removed and post-baked at 130 ° C. for 30 minutes to obtain a film in which a transparent film, a transparent electrode layer, and a photocurable resin layer pattern for etching were formed on a transparent film substrate.
  • a film in which a transparent film, a transparent electrode layer, and a photocurable resin layer pattern for etching are formed on a transparent film substrate is immersed in an etching tank containing an etching solution for ITO (hydrogen acid, potassium chloride aqueous solution, liquid temperature 30 ° C.). Then, the process was performed for 100 seconds to dissolve and remove the transparent electrode layer in the exposed region not covered with the photocurable resin layer for etching, to obtain a film with a transparent electrode pattern having a photocurable resin layer pattern for etching. Etched.
  • ITO hydrochloride aqueous solution
  • a film with a transparent electrode pattern with a photocurable resin layer pattern for etching was applied to a resist stripping solution (N-methyl-2-pyrrolidone, monoethanolamine, surfactant (trade name: Surfinol 465, air).
  • a resist stripping solution N-methyl-2-pyrrolidone, monoethanolamine, surfactant (trade name: Surfinol 465, air).
  • a resist stripping tank containing Products Japan Co., Ltd.
  • liquid temperature 45 ° C. liquid temperature 45 ° C.
  • the transfer was carried out using a vacuum laminator manufactured by MCK under the conditions of a transparent film substrate temperature: 40 ° C., a rubber roller temperature of 100 ° C., a linear pressure of 3 N / cm, and a transport speed of 2 m / min.
  • a proximity type exposure machine manufactured by Hitachi High-Tech Electronics Engineering Co., Ltd.
  • the surface of the exposure mask quartz exposure mask having a pattern for forming an electrode protective film
  • the temporary support are brought into close contact with each other.
  • Pattern exposure was performed with an exposure amount of 100 mJ / cm 2 (i-line) via the temporary support.
  • Example 6 After peeling off the temporary support, development treatment was carried out at 32 ° C. in a 1% sodium carbonate aqueous solution for 60 seconds. Then, the residue was removed by injecting ultrapure water from the ultrapure water cleaning nozzle onto the transparent film substrate after the development treatment. Subsequently, air was blown to remove water on the transparent film substrate, and post-baking treatment was performed at 145 ° C. for 30 minutes, and the transparent film, the transparent electrode pattern, and the cured product of the photosensitive resin layer were formed on the transparent film substrate. A laminated body was formed which was laminated in order from the beginning. In Example 6, a laminated body in which a transparent film, a transparent electrode pattern, a cured product of a refractive index adjusting layer and a photosensitive resin layer were laminated in order from the substrate was formed on a transparent film substrate.
  • the arithmetic mean roughness Ra of the surface of the protective film on the photosensitive resin layer side is more than 150 nm. It was found that the peelability of the protective film was inferior (Comparative Example 3).
  • the photosensitive resin layer is a photosensitive resin layer having a breaking elongation at 120 ° C. after curing of 15% or more, and the arithmetic average roughness Ra of the surface of the temporary support on the photosensitive resin layer side is 50 nm.
  • the arithmetic average roughness Ra of the surface of the protective film on the photosensitive resin layer side is 150 nm or less, the temporary support and the protective film are excellently peelable, and the photosensitive resin layer after transfer is cured. It was found that the film was excellent in punching workability (Examples 1 to 8).
  • Electrode protective film for touch panel 18A Photosensitive resin layer 20: First refractive index adjustment layer 20A: Refractive index adjustment layer 30: Touch panel 32: Substrate 34: Transparent electrode pattern 36: Second refractive index adjustment layer 40: First region where transparent electrode pattern exists 42: Second region where transparent electrode pattern does not exist 56: Route wiring 70: First transparent electrode pattern 72 : Second transparent electrode pattern 74: Image display area 75: Image non-display area 90: Touch panel

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Abstract

La présente invention aborde le problème de la fourniture : d'un film de transfert, qui a une excellente aptitude au pelage d'un support temporaire et d'un film protecteur, et une excellente aptitude au traitement par poinçonnage d'un film durci obtenu par durcissement d'une couche de résine photosensible après transfert ; d'un procédé de fabrication d'un stratifié ; et d'un procédé de fabrication d'un panneau tactile. Le film de transfert présente un support temporaire, une couche de résine photosensible, et un film protecteur dans cet ordre, l'allongement de rupture à 120 °C d'un film durci obtenu par durcissement de la couche de résine photosensible étant supérieur ou égal à 15 %, la rugosité moyenne arithmétique Ra de la surface du support temporaire sur le côté de la couche de résine photosensible est inférieure ou égale à 50 nm, et la rugosité moyenne arithmétique Ra de la surface du film protecteur sur le côté de la couche photosensible est inférieure ou égale à 150 nm.
PCT/JP2020/022684 2019-07-12 2020-06-09 Film de transfert, procédé de fabrication de stratifié et procédé de fabrication de panneau tactile WO2021010058A1 (fr)

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JP2021532726A JP7213981B2 (ja) 2019-07-12 2020-06-09 転写フィルム、積層体の製造方法およびタッチパネルの製造方法
CN202080045617.9A CN114026498A (zh) 2019-07-12 2020-06-09 转印膜、层叠体的制造方法及触摸面板的制造方法

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JP2002144504A (ja) * 2000-09-04 2002-05-21 Toray Ind Inc ポリオレフィンフィルムおよび感光製版用フォトレジストカバーフィルム
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