WO2019186781A1 - Film de transfert, film durci et procédé de formation associé, et composant électrique - Google Patents

Film de transfert, film durci et procédé de formation associé, et composant électrique Download PDF

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Publication number
WO2019186781A1
WO2019186781A1 PCT/JP2018/012810 JP2018012810W WO2019186781A1 WO 2019186781 A1 WO2019186781 A1 WO 2019186781A1 JP 2018012810 W JP2018012810 W JP 2018012810W WO 2019186781 A1 WO2019186781 A1 WO 2019186781A1
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Prior art keywords
resin layer
meth
acrylate
component
film
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PCT/JP2018/012810
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English (en)
Japanese (ja)
Inventor
雅彦 海老原
向　郁夫
田仲　裕之
征志 南
匠 渡邊
智紀 寺脇
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日立化成株式会社
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Priority to PCT/JP2018/012810 priority Critical patent/WO2019186781A1/fr
Publication of WO2019186781A1 publication Critical patent/WO2019186781A1/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
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/095—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having more than one photosensitive layer
    • 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 transfer film, a cured film, a method for forming the same, and an electronic component.
  • a projected capacitive touch panel In general, in a projected capacitive touch panel, a plurality of X electrodes and a plurality of Y electrodes orthogonal to the X electrodes have a two-layer structure in order to express two-dimensional coordinates based on the X and Y axes. Forming. As a material for these electrodes, ITO (Indium-Tin-Oxide) is the mainstream.
  • the frame area of the touch panel is an area where the touch position cannot be detected, reducing the area of the frame area is an important factor for improving the product value.
  • a metal wiring such as copper is formed in the frame region in order to transmit a touch position detection signal.
  • a corrosive component such as moisture or salt may enter the inside from the sensing region.
  • the metal wiring corrodes, and there is a risk of an increase in electrical resistance between the electrode and the drive circuit, or disconnection.
  • a photosensitive resin composition layer containing a di (meth) acrylate compound having a dicyclopentanyl structure or a dicyclopentenyl structure is provided on a touch panel substrate, and the photosensitive resin composition
  • a method of forming a cured film of the photosensitive resin composition that covers a part or all of the substrate after removing a part other than the predetermined part after curing a predetermined part of the physical layer by irradiation with actinic rays. See Patent Document 1 below. According to this method, a cured film having a sufficiently low moisture permeability can be formed on the touch panel substrate.
  • the projected capacitive touch panel has a problem of so-called “bone appearance phenomenon” in which the electrode pattern is reflected on the screen in the sensing region.
  • the first curable transparent resin layer having a low refractive index adjusted to a specific refractive index range and the second curable transparent resin layer having a high refractive index are adjacent to each other.
  • a transfer film is disclosed (see Patent Document 2 below).
  • Patent Document 2 is not sufficient in suppressing the bone appearance phenomenon.
  • the present invention provides a transfer film capable of forming a cured film having an improved function of suppressing the appearance of bone phenomenon, a cured film obtained using the transfer film, a method for forming the same, and an electron including the cured film.
  • the purpose is to provide parts.
  • the diffuse reflectance of the cured film is set within a predetermined range. By adjusting, it has been found that the effect of suppressing the bone appearance phenomenon can be obtained more remarkably, and the present invention has been completed.
  • one aspect of the present invention is a support film, a first resin layer provided on the support film, and a second resin layer containing a metal oxide provided on the first resin layer. And a laminate including the transfer film.
  • the first resin layer is a photosensitive resin composition layer
  • the laminate is laminated at an exposure amount of 1000 mJ / cm 2 from the opposite side of the first resin layer to the second resin layer side.
  • the body is exposed (for example, irradiated with ultraviolet rays), heated at 140 ° C. for 2 hours, and then light having a wavelength of 400 nm obtained by measuring by the SCE method from the opposite side of the first resin layer to the second resin layer side.
  • the diffuse reflectance with respect to is 0.20% or less.
  • the cured laminate (the laminate is exposed at an exposure amount of 1000 mJ / cm 2 from the side opposite to the second resin layer side of the first resin layer of the laminate,
  • the cured product obtained by heating the laminate at 140 ° C. for 2 hours it is possible to improve the function of suppressing the bone appearance phenomenon.
  • the reason why such an effect is obtained is not clear, but is presumed as follows. That is, usually obtained by curing a laminate comprising a photosensitive resin composition layer and a resin layer containing a metal oxide (for example, a high refractive index layer having a refractive index of 1.50 or more at a wavelength of 633 nm).
  • the cured film to be formed When the cured film to be formed is provided on a transparent electrode pattern such as ITO, the cured film forms a regular reflection light from a portion where the transparent electrode pattern such as ITO is formed and a transparent electrode pattern such as ITO. It is considered that the bone appearance phenomenon is suppressed because the specularly reflected light from the unexposed portion interferes with each other and the color difference due to optical reflection is reduced.
  • the conventional transfer film light in the wavelength region near 400 nm cannot be sufficiently interfered, and it is assumed that the bone appearance phenomenon has occurred due to the light in the wavelength region.
  • the diffuse reflectance at a wavelength of 400 nm of the cured laminate is 0.20% or less, so that the bone appearance phenomenon due to light having a wavelength near 400 nm is suppressed. It is presumed that a more remarkable effect of suppressing the bone appearance phenomenon can be obtained.
  • the metal oxide may contain at least one selected from the group consisting of zirconium oxide, titanium oxide, tin oxide, zinc oxide, indium tin oxide, indium oxide, aluminum oxide, silicon oxide, and yttrium oxide.
  • zirconium oxide titanium oxide, tin oxide, zinc oxide, indium tin oxide, indium oxide, aluminum oxide, silicon oxide, and yttrium oxide.
  • the refractive index of the second resin layer at a wavelength of 633 nm and the diffuse reflectance can be easily controlled, and the effect of suppressing the bone appearance phenomenon can be more easily obtained.
  • the second resin layer is composed of (meth) acrylic acid, glycidyl (meth) acrylate, benzyl (meth) acrylate, styrene, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, A polymer having a structural unit derived from at least one compound selected from the group consisting of cyclohexyl (meth) acrylate and 2-ethylhexyl (meth) acrylate may be contained.
  • the second resin layer is excellent in alkali developability, and the diffuse reflectance can be easily controlled.
  • the first resin layer may contain a binder polymer, a photopolymerizable compound, and a photopolymerization initiator.
  • the photopolymerization initiator may contain at least one selected from the group consisting of oxime ester compounds and phosphine oxide compounds.
  • a patterned cured film (cured film pattern) can be formed with sufficient resolution even with a thin film (for example, a thin film having a thickness of 10 ⁇ m or less).
  • the binder polymer may have a carboxyl group, (meth) acrylic acid, glycidyl (meth) acrylate, benzyl (meth) acrylate, styrene, methyl (meth) acrylate, ethyl (meth) acrylate, ( It may have a structural unit derived from at least one compound selected from the group consisting of butyl (meth) acrylate, cyclohexyl (meth) acrylate and 2-ethylhexyl (meth) acrylate. In this case, the alkali developability, patterning property and transparency of the first resin layer can be improved.
  • the first resin layer may contain a phosphate ester having an ethylenically unsaturated group. In this case, the adhesion to the transparent electrode pattern can be improved and the occurrence of development residue can be reduced.
  • the thickness of the second resin layer may be 10 to 1000 nm.
  • the diffuse reflectance can be reduced, and the reflected light intensity of the entire touch screen in the touch panel can be further reduced.
  • the thickness of the laminate may be 30 ⁇ m or less. In this case, the followability at the time of laminating the first resin layer and the second resin layer to the base material can be improved.
  • One aspect of the present invention is a step of laminating a laminate of the transfer film on a substrate so that the second resin layer is in close contact with the substrate, and exposing a predetermined portion of the laminate on the substrate.
  • the present invention relates to a method for forming a cured film comprising: a step and a step of removing a portion other than the exposed predetermined portion to form a patterned cured film. According to this method, a patterned cured film having an excellent function of suppressing the bone appearance phenomenon can be obtained.
  • One aspect of the present invention relates to a cured film formed by curing the first resin layer and the second resin layer of the laminate in the transfer film.
  • This cured film is excellent in the function of suppressing the bone appearance phenomenon.
  • One aspect of the present invention relates to an electronic component including the above cured film.
  • this electronic component the above-mentioned bone appearance phenomenon is suppressed.
  • the transfer film which can form the cured film with the suppression function of a bone appearance phenomenon improved, the cured film obtained using this transfer film, its formation method, and an electron provided with this cured film Parts can be provided.
  • (meth) acrylic acid means acrylic acid or methacrylic acid
  • (meth) acrylate means acrylate or a corresponding methacrylate.
  • a or B only needs to include one of A and B, or may include both.
  • process is not limited to an independent process, and even if it cannot be clearly distinguished from other processes, the term “process” is used as long as the intended action of the process is achieved. included.
  • the numerical range indicated by using “to” indicates a range including the numerical values described before and after “to” as the minimum value and the maximum value, respectively.
  • the upper limit value and lower limit value individually described as numerical ranges can be arbitrarily combined.
  • each component in the composition is the sum of the plurality of substances present in the composition unless there is a specific indication when there are a plurality of substances corresponding to each component in the composition. Means quantity.
  • the exemplary materials may be used alone or in combination of two or more unless otherwise specified.
  • the “exposure amount” is a measured value at i-line (wavelength 365 nm).
  • a transfer film includes a support film, a first resin layer provided on the support film, and a second resin layer containing a metal oxide provided on the first resin layer. Including a laminate.
  • the first resin layer is a photosensitive resin composition layer.
  • the above laminate has a diffuse reflectance of 0.20 for light having a wavelength of 400 nm obtained by measuring with the SCE method (Special component excluded method) from the side opposite to the second resin layer side of the first resin layer after curing. % Or less.
  • the diffuse reflectance of a cured film obtained by curing the laminate is 0.20% or less.
  • after curing means that after the first resin layer and the second resin layer in the laminate are cured (for example, the first resin layer and the second resin layer are cured to a curing reaction rate of 70% or more). After).
  • the laminate is exposed at an exposure amount of 1000 mJ / cm 2 from the opposite side of the first resin layer to the second resin layer side.
  • the diffuse reflectance with respect to light having a wavelength of 400 nm obtained by measuring by the SCE method from the side opposite to the second resin layer side in the first resin layer is 0.20% or less
  • the second resin layer is thermosetting, the laminate is heated at 140 ° C. for 2 hours and then measured by the SCE method from the opposite side of the first resin layer to the second resin layer side.
  • the diffuse reflectance with respect to light having a wavelength of 400 nm is 0.20% or less.
  • the laminate when the second resin layer is photocurable, the laminate is laminated at an exposure amount of 1000 mJ / cm 2 from the opposite side of the first resin layer to the second resin layer side. It can be cured by exposing the body.
  • the laminate exposes the laminate with an exposure amount of 1000 mJ / cm 2 from the opposite side of the first resin layer to the second resin layer side. Can be cured by heating for 2 hours. Therefore, regardless of whether the second resin layer is curable (photo-curable or thermosetting), 1000 mJ / cm 2 from the opposite side of the first resin layer to the second resin layer side. It is obtained by exposing the laminate with an exposure amount, heating the exposed laminate at 140 ° C. for 2 hours, and measuring by the SCE method from the side opposite to the second resin layer side in the first resin layer.
  • the effect of the present invention can be obtained if the diffuse reflectance for light having a wavelength of 400 nm is 0.20% or less.
  • the diffuse reflectance is measured by the following method.
  • a laminator manufactured by Hitachi Chemical Co., Ltd., product name “HLM-3000 type”
  • the second resin layer of the transfer film facing the substrate (for example, a polycarbonate substrate having a thickness of 1 mm).
  • Laminate Lamination conditions are, for example, 110 ° C. and 0.4 MPa.
  • the laminate is irradiated with actinic rays from the first resin layer side with an exposure amount of 2 .
  • the support film is transparent, the active light is irradiated as it is.
  • the support film is opaque, the support film is removed and then the active light is applied.
  • actinic rays are irradiated without peeling off the support film, the film is left at room temperature (25 ° C.) for 15 minutes after exposure, and then the support film is peeled off.
  • a diffuse reflectance measurement sample is obtained.
  • the laminate is heated at 140 ° C. for 2 hours before or after peeling of the support film.
  • the diffuse reflectance of the measurement sample is measured by allowing light to enter from the first resin layer side, and SCE. Measure by method.
  • the diffuse reflectance of the substrate is measured, and the difference between the diffuse reflectance of the measurement sample and the diffuse reflectance of the substrate ([diffuse reflectance of measurement sample] ⁇ [diffuse reflectance of substrate]) is calculated. Let it be the diffuse reflectance of the laminate after curing.
  • the above diffuse reflectance is preferably 0.18% or less, more preferably 0.16% or less, and further preferably 0.15% or less, from the viewpoint of further improving the suppression function of the bone appearance phenomenon.
  • the diffuse reflectance may be 0% or more.
  • the diffuse reflectance is, for example, the type of resin contained in the first resin layer, the type and amount of resin, silane coupling agent, particles, etc. contained in the second resin layer, the first resin layer and the second resin layer. It can be adjusted by the thickness of the resin layer.
  • FIG. 1 is a schematic cross-sectional view showing a transfer film of one embodiment.
  • a transfer film 1 shown in FIG. 1 includes a support film 10, a first resin layer 20 provided on the support film 10, and a second resin layer provided on the first resin layer 20.
  • 30 is a photosensitive refractive index adjusting film.
  • the transfer film may include a protective film 15 provided on the opposite side of the second resin layer 30 from the first resin layer 20 as shown in FIG.
  • FIG. 2 is a schematic cross-sectional view showing an embodiment in which the transfer film of the embodiment is used for a substrate with a transparent electrode pattern.
  • a cured product (second cured resin layer) 32 of a second resin layer is provided on a substrate 50 with a transparent electrode pattern 50a such as ITO so as to cover the pattern 50a.
  • a cured product (first cured resin layer) 22 of the resin layer is provided, and the transparent laminate 100 is configured. That is, FIG. 2 shows a transparent laminate 100 provided with a patterned cured film (cured film pattern, cured product of laminate) 60 formed on the substrate 50 with a transparent electrode pattern 50a formed using the transfer film of one embodiment. Indicates.
  • the transparent electrode pattern 50a may be a metal wiring.
  • a cured film satisfying both the function of protecting the transparent electrode or the metal wiring in the frame area in the touch panel and the function of suppressing the visualization of the transparent electrode pattern or improving the visibility of the sensing area is formed at once. be able to.
  • a polymer film As the support film 10, for example, a polymer film can be used.
  • the polymer film include films of polyethylene terephthalate, polycarbonate, polyethylene, polypropylene, polyethersulfone, cycloolefin polymer, and the like.
  • the thickness of the support film 10 is preferably 5 ⁇ m or more, more preferably 10 ⁇ m or more, and even more preferably 15 ⁇ m or more from the viewpoint of excellent mechanical strength.
  • the thickness of the support film 10 is preferably 100 ⁇ m or less, more preferably 70 ⁇ m or less, still more preferably 40 ⁇ m or less, and even more preferably 35 ⁇ m or less from the viewpoint of suppressing a reduction in resolution when irradiating active light through the support film 10. Particularly preferred. From these viewpoints, the thickness of the support film 10 is preferably 5 to 100 ⁇ m, more preferably 10 to 70 ⁇ m, still more preferably 15 to 40 ⁇ m, and particularly preferably 15 to 35 ⁇ m.
  • the first resin layer 20 is formed of a curable resin composition.
  • the first resin layer 20 is a layer (photosensitive resin composition layer) formed of a photosensitive resin composition from the viewpoint of easily forming a cured film having a desired shape.
  • the first resin layer 20 includes a binder polymer (hereinafter also referred to as “first binder polymer” or “(A) component”), a photopolymerizable compound (hereinafter also referred to as “(B) component”), It is preferably formed from a photosensitive resin composition containing a photopolymerization initiator (hereinafter also referred to as “component (C)”).
  • a binder polymer having a carboxyl group is preferably used as the component (A) from the viewpoint of enabling patterning by alkali development.
  • a co-polymer having a structural unit derived from (meth) acrylic acid and a structural unit derived from (meth) acrylic acid alkyl ester Coalescence is preferred.
  • the copolymer may contain in the structural unit other monomers that can be copolymerized with the (meth) acrylic acid or the (meth) acrylic acid alkyl ester. Specific examples include glycidyl (meth) acrylate, benzyl (meth) acrylate, and styrene.
  • the component may have an ethylenically unsaturated group.
  • the (A) component which has an ethylenically unsaturated group shall not be contained in (B) component in this specification.
  • Examples of the (meth) acrylic acid alkyl ester include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, Examples thereof include hydroxylethyl methacrylate.
  • the component (A) contains (meth) acrylic acid, (meth) acrylic acid glycidyl, and (meth) acrylic acid from the viewpoint of alkali developability (particularly alkali developability with respect to an aqueous inorganic alkali solution), patternability, transparency, and reduction of diffuse reflectance.
  • benzyl (meth) acrylate Selected from the group consisting of benzyl (meth) acrylate, styrene, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, cyclohexyl (meth) acrylate and 2-ethylhexyl (meth) acrylate It is preferable to include a binder polymer having a structural unit derived from at least one compound.
  • the weight average molecular weight of the component (A) is preferably 10,000 or more, more preferably 15,000 or more, and still more preferably 30,000 or more, from the viewpoint of resolution and easy adjustment of the diffuse reflectance to a desired range. 40,000 or more is particularly preferable.
  • the weight average molecular weight of the component (A) is preferably 200,000 or less, more preferably 150,000 or less, and particularly preferably 100,000 or less from the viewpoint of resolution.
  • the component (A) weight average molecular weight may be 60,000 or less. From these viewpoints, the weight average molecular weight of the component (A) is preferably 10,000 to 200,000, more preferably 15,000 to 150,000, still more preferably 30,000 to 150,000, and 30,000. To 100,000 is particularly preferred, and 40,000 to 100,000 is very particularly preferred.
  • Component (A) The weight average molecular weight may be 40,000 to 60,000. In addition, a weight average molecular weight can be measured by the gel permeation chromatography method with reference to the Example of this specification.
  • the acid value of the component (A) is preferably 75 mgKOH / g or more from the viewpoint of easily forming a cured film having a desired shape by alkali development and easily adjusting the diffuse reflectance to a desired range.
  • the acid value of the component (A) may be 90 mgKOH / g or more.
  • the acid value of the component (A) is preferably 200 mgKOH / g or less from the viewpoint of achieving both controllability of the cured film shape and rust prevention of the cured film and easily adjusting the diffuse reflectance to a desired range. 150 mgKOH / g or less is more preferable, and 120 mgKOH / g or less is still more preferable.
  • the acid value of the component (A) is preferably 75 to 200 mgKOH / g, more preferably 75 to 150 mgKOH / g, and still more preferably 75 to 120 mgKOH / g.
  • the acid value of the component (A) may be 90 to 150 mgKOH / g.
  • an acid value can be measured with reference to the Example of this specification.
  • the content of the component (A) is preferably 35 parts by mass or more with respect to 100 parts by mass of the total amount of the component (A) and the component (B), from the viewpoint of maintaining pattern formability and rust prevention of the cured film. 40 parts by mass or more is more preferable, 50 parts by mass or more is further preferable, and 55 parts by mass or more is particularly preferable.
  • the content of the component (A) is preferably 85 parts by mass or less, and 80 parts by mass or less with respect to 100 parts by mass of the total amount of the component (A) and the component (B), from the viewpoint of excellent coating properties of the resin composition. Is more preferable, 70 mass parts or less are still more preferable, and 65 mass parts or less are especially preferable.
  • the content of the component (A) is preferably 35 to 85 parts by weight, more preferably 40 to 80 parts by weight with respect to 100 parts by weight of the total amount of the components (A) and (B), Is more preferably 70 parts by mass, and particularly preferably 55-65 parts by mass.
  • (B) component: photopolymerizable compound As the component (B), a photopolymerizable compound having an ethylenically unsaturated group can be used.
  • the photopolymerizable compound having an ethylenically unsaturated group include a monofunctional vinyl monomer, a bifunctional vinyl monomer, or a polyfunctional vinyl monomer having at least three polymerizable ethylenically unsaturated groups.
  • Examples of the monofunctional vinyl monomer include those exemplified as monomers used for the synthesis of a copolymer which is a suitable example of the component (A).
  • bifunctional vinyl monomer examples include polyethylene glycol di (meth) acrylate, trimethylolpropane di (meth) acrylate, polypropylene glycol di (meth) acrylate, 2,2-bis (4- (meth) acryloxypolyethoxypolypropoxy Phenyl) propane, bisphenol A diglycidyl ether di (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, and the like.
  • the polyfunctional vinyl monomer having at least three polymerizable ethylenically unsaturated groups conventionally known ones can be used without particular limitation.
  • the polyfunctional vinyl monomer includes a (meth) acrylate compound having a skeleton derived from trimethylolpropane such as trimethylolpropane tri (meth) acrylate; tetramethylolmethane (Meth) acrylate compounds having a skeleton derived from tetramethylolmethane such as tri (meth) acrylate and tetramethylolmethanetetra (meth) acrylate; derived from pentaerythritol such as pentaerythritol tri (meth) acrylate and pentaerythritol tetra (meth) acrylate (Meth) acrylate compounds having the following skeleton: bones derived from dipentaerythritol such
  • the polyfunctional vinyl monomer preferably includes a di (meth) acrylate compound having a dicyclopentanyl structure or a dicyclopentenyl structure, and has a dicyclopentanyl structure, from the viewpoint of inhibiting corrosion of metal wiring and transparent electrodes. More preferably, it contains a di (meth) acrylate compound. From the viewpoint of suppressing corrosion of the metal wiring and the transparent electrode, it is preferable to include a compound represented by the following general formula (1) as a di (meth) acrylate compound having a dicyclopentanyl structure or a dicyclopentenyl structure.
  • R 1 and R 2 each independently represent a hydrogen atom or a methyl group
  • X represents a divalent group having a dicyclopentanyl structure or a dicyclopentenyl structure
  • R 3 And R 4 each independently represents an alkylene group having 1 to 4 carbon atoms
  • n and m each independently represents an integer of 0 to 2
  • p and q each independently represents an integer of 0 or more
  • p + q 0 to 10 is selected.
  • R 3 and R 4 are each independently preferably an ethylene group or a propylene group, and more preferably an ethylene group.
  • the propylene group may be either an n-isopropylene group or an isopropylene group.
  • n and m indicate how much a methylene group is added in the molecule.
  • p and q indicate how much an alkoxy group having 1 to 4 carbon atoms is added to the molecule.
  • p + q is 2 or more, two or more R 3 and R 4 may be the same or different.
  • the compound represented by the general formula (1) realizes low moisture permeability of the film because the divalent group having a dicyclopentanyl structure or dicyclopentenyl structure contained in X has a bulky structure. Therefore, it is considered that the corrosion resistance of the metal wiring and the transparent electrode is improved.
  • the dicyclopentanyl structure and the dicyclopentenyl structure can also be referred to as a tricyclodecane skeleton and a tricyclodecene skeleton, respectively.
  • the “tricyclodecane skeleton” and the “tricyclodecene skeleton” refer to the following structures (where each bond is an arbitrary position).
  • Examples of the compound represented by the general formula (1) include tricyclodecane dimethanol diacrylate represented by the following formula (2). This is available as A-DCP (manufactured by Shin-Nakamura Chemical Co., Ltd., product name).
  • the content of the di (meth) acrylate compound having a dicyclopentanyl structure or a dicyclopentenyl structure is 50 with respect to 100 parts by mass of the total amount of the component (B) from the viewpoint of suppressing corrosion of the metal wiring and the transparent electrode. It is preferably at least 70 parts by weight, more preferably at least 70 parts by weight, even more preferably at least 80 parts by weight.
  • the content of the di (meth) acrylate compound having a dicyclopentanyl structure or a dicyclopentenyl structure may be 100 parts by mass with respect to 100 parts by mass of the total amount of the component (B).
  • the ratio to be used is not particularly limited, but photocurability and electrode corrosion From the viewpoint of preventing the polymerization, the proportion of the monomer having at least three polymerizable ethylenically unsaturated groups in the molecule is 30 mass out of 100 mass parts of the total amount of the photopolymerizable compound contained in the photosensitive resin composition. Part or more, 50 parts by mass or more, or 75 parts by mass or more.
  • the component (C) any conventionally known photopolymerization initiator can be used without particular limitation, but a highly transparent photopolymerization initiator is preferred.
  • the component (C) is at least one selected from the group consisting of oxime ester compounds and phosphine oxide compounds. It is preferable that an oxime ester compound is included.
  • Examples of the phosphine oxide compound include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide.
  • the oxime ester compound is preferably at least one selected from the group consisting of a compound represented by the following formula (3), a compound represented by the following formula (4), and a compound represented by the following formula (5). Used.
  • R 11 and R 12 each independently represents an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, a phenyl group, or a tolyl group.
  • Preferred is an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 4 to 6 carbon atoms, a phenyl group or a tolyl group, an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 4 to 6 carbon atoms, a phenyl group or tolyl
  • a group is more preferable, and a methyl group, a cyclopentyl group, a phenyl group, or a tolyl group is still more preferable.
  • R 13 represents —H, —OH, —COOH, —O (CH 2 ) OH, —O (CH 2 ) 2 OH, —COO (CH 2 ) OH or —COO (CH 2 ) 2 OH.
  • —H, —O (CH 2 ) OH, —O (CH 2 ) 2 OH, —COO (CH 2 ) OH, or —COO (CH 2 ) 2 OH are preferred, —H, —O (CH 2 ) 2 More preferred is OH or —COO (CH 2 ) 2 OH.
  • each R 14 represents an alkyl group having 1 to 6 carbon atoms, and is preferably a propyl group.
  • the plurality of R 14 may be the same or different.
  • R 15 represents NO 2 or ArCO (wherein Ar represents a substituted or unsubstituted aryl group), and Ar is preferably a tolyl group.
  • Examples of the substituent in the case of having a substituent include an alkyl group having 1 to 6 carbon atoms.
  • R 16 and R 17 each independently represent an alkyl group having 1 to 12 carbon atoms, a phenyl group, or a tolyl group, preferably a methyl group, a phenyl group, or a tolyl group.
  • R 18 represents an alkyl group having 1 to 6 carbon atoms, preferably an ethyl group.
  • R 19 is an organic group having an acetal bond, and a substituent corresponding to R 19 in a compound represented by the formula (5-1) described later is preferable.
  • R 20 and R 21 each independently represents an alkyl group having 1 to 12 carbon atoms, a phenyl group or a tolyl group, preferably a methyl group, a phenyl group or a tolyl group, and more preferably a methyl group.
  • R 22 represents an alkyl group having 1 to 6 carbon atoms.
  • n represents an integer of 0 to 4.
  • Examples of the compound represented by the above formula (3) include a compound represented by the following formula (3-1) and a compound represented by the following formula (3-2).
  • a compound represented by the following formula (3-1) is available as IRGACURE OXE01 (manufactured by BASF Japan Ltd., product name).
  • Examples of the compound represented by the above formula (4) include a compound represented by the following formula (4-1).
  • a compound represented by the following formula (4-1) is available as DFI-091 (product name, manufactured by Daito Chemix Co., Ltd.).
  • Examples of the compound represented by the above formula (5) include a compound represented by the following formula (5-1).
  • a compound represented by the following formula (5-1) is available as Adekaoptomer N-1919 (manufactured by ADEKA, product name).
  • oxime ester compounds it is preferable to use a compound represented by the following formula (6), a compound represented by the following formula (7), or the like.
  • the compound represented by the above formula (3-1) is very preferable. Whether the compound represented by the above formula (3-1) is contained in the cured film can be confirmed by pyrolysis gas chromatograph mass spectrometry of the cured film described in International Publication No. 2013/084875.
  • the content of the component (C) is preferably 0.1 parts by mass or more, and preferably 1 part by mass or more with respect to 100 parts by mass of the total amount of the components (A) and (B), from the viewpoint of excellent photosensitivity and resolution. More preferred.
  • the content of the component (C) is preferably 10 parts by mass or less and more preferably 5 parts by mass or less with respect to 100 parts by mass of the total amount of the component (A) and the component (B) from the viewpoint of excellent photosensitivity and resolution. 3 parts by mass or less is more preferable, and 2 parts by mass or less is particularly preferable.
  • the content of the component (C) is preferably 0.1 to 10 parts by mass, more preferably 1 to 5 parts by mass with respect to 100 parts by mass of the total amount of the components (A) and (B). 1 to 3 parts by mass is more preferable, and 1 to 2 parts by mass is particularly preferable.
  • the photosensitive resin composition forming the first resin layer 20 is a triazole compound having a mercapto group, a tetrazole compound having a mercapto group, a thiadiazole compound having a mercapto group, from the viewpoint of further improving the rust prevention property of the cured film. It is preferable to further contain a triazole compound having an amino group or a tetrazole compound having an amino group (hereinafter also referred to as “component (D)”).
  • component (D) a triazole compound having an amino group or a tetrazole compound having an amino group
  • the triazole compound having a mercapto group include 3-mercapto-triazole (manufactured by Wako Pure Chemical Industries, Ltd., product name: 3MT).
  • the thiadiazole compound having a mercapto group include 2-amino-5-mercapto-1,3,4-thiadiazole (manufactured by Wako Pure Chemical Industries,
  • triazole compound having an amino group examples include benzotriazole, 1H-benzotriazole-1-acetonitrile, benzotriazole-5-carboxylic acid, 1H-benzotriazole-1-methanol, carboxybenzotriazole, etc. , 3-mercaptotriazole, 5-mercaptotriazole, and other triazole compounds containing a mercapto group are substituted with amino groups.
  • tetrazole compounds having an amino group examples include 5-amino-1H-tetrazole, 1-methyl-5-amino-tetrazole, 1-methyl-5-mercapto-1H-tetrazole, and 1-carboxymethyl-5-amino-tetrazole.
  • Etc. These tetrazole compounds may be water-soluble salts thereof. Specific examples include alkali metal salts of 1-methyl-5-amino-tetrazole such as sodium, potassium and lithium.
  • the content is 100 parts by mass with respect to the total amount of the component (A) and the component (B) from the viewpoint of further improving the rust prevention property of the cured film.
  • 0.05 parts by mass or more preferably 0.1 parts by mass or more, more preferably 0.2 parts by mass or more, and particularly preferably 0.3 parts by mass or more.
  • the content of the component (D) is preferably 5.0 parts by mass or less with respect to 100 parts by mass of the total amount of the component (A) and the component (B), from the viewpoint of excellent transparency of the cured film, and is 2.0 masses. Part or less is more preferable, 1.0 part by weight or less is more preferable, and 0.8 part by weight or less is particularly preferable. From these viewpoints, 0.05 to 5.0 parts by mass is preferable, 0.1 to 2.0 parts by mass is more preferable, 0.2 to 1.0 parts by mass is further preferable, and 0.3 to 0.8 parts by mass is preferable. Part by mass is particularly preferred.
  • the photosensitive resin composition comprises a phosphate ester having an ethylenically unsaturated group (hereinafter also referred to as “component (E)”) from the viewpoint of adhesion to the ITO electrode patterned substrate and prevention of development residue. It is preferable to contain.
  • component (E) a phosphate ester having an ethylenically unsaturated group
  • the phosphate ester having an ethylenically unsaturated group may overlap with the component (B), but in the present specification, the component (E) is not included in the component (B).
  • the photosensitive resin composition contains the component (E)
  • the content is improved from the viewpoint of preventing the development residue while improving the adhesion to the substrate with the ITO electrode pattern, and the component (A) and (B )
  • the total amount of components is preferably 0.05 parts by mass or more, more preferably 0.1 parts by mass or more, and still more preferably 0.15 parts by mass or more with respect to 100 parts by mass.
  • the content of the component (E) is improved from the viewpoint of preventing the development residue while improving the adhesion to the substrate with the ITO electrode pattern, with respect to 100 parts by mass of the total amount of the component (A) and the component (B). 5.0 parts by mass or less is preferable, 4.0 parts by mass or less is more preferable, and 3.0 parts by mass or less is still more preferable.
  • adhesion imparting agents such as silane coupling agents, rust preventive agents, leveling agents, plasticizers, fillers, antifoaming agents, flame retardants, Stabilizers, antioxidants, fragrances, thermal crosslinking agents, polymerization inhibitors and the like can be contained in an amount of about 0.01 to 20 parts by mass with respect to 100 parts by mass of the total amount of component (A) and component (B). . These can be used alone or in combination of two or more.
  • said "photosensitive resin composition” means the composition of the state which does not contain the solvent mentioned later, and content of each component is content with respect to component total other than the solvent mentioned later.
  • the content of the metal oxide in the photosensitive resin composition is usually smaller than the content of the metal oxide in the resin composition forming the second resin layer described later.
  • the content of the metal oxide in the photosensitive resin composition may be 10% by mass or less, 5% by mass or less, or 1% by mass or less, and 0% by mass based on the total mass of the photosensitive resin composition. May be.
  • the refractive index at a wavelength of 633 nm of the first resin layer after curing is usually smaller than the refractive index at a wavelength of 633 nm of the second resin layer described later.
  • the refractive index of the first resin layer after curing at a wavelength of 633 nm is usually 1.40 or more and 1.49 or less.
  • the refractive index at a wavelength of 633 nm of the first resin layer 20 may be appropriately set so that the refractive index at a wavelength of 633 nm of the cured first resin layer falls within the above range.
  • the refractive index of the first resin layer 20 at a wavelength of 633 nm may be 1.40 to 1.49.
  • the thickness of the first resin layer 20 is preferably 15 ⁇ m or less, more preferably 10 ⁇ m or less, from the viewpoint of sufficient effects as a protective film and the reduction of the diffuse reflectance of the cured film. 8 ⁇ m or less is more preferable.
  • the thickness of the first resin layer 20 (thickness after drying) is preferably 2 ⁇ m or more from the viewpoint of sufficiently providing a protective film and sufficiently embedding a step on the surface of the substrate with a transparent electrode pattern. The above is more preferable. That is, the thickness of the first resin layer 20 (thickness after drying) is preferably 2 to 15 ⁇ m, more preferably 2 to 10 ⁇ m, still more preferably 3 to 8 ⁇ m.
  • the second resin layer 30 Since the second resin layer 30 contains a metal oxide, it has a high refractive index.
  • the refractive index at 633 nm of the second resin layer 30 is, for example, 1.50 or more.
  • the second resin layer 30 contains a metal oxide and has a high refractive index (for example, the refractive index at 633 nm is 1.50 or more), when the transparent laminated body 100 shown in FIG.
  • the cured film has a refractive index of a transparent electrode pattern 50a such as ITO and various members used on the first cured resin layer 22 (for example, a cover glass and a transparent electrode used when modularized) It tends to be an intermediate value of the refractive index of the transparent adhesive film (OCA, Optical Clear Adhesive) that bonds the pattern.
  • OCA Optical Clear Adhesive
  • the refractive index can be measured with reference to the examples in this specification.
  • the refractive index at 633 nm of the second resin layer 30 may be 1.55 or more, or 1.60 or more, and 1.90 or less, 1. It may be 85 or less or 1.75 or less. That is, the refractive index of the second resin layer 30 at a wavelength of 633 nm may be, for example, 1.50 to 1.90, 1.55 to 1.85, or 1.60 to 1.75. In the present embodiment, in particular, when the refractive index at 633 nm of the second resin layer 30 is 1.60 or more, the effect obtained by setting the diffuse reflectance of the cured film to 0.20% or less becomes remarkable.
  • the resin composition forming the second resin layer 30 may be a curable (eg, photocurable or thermosetting) resin composition, and is preferably photocurable.
  • the resin composition forming the second resin layer 30 is not necessarily required to contain a photopolymerization component such as a photopolymerizable compound or a photopolymerization initiator, and is caused by a photopolymerization component that migrates from an adjacent resin layer. Then, the resin composition may be photocured.
  • the second resin layer 30 contains, for example, a binder polymer (hereinafter also referred to as “second binder polymer”) and a metal oxide (hereinafter also referred to as “(F) component”). That is, the resin composition forming the second resin layer 30 contains, for example, a second binder polymer and a metal oxide.
  • the second resin layer 30 (resin composition forming the second resin layer 30) may further contain a surface treatment agent (hereinafter also referred to as “component (G)”). 20 may contain the components (B) to (E) and other additives (excluding those corresponding to the component (G)).
  • said "resin composition which forms the 2nd resin layer 30" means the composition of the state which does not contain the solvent mentioned later, and content of each component mentioned later is with respect to component whole quantity other than the solvent mentioned later. Content.
  • [Second binder polymer] As the second binder polymer, compounds exemplified in the component (A) used for the first resin layer 20 can be preferably used.
  • the acid value of the second binder polymer reduces the diffuse reflectance of the cured film and the viewpoint of improving the alkali developability of the second resin layer when the second resin layer is bonded to the first resin layer. From the viewpoint, for example, 80 mgKOH / g or more is preferable, 100 mgKOH / g or more is more preferable, and 120 mgKOH / g or more is more preferable.
  • the acid value is preferably 200 mgKOH / g or less, more preferably 175 mgKOH / g or less, and still more preferably 160 mgKOH / g or less, from the viewpoint of achieving both controllability of the cured film shape and rust prevention of the cured film.
  • the acid value of the binder polymer 80 to 200 mgKOH / g is preferable, 100 to 175 mgKOH / g is more preferable, and 120 to 160 mgKOH / g is still more preferable.
  • a carboxyl group is imparted to the side chain of the binder polymer.
  • the acid value of the second binder polymer can be measured in the same manner as the acid value of the first binder polymer.
  • the weight average molecular weight of the second binder polymer is preferably 10,000 or more from the viewpoint of resolution.
  • the weight average molecular weight of the second binder polymer is preferably 200,000 or less, more preferably 150,000 or less, still more preferably 100,000 or less, particularly preferably 85,000 or less, from the viewpoint of resolution, 70,000.
  • the following are highly preferred. From these viewpoints, the weight average molecular weight of the second binder polymer is preferably 10,000 to 200,000, more preferably 10,000 to 150,000, still more preferably 10,000 to 100,000. 000 to 85,000 is particularly preferable, and 10,000 to 70,000 is very preferable.
  • the weight average molecular weight of a 2nd binder polymer can be measured similarly to the weight average molecular weight measurement of a 1st binder polymer.
  • the content of the second binder polymer in the second resin layer 30 is preferably 40 parts by mass or more and more preferably 50 parts by mass or more with respect to 100 parts by mass of the total amount of the second binder polymer and the component (B). 60 parts by mass or more is more preferable.
  • the content of the second binder polymer in the second resin layer 30 is preferably 80 parts by mass or less with respect to 100 parts by mass of the total amount of the second binder polymer and the component (B). From these viewpoints, the content of the second binder polymer in the second resin layer 30 is preferably 40 to 80 parts by mass with respect to 100 parts by mass of the total amount of the second binder polymer and the component (B). ⁇ 80 parts by mass is more preferred, and 60 ⁇ 80 parts by mass is even more preferred.
  • the refractive index at a wavelength of 633 nm of the second resin layer can be improved, and more excellent transparency can be obtained. Moreover, developability can be improved, suppressing adsorption
  • the refractive index at a wavelength of 633 nm of the second resin layer can be easily controlled, and the refractive index at a wavelength of 633 nm is 1.50 or more from the viewpoint of easily obtaining better transparency.
  • Metal oxides are preferred.
  • the component (F) may be metal oxide particles or metal oxide fine particles. As the component (F), one type of particle can be used alone, or two or more types of particles can be used in combination.
  • the average particle diameter D50 of the particulate metal oxide may be 70 nm or less from the viewpoint of easily adjusting the diffuse reflectance to a desired range, and may be 5 nm or more and 10 nm. Or more than 15 nm.
  • the metal oxide includes zirconium oxide, titanium oxide, tin oxide, zinc oxide, indium tin oxide, indium oxide, aluminum oxide from the viewpoint of improving the refractive index of the second resin layer and reducing the diffuse reflectance of the cured film. It is preferable to include at least one selected from the group consisting of silicon oxide and yttrium oxide, and it is more preferable to include at least one selected from the group consisting of zirconium oxide and titanium oxide. In particular, when containing at least one selected from the group consisting of zirconium oxide and titanium oxide, it is possible to more suitably achieve both improvement of the refractive index of the second resin layer and reduction of the diffuse reflectance of the cured film.
  • zirconium oxide particles when the material of the transparent electrode is ITO, it is preferable to use zirconium oxide nanoparticles from the viewpoint of improving the refractive index and adhesion between the ITO and the transparent substrate.
  • the particle size distribution Dmax of the zirconium oxide nanoparticles is preferably 40 nm or less from the viewpoint of adhesion to ITO and the transparent substrate and from the viewpoint of easily adjusting the diffuse reflectance to a desired range.
  • Zirconium oxide nanoparticles are OZ-S30K (product name, manufactured by Nissan Chemical Industries, Ltd.), OZ-S40K-AC (product name, manufactured by Nissan Chemical Industries, Ltd.), SZR-K (dispersion of zirconium oxide methyl ethyl ketone, Sakai Chemical). Kogyo Co., Ltd., product name) and SZR-M (zirconium oxide methanol dispersion, Sakai Chemical Industry Co., Ltd., product name) are commercially available.
  • the particle size distribution Dmax of the titanium oxide nanoparticles is preferably 50 nm or less, and more preferably 10 nm or more. That is, the particle size distribution Dmax of the titanium oxide nanoparticles is preferably 10 to 50 nm.
  • a sulfide containing atoms such as Mg, Al, Si, Ca, Cr, Cu, Zn, and Ba can be used in addition to the metal oxide.
  • the content of the component (F) can improve the refractive index of the second resin layer, from the viewpoint of easily obtaining better transparency, from the viewpoint of improving developability, and from the viewpoint of reducing diffuse reflectance. Therefore, 20 parts by mass or more is preferable with respect to 100 parts by mass of the second resin composition, 40 parts by mass or more is more preferable, 70 parts by mass or more is further preferable, 75 parts by mass or more is even more preferable, and 80 parts by mass or more. Is particularly preferred.
  • the content of the component (F) is preferably 90 parts by mass or less with respect to 100 parts by mass of the second resin composition, from the viewpoint of improving developability and the viewpoint of easily adjusting the diffuse reflectance to a desired range. 85 mass parts or less are more preferable.
  • the content of the component (F) is 20 to 90 parts by weight, 40 to 90 parts by weight, 70 to 90 parts by weight with respect to 100 parts by weight of the resin composition forming the second resin layer 30. It may be 70 to 85 parts by weight, 75 to 90 parts by weight, 75 to 85 parts by weight, 80 to 90 parts by weight, or 80 to 85 parts by weight.
  • the component (G) contributes to the improvement in dispersibility of the component (F) in the second resin layer. Therefore, when the second resin layer contains the component (G), the component (F) tends to be present in the second resin layer in a well dispersed state, and the diffuse reflectance of the cured film can be easily reduced.
  • the component (G) include silane coupling agents and organometallic complexes (such as Al metal complexes). Among these, a silane coupling agent is preferably used from the viewpoint of being excellent in the effect of reducing the diffuse reflectance.
  • silane coupling agent examples include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacrylate.
  • the component (G) may exist in a state of being bonded to the surface of the component (F).
  • the component (F) may be surface-treated with the component (G), and the component (G) may be bonded to the surface of the component (F).
  • the content of the component (G) is preferably from 0.1 to 100 parts by mass of the component (F) from the viewpoint of easily obtaining the effect of improving the dispersibility of the component (F) and easily reducing the diffuse reflectance of the cured film.
  • the amount is preferably 5 parts by mass or more, more preferably 1.0 part by mass or more, and further preferably 2.0 parts by mass or more.
  • the content of the component (G) may be 10 parts by mass or less with respect to 100 parts by mass of the component (F) from the viewpoint of excellent curability of the resin composition and reduction of diffuse reflectance. Or 3 parts by mass or less.
  • the thickness of the second resin layer 30 is preferably 10 nm or more, more preferably 20 nm or more, still more preferably 30 nm or more, and particularly preferably 40 nm or more.
  • the thickness of the second resin layer 30 is preferably 1000 nm or less, more preferably 500 nm or less, still more preferably 100 nm or less, still more preferably 80 nm or less, and particularly preferably 60 nm or less.
  • the thickness of the second resin layer 30 after drying may be, for example, 10 to 1000 nm, 20 to 500 nm, 30 to 100 nm, 40 to 80 nm, or 40 to 60 nm.
  • the transfer film of the embodiment may include other layers appropriately selected as long as the effects of the present invention are obtained. There is no restriction
  • a cushion layer, an oxygen shielding layer, a release layer, an adhesive layer, and the like can be given.
  • the transfer film may have these layers individually by 1 type, and may have 2 or more types. Moreover, you may have 2 or more of the same kind of layers.
  • the first resin layer 20 and the second resin layer 30 are adjacent to each other, but the other resin layer 20 is between the first resin layer 20 and the second resin layer 30. A layer may be present.
  • the 1st resin layer 20 and the support film 10 are adjacent, the said other layer may exist between the 1st resin layer 20 and the support film 10.
  • Examples of the protective film 15 include polyethylene, polypropylene, polyethylene terephthalate, polycarbonate, a polyethylene-vinyl acetate copolymer, a polyethylene-vinyl acetate copolymer film, and a laminated film of these films and polyethylene.
  • the thickness of the protective film 15 may be 5 ⁇ m or more, and may be 100 ⁇ m or less.
  • the thickness of the protective film 15 is preferably 70 ⁇ m or less, more preferably 60 ⁇ m or less, still more preferably 50 ⁇ m or less, and particularly preferably 40 ⁇ m or less, from the viewpoint of storing in a roll.
  • the transfer film 1 is, for example, a coating liquid containing a resin composition (photosensitive resin composition) that forms the first resin layer 20 and a coating composition that contains a resin composition that forms the second resin layer 30.
  • a resin composition photosensitive resin composition
  • Each liquid can be prepared, and each can be obtained by apply
  • the transfer film 1 is coated with a coating solution containing a resin composition for forming the first resin layer 20 on the support film 10 and dried, and then the second resin is formed on the first resin layer 20. It can also form by apply
  • the coating liquid uniformly dissolves or disperses each component constituting the resin composition forming the first resin layer 20 and the resin composition forming the second resin layer 30 according to this embodiment described above in a solvent. Can be obtained.
  • the resin composition that forms the second resin layer 30 includes the component (G)
  • all the components are mixed at once. However, after the (F) component and the (G) component are mixed to obtain a mixture, the obtained mixture is mixed with the other components other than the (F) component and the (G) component. Is preferred.
  • the surface of the component (F) is treated with the component (G), and the second resin layer 30
  • the dispersibility of the component (F) is improved. This makes it easier to reduce the diffuse reflectance.
  • the solvent used as the coating solution is not particularly limited, and known ones can be used. Solvents used as coating solutions are, for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, toluene, methanol, ethanol, propanol, butanol, methylene glycol, ethylene glycol, propylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol Examples include ethyl methyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, chloroform, and methylene chloride.
  • Application methods include, for example, doctor blade coating method, Meyer bar coating method, roll coating method, screen coating method, spinner coating method, inkjet coating method, spray coating method, dip coating method, gravure coating method, curtain coating method, die coating method. Law.
  • the drying conditions are not particularly limited, but the drying temperature is preferably 60 to 130 ° C., and the drying time is preferably 0.5 to 30 minutes.
  • the thickness of the laminate 40 including the first resin layer 20 and the second resin layer 30 is preferably 30 ⁇ m or less, more preferably 20 ⁇ m or less, and even more preferably 10 ⁇ m or less from the viewpoint of improving the followability during lamination. Furthermore, from the viewpoint of rust prevention, taking into account the possibility of pinholes due to protrusions on the substrate, it is preferably 1 ⁇ m or more, preferably 2 ⁇ m or more, and more preferably 2 ⁇ m or more. If it is 3 micrometers or more, it will become possible to suppress the influence by the protrusion of a base material, and to maintain rust prevention property.
  • the film (transfer film) described above is used after being transferred to a substrate or the like. That is, the present invention is a laminate comprising a support film, a first resin layer provided on the support film, and a second resin layer containing a metal oxide provided on the first resin layer. And the application of the film comprising the body to the transfer of the laminate.
  • a method for forming a cured film using a transfer film includes a step of laminating a laminate 40 of the transfer film 1 on a base material 50 so that the second resin layer 30 is in close contact with the base material 50, and a base material A step of exposing a predetermined portion of the laminate 40 on the substrate 50 and a step of removing a portion other than the exposed predetermined portion to form a patterned cured film 60.
  • the laminate 40 in the transfer film is sufficiently cured to cure the laminate 40 (eg, a cured film cured at a curing reaction rate of 70% or more). Can be obtained.
  • the laminate is exposed to the laminate 40 with an exposure amount of 1000 mJ / cm 2 from the opposite side of the first resin layer 20 to the second resin layer 30 side, and heated at 140 ° C. for 2 hours.
  • Can be sufficiently cured for example, cured to a curing reaction rate of 70% or more
  • the curing condition of the laminate is not limited to this as long as the laminate 40 can be sufficiently cured. Details of the method of forming the cured film 60 will be described below.
  • Examples of the substrate 50 include glass, plastic, ceramic, resin-made substrates used for touch panels, and the like.
  • the resin base material include a polyester resin, a polystyrene resin, an olefin resin, a polybutylene terephthalate resin, a polycarbonate resin, and an acrylic resin base material. These substrates are preferably transparent.
  • a transparent electrode pattern 50a which is a target for forming the cured film 60, is provided.
  • the transparent electrode can be formed using a conductive metal oxide film such as ITO and IZO (Indium Zinc Oxide, indium oxide-zinc oxide).
  • the transparent electrode can also be formed using a photosensitive film having a photocurable resin layer using conductive fibers such as silver fibers and carbon nanotubes.
  • the transparent electrode pattern 50a may be a metal wiring.
  • the metal wiring can be formed by a method such as screen printing or vapor deposition using a conductive material such as Au, Ag, Cu, Al, Mo, and C, for example.
  • a refractive index adjustment layer, an insulating layer, or the like may be provided between the base material 50, the transparent electrode, and the metal wiring.
  • the laminate 40 of the transfer film 1 is placed on the surface of the substrate 50 (substrate with a transparent electrode pattern), and the second resin layer 30 is placed on the surface.
  • Lamination is performed by pressure bonding from the support film 10 side so as to be in close contact.
  • the pressing means include a pressing roll.
  • the pressure roll may be provided with a heating means so that it can be heat-pressure bonded.
  • the heating temperature for thermocompression bonding is such that the adhesiveness between the second resin layer 30 and the substrate 50 and the components of the first resin layer 20 and the second resin layer 30 are not easily cured or thermally decomposed. In view of the above, it is preferably 25 to 160 ° C, more preferably 25 to 150 ° C, and further preferably 30 to 150 ° C.
  • the 2nd resin layer 30 is thermosetting, it is preferable that it is the temperature which the 2nd resin layer does not thermoset, for example, it is preferable that it is 130 degrees C or less.
  • the pressure during the thermocompression bonding is 50 to 1 ⁇ 10 5 N / m, preferably 2.5 ⁇ 10 2 to 5 ⁇ 10 4 N / m, more preferably 5 ⁇ 10 2 to 4 ⁇ 10 4 N / m.
  • the preheating treatment of the base material 50 is not necessarily required, but the base material 50 is preliminarily used in order to further improve the adhesion between the second resin layer and the base material. You may heat-process.
  • the treatment temperature at this time is preferably 30 to 150 ° C.
  • actinic rays are radiated in a pattern on the predetermined portions of the second resin layer 30 and the first resin layer 20 after transfer, for example, via a photomask.
  • the support film 10 on the first resin layer 20 is transparent when irradiating the actinic light, the actinic light can be irradiated as it is.
  • the support film 10 is opaque, the actinic light is removed after the support film 10 is removed. Irradiate.
  • a known active light source can be used as the active light source.
  • the pattern in this specification is not limited to the shape of the fine wiring that forms the circuit, but also includes the shape in which only the connection portion with the other base material is removed in a rectangular shape and the shape in which only the frame portion of the base material is removed. It is.
  • the irradiation amount of actinic rays is 1 ⁇ 10 2 to 1 ⁇ 10 4 J / m 2 , and heating can be accompanied during irradiation. If the irradiation amount of this actinic ray is 1 ⁇ 10 2 J / m 2 or more, photocuring can sufficiently proceed, and if it is 1 ⁇ 10 4 J / m 2 or less, the first resin There is a tendency that discoloration of the layer and the second resin layer can be suppressed.
  • the development step is preferably performed by a known method such as spraying, showering, rocking dipping, brushing, or scrubbing using an aqueous alkaline solution as a developing solution.
  • spray development is preferably performed using an alkaline aqueous solution from the viewpoint of environment and safety.
  • the development temperature and time can be adjusted within a conventionally known range.
  • the cured film 60 is a cured film (cured product of the laminated body 40) obtained by curing the laminated body 40 including the first resin layer 20 and the second resin layer 30 of the transfer film 1, for example, a pattern It is formed in a shape.
  • the cured film 60 includes a first cured resin layer 22 and a second cured resin layer 32.
  • the cured film 60 can be used, for example, as an electrode protective film for a touch panel; a planarizing film and an interlayer insulating film for a display element such as a liquid crystal or an organic EL; a protective film for a color filter; a solder resist film for a printed wiring board. is there.
  • Moisture permeability of the cured film 60, from the viewpoint of corrosion inhibition of the metal wiring and the transparent electrode is preferably less 350g / m 2 ⁇ 24h, 300g / m or less, more preferably 2 ⁇ 24h, 250g / m 2 ⁇ 24h or less is more 200 g / m 2 ⁇ 24 h or less is particularly preferable.
  • the moisture permeability is measured by the method shown below.
  • the protective film of the transfer film is peeled off, and the roll temperature is 100 ° C. so that the second resin layer is in close contact with the filter paper (manufactured by Advantech, No.5C, ⁇ 90 mm circle, 130 ⁇ m thick).
  • Lamination is performed under conditions of a feed rate of 0.6 m / min and a pressure bonding pressure (cylinder pressure) of 0.5 MPa.
  • a parallel light exposure machine EXM1201 manufactured by Oak Manufacturing Co., Ltd.
  • a moisture permeability measurement sample in which a cured film (cured film obtained by curing the laminate) is formed on the filter paper is obtained.
  • moisture permeability is measured with reference to JIS standards (Z0208, cup method). Specifically, a circular sample in which a hygroscopic agent (20 g of calcium chloride (anhydrous)) is placed in a measuring cup ( ⁇ 60 mm, depth 15 mm), and the moisture permeability measurement sample is cut into a size of 70 mm in diameter with scissors. Cover the measuring cup with a piece.
  • the sample is left in a constant temperature and humidity chamber for 24 hours under conditions of 60 ° C. and 90% RH, and the moisture permeability is calculated from the change in the total mass of the measurement cup, the hygroscopic agent, and the circular sample piece before and after being left.
  • the minimum value of the transmittance of the cured film 60 at a wavelength of 400 to 700 nm is preferably 90% or more. More specifically, it is preferably 90.00% or more, more preferably 90.50% or more, and still more preferably 90.70% or more. If the transmittance at a wavelength of 400 to 700 nm, which is a general visible light wavelength range, is 90% or more, the image display quality, color tone, and luminance in the sensing area are reduced when the transparent electrode in the sensing area of the touch panel is protected. Can be sufficiently suppressed. The maximum value of the transmittance is usually 100% or less.
  • the visible light transmittance is measured by the following method.
  • the protective film of the transfer film is peeled off, and a laminator (manufactured by Hitachi Chemical Co., Ltd., product name: so that the second resin layer is in close contact with a glass substrate having a thickness of 0.7 mm and a length of 10 cm ⁇ width of 10 cm. HLM-3000 type) under the conditions of a roll temperature of 120 ° C., a substrate feed speed of 1 m / min, and a pressure (cylinder pressure) of 4 ⁇ 10 5 Pa (linear pressure is 9.8 ⁇ 10 3 N / m).
  • Lamination is performed to produce a laminated sample in which the glass substrate, the second resin layer, the first resin layer, and the support film are laminated in this order.
  • the obtained laminated sample was exposed to 5 ⁇ 10 2 J from the upper side of the first resin layer (photosensitive resin composition layer) side using a parallel light exposure machine (EXM1201 manufactured by Oak Manufacturing Co., Ltd.). / M 2 (measured value at a wavelength of 365 nm), after irradiation with ultraviolet rays, the support film was removed and heated in a box-type dryer (model number: NV50-CA, manufactured by Mitsubishi Electric Corporation) for 30 minutes. Allow to stand to obtain a transmittance measurement sample.
  • a parallel light exposure machine EXM1201 manufactured by Oak Manufacturing Co., Ltd.
  • M 2 measured value at a wavelength of 365 nm
  • the visible light transmittance of the obtained transmittance measurement sample is measured in a measurement wavelength range of 400 to 700 nm using a haze meter (manufactured by Nippon Denshoku Industries Co., Ltd., product name: NDH 7000).
  • the electronic component according to this embodiment includes a cured film formed using a transfer film. This cured film is preferably formed in a pattern. Examples of the electronic component include a touch panel, a liquid crystal display, an organic electroluminescence, a solar cell module, a printed wiring board, and electronic paper.
  • FIG. 3 is a schematic top view showing an example of a capacitive touch panel.
  • the touch panel shown in FIG. 3 has a sensing area 102 for detecting a touch position coordinate on one side of a transparent substrate 101, and the transparent electrode 103 and the transparent electrode 104 for detecting a capacitance change in this area are transparent. It is provided on the base material 101.
  • the transparent electrode 103 and the transparent electrode 104 detect the X position coordinate and the Y position coordinate of the touch position, respectively.
  • a metal wiring 105 for transmitting a touch position detection signal from the transparent electrode 103 and the transparent electrode 104 to an external circuit is provided on the transparent substrate 101. Further, the metal wiring 105 and the transparent electrode 103 and the transparent electrode 104 are connected by a connection electrode 106 provided on the transparent electrode 103 and the transparent electrode 104. In addition, a connection terminal 107 for connection to an external circuit is provided at the end of the metal wiring 105 opposite to the connection portion between the transparent electrode 103 and the transparent electrode 104.
  • the transparent electrode 103 As shown in FIG. 3, by forming the cured film pattern 123, the transparent electrode 103, the transparent electrode 104, the metal wiring 105, the connection electrode 106, the function of the protective film of the connection terminal 107, and the transparent electrode pattern are formed. It simultaneously performs a bone appearance suppression function (for example, a refractive index adjustment function) of the sensing region 102.
  • a bone appearance suppression function for example, a refractive index adjustment function
  • the acid value was measured by a neutralization titration method based on JIS K0070 as shown below.
  • the binder polymer solution was heated at 130 ° C. for 1 hour to remove volatile matter, thereby obtaining a solid content.
  • 30 g of acetone was added to the binder polymer, and this was uniformly dissolved to obtain a resin solution.
  • an appropriate amount of an indicator, phenolphthalein was added to the resin solution, and neutralization titration was performed using a 0.1 mol / L potassium hydroxide aqueous solution.
  • the acid value was computed by following Formula.
  • Acid value 0.1 ⁇ V ⁇ f 1 ⁇ 56.1 / (Wp ⁇ I / 100)
  • V is a titration amount (mL) of 0.1 mol / L potassium hydroxide aqueous solution used for titration
  • f 1 is a factor (concentration conversion factor) of 0.1 mol / L potassium hydroxide aqueous solution
  • Wp is measured.
  • the mass (g) of the resin solution, I represents the ratio (mass%) of the non-volatile content in the measured resin solution.)
  • component (A2) Binder polymer solution (A2) -Component (B)
  • A-DCP Tricyclodecane dimethanol diacrylate (made by Shin-Nakamura Chemical Co., Ltd., product name)
  • Component PM-21 Phosphoric acid ester having an ethylenically unsaturated group (product name) manufactured by Nippon Kayaku Co., Ltd.
  • component (A1) Binder polymer solution (A1)
  • A2) Binder polymer solution (A2)
  • component FA-321M ethoxylated bisphenol A dimethacrylate (product name, manufactured by Hitachi Chemical Co., Ltd.)
  • Example 1 ⁇ Preparation of monolayer film A provided with the first resin layer>
  • the coating solution 1 is applied onto a 16 ⁇ m thick polyethylene terephthalate film (support film, manufactured by Toray Industries, Inc., product name: FB40), dried at 100 ° C. for 3 minutes to remove the solvent, and the first resin layer is removed. Formed. The amount of the coating solution was adjusted so that the thickness after drying was 8 ⁇ m.
  • the coating solution IM-1 was applied onto a 30 ⁇ m-thick polypropylene film (protective film, manufactured by Oji F-Tex Co., Ltd.) and dried at 100 ° C. for 3 minutes to remove the solvent, thereby forming a second resin layer.
  • the amount of the coating solution was adjusted so that the thickness after drying was 80 nm.
  • the thickness of the first resin layer in the single-layer film A produced above was measured with a digital thickness gauge (manufactured by Nikon Corporation, product name: DIGIMICROSTAND MS-5C). Moreover, the thickness of the 2nd resin layer in the single layer film B produced above was measured by F20 (Filmtrics Co., Ltd. product name). The thickness of the first resin layer was 8 ⁇ m, and the thickness of the second resin layer was 80 nm.
  • the laminated body (laminated body composed of the first resin layer and the second resin layer) was irradiated with light from the support film side with an exposure amount (measured value at i-line (wavelength 365 nm)). After exposure, after standing at room temperature (25 ° C.) for 15 minutes, the support film was peeled off, and the diffused reflectance in which the second resin layer after exposure and the first resin layer were provided in this order on the polycarbonate substrate A measurement sample (measurement sample A) was prepared.
  • EXM-1201 extra-high pressure mercury lamp
  • the diffuse reflectance of the sample A for measurement is measured by the SCE method with light incident from the first resin layer side. did.
  • the diffuse reflectance at a wavelength of 400 nm of the measurement sample A using the transfer film of Example 1 was 0.21%.
  • the diffuse reflectance of a polycarbonate substrate (product name “Iupilon” manufactured by Mitsubishi Gas Chemical Co., Ltd.) was measured by the SCE method.
  • the diffuse reflectance of the polycarbonate substrate at a wavelength of 400 nm was 0.07%.
  • the value obtained by subtracting the diffuse reflectance of the polycarbonate substrate from the diffuse reflectance of the sample A for measurement is the diffuse reflectance at a wavelength of 400 nm after curing of the laminate in the transfer film of Example 1 (cure obtained by curing the laminate) The diffuse reflectance of the film).
  • the results are shown in Table 5.
  • the sample A2 for measurement was prepared in the same manner as the sample A for measurement, except that the laminate was heated at 140 ° C. for 2 hours before the support film was peeled off. When the diffuse reflectance of sample A2 was measured, it was confirmed that the diffuse reflectance at a wavelength of 400 nm was 0.21% as in measurement sample A.
  • the coating liquid IM-1 was uniformly applied on a glass substrate having a thickness of 0.7 mm, 10 cm long ⁇ 10 cm wide with a spin coater, and dried with a hot air convection dryer at 100 ° C. for 3 minutes to remove the solvent. A second resin layer was formed. Next, the second resin layer obtained above was allowed to stand for 30 minutes in a box-type dryer (model number: NV50-CA, manufactured by Mitsubishi Electric Corporation) heated to 140 ° C., and the second resin layer was A sample for refractive index measurement was obtained.
  • a box-type dryer model number: NV50-CA, manufactured by Mitsubishi Electric Corporation
  • the refractive index at a wavelength of 633 nm of a sample for refractive index measurement obtained by ETA-TCM (product name, manufactured by AudioDev GmbH) was measured.
  • the results are shown in Table 5.
  • the film thickness of the second resin layer used for the measurement was the same as that of the second resin layer in the transfer film (80 nm).
  • Examples 2 to 7 and Comparative Examples 1 to 4 The production of the single layer film B provided with the second resin layer was carried out in the same manner as in Example 1 except that the coating liquids IM-2 to IM-11 were used instead of the coating liquid IM-1.
  • Single layer films B of Examples 2 to 7 and Comparative Examples 1 to 4 were prepared.
  • Transfer films of Examples 2 to 7 and Comparative Examples 1 to 4 were prepared in the same manner as in Example 1 except that the obtained monolayer film B was used in the production of the transfer film. Further, in the same manner as in Example 1, the diffuse reflectance and refractive index were measured. The results are shown in Tables 5 and 6.
  • an evaluation sample was prepared according to the following procedure. Using the laminator (manufactured by Hitachi Chemical Co., Ltd., product name: HLM-3000) so that the protective film of the transfer film prepared above is peeled off and the second resin layer is in close contact with both surfaces of the ITO pattern base material. , Roll temperature 110 ° C., substrate feed rate 1 m / min, pressure bonding pressure (cylinder pressure) 0.4 MPa (thickness 0.1 mm, length 10 cm ⁇ width 10 cm, ITO pattern substrate was used. Was laminated under the condition of 9.8 ⁇ 10 3 N / m).
  • an exposure dose of 1000 mJ / cm 2 (upper side of both main surfaces) is used on both main surfaces of the laminate using a parallel light exposure machine (manufactured by Oak Manufacturing Co., Ltd., product name “EXM-1201”).
  • EXM-1201 Ultraviolet rays were irradiated with i rays (measured value at a wavelength of 365 nm). After exposure, the substrate was left at room temperature (25 ° C.) for 15 minutes, and then the support film was peeled off and removed.
  • the ITO pattern is hardly visible
  • B The ITO pattern is slightly visible depending on the viewing angle
  • C The ITO pattern is slightly visible regardless of the angle
  • D The ITO pattern is clearly visible
  • SYMBOLS 1 Transfer film, 10 ... Support film, 15 ... Protective film, 20 ... 1st resin layer, 30 ... 2nd resin layer, 22 ... 1st cured resin layer, 32 ... 2nd cured resin layer, 40 DESCRIPTION OF SYMBOLS ... Laminated body, 50 ... Base material with transparent electrode pattern, 50a ... Transparent electrode pattern, 60 ... Hardened

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Abstract

La présente invention concerne un film de transfert (1) qui comprend un film de support (10) et un corps stratifié (40) comprenant une première couche de résine (20) disposée sur le film de support (10) et une seconde couche de résine comprenant un oxyde métallique (30) et étant disposée sur la première couche de résine (20), la première couche de résine (20) constituant une couche de composition de résine sensible à la lumière, et le corps stratifié (40) ayant une réflectivité diffuse n'excédant pas 0,20 % par rapport à de la lumière ayant une longueur d'onde de 400 nm tel que déterminé par l'exposition du corps stratifié (40) à 1000 mJ/cm2 de lumière en allant du côté opposé de la première couche de résine (20) vers la seconde couche de résine (30), par le chauffage à 140 °C pendant deux heures, puis par la réalisation de mesures à l'aide d'un schéma SCE en partant du côté opposé de la première couche de résine (20) et en allant vers la seconde couche de résine (30).
PCT/JP2018/012810 2018-03-28 2018-03-28 Film de transfert, film durci et procédé de formation associé, et composant électrique WO2019186781A1 (fr)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017175642A1 (fr) * 2016-04-04 2017-10-12 日立化成株式会社 Film de modulation d'indice de réfraction photosensible, procédé de formation d'un motif de film durci, film durci et composant électronique
JP2017201352A (ja) * 2016-05-02 2017-11-09 日立化成株式会社 転写形感光性屈折率調整フィルム、屈折率調整パターンの形成方法及び電子部品

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017175642A1 (fr) * 2016-04-04 2017-10-12 日立化成株式会社 Film de modulation d'indice de réfraction photosensible, procédé de formation d'un motif de film durci, film durci et composant électronique
JP2017201352A (ja) * 2016-05-02 2017-11-09 日立化成株式会社 転写形感光性屈折率調整フィルム、屈折率調整パターンの形成方法及び電子部品

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