CN110462560A - Transfer printing type photosensitive film, the forming method for solidifying film figure, cured film and touch panel - Google Patents

Transfer printing type photosensitive film, the forming method for solidifying film figure, cured film and touch panel Download PDF

Info

Publication number
CN110462560A
CN110462560A CN201780089046.7A CN201780089046A CN110462560A CN 110462560 A CN110462560 A CN 110462560A CN 201780089046 A CN201780089046 A CN 201780089046A CN 110462560 A CN110462560 A CN 110462560A
Authority
CN
China
Prior art keywords
resin layer
film
transfer printing
type photosensitive
printing type
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201780089046.7A
Other languages
Chinese (zh)
Other versions
CN110462560B (en
Inventor
南征志
向郁夫
吉田英树
渡边治
渡部和仁
渡边匠
鲇濑友洋
海老原雅彦
奥田唯史
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Resonac Corp
Original Assignee
Hitachi Chemical Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=63674599&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=CN110462560(A) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Hitachi Chemical Co Ltd filed Critical Hitachi Chemical Co Ltd
Publication of CN110462560A publication Critical patent/CN110462560A/en
Application granted granted Critical
Publication of CN110462560B publication Critical patent/CN110462560B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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

Landscapes

  • Engineering & Computer Science (AREA)
  • General Engineering & Computer Science (AREA)
  • Theoretical Computer Science (AREA)
  • Human Computer Interaction (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Materials For Photolithography (AREA)
  • Laminated Bodies (AREA)

Abstract

The present invention relates to transfer printing type photosensitive film, the forming method for solidifying film figure, cured film and touch panels; the first resin layer that the transfer printing type photosensitive film has support membrane and is set on the support membrane, the first resin layer include photopolymerizable compound and acylphosphine oxide system Photoepolymerizationinitiater initiater with tricyclodecane skeleton or tricyclo decene skeleton.

Description

Transfer printing type photosensitive film, the forming method for solidifying film figure, cured film and touch panel
Technical field
The present invention relates to transfer printing type photosensitive film, the forming method for solidifying film figure, cured film and touch panels.
Background technique
The small electricals such as the large scale electronic equipments such as PC and TV, auto navigation, mobile phone, smart phone, electronic dictionary Sub- equipment, OA (Office Automation, office automation), FA (Factory Automation, factory automation) equipment Deng display equipment etc. in use liquid crystal display element and touch panel (touch sensor).
The various modes of touch panel have been practical, in recent years, the benefit of the touch panel of projection type electrostatic capacitance method With promoting.In general, in the touch panel of projection type electrostatic capacitance method, in order to show the two dimension being made of X-axis and Y-axis Coordinate, multiple X electrodes and the multiple Y electrodes orthogonal with the X electrode form 2 layers of structure.As the material of these electrodes, ITO (Indium-Tin-Oxide, tin indium oxide) is mainstream.
However, since the frame region of touch panel is can not to detect the region of touch location, so the constriction rim area The area in domain is the important element for improving value of the product.In general, in frame region, in order to transmit touch location Detection signal and the metal line for being formed with copper etc..In touch panel, with the corrosion compositions such as moisture when finger tip contacts or salinity Inside is invaded from sensitive zones sometimes.It, may above-mentioned metal line if corrosion composition invades the inside of touch panel Corrode, the resistance between electrode and driving circuit increases or broken string.
The corrosion of metal line in order to prevent, proposes following methods: setting contains and has on touch panel substrate The photosensitive polymer combination layer of two (methyl) acrylate compounds of bicyclopentyl structure or dicyclopentenyl based structures, passes through After the irradiation of active ray solidifies the prescribed portion of the photosensitive polymer combination layer, the part other than prescribed portion is removed, Form the cured film of some or all of photosensitive polymer combination of covering substrate (referring to following patent documents 1).Pass through This method can form the cured film with sufficient low-moisture permeability on touch panel substrate.
On the other hand, in the touch panel of projection type electrostatic capacitance method, be formed with the part of transparent electrode pattern with Color difference becomes larger due to the difference of optical reflective characteristics for the part of not formed transparent electrode pattern, and there are transparent electrode figures when modularization Case mirrors the problem of so-called " the visible phenomenon of shadow " on picture.In addition, between substrate and transparent electrode or being used for module The protection glass used when change the visibility Nian Jie with transparent electrode pattern improves film (OCA:Optical Clear Adhesive, Optical transparent adhesive) and transparent electrode pattern between there is also intensities of reflected light to increase, makes the decrease in transmission of picture The problem of.
In this regard, a kind of transparent conductive resin substrate is for example disclosed in following patent documents 2, by substrate and thoroughly Refractive index matching layers (optical adjustment layer) (hereinafter referred to as " IM layers ") are set between prescribed electrode pattern and are formed with transparent electricity to reduce The color difference of the part of pole figure case and the part that transparent electrode pattern is not formed prevents the transmissivity of shadow visible phenomenon and picture It reduces.
In addition, as transparent electrode pattern is prevented, by the method depending on recognizing, disclosing makes to adjust for example in following patent documents 3 First curability transparent resin layer of the whole low-refraction for specific ranges of indices of refraction and the second curability of high refractive index are saturating Bright resin layer adjacently existing transfer film.
Existing technical literature
Patent document
Patent document 1: Japanese Unexamined Patent Publication 2015-121929 bulletin
Patent document 2: Japanese Unexamined Patent Publication 8-240800 bulletin
Patent document 3: No. 2014/084112 pamphlet of International Publication No.
Summary of the invention
Problems to be solved by the invention
Transfer of the present inventors to the photosensitive polymer combination containing two (methyl) acrylate compounds has been used Type photosensitive film is studied, and two (methyl) acrylate compounds have bicyclopentyl structure (hereinafter referred to as tricyclic Decane skeleton) or dicyclopentenyl based structures (hereinafter referred to as tricyclo decene skeleton).Also, in research by the transfer printing type photosensitive film It is found in the low-moisture permeability for solidifying film figure of formation and the raising of adaptation, cured film is formd on transparent electrode pattern When, even if being provided with transparent electrode pattern on IM layers, can also see more significantly sometimes electrode pattern (occur pattern can See).
The research of the main reason for the present inventors are visible to pattern further progress, as a result, it has been found that, it is being set to ITO electricity The surface of cured film in pole figure case produces recess (also referred to as difference of height), can be by depending on recognizing, i.e., " pattern is visible ".
It can inhibit difference of height on electrode pattern and be formed well to have the purpose of the present invention is to provide one kind The transfer printing type photosensitive film for solidifying film figure of sufficient low-moisture permeability and the cured film figure for using the transfer printing type photosensitive film The forming method and touch panel of case.
Means for solving the problems
In order to solve the above problems, the main reason for the present inventors generate difference of height is studied, and as a result confirms, When forming cured film in ITO electrode and on IM layers with the same terms, the reactivity of the photo-sensitive resin on IM layer is set It is smaller than in ITO electrode, it is based on the situation, the main reason for being recessed supposition is generated and is: 1) is unreacted in exposure process The low position of the reactivity of photopolymerizable compound from photo-sensitive resin is shifted to high position, and 2) after to exposure, development The annealing operation that is heated of photo-sensitive resin in, unreacted photopolymerizable compound volatilization and high in reactivity It is poor to occur to be heat-shrinked between position and low position.Also, the present inventors from the viewpoint of inhibit the phenomenon that it is above-mentioned 1) and 2), Using the difference of height evaluation test of the exposure process and annealing operation with the difference provided with light exposure to photo-sensitive resin Composition is studied, as a result, it has been found that, made by combining specific photopolymerizable compound with specific Photoepolymerizationinitiater initiater With it is poor being able to suppress reactivity, and difference of height can be reduced, so as to complete the present invention.It should be noted that only with for Reduction unreacted photopolymerizable compound and when the method for the amount that increases Photoepolymerizationinitiater initiater, it is residual to generate development sometimes Slag, it is difficult to form solidification film figure well.
The present invention provides a kind of transfer printing type photosensitive film, the first resin for having support membrane and being set on the support membrane Layer, the first resin layer include photopolymerizable compound and acylphosphine oxide with tricyclodecane skeleton or tricyclo decene skeleton It is Photoepolymerizationinitiater initiater.
Transfer printing type photosensitive film according to the present invention, by being able to suppress on transparent electrode pattern with above-mentioned composition Difference of height and the film figure of formation solidification well.Solidify film figure and can be used as the rust-preventing film of electrode pattern and functions.
Wherein, as said effect is obtained the reasons why, consider due to using acylphosphine oxide system Photoepolymerizationinitiater initiater, Even the big photopolymerizable compound of molecular weight can also obtain sufficient polymerization reaction rate, thus, it is possible to inhibit it is above-mentioned 1) and 2) the phenomenon that.
When improving the use level with the photopolymerizable compound of tricyclodecane skeleton or tricyclo decene skeleton, for solid The low moisture-inhibiting and adaptation raising for changing film figure are effective, but the solidification film figure being set on transparent electrode pattern generates Difference of height have bigger tendency.According to the present invention, by that will have the photopolymerization of tricyclodecane skeleton or tricyclo decene skeleton Property compound is combined with acylphosphine oxide system Photoepolymerizationinitiater initiater, is able to suppress difference of height, and be capable of forming with high level Low-moisture permeability and high adhesion solidification film figure.
Above-mentioned acylphosphine oxide system Photoepolymerizationinitiater initiater also may include 2,4,6- trimethylbenzoy-dipheny-oxygen Change phosphine.In this case, it is capable of forming that low-moisture permeability, tone (especially yellow is turned down, close to neutral tone) is excellent consolidates Change film figure.
Above-mentioned first resin layer can further include oxime ester system Photoepolymerizationinitiater initiater.By the way that acylphosphine oxide system light is gathered Conjunction initiator is used in combination with oxime ester system Photoepolymerizationinitiater initiater, can further decrease the moisture permeability for being formed by and solidifying film figure.
The transfer printing type photosensitive film of aforementioned present invention, which can be further equipped with to be arranged on the first resin layer, contains metal Second resin layer of oxide particle.
By above-mentioned transfer printing type photosensitive film, can be formed well on electrode pattern can inhibit difference of height Inhibit the solidification film figure of the visible phenomenon of shadow simultaneously.
The present invention also provides a kind of the 1st forming methods for solidifying film figure, have: in the substrate with electrode pattern On, by the first resin layer of transfer printing type photosensitive film of the invention with the side for being provided with electrode pattern of substrate and the first resin The process that the closely sealed mode of layer is laminated, and after being exposed to the prescribed portion of the first resin layer on substrate, remove institute The part other than prescribed portion is stated, the process for forming some or all of solidification film figure of covering electrode pattern.
The present invention also provides a kind of the 2nd forming methods for solidifying film figure, have: in the substrate with electrode pattern On, by the second resin layer of the transfer printing type photosensitive film of the aforementioned present invention with the second resin layer and the first resin layer with substrate The side for being provided with electrode pattern and the process that is laminated of the closely sealed mode of the second resin layer, and to the second tree on substrate After the prescribed portion of rouge layer and the first resin layer is exposed, the part other than prescribed portion is removed, forms covering electrode pattern Some or all of solidification film figure process.
By the 1st and the 2nd forming method for solidifying film figure of aforementioned present invention, height can be inhibited on electrode pattern Solidification film figure is formed while poor well.In addition, the 2nd forming method for solidifying film figure through the invention, cured film Pattern can have the function of refractive index adjustment.
It is by the first tree in the transfer printing type photosensitive film by aforementioned present invention the present invention also provides a kind of cured film Rouge layer is solidified to form.
It is the transfer printing type sense by that will have the aforementioned present invention of the second resin layer the present invention also provides a kind of cured film The first resin layer in photosensitiveness film individually solidifies or is solidified to form both the first resin layer and the second resin layer.
The present invention also provides a kind of touch panel, has the first tree in the transfer printing type photosensitive film by aforementioned present invention The solidfied material of rouge layer or the second resin layer in the transfer printing type photosensitive film of the aforementioned present invention with the second resin layer are consolidated The solidification film figure that the solidfied material of compound and the first resin layer is constituted.
Invention effect
By the invention it is possible to which cured film figure can be formed well while inhibiting difference of height on electrode pattern by providing The transfer printing type photosensitive film of case and the forming method and touch panel for solidifying film figure for using the transfer printing type photosensitive film.
Detailed description of the invention
Fig. 1 is the constructed profile for indicating the transfer printing type photosensitive film of an embodiment of the invention.
Fig. 2 is the transfer printing type for indicating to have using an embodiment of the invention on the substrate with transparent electrode pattern The constructed profile for the laminated body for solidifying film figure that photosensitive film is formed.
Fig. 3 is the diagrammatic top view for indicating the touch panel of an embodiment of the invention.
Fig. 4 is the constructed profile for illustrating difference of height evaluation method of the invention.
Specific embodiment
Hereinafter, according to circumstances mode for carrying out the present invention is described in detail referring to attached drawing.But the present invention is simultaneously It is not limited to the following embodiments and the accompanying drawings.It should be noted that " (methyl) acrylic acid " refers to acrylic acid or methyl in this specification Acrylic acid, " (methyl) acrylate " refer to acrylate or corresponding methacrylate." A or B " may include A and Any of B also may include both sides.
In addition, in the present specification, " layer " this term with top view when being observed, in addition to being formed in entire surface Other than the structure of shape, also comprising the structure for the shape being formed in a part.In addition, in the present specification, " process " this Term refers not only to independent process, and in the case where can not clearly distinguish with other processes, as long as realizing the process Desired effect, then be also contained in this term.In addition, the numberical range for using "~" to indicate is indicated with the front and back institute of "~" The numerical value of record is respectively as minimum value and maximum value and the range that is included.
In addition, in this specification, about the content of each ingredient in composition, exist in the composition it is a variety of belong to it is each at In the case where the substance divided, unless otherwise specified, then refer to the total amount of many kinds of substance present in composition.In addition, Exemplary materials unless otherwise specified, may be used singly or in combination of two or more.
In addition, in the numberical range periodically recorded in the present specification, the upper limit value of the numberical range in a certain stage Or lower limit value also could alternatively be the upper limit or lower limit of the numberical range in other stages.In addition, recording in the present specification Numberical range in, the upper limit or lower limit of the numberical range also could alternatively be value shown in embodiment.
<transfer printing type photosensitive film>
The first resin layer that the transfer printing type photosensitive film of present embodiment has support membrane and is set on the support membrane.This The transfer printing type photosensitive film of embodiment is also possible to be further equipped with the metal oxidation containing being arranged on photo-sensitive resin The transfer printing type photosensitive film of second resin layer of object particle.These transfer printing type photosensitive films, which can also have, to be arranged in photonasty tree Protective film on rouge layer or on the second resin layer.
Fig. 1 is the constructed profile for indicating the transfer printing type photosensitive film of an embodiment of the invention.Shown in FIG. 1 turn Print type photosensitive film 1 has support membrane 10, is arranged on support membrane 10 the first resin layer 20 is arranged on the first resin layer 20 The second resin layer 30 and the protective film 40 that is arranged on the second resin layer 30.
By using above-mentioned transfer printing type photosensitive film, such as satisfaction protection can be formed positioned at touch panel by pattern together The function of transparent electrode and not visibleization of transparent electrode pattern of the metal line or touch panel of frame improve touch picture The cured film of both functions of the visibility in face.
(support membrane)
As support membrane 10, polymer film can be used.As the material of polymer film, such as poly- terephthaldehyde can be enumerated Sour glycol ester, polycarbonate, polyethylene, polypropylene, polyether sulfone, cyclic olefin polymer etc..
From the viewpoint of ensuring spreadability and resolution ratio when irradiating active ray across support membrane 10 inhibited to reduce, branch The thickness for supportting film 10 is preferably 5~100 μm, more preferably 10~70 μm, further preferably 15~40 μm, particularly preferably 15 ~35 μm.
(the first resin layer)
First resin layer 20 is preferably by containing binder polymer (hereinafter also referred to (A) ingredient), photopolymerizable compound The photosensitive polymer combination of (hereinafter also referred to (B) ingredient) and Photoepolymerizationinitiater initiater (hereinafter also referred to (C) ingredient) is formed.
<binder polymer>
It is from the viewpoint of being able to carry out patterning by alkali development, it is preferable to use poly- with carboxyl as (A) ingredient Close object.
(A) ingredient preferably comprises the copolymerization of the structural unit from (methyl) acrylic acid and (methyl) alkyl acrylate Object.Above-mentioned copolymer can also contain in Component units can be total with above-mentioned (methyl) acrylic acid, (methyl) alkyl acrylate Poly- other monomers.As other monomers, (methyl) glycidyl acrylate, (methyl) acrylic acid benzyl can be specifically enumerated Ester, styrene, (methyl) cyclohexyl acrylate etc..
As above-mentioned (methyl) alkyl acrylate, can enumerate (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) butyl acrylate, (methyl) acrylic acid-2-ethyl caproite, (methyl) hydroxy-ethyl acrylate etc..
Wherein, go out from the viewpoint of alkali-developable (especially to the developability of inorganic base aqueous solution), patterning property, the transparency Hair preferably has from selected from by (methyl) acrylic acid, (methyl) glycidyl acrylate, (methyl) benzyl acrylate, benzene Ethylene, (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) butyl acrylate, (methyl) acrylic acid 2- ethyl hexyl Ester, (methyl) cyclohexyl acrylate, (methyl) acrylic acid dicyclopentenyl ester, (methyl) acrylic acid dicyclopentenyl oxygroup ester, (first Base) dicyclopentanyl acrylate, (methyl) acrylic acid bicyclopentyl oxygroup ester, (methyl) phenoxyethyl acrylate, (methyl) third Olefin(e) acid isobornyl thiocyanoacetate, N-cyclohexylmaleimide, (methyl) Hydroxyethyl Acrylate and (methyl) hydroxy butyl acrylate composition At least one of the group structural unit of compound binder polymer, more preferably have from selected from by (methyl) propylene Acid, (methyl) glycidyl acrylate, (methyl) benzyl acrylate, styrene, (methyl) methyl acrylate, (methyl) propylene In the group that acetoacetic ester, (methyl) butyl acrylate, (methyl) 2-EHA and (methyl) cyclohexyl acrylate form At least one compound structural unit binder polymer, particularly preferably have from be selected from (methyl) acrylic acid, (first Base) alkyl acrylate, (methyl) glycidyl acrylate and (methyl) cyclohexyl acrylate structural unit adhesive Polymer.In addition, binder polymer can also be by making isocyanate ethyl (methyl) acrylate or (methyl) propylene Acid glycidyl ester with include at least (methyl) Hydroxyethyl Acrylate or (methyl) hydroxy butyl acrylate as above structure (methyl) Hydroxyethyl Acrylate or (methyl) hydroxy butyl acrylate of the copolymer of unit carry out obtained from addition reaction.
In the present embodiment, it from the viewpoint of the moisture permeability for reducing cured film, can be used containing having in side chain The group of branched structure and/or alicyclic structure has ethylenic bond insatiable hunger in group of the side chain with acidic-group and in side chain With the binder polymer of the group of group.Have the group of branched structure and/or alicyclic structure can be by containing in side chain It is imported in the monomer of group of the side chain with branched structure or the monomer containing the group in side chain with alicyclic structure.In Group of the side chain with acidic-group can be imported by the monomer containing the group in side chain with acidic-group.
As the concrete example of the monomer containing the group in side chain with branched structure, such as (methyl) acrylic acid can be enumerated Isopropyl ester, (methyl) isobutyl acrylate, (methyl) sec-butyl acrylate, (methyl) tert-butyl acrylate, (methyl) acrylic acid Isopentyl ester, (methyl) t-amyl, (methyl) acrylic acid sec- isopentyl ester, (methyl) acrylic acid 2- monooctyl ester, (methyl) propylene Sour 3- monooctyl ester, the tertiary monooctyl ester of (methyl) acrylic acid etc..Wherein, preferably (methyl) isopropyl acrylate, (methyl) isobutyl acrylate, Tert-butyl Methacrylate, further preferred isopropyl methacrylate, Tert-butyl Methacrylate.
As the concrete example of the monomer containing the group in side chain with alicyclic structure, such as can enumerate with carbon atom number For (methyl) acrylate of 5~20 alicyclic type hydrocarbons.As a more specific example, such as (methyl) acrylic acid can be enumerated (bicyclic [2.2.1] heptyl -2) ester, (methyl) acrylic acid) -1- Buddha's warrior attendant alkyl ester, (methyl) acrylic acid -2- Buddha's warrior attendant alkyl ester, (methyl) Acrylic acid-3- methyl-1-Buddha's warrior attendant alkyl ester, (methyl) acrylic acid-3,5- dimethyl-1- Buddha's warrior attendant alkyl ester, (methyl) acrylic acid-3- second The rigid alkyl ester of fund, (methyl) acrylic acid -3- methyl -5- ethyl -1- Buddha's warrior attendant alkyl ester, (methyl) acrylic acid -3,5,8- triethyl group -1- Buddha's warrior attendant alkyl ester, (methyl) acrylic acid -3,5- dimethyl -8- ethyl -1- Buddha's warrior attendant alkyl ester, (methyl) acrylic acid 2- methyl -2- Buddha's warrior attendant Alkyl ester, (methyl) acrylic acid 2- ethyl -2- Buddha's warrior attendant alkyl ester, (methyl) acrylic acid 3- hydroxyl -1- Buddha's warrior attendant alkyl ester, (methyl) acrylic acid Octahydro -4,7- methanoindene -5- base ester, (methyl) acrylic acid octahydro -4,7- methanoindene -1- base methyl esters, (methyl) acrylic acid -1- are thin Lotus ester, (methyl) dicyclopentanyl acrylate, (methyl) acrylic acid -3- hydroxyl -2,6,6- trimethyl-bicyclo [3.1.1] heptyl ester, (methyl) acrylic acid -3,7,7- trimethyl -4- hydroxyl-bicyclic [4.1.0] heptyl ester, (methyl) acrylic acid) (drop) norbornene ester, (first Base) isobornyl acrylate, (methyl) acrylic acid turnip ester, (methyl) acrylic acid -2,2,5- trimethylcyclohexyl, (methyl) propylene Sour cyclohexyl etc..In these (methyl) acrylate, preferably (methyl) cyclohexyl acrylate, (methyl) acrylic acid (drop) borneol Ester, (methyl) isobornyl acrylate, (methyl) acrylic acid -1- Buddha's warrior attendant alkyl ester, (methyl) acrylic acid -2- Buddha's warrior attendant alkyl ester, (first Base) acrylic acid turnip ester, (methyl) acrylic acid 1- menthyl ester, (methyl) dicyclopentanyl acrylate, particularly preferred (methyl) acrylic acid Cyclohexyl, (methyl) acrylic acid (drop) norbornene ester, (methyl) isobornyl acrylate, (methyl) acrylic acid -2- Buddha's warrior attendant alkyl ester.
The group that there is branched structure and/or alicyclic structure in side chain by containing (A) ingredient, available and substrate Good adaptation, particularly good adaptation with the substrate with refractive index matching layers.In addition, by having in side Chain has the group of alicyclic structure, can reduce the moisture permeability of cured film.
It, can be appropriate from well known monomer as the concrete example of the monomer containing the group in side chain with acidic-group Selection, for example, can enumerate (methyl) acrylic acid, vinyl benzoate, maleic acid, maleic acid mono alkyl ester, fumaric acid, itaconic acid, The addition of crotonic acid, cinnamic acid, sorbic acid, alpha-cyano cinnamic acid, acrylic acid dimer, the monomer with hydroxyl and cyclic acid anhydride Reactant, ω-carboxyl-polycaprolactone list (methyl) acrylate etc..The monomer suitably manufactured can be used in they, can also make Use commercially available product.
The group for having acidic-group in side chain by containing (A) ingredient, can be patterned by alkali development.
As the group in side chain with ethylenically unsaturated groups, it is not particularly limited, as ethylenic bond unsaturated group Group, preferably (methyl) acryloyl group.As long as in addition, connection ester group, amide groups, the amino of ethylenically unsaturated groups and monomer The linking group of the divalents such as formoxyl, is just not particularly limited.Side chain import ethylenically unsaturated groups method can be from public affairs It is suitably selected in the method known, such as (methyl) propylene that the addition on the group with acidic-group has epoxy group can be enumerated The method of acid esters, addition has the method for (methyl) acrylate of isocyanate group, has on the group with hydroxyl Addition has the method etc. of (methyl) acrylate of hydroxyl on the group of isocyanate group.Wherein, with acidic-group There is the method for (methyl) acrylate of epoxy group to be easiest to manufacture for addition on repetitive unit, excellent from the angle of low cost Choosing.
The group for having ethylenically unsaturated groups in side chain by containing (A) ingredient, can obtain good with substrate Good adaptation, particularly the good adaptation with the substrate with refractive index matching layers.In addition, can reduce cured film Moisture permeability.
It is counted on the basis of the monomer total amount of composition (A) ingredient, is formed in side chain with branched structure and/or alicyclic structure The ratio of the monomer of group is preferably 10~70 moles of %, more preferably 15~65 moles of %, and further preferably 20~60 rub You are %.In addition, counting on the basis of the monomer total amount of composition (A) ingredient, it is formed in the monomer of group of the side chain with acidic-group Ratio be preferably 5~70 moles of %, more preferably 10~60 moles of %, further preferably 20~50 moles of %.In addition, with It is counted on the basis of the monomer total amount of composition (A) ingredient, is formed in the ratio of the monomer of group of the side chain with ethylenically unsaturated groups Example is preferably 5~70 moles of %, more preferably 10~60 moles of %, further preferably 20~50 moles of %.On meeting The ratio of monomer is stated, plyability, the Ji Yuke for improving the patterning and substrate that carry out by alkali development well can be balanced The good adaptation of substrate with refractive index matching layers.
From the viewpoint of resolution ratio, the weight average molecular weight of (A) ingredient is preferably 10000~200000, more preferably 15000~150000, further preferably 30000~150000, particularly preferably 30000~100000, highly preferred is 40000 ~100000.Wherein, weight average molecular weight can be surveyed by the gel permeation chromatography recorded in the embodiment of this specification It is fixed.
From the viewpoint of being readily formed the cured film with desired shape (solidification film figure) by alkali development, (A) acid value of ingredient is preferably 75mgKOH/g or more.In addition, from the control easiness and solidification of seeking to take into account cured film shape From the perspective of the rust-preventing characteristic of film, the acid value of (A) ingredient is preferably 75~200mgKOH/g, more preferably 75~150mgKOH/ G, further preferably 75~120mgKOH/g.Wherein, acid value can by the method recorded in the embodiment of this specification into Row measurement.
Wherein, the first resin layer 20 can also be further containing other viscous in addition to above-mentioned (A) binder polymer Binder polymer.
<photopolymerizable compound>
As (B) ingredient, the compound with tricyclodecane skeleton or tricyclo decene skeleton can be enumerated.From inhibition hardware cloth From the perspective of the corrosion of line and transparent electrode pattern, as the compound with tricyclodecane skeleton or tricyclo decene skeleton, Preferably comprise two (methyl) acrylate compounds shown in the following general formula (B-1).
[chemical formula number 1]
[in general formula (B-1), R1And R2Each independently represent hydrogen atom or methyl, X indicate to have tricyclodecane skeleton or The divalent group of tricyclo decene skeleton, R3And R4The alkylidene that carbon atom number is 1~4 is each independently represented, n and m are respectively independent Ground indicates that 0~2 integer, p and q each independently represent 0 or more integer, be chosen such that p+q=0~10 to p and q.]
In above-mentioned general formula (B-1), R3And R4Preferably ethylidene or propylidene, more preferably ethylidene.In addition, propylidene It is also possible to any one of n- isopropylidene and isopropylidene.
According to above-mentioned general formula (B-1) compound represented, by with tricyclodecane skeleton contained by X or tricyclo decene bone The divalent group of frame has bulky structure, can be realized the low-moisture permeability of cured film, improves metal line and transparent electrode Corrosion-inhibiting.Here, " tricyclodecane skeleton " and " tricyclo decene skeleton " in this specification refers respectively to structure below (bonding position is arbitrary position respectively).
[chemical formula number 2]
As the compound with tricyclodecane skeleton or tricyclo decene skeleton, from the obtained low moisture-inhibiting for solidifying film figure Property from the perspective of, preferably Tricyclodecane Dimethanol two (methyl) acrylate etc. have tricyclodecane skeleton compound.It Can be obtained with DCP and A-DCP (being the village Xin Zhong chemical industry Co. Ltd. system).
From the viewpoint of reducing moisture permeability and difference of height, there is tricyclodecane skeleton or tricyclo decene in (B) ingredient The ratio of the compound of skeleton is preferably 100 mass parts of total amount of photopolymerizable compound contained in photosensitive polymer combination In 50 mass parts more than, more than more preferably 70 mass parts, more than further preferably 80 mass parts.
As (B) ingredient, that is, photopolymerizable compound, it can be used and there is tricyclodecane skeleton or tricyclo decene skeleton Compound is different, photopolymerizable compounds with ethylenically unsaturated groups.As with ethylenically unsaturated groups Photopolymerizable compound, such as can enumerate in the molecule with a polymerizable ethylenically unsaturated groups simple function second There are two two functional vinyl monomers of polymerizable ethylenically unsaturated groups or intramoleculars for alkenyl monomer, in the molecule tool Polyfunctional vinyl monomer at least three polymerizable ethylenically unsaturated groups.
About the content of (A) ingredient and (B) ingredient, relative to 100 mass parts of total amount of (A) ingredient and (B) ingredient, (A) Ingredient is preferably 35~85 mass parts, more preferably 40~80 mass parts, further preferably 50~70 mass parts, particularly preferably For 55~65 mass parts.
From the viewpoint of improving the low moisture-inhibiting for solidifying film figure and adaptation, relative to (A) ingredient and (B) ingredient 100 mass parts of total amount, the compound with tricyclodecane skeleton or tricyclo decene skeleton is preferably 5 mass parts or more, more preferably More than 10 mass parts, more than further preferably 20 mass parts, more than particularly preferably 25 mass parts.In present embodiment In, it is poly- as light by being combined in the compound with tricyclodecane skeleton or tricyclo decene skeleton cooperated using aforementioned proportion The aftermentioned acylphosphine oxide system Photoepolymerizationinitiater initiater for closing initiator is capable of forming and inhibits difference of height and have the low of high level The solidification film figure of penetrability and high adhesion.
<Photoepolymerizationinitiater initiater>
As (C) ingredient, acylphosphine oxide system Photoepolymerizationinitiater initiater is used.(C) ingredient also can be used together except acyl group aoxidizes Known Photoepolymerizationinitiater initiater other than phosphine system Photoepolymerizationinitiater initiater.
As acylphosphine oxide system Photoepolymerizationinitiater initiater, 2 can be enumerated, 4,6- trimethylbenzoy-diphenies-oxidation Phosphine, bis- (2,4,6- trimethylbenzoyl)-phenyl phosphine oxides, 2,4,6- trimethylbenzoyl-phosphinate.Acyl group oxidation Phosphine system Photoepolymerizationinitiater initiater can be with IRGACURE TPO, 819 IRGACURE, IRGACURE TPO-L (above by BASF plants of formulas Commercial firm's system, ProductName) it obtains.By using acylphosphine oxide system Photoepolymerizationinitiater initiater, can be obtained in photo-sensitive resin Sufficient polymerization reaction rate, it is visible to be able to suppress pattern.
As the Photoepolymerizationinitiater initiater in addition to acylphosphine oxide system Photoepolymerizationinitiater initiater, the photopolymerization of oxime ester system can be enumerated and drawn Send out agent.By the way that acylphosphine oxide system Photoepolymerizationinitiater initiater to be used in combination with oxime ester system Photoepolymerizationinitiater initiater, institute can be further decreased The moisture permeability for solidifying film figure of formation.
Oxime ester system Photoepolymerizationinitiater initiater is preferably the following general formula (1) compound represented, chemical combination shown in the following general formula (2) Object or the following general formula (3) compound represented.
[chemical formula number 3]
In formula (1), R11And R12Each independently representing alkyl, carbon atom number that carbon atom number is 1~12 is 4~10 Naphthenic base that alkyl that naphthenic base, phenyl or tolyl, preferably carbon atom number are 1~8, carbon atom number are 4~6, phenyl or Naphthenic base, phenyl or the tolyl that alkyl that tolyl, more preferably carbon atom number are 1~4, carbon atom number are 4~6, into one Step is preferably methyl, cyclopenta, phenyl or tolyl.R13Expression-H ,-OH ,-COOH ,-O (CH2)OH、-O(CH2)2OH、-COO (CH2) OH or-COO (CH2)2OH, preferably-H ,-O (CH2)OH、-O(CH2)2OH、-COO(CH2) OH or-COO (CH2)2OH, more Preferably-H ,-O (CH2)2OH or-COO (CH2)2OH。
[chemical formula number 4]
In formula (2), 2 R14Each independently represent the alkyl that carbon atom number is 1~6, preferably propyl.R15Indicate NO2 Or ArCO (wherein, Ar indicates aryl), as Ar, preferably tolyl.R16And R17Each independently represent carbon atom number be 1~ 12 alkyl, phenyl or tolyl, preferably methyl, phenyl or tolyl.
[chemical formula number 5]
In formula (3), R18Indicate that carbon atom number is 1~6 alkyl, preferably ethyl.R19For the organic group with acetal bonds Group, preferably with R possessed by aftermentioned formula (3-1) compound represented19Corresponding substituent group.R20And R21Each independently Indicate that carbon atom number is 1~12 alkyl, phenyl or tolyl, preferably methyl, phenyl or tolyl, more preferably methyl. R22Indicate hydrogen atom or alkyl.
Above-mentioned general formula (1) compound represented can be obtained with IRGACURE OXE 01 (BASF Co. Ltd. system, ProductName) .
Above-mentioned general formula (2) compound represented can be obtained with DFI-091 (DAITO CHEMIX Co. Ltd. system, ProductName) .
Above-mentioned general formula (3) compound represented can (Asahi Denka Co., Ltd.'s system produces with Adeka Optomer N-1919 The name of an article) it obtains.
From photo sensitivity and the angle of excellent in resolution, relative to 100 mass parts of total amount of (A) ingredient and (B) ingredient, (C) content of ingredient is preferably 0.1~10 mass parts, more preferably 1~5 mass parts, further preferably 1~3 mass parts, special It You Xuanwei not 1~2 mass parts.
From the viewpoint of exposing sensitivity, the ratio of the acylphosphine oxide system Photoepolymerizationinitiater initiater in (C) ingredient is preferably It is more than 1 mass parts in 100 mass parts of total amount of Photoepolymerizationinitiater initiater contained in photosensitive polymer combination, more preferably 3 More than mass parts, more than further preferably 5 mass parts.
In addition, in the case where acylphosphine oxide system Photoepolymerizationinitiater initiater and oxime ester compound to be used in combination, visible from pattern, From the perspective of reliability, tone, curability, the mass ratio of acylphosphine oxide system Photoepolymerizationinitiater initiater and oxime ester compound is preferred For 8:1~0.5:1, more preferably 4:1~2:1.
From the viewpoint of the rust-preventing characteristic for further increasing cured film, the photosensitive polymer combination of present embodiment is preferred Also containing selected from by the triazole compounds with sulfydryl, the tetrazole compound with sulfydryl, the thiadiazole compound with sulfydryl, At least one of the group that triazole compounds with amino and the tetrazole compound with amino are constituted compound is (following to be also referred to as For (D) ingredient).As the triazole compounds with sulfydryl, for example, can enumerate 3- sulfydryl-triazole (Wako Pure Chemicals Co., Ltd. system, ProductName: 3MT).In addition, as the thiadiazole compound with sulfydryl, such as 2- amino -5- sulfydryl -1,3,4- thiophene can be enumerated Diazole (Wako Pure Chemicals Co., Ltd. system, ProductName: ATT).
As the above-mentioned triazole compounds with amino, such as benzotriazole, 1H- benzotriazole -1- acetonitrile, benzene can be enumerated And the substitutions such as triazole -5- carboxylic acid, 1H- benzotriazole -1- methanol, carboxyl benzotriazole have the compound of amino, in 3- sulfydryl three Replacing on the triazole compounds containing sulfydryl such as azoles, 5- mercapto-triazole has compound of amino etc..
As the above-mentioned tetrazole compound with amino, such as 5- amino -1H-TETRAZOLE, 1- methyl -5- amino-can be enumerated Tetrazolium, 1- methyl -5- sulfydryl -1H-TETRAZOLE, 1- carboxymethyl -5- Amino-tetrazol etc..These tetrazole compounds can also be its water Soluble.As concrete example, alkali metal salts such as sodium, potassium, the lithium of 1- methyl -5- Amino-tetrazol etc. can be enumerated.
When photosensitive polymer combination contains (D) ingredient, total amount 100 matter of the content relative to (A) ingredient and (B) ingredient Amount part, preferably 0.05~5.0 mass parts, more preferably 0.1~2.0 mass parts, further preferably 0.2~1.0 mass parts, Particularly preferably 0.3~0.8 mass parts.
It, can be with as other additives in the photosensitive polymer combination of the first resin layer for forming present embodiment Tool as desired relative to 100 mass parts of total amount of (A) ingredient and (B) ingredient, respectively containing 0.01~20 mass parts or so There are adaptations imparting agent, antirust agent, levelling agent, plasticizer, the fillings such as phosphate, the silane coupling agent of ethylenically unsaturated groups Agent, defoaming agent, fire retardant, stabilizer, antioxidant, fragrance, thermal cross-linking agent, polymerization inhibitor etc..They can be used alone or group It closes and uses two or more.
The thickness of first resin layer can be 1~15 μm, preferably 2~10 μm, more preferably 3~8 μm, further preferably It is 4~6 μm, particularly preferably 5~6 μm.By making, the defect with a thickness of 1~15 μm, when being capable of forming coating is few, the transparency is excellent Different film.In addition, the thickness (thickness for solidifying film figure) of the first resin layer after solidifying is it is also preferred that within the above range.
(the second resin layer)
Second resin layer 30 is the layer containing metal oxide particle.Second resin layer 30 is by containing metal oxide grain Son can have the relatively high refractive index compared with the first resin layer 20.Refractive index of second resin layer 30 at 633nm is preferred In the range of 1.40~1.90, more preferably 1.50~1.90, further preferably 1.53~1.85, particularly preferably 1.55 ~1.75.In addition, the second resin layer after solidification is at 633nm in the case where the second resin layer contains curability composition Refractive index is it is also preferred that within the above range.
If refractive index of second resin layer 30 at 633nm is within the above range, exist film figure setting will be solidified In the case where on the transparent electrode patterns such as ITO, it can reach and solidify the various parts used on film figure (such as when modularization What is used will protect the glass OCA Nian Jie with transparent electrode pattern) refractive index median, can reduce and be formed with ITO etc. The part of transparent electrode pattern and the part for the transparent electrode pattern for ITO being not formed etc. between because of caused by optical reflection Color difference can prevent the visible phenomenon of shadow.In addition, can reduce the intensity of reflected light of picture entirety, it is able to suppress on picture Decrease in transmission.
The refractive index of the transparent electrodes such as ITO is preferably 1.80~2.10, and more preferably 1.85~2.05, further preferably 1.90~2.00.In addition, the refractive index of the components such as OCA is preferably 1.45~1.55, and more preferably 1.47~1.53, it is further excellent It is selected as 1.48~1.51.
Minimum light transmittance of second resin layer 30 in the wavelength region of 450~650nm is preferably 80% or more, more preferably It is 85% or more, further preferably 90% or more.In addition, in the case where the second resin layer contains curability composition, solidification Minimum light transmittance of the second resin layer afterwards in the wavelength region of 450~650nm is it is also preferred that within the above range.
Second resin layer 30 can be containing above-mentioned (A) ingredient, (B) ingredient and (C) ingredient, as needed, can also be into One step contains above-mentioned (D) ingredient.Second resin layer 30 must not necessarily contain the photo-polymerization compositions such as (B) ingredient, (C) ingredient, The photo-polymerization composition from the resin layer transfer abutted by layer formation be can use to make the second resin layer photocuring.
Second resin layer 30 contains metal oxide particle (hereinafter also referred to (E) ingredient).As metal oxide particle, The metal oxide particle for being particularly preferably 1.50 or more containing the refractive index under wavelength 633nm.Preparing transfer printing type sense as a result, When photosensitiveness film, the transparency and the refractive index under wavelength 633nm that can be improved the second resin layer.In addition, can inhibit to base Developability is improved while the absorption of material.
As metal oxide particle, can enumerate by zirconium oxide, titanium oxide, tin oxide, zinc oxide, tin indium oxide, oxidation The particle that the metal oxides such as indium, aluminium oxide, yttrium oxide are constituted.Wherein, from the viewpoint of inhibiting the visible phenomenon of shadow, preferably The particle of zirconium oxide or titanium oxide.
As Zirconia particles, in the case where the material of transparent electrode is ITO, from raising refractive index and with ITO and thoroughly , it is preferable to use zirconium oxide nano-particle from the perspective of the adaptation of bright substrate.In zirconium oxide nano-particle, preferred size distribution Dmax is 40nm or less.
Zirconium oxide nano-particle can be with OZ-S30K (Nissan Chemical Ind Ltd's system, ProductName), OZ-S40K-AC (Nissan Chemical Ind Ltd's system, ProductName), SZR-K (zirconium oxide methyl ethyl ketone dispersion liquid, Sakai Chemical Industry Co., Ltd. System, ProductName), SZR-M (zirconium oxide methanol dispersion liquid, Sakai Chemical Industry Co., Ltd.'s system, ProductName) is from commercially-available.
Titanium oxide nanoparticles can also be contained in second resin layer 30 and be used as (E) ingredient.In addition, titanium oxide nanoparticles In, it is 50nm hereinafter, more preferably 10~50nm that preferred size, which is distributed Dmax,.
As (E) ingredient, other than above-mentioned metal oxide particle, can also use for example containing Mg, Al, Si, Ca, The equiatomic oxide particle of Cr, Cu, Zn, Ba or sulfide particles.They can be used alone or make two or more combinations With.
In addition, can also use the compound for example with triazine ring other than above-mentioned metal oxide particle, have The organic compounds such as the compound of isocyanuric acid skeleton, compound with fluorene skeleton.Thereby, it is possible to improve under wavelength 633nm Refractive index.
The thickness of above-mentioned second resin layer 30 can be 0.01~1 μm, preferably 0.03~0.5 μm, more preferably 0.04 ~0.3 μm, further preferably 0.07~0.25 μm, particularly preferably 0.05~0.2 μm.By making with a thickness of 0.01~1 μm, The intensity of reflected light of above-mentioned picture entirety can be further decreased.In addition, the thickness of the second resin layer after solidifying it is also preferred that In above range.
The refractive index of second resin layer 30 is single layer, film thickness on film thickness direction in uniform situation in the second resin layer, ETA-TCM (AudioDevGmbH Co. Ltd. system, ProductName) can be used to find out as follows.Wherein, measurement below is 25 It is carried out under conditions of DEG C.
(1) coating fluid for being used to form the second resin layer is uniformly coated to thick 0.7mm, vertical 10cm × cross with spin coater It is 3 minutes dry with 100 DEG C of hot wind detention drying machines on the glass baseplate of 10cm, solvent is removed, the second resin layer is formed.
(2) then, in the box like dryer (Mitsubishi Electric Corporation's system, model: NV50-CA) for being heated to 140 DEG C 30 minutes are stood, the detecting refractive index sample with the second resin layer is obtained.
(3) then, for obtained detecting refractive index sample, ETA-TCM (AudioDevGmbH Co., Ltd. is utilized System, ProductName) measurement wavelength 633nm under refractive index.
The refractive index of first resin layer of single layer can also measure by the same method.It should be noted that transferring In the mode of type photosensitive film, due to being difficult to measure the refractive index of the second resin layer single layer, the guarantor of the second resin layer is used The value of the most surface layer of cuticula side.
(other layers)
Its suitably selected can be arranged in transfer printing type photosensitive film of the invention in the range of effect of the present invention can be obtained Its layer.It as above-mentioned other layers, is not particularly limited, can suitably be selected according to purpose, such as buffer layer, oxygen masking can be enumerated Layer, peeling layer, adhesive layer etc..Transfer printing type photosensitive film can individually have a kind of these layer, it is possible to have two or more.Separately Outside, it is possible to have 2 or more layers of the same race.
(protective film)
As protective film 40, such as polyethylene can be enumerated, polypropylene, polyethylene terephthalate, polycarbonate, gathered The stacked film of vinyl-vinyl acetate copolymer, the film of polyethylene vinyl acetate copolymer and these films and polyethylene Deng.
The thickness of protective film 40 is preferably 5~100 μm, from the sight for being rolled into a roll to take care of by transfer printing type photosensitive film 1 Point set out, preferably 70 μm hereinafter, more preferably 60 μm hereinafter, further preferably 50 μm hereinafter, particularly preferably 40 μm with Under.
Solidify membrane part made of solidifying the first resin layer 20 and the second resin layer 30 in transfer printing type photosensitive film 1 The minimum of the total light transmittance (Tt) of (in addition to support membrane 10 and protective film 40) in the visible light region of 400~700nm of wavelength Value preferably 90.00% or more, more preferably 90.50% or more, further preferably 90.70% or more.If common can Total light transmittance in light-exposed wavelength region i.e. 400~700nm is 90.00% or more, then in protection touch panel (touch sensing Device) induction region transparent electrode in the case where, can sufficiently inhibit the display quality of image, tone, brightness of induction region It reduces.
The first resin layer 20, the second resin layer 30 of transfer printing type photosensitive film 1 for example can be by preparing the first resin layer shape At with coating fluid and the second resin layer formation coating fluid, being respectively coated on support membrane 10, on protective film 40 and done It is dry to be formed.Also, transfer printing type photosensitive film 1 can be by that will be formed with the support membrane 10 of the first resin layer 20 and be formed with the The protective film 40 of two resin layers 30 is bonded to be formed with the first resin layer 20 state opposite with the second resin layer 30.In addition, turning Print type photosensitive film 1 can also be gone forward side by side by being coated with the coating fluid containing the first resin layer formation coating fluid on support membrane 10 Then row drying is coated with the second resin formation coating fluid on the first resin layer 20 and is dried, bonding protective film 40 It is formed.
Coating fluid can by will constitute the photosensitive polymer combination of above-mentioned present embodiment, the second resin layer it is each at Divide equably to be dissolved or dispersed in solvent and obtain.
The solvent used as coating fluid is not particularly limited, and well known solvent can be used.Can specifically enumerate acetone, Methyl ethyl ketone, methyl iso-butyl ketone (MIBK), toluene, methanol, ethyl alcohol, propyl alcohol, butanol, methylene glycol, ethylene glycol, propylene glycol, ethylene glycol Monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol diethyl ether, propylene glycol Monomethyl ether, ethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetic acid esters, propylene glycol methyl ether acetate, chloroform, dichloro Methane etc..
As coating method, scraper for coating method, Meyer wire rod rubbing method, rolling method, silk screen rubbing method, spin coating can be enumerated Method, ink-jet application method, spray coating method, dip coating, gravure coating process, curtain coating processes, die coating method etc..
Drying condition is not particularly limited, and drying temperature is preferably 60~130 DEG C, and drying time is preferably 0.5~30 point Clock.
[forming method for solidifying film figure]
Fig. 2 is the transfer printing type for indicating to have using an embodiment of the invention on the substrate with transparent electrode pattern The constructed profile of the laminated body for the cured film that photosensitive film is formed.Laminated body 100 shown in Fig. 2 has with transparent electrode figure The substrate 50 with transparent electrode pattern of case 50a and the transparent electrode pattern 50a that the substrate 50 with transparent electrode pattern is set On cured film 60.Cured film 60 is the cured film being made of cured first resin layer 22 and cured second resin layer 32, It is to be formed using the transfer printing type photosensitive film 1 of present embodiment.Cured film 60 meets the function of protection transparent electrode pattern 50a Both visual functions of picture are touched with not visibleization of transparent electrode pattern 50a or raising.Hereinafter, to transparent electricity The embodiment that the manufacturing method of the laminated body of cured film is formed on the substrate of pole figure case is illustrated.
Laminating process-
Firstly, after the protective film 40 of removing transfer printing type photosensitive film 1, by the second resin layer 30, the first resin layer 20 and branch Support film 10 is crimped on the surface of the substrate 50 with transparent electrode pattern from 30 side of the second resin layer, is thus laminated and (is turned Print).As compression joint mechanism, crimping roller can be enumerated.Crimping roller can also have heating mechanism to be able to carry out heating crimping.
From the viewpoint and the first resin layer 20 of the second resin layer 30 and the adaptation of the substrate 50 with transparent electrode pattern Or second the constituent of resin layer 30 be not easy from the perspective of being thermally cured or thermally decomposing, carry out heating temperature when heating crimping Preferably 10~160 DEG C of degree, more preferably 20~150 DEG C, further preferably 30~150 DEG C.
In addition, from the adaptation for substantially ensuring the second resin layer 30 and the substrate 50 with transparent electrode pattern and inhibiting band From the perspective of the substrate 50 of transparent electrode pattern deforms, crimping pressure when heating crimping is preferably calculated as 50~1 with line pressure × 105N/m, more preferably 2.5 × 102~5 × 104N/m, further preferably 5 × 102~4 × 104N/m。
If carrying out heating crimping to transfer printing type photosensitive film 1 as described above, it is not necessarily required to band transparent electrode pattern Substrate 50 the pre-heat treatment, but from the adaptation for further increasing the second resin layer 30 with the substrate 50 with transparent electrode pattern From the perspective of, the pre-heat treatment can also be carried out to the substrate 50 with transparent electrode pattern.Treatment temperature at this time is preferably 30 ~150 DEG C.
(substrate)
As the substrate of substrate 50 of the composition with transparent electrode pattern, such as can enumerate for touch panel (touch sensing Device) the substrates such as glass plate, plastic plate, ceramic wafer.
(transparent electrode and metal line)
The electric conductivity such as ITO and IZO (Indium Zinc Oxide, indium oxide-zinc oxide) can be used for example in transparent electrode Metal oxide film is formed.Use the electric conductivity such as silver fiber and carbon nanotube fine in addition, transparent electrode also can be used to have The photosensitive film of the light-cured resin layer of dimension is formed.The conductions such as Au, Ag, Cu, Al, Mo, C can be used for example in metal line Property material, formed by the methods of silk-screen printing, vapor deposition.In addition, can also be arranged between substrate and electrode on substrate There are insulating layer or refractive index matching layers.Refractive index matching layers can have composition identical with above-mentioned second resin layer 30.
Exposure process-
Then, the prescribed portion of the first resin layer and the second resin layer after transfer is shone across photomask with pattern-like Penetrate active ray.When irradiating active ray, in the case where the support membrane 10 on the first resin layer and the second resin layer is transparent, Active ray can be irradiated after removing support membrane in the case where support membrane is opaque with direct irradiation active ray.As work Property light light source, well known active light source can be used.In addition, in the present specification, pattern is not limited to form the micro- of circuit The shape of thin wires also includes only removing the interconnecting piece with other substrates for rectangular shape and only by the frame portion of substrate Shape etc. after removing.
The exposure of active ray is 1 × 102~1 × 104J/m2, when irradiation, can also be with heating.If the active ray Exposure be 1 × 102J/m2More than, then the first resin layer and the photocuring of the second resin layer can be made to be sufficiently carried out, if It is 1 × 104J/m2Hereinafter, then there is the tendency for being able to suppress the first resin layer and the discoloration of the second resin layer.
Then, the unexposed portion of the first resin layer and the second resin layer after active ray irradiation, shape are removed with developer solution At some or all of cured film (refractive index adjustment pattern) 60 of covering transparent electrode.Wherein, after irradiating active ray, In In the case where being laminated with support membrane 10 on first resin layer and the second resin layer, developing procedure is carried out after being removed.
Developer solution well known to aqueous alkali, water system developer solution, organic solvent etc. can be used in developing procedure, by being sprayed, Spray, swing dipping, scrub, method well known to nog plate etc. carries out.Wherein, from the viewpoint of environment, safety, preferably make Spray development is carried out with aqueous alkali.Wherein, development temperature and time can be adjusted in known range.
In the present embodiment, solidification film figure is formd using transfer printing type photosensitive film, using without the second tree In the case where the transfer printing type photosensitive film of rouge layer, solidification film figure can also be formed in the same way.
(cured film)
Cured film of the invention can be the first resin layer of the transfer printing type photosensitive film of present embodiment and the second tree Cured film obtained from the solidification of rouge layer.Wherein, such as in the most of of the second resin layer do not exposed by the covering of the first resin layer In the case where, the second resin layer is not necessarily required to be cured.Cured film of the invention further includes such first resin layer solidification And the uncured situation of the second resin layer.Cured film of the invention is preferably formed into pattern-like.
Cured film of the invention is also possible to make first in the case where transfer printing type photosensitive film does not have the second resin layer Cured film obtained from resin layer solidification.
The transfer printing type photosensitive film of present embodiment can be adapted for the formation of the protective film in various electronic components.This reality The electronic component for applying mode has the solidification film figure formed using transfer printing type photosensitive film.As electronic component, can enumerate Touch sensor, touch panel, liquid crystal display, organic electroluminescent device, solar cell module, printed wiring board, electricity Sub- paper etc..
For example, touch sensor can have laminated body 100 shown in Fig. 2.It is the moulds such as touch panel in touch sensor When block, the OCA that glass will be protected be bonded with laminated body 100 can be used.
Fig. 3 is the diagrammatic top view for indicating the touch panel of an embodiment of the invention.Electrostatic electricity is shown in Fig. 3 One example of the touch panel of appearance formula.Touch panel shown in Fig. 3 has on the single side of transparent substrate 101 for detecting touching The touch picture 102 for touching position coordinates, is provided with the saturating of the electrostatic capacitance change for detecting the region in transparent substrate 101 Prescribed electrode 103 and transparent electrode 104.
Transparent electrode 103 and transparent electrode 104 detect the X position coordinate and Y location coordinate of touch location respectively.
It is provided in transparent substrate 101 and is touched for being transmitted from transparent electrode 103 and transparent electrode 104 to external circuit The lead-out wiring 105 of the detection signal of position.In addition, lead-out wiring 105, transparent electrode 103 and transparent electrode 104 pass through setting Connection electrode 106 in transparent electrode 103 and transparent electrode 104 connects.In addition, lead-out wiring 105 and transparent electrode 103 and the end of interconnecting piece opposite side of transparent electrode 104 be provided with the connection terminal 107 connecting with external circuit.
As shown in figure 3, in the touch panel of present embodiment, using the transfer printing type photosensitive film of present embodiment, across It is more formed with the part of transparent electrode pattern and the part of not formed transparent electrode pattern and is formed with solidification film figure 123.Gu Change film figure 123 to be made of cured first resin layer and cured second resin layer.It should be noted that not having in use In the case where the transfer printing type photosensitive film of second resin layer, solidification film figure 123 is made of cured first resin layer.By this Solidify film figure 123, protection transparent electrode 103, transparent electrode 104, lead-out wiring 105, connection electrode 106 can be played simultaneously And the shadow for the induction region (touching picture) 102 that the function and preventing of connection terminal 107 is formed by transparent electrode pattern can See the function of phenomenon.In addition, solidifying the height on the surface of film figure 123 by using the transfer printing type photosensitive film of present embodiment Low difference is variable enough to small.
Embodiment
Hereinafter, further specifically describing the present invention by embodiment and comparative example, but the present invention is not limited to following Embodiment.
[production of binder polymer solution]
(synthesis example A1)
It is previously added 1- methoxy-2-propanol (Daicel chemical industry Co. Ltd. system) 85.7 mass in the reaction vessel Part, it is warming up to 80 DEG C.On the other hand, by 46 mass parts of cyclohexyl methacrylate, 2 mass parts of methyl methacrylate, methyl 52 mass parts of acrylic acid and the mixing of azo system polymerization initiator (He Guangchun medicine corporation, V-601) 10 mass parts, obtain mixing molten Liquid.The mixed solution is used in a nitrogen atmosphere in the above-mentioned reaction vessel for being added drop-wise to 80 DEG C for 2 hours.It is set to react 4 after dropwise addition Hour, obtain acrylic resin soln.
Then, 2.5 mass parts of Hydroquinone monomethylether and tetraethylammonium bromide are added in Xiang Shangshu acrylic resin soln 8.4 mass parts, then with 2 hours dropwise addition 32 mass parts of glycidyl methacrylate.After dropwise addition. while being blown into air It reacts it 4 hours, is then added as the propylene glycol monomethyl ether of solvent, reaches solid component concentration To 45 mass %, binder polymer solution A1 is obtained.Wherein, additive amount is adjusted, cyclohexyl methacrylate, metering system are made Sour methyl esters, methacrylic acid and glycidyl methacrylate reach x:l:y:z=46mol%:2mol%:20mol%: 32mol%.
(synthesis example A2)
Propylene glycol is added in the flask for having blender, reflux cooler, inertness gas introduction port and thermometer 62 mass parts of 62 mass parts of monomethyl ether and toluene, are warming up to 80 DEG C in a nitrogen atmosphere, and reaction temperature is maintained at 80 DEG C ± 2 DEG C, while 1 compound represented of table and 2, bis- (isobutyronitrile) 1.5 mass parts of 2 '-azos were equably added dropwise with 4 hours.After dropwise addition, It is persistently stirred 6 hours at 80 DEG C ± 2 DEG C, it is poly- to obtain the adhesive that weight average molecular weight is 30000, acid value is 156.6mgKOH/g Polymer solution A2 (solid component is 45 mass %).
[table 1]
(embodiment 1~13 and comparative example 1~11)
[the first resin layer forms the production for using coating fluid]
By ingredient shown in table 2 and 3 with use level shown in the table (unit: mass parts) cooperation, mixed using blender 15 minutes, coating fluid was used in production the first resin layer formation.In table 2 and 3, the use level of (A) ingredient indicates the cooperation of solid component Amount.Wherein, coating fluid uses methyl ethyl ketone as solvent and is adjusted to solid component as 20~30 mass %.
[the second resin layer forms the production for using coating fluid]
By ingredient shown in table 3 with use level shown in the table (unit: mass parts) cooperation, 15 points are mixed using blender Coating fluid is used in clock, production the second resin layer formation.In table 3, the use level of (A) ingredient indicates the use level of solid component.
The mark of ingredient in table 2~5 indicates meaning below.
[(A) ingredient]
A1: the binder polymer solution made by the above method
A2: the binder polymer solution made by the above method
[(B) ingredient]
A-DCP: Tricyclodecane Dimethanol diacrylate (village Xin Zhong Chemical Co., Ltd. system, ProductName)
DPHA: dipentaerythritol hexaacrylate (village Xin Zhong chemistry system, ProductName " A-DPH ")
[(C) ingredient]
TPO:2,4,6- trimethylbenzoy-dipheny-phosphine oxide (BASF Co. Ltd. system, ProductName " IRGACURE TPO”)
819: bis- (2,4,6- trimethylbenzoyl)-phenyl phosphine oxide (BASF Co. Ltd. systems, ProductName “IRGACURE 819”)
[(BASF Co. Ltd. system produces 4- (thiophenyl) phenyl -1,2- octanedione 2- (O- benzoyl oxime) OXE 01:1- The name of an article " IRGACURE OXE 01 ")
OXE 02:1- [9- ethyl -6- (2- methyl benzoyl) -9H- carbazole -3- base]-ethyl ketone 1- (O- acetyl group oxime) (BASF Co. Ltd. system, ProductName " IRGACURE OXE 02 ")
184:1- hydroxy-cyclohexyl-phenyl -one (BASF Co. Ltd. system, ProductName " IRGACURE184 ")
651:2,2- dimethoxy -1,2- diphenylethane -1- ketone (BASF Co. Ltd. system, ProductName " IRGACURE 651”)
754: oxygen phenylacetic acid 2- (2- oxo -2- phenylacetyl oxygroup ethyoxyl) ethyl ester and oxygen phenylacetic acid 2- (2- hydroxyl Base oxethyl) ethyl ester mixture (BASF Co. Ltd. system, ProductName " IRGACURE754 ")
[(E) ingredient]
E1: zirconium oxide nano-particle dispersion liquid (Nissan Chemical Ind Ltd's system, ProductName " OZ-S30K ")
[production of transfer printing type photosensitive film]
(the case where the second resin layer of band)
As protective film, polypropylene screen (the prince F-Tex Co. Ltd. system, ProductName: ES- with a thickness of 30 μm are used 201), the second resin layer formation of above-mentioned production is equably coated on protective film with coating fluid using die coating machine, with 110 DEG C Hot wind detention drying machine dry 3 minutes, remove solvent, formed with a thickness of 60nm, the second resin layer that refractive index is 1.4.
As support membrane, using the polyethylene terephthalate film with a thickness of 16 μm, (Toray Co. Ltd. system is produced The name of an article: FB40), the first resin layer formation of above-mentioned production is uniformly coated to support membrane with coating fluid using comma coater On, it is 3 minutes dry with 110 DEG C of hot wind convection type drying machines, solvent is removed, the first resin layer with a thickness of 8 μm is formed.
Then, the protective film with the second resin layer and the support membrane with the first resin layer are used into stacking machine (Hitachi Chemical conversion Co. Ltd. system, ProductName: HLM-3000 type) it is bonded at 23 DEG C, production is sequentially laminated with protective film, the second resin The transfer printing type photosensitive film of layer, the first resin layer and support membrane.
(not having the case where the second resin layer)
As support membrane, using the polyethylene terephthalate film with a thickness of 16 μm, (Toray Co. Ltd. system is produced The name of an article: FB40), the first resin layer formation of above-mentioned production is uniformly coated to support membrane with coating fluid using comma coater On, it is 3 minutes dry with 110 DEG C of hot wind convection type drying machines, solvent is removed, the first resin layer with a thickness of 8 μm is formed.
Then, support membrane with the first resin layer will be obtained and as protective film with a thickness of 30 μm of polypropylene screen (prince F-Tex Co. Ltd. system, ProductName: ES-201) is bonded at 23 DEG C, and production is sequentially laminated with protective film, the first resin The transfer printing type photosensitive film of layer and support membrane.
[difference of height evaluation test]
Firstly, referring to Fig. 4 to for evaluating the cured film depression in the surface (difference of height) formed by transfer printing type photosensitive film Test be illustrated.The transfer printing type photosensitive film for not having the second resin layer is carried out it should be noted that being shown in Fig. 4 The case where evaluation, removes the first resin layer 20 in the case where evaluating the transfer printing type photosensitive film with the second resin layer It is in addition same as the stepped construction of the first resin layer and the second resin layer.
Prepare the substrate 52 (ITO substrate) of evaluation.By transfer printing type photosensitive film obtained in embodiment and comparative example Protect film stripping, and make the first resin layer 20 or transfer printing type photosensitive film have the second resin layer in the case where, make the second tree Rouge layer 30 is opposite with substrate, is laminated under conditions of 100 DEG C, 0.6m/min, 0.4MPa.
It is after lamination, substrate is cooling, reach 23 DEG C of time point in the temperature of substrate, using from 10 side of support membrane has height The exposure machine (ORC Mfg. Co., Ltd.'s manufacture, trade name: EXM-1201) of pressure mercury lamp, with 50mJ/cm2Light exposure L1, every Mask 70 with predetermined pattern carry out light irradiation (referring to (a) of Fig. 4).
Then, mask 70 is removed, with 10mJ/cm2Light exposure L2 carry out light irradiation (referring to Fig. 4 (b)).
Then, support membrane 10 is removed, with 375mJ/cm2Light exposure L3 carry out light irradiation (referring to Fig. 4 (c)).
Then, after the annealing that heating 30 minutes is carried out at 140 DEG C, measurement light exposure adds up to 435mJ/cm2Height it is anti- Should rate part surface S1 and light exposure add up to 385mJ/cm2Low reaction rate part surface S2 between difference of height G (nm) (referring to (d) of Fig. 4).Wherein, difference of height G (nm) is measured by laser microscope (Lasertec corporation).
If difference of height be 120nm hereinafter, if can be adequately suppressed pattern visible.In addition, forming stacking shown in Fig. 2 In the case where body 100, if cured film depression in the surface difference of height be 120nm hereinafter, if can play following effect.Using stacking When body 100 forms the modules such as touch panel, OCA is used in order to which glass will be protected Nian Jie with laminated body 100.However, OCA is required Closely sealed cured film has a closely sealed reliability under high temperature and humidity, but the case where solidifying film surface there are fine differences of height Under, OCA is led to the problem of due to difference of height sometimes and floats (removing).If solidify film surface difference of height be 120nm with Under, then it is able to suppress the generation of the above problem, improves closely sealed reliability of the OCA under high temperature and humidity.
[the visible evaluation of pattern]
Sample after annealing obtained in difference of height evaluation test is fixed on black plate, from oblique irradiation light, is led to It crosses and is visually observed, evaluated according to following benchmark.
Zero: can't see or be not readily apparent pattern.
×: it can see pattern.
[moisture permeability of cured film]
Prepare 5 transfer printing type photosensitive films.Firstly, by the protection film stripping of the 1st transfer printing type photosensitive film, by it in roller Temperature is 100 DEG C, substrate conveying speed is 0.6m/ minutes, crimping pressure (drum pressure) is laminated under conditions of being 0.5MPa Filter paper (Advantec system, No.5C, the circle of Φ 90mm, with a thickness of 130 μm) on.Then, film stripping will be supported, the 2nd is turned The protection film stripping of print type photosensitive film is laminated on the first resin layer being laminated on filter paper.By repeating the operation, production It is laminated on filter paper with a thickness of 40 μm of the first resin layer (i.e. the first resin layer is 5 layers) and the laminated body of support membrane.
It should be noted that in the case where transfer printing type photosensitive film has the second resin layer, according to similar to the above Step is produced on the layer being laminated on filter paper with a thickness of about 40 μm of the first resin layer and this 5 layers of the second resin layer and support membrane Stack.
Using parallel rays exposure machine (ORC Mfg. Co., Ltd.'s system, EXM1201) from support film surface vertical direction with 0.6J/m2Light exposure to above-mentioned laminated body irradiate ultraviolet light.
Then, will irradiate the laminated body of above-mentioned ultraviolet light support film stripping remove, and then from laminated body it is vertical on Side is with 1 × 104J/m2Exposure ultraviolet light.The moisture permeability measurement examination that cured film is formed on filter paper is obtained as a result, Sample.
Then, implement moisture permeability measurement with reference to JIS standard (Z0208, agar diffusion method).Firstly, in measurement cup (Φ 60mm, depth 15mm, Murai Co., Ltd.'s member make institute) in be added hygroscopic material (calcium chloride (anhydrous) of 20g).Then, using from above-mentioned The circular specimen piece for the size that diameter is 70mm is cut into hygrometry with sample with scissors, is covered on said determination cup.In constant temperature In constant humidity slot, placed 24 hours under conditions of 40 DEG C, 90%RH.According to the measurement cup, hygroscopic agent and round examination for placing front and back The variation of the gross mass of print calculates moisture permeability.If moisture permeability is 200g/m2For 24 hours hereinafter, then rust-preventing characteristic is good.
Symbol description
1 transfer printing type photosensitive film
10 support membranes
20 first resin layers
22 cured first resin layers
30 second resin layers
32 cured second resin layers
40 protective films
50 substrates with transparent electrode pattern
50a transparent electrode pattern
60 cured films
100 laminated bodies
101 transparent substrates
102 sensitive zones
103,104 transparent electrode
105 lead-out wirings
106 connection electrodes
107 connection terminals
123 solidification film figures

Claims (14)

1. a kind of transfer printing type photosensitive film, has:
Support membrane, and
The first resin layer being set on the support membrane；
First resin layer includes photopolymerizable compound and acyl group oxygen with tricyclodecane skeleton or tricyclo decene skeleton Change phosphine system Photoepolymerizationinitiater initiater.
2. transfer printing type photosensitive film according to claim 1, wherein
Acylphosphine oxide system Photoepolymerizationinitiater initiater includes 2,4,6- trimethylbenzoy-dipheny-phosphine oxide.
3. transfer printing type photosensitive film according to claim 1 or 2, wherein
First resin layer also includes oxime ester system Photoepolymerizationinitiater initiater.
4. transfer printing type photosensitive film described in any one of claim 1 to 3, wherein
First resin layer include binder polymer, described adhesive polymer contain side chain have branched structure and/ Or alicyclic structure group, in group of the side chain with acidic-group and in side chain there is the base of ethylenically unsaturated groups Group.
5. transfer printing type photosensitive film according to any one of claims 1 to 4, is also equipped with:
The second resin layer containing metal oxide particle on first resin layer is set.
6. transfer printing type photosensitive film according to claim 5, wherein
Second resin layer includes the photopolymerizable compound with tricyclodecane skeleton or tricyclo decene skeleton.
7. transfer printing type photosensitive film described according to claim 1~any one of 6, be used for ITO electrode pattern and Cured film is formed on the substrate of refractive index matching layers.
8. a kind of forming method for solidifying film figure, has:
On the substrate with electrode pattern, by described the of transfer printing type photosensitive film according to any one of claims 1 to 4 One resin layer is laminated with the side for being provided with electrode pattern of the substrate and the closely sealed mode of first resin layer Process, and
After being exposed to the prescribed portion of first resin layer on the substrate, the portion other than the prescribed portion is removed Point, form the process for covering some or all of solidification film figure of the electrode pattern.
9. a kind of forming method for solidifying film figure, has:
On the substrate with electrode pattern, by second resin layer of transfer printing type photosensitive film described in claim 5 or 6 With first resin layer with the side for being provided with the electrode pattern of the substrate and the closely sealed side of second resin layer The process that formula is laminated, and
After being exposed to the prescribed portion of second resin layer and first resin layer on the substrate, described in removing Part other than prescribed portion forms the process for covering some or all of solidification film figure of the electrode pattern.
It is by will be described in transfer printing type photosensitive film according to any one of claims 1 to 4 10. a kind of cured film What the first resin layer was solidified to form.
It is by by first resin in transfer printing type photosensitive film described in claim 5 or 6 11. a kind of cured film Layer individually solidifies or is solidified to form both first resin layer and second resin layer.
12. a kind of laminated body, the resin solidification for including the substrate with electrode pattern and being arranged on the electrode pattern Film, wherein
The resin cured film has difference of height in the surface side opposite with the electrode pattern,
The difference of height is 120nm or less.
13. laminated body according to claim 12, wherein
The resin cured film includes the compound with tricyclodecane skeleton or tricyclo decene skeleton.
14. a kind of touch panel has as described in transfer printing type photosensitive film according to any one of claims 1 to 4 The cured film of first resin layer or second resin layer in transfer printing type photosensitive film described in claim 5 or 6 are consolidated Change the solidification film figure of the cured film composition of film and first resin layer.
CN201780089046.7A 2017-03-28 2017-03-28 Transfer photosensitive film Active CN110462560B (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/JP2017/012679 WO2018179095A1 (en) 2017-03-28 2017-03-28 Transfer-type photosensitive film, method for forming cured film pattern, cured film and touch panel

Publications (2)

Publication Number Publication Date
CN110462560A true CN110462560A (en) 2019-11-15
CN110462560B CN110462560B (en) 2023-07-28

Family

ID=63674599

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201780089046.7A Active CN110462560B (en) 2017-03-28 2017-03-28 Transfer photosensitive film

Country Status (4)

Country Link
JP (3) JP7210091B2 (en)
CN (1) CN110462560B (en)
TW (1) TWI776873B (en)
WO (1) WO2018179095A1 (en)

Citations (32)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08240800A (en) * 1995-03-03 1996-09-17 Asahi Glass Co Ltd Resin substrate for liqud crystal display
US20020106568A1 (en) * 2000-12-05 2002-08-08 Nippon Shokubai Co., Ltd. Photosensitive resin composition, its use, lactone-ring-containing polymer, and production process therefor
JP2003200577A (en) * 2002-01-08 2003-07-15 Canon Inc Recording element unit and recorder
CN1580953A (en) * 2003-08-15 2005-02-16 富士胶片株式会社 Light-sensitive transfer sheet, light-sensitive layers, picture pattern forming method and layout pattern forming method
CN1612042A (en) * 2003-10-27 2005-05-04 住友化学株式会社 Colouring photosensitive resin composition
JP2005189574A (en) * 2003-12-26 2005-07-14 Sumitomo Chemical Co Ltd Photosensitive resin composition
CN1641481A (en) * 2004-01-14 2005-07-20 富士胶片株式会社 Light-sensitive transfer sheet, light-sensitive layers, method for forming image pattern and method for distribution pattern
CN101114124A (en) * 2006-07-26 2008-01-30 富士胶片株式会社 Photosensitive composition, photosensitive resin transfer film, manufacturing method of photo spacer, substrate for liquid crystal display device, and liquid crystal display device
JP2008274003A (en) * 2007-04-25 2008-11-13 Hitachi Chem Co Ltd Phosphorus-containing compound, resin composition containing the same, photosensitive film by using resin composition, method for forming resist pattern and printed wiring board
JP2009175730A (en) * 2007-12-28 2009-08-06 Fujifilm Corp Photosensitive resin composition, photo spacer, forming method for it, protective film, coloring pattern, substrate for display device and display device
JP2010139993A (en) * 2008-12-15 2010-06-24 Hitachi Chem Co Ltd Photosensitive resin composition and photosensitive element
CN102272887A (en) * 2009-01-08 2011-12-07 株式会社普利司通 Photocurable transfer sheet, and method for forming uneven pattern using same
JP2011248188A (en) * 2010-05-28 2011-12-08 Hitachi Chem Co Ltd Photosensitive resin composition, photosensitive film, and permanent resist
CN102341753A (en) * 2009-03-13 2012-02-01 日立化成工业株式会社 Photosensitive resin composition, and photosensitive element, resist pattern formation method and printed circuit board production method each utilizing same
CN102529257A (en) * 2010-12-22 2012-07-04 日本合成化学工业株式会社 Transfer printing laminated body
CN102687067A (en) * 2009-09-29 2012-09-19 富士胶片株式会社 Photosensitive resin composition for photospacer, photosensitive resin transfer material, photospacer and process for production thereof, substrate for liquid crystal display device, and liquid crystal display device
JP2013064973A (en) * 2011-08-26 2013-04-11 Toppan Printing Co Ltd Photosensitive resin composition, material for touch panel, touch panel protective film, touch panel insulating film, and touch panel
JP5304973B1 (en) * 2011-12-05 2013-10-02 日立化成株式会社 Method for forming protective film of electrode for touch panel, photosensitive resin composition and photosensitive element, and method for manufacturing touch panel
JP2013200577A (en) * 2011-12-05 2013-10-03 Hitachi Chemical Co Ltd Formation method of cured resin film pattern, photosensitive resin composition, photosensitive element, manufacturing method of touch panel and cured resin film
CN103376659A (en) * 2012-04-25 2013-10-30 住友化学株式会社 Photosensitive resin composition
WO2014084112A1 (en) * 2012-11-30 2014-06-05 富士フイルム株式会社 Transfer film, transparent laminate, method for producing transfer film, method for producing transparent laminate, capacitive input device, and image display device
JP2014115672A (en) * 2014-01-24 2014-06-26 Hitachi Chemical Co Ltd Photosensitive element, solder resist and printed wiring board using photosensitive resin composition
CN103975296A (en) * 2011-12-05 2014-08-06 日立化成株式会社 Method of forming protective film for touch panel electrode, photosensitive resin composition and photosensitive element, and method of manufacturing touch panel
US20140363767A1 (en) * 2011-12-05 2014-12-11 Hitachi Chemical Company, Ltd. Method for forming resin cured film pattern, photosensitive resin composition, photosensitive element, method for producing touch panel, and resin cured film
WO2015030151A1 (en) * 2013-08-30 2015-03-05 Canon Kabushiki Kaisha Curable composition for photoimprint and method of producing film, optical component, circuit board, or electronic component using the composition
JP2015121929A (en) * 2013-12-24 2015-07-02 日立化成株式会社 Method for manufacturing touch panel substrate with cured film, photosensitive resin composition and photosensitive element used for the method, and touch panel
JP2015193676A (en) * 2014-03-31 2015-11-05 東洋インキＳｃホールディングス株式会社 Active energy ray-curable ink and printed matter
WO2016031665A1 (en) * 2014-08-29 2016-03-03 富士フイルム株式会社 Composition for forming touch panel electrode protective film, transfer film, layered body, protective film for touch panel electrode and method for forming same, capacitance-type input device, and image display device
CN105517648A (en) * 2014-12-10 2016-04-20 互应化学工业株式会社 Liquid solder resist composition and coated printed wiring board
JP2016139043A (en) * 2015-01-28 2016-08-04 互応化学工業株式会社 Photosensitive resin composition, printed wire board, dry film with support, and multilayer printed wire board
CN105934478A (en) * 2014-01-29 2016-09-07 日立化成株式会社 Resin composition, method for manufacturing semiconductor device using resin composition, and solid-state imaging element
WO2016181422A1 (en) * 2015-05-11 2016-11-17 日立化成株式会社 Transfer-type photosensitive refractive index adjustment film, method for forming refractive index adjustment pattern, and electronic component

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5447939B2 (en) * 2009-07-29 2014-03-19 日立化成株式会社 Photosensitive resin composition and photosensitive film
JP2012078528A (en) * 2010-09-30 2012-04-19 Fujifilm Corp Photosensitive composition, photosensitive resin transfer film, resin pattern and production method of resin pattern, substrate for liquid crystal display device, and liquid crystal display device
JP2012255925A (en) * 2011-06-09 2012-12-27 Hitachi Chem Co Ltd Photosensitive resin composition, and photosensitive element and permanent resist using the same
JP5821481B2 (en) * 2011-09-30 2015-11-24 東レ株式会社 Negative photosensitive resin composition and protective film and touch panel member using the same
JP5534282B2 (en) * 2012-04-27 2014-06-25 日産化学工業株式会社 Imprint material
JP6415217B2 (en) * 2014-09-26 2018-10-31 東京応化工業株式会社 Structure with planarization layer
KR102493938B1 (en) * 2015-01-28 2023-01-30 고오 가가쿠고교 가부시키가이샤 Method for producing carboxyl group-containing resin, photosensitive resin composition, dry film, printed wiring board, and carboxyl group-containing resin

Patent Citations (32)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08240800A (en) * 1995-03-03 1996-09-17 Asahi Glass Co Ltd Resin substrate for liqud crystal display
US20020106568A1 (en) * 2000-12-05 2002-08-08 Nippon Shokubai Co., Ltd. Photosensitive resin composition, its use, lactone-ring-containing polymer, and production process therefor
JP2003200577A (en) * 2002-01-08 2003-07-15 Canon Inc Recording element unit and recorder
CN1580953A (en) * 2003-08-15 2005-02-16 富士胶片株式会社 Light-sensitive transfer sheet, light-sensitive layers, picture pattern forming method and layout pattern forming method
CN1612042A (en) * 2003-10-27 2005-05-04 住友化学株式会社 Colouring photosensitive resin composition
JP2005189574A (en) * 2003-12-26 2005-07-14 Sumitomo Chemical Co Ltd Photosensitive resin composition
CN1641481A (en) * 2004-01-14 2005-07-20 富士胶片株式会社 Light-sensitive transfer sheet, light-sensitive layers, method for forming image pattern and method for distribution pattern
CN101114124A (en) * 2006-07-26 2008-01-30 富士胶片株式会社 Photosensitive composition, photosensitive resin transfer film, manufacturing method of photo spacer, substrate for liquid crystal display device, and liquid crystal display device
JP2008274003A (en) * 2007-04-25 2008-11-13 Hitachi Chem Co Ltd Phosphorus-containing compound, resin composition containing the same, photosensitive film by using resin composition, method for forming resist pattern and printed wiring board
JP2009175730A (en) * 2007-12-28 2009-08-06 Fujifilm Corp Photosensitive resin composition, photo spacer, forming method for it, protective film, coloring pattern, substrate for display device and display device
JP2010139993A (en) * 2008-12-15 2010-06-24 Hitachi Chem Co Ltd Photosensitive resin composition and photosensitive element
CN102272887A (en) * 2009-01-08 2011-12-07 株式会社普利司通 Photocurable transfer sheet, and method for forming uneven pattern using same
CN102341753A (en) * 2009-03-13 2012-02-01 日立化成工业株式会社 Photosensitive resin composition, and photosensitive element, resist pattern formation method and printed circuit board production method each utilizing same
CN102687067A (en) * 2009-09-29 2012-09-19 富士胶片株式会社 Photosensitive resin composition for photospacer, photosensitive resin transfer material, photospacer and process for production thereof, substrate for liquid crystal display device, and liquid crystal display device
JP2011248188A (en) * 2010-05-28 2011-12-08 Hitachi Chem Co Ltd Photosensitive resin composition, photosensitive film, and permanent resist
CN102529257A (en) * 2010-12-22 2012-07-04 日本合成化学工业株式会社 Transfer printing laminated body
JP2013064973A (en) * 2011-08-26 2013-04-11 Toppan Printing Co Ltd Photosensitive resin composition, material for touch panel, touch panel protective film, touch panel insulating film, and touch panel
CN103975296A (en) * 2011-12-05 2014-08-06 日立化成株式会社 Method of forming protective film for touch panel electrode, photosensitive resin composition and photosensitive element, and method of manufacturing touch panel
JP2013200577A (en) * 2011-12-05 2013-10-03 Hitachi Chemical Co Ltd Formation method of cured resin film pattern, photosensitive resin composition, photosensitive element, manufacturing method of touch panel and cured resin film
JP5304973B1 (en) * 2011-12-05 2013-10-02 日立化成株式会社 Method for forming protective film of electrode for touch panel, photosensitive resin composition and photosensitive element, and method for manufacturing touch panel
US20140363767A1 (en) * 2011-12-05 2014-12-11 Hitachi Chemical Company, Ltd. Method for forming resin cured film pattern, photosensitive resin composition, photosensitive element, method for producing touch panel, and resin cured film
CN103376659A (en) * 2012-04-25 2013-10-30 住友化学株式会社 Photosensitive resin composition
WO2014084112A1 (en) * 2012-11-30 2014-06-05 富士フイルム株式会社 Transfer film, transparent laminate, method for producing transfer film, method for producing transparent laminate, capacitive input device, and image display device
WO2015030151A1 (en) * 2013-08-30 2015-03-05 Canon Kabushiki Kaisha Curable composition for photoimprint and method of producing film, optical component, circuit board, or electronic component using the composition
JP2015121929A (en) * 2013-12-24 2015-07-02 日立化成株式会社 Method for manufacturing touch panel substrate with cured film, photosensitive resin composition and photosensitive element used for the method, and touch panel
JP2014115672A (en) * 2014-01-24 2014-06-26 Hitachi Chemical Co Ltd Photosensitive element, solder resist and printed wiring board using photosensitive resin composition
CN105934478A (en) * 2014-01-29 2016-09-07 日立化成株式会社 Resin composition, method for manufacturing semiconductor device using resin composition, and solid-state imaging element
JP2015193676A (en) * 2014-03-31 2015-11-05 東洋インキＳｃホールディングス株式会社 Active energy ray-curable ink and printed matter
WO2016031665A1 (en) * 2014-08-29 2016-03-03 富士フイルム株式会社 Composition for forming touch panel electrode protective film, transfer film, layered body, protective film for touch panel electrode and method for forming same, capacitance-type input device, and image display device
CN105517648A (en) * 2014-12-10 2016-04-20 互应化学工业株式会社 Liquid solder resist composition and coated printed wiring board
JP2016139043A (en) * 2015-01-28 2016-08-04 互応化学工業株式会社 Photosensitive resin composition, printed wire board, dry film with support, and multilayer printed wire board
WO2016181422A1 (en) * 2015-05-11 2016-11-17 日立化成株式会社 Transfer-type photosensitive refractive index adjustment film, method for forming refractive index adjustment pattern, and electronic component

Also Published As

Publication number Publication date
JP2022121441A (en) 2022-08-19
CN110462560B (en) 2023-07-28
TWI776873B (en) 2022-09-11
WO2018179095A1 (en) 2018-10-04
JPWO2018179095A1 (en) 2020-01-30
JP2024133548A (en) 2024-10-02
JP7210091B2 (en) 2023-01-23
TW201902955A (en) 2019-01-16

Similar Documents

Publication Publication Date Title
KR101989644B1 (en) Method for forming protective film on electrode for touch panel, photosensitive resin composition and photosensitive element, and method for manufacturing touch panel
JP6400289B2 (en) Base material for touch panel with cured film and method for producing the same, photosensitive element and touch panel
WO2016181422A1 (en) Transfer-type photosensitive refractive index adjustment film, method for forming refractive index adjustment pattern, and electronic component
JP6551277B2 (en) Method for producing cured substrate with touch panel, photosensitive resin composition used therefor, photosensitive element and touch panel
WO2016002026A1 (en) Photosensitive refractive index-adjusting transfer film
JP2018165788A (en) Transfer photosensitive film, curable resin patterning method, and touch panel
US20180284920A1 (en) Transfer-type photosensitive film for refractive-index modulation
JP2017181541A (en) Photosensitive film, photosensitive refractive index adjusting film, method for forming refractive index adjusting pattern, cured film and electronic component
JP2017201352A (en) Transfer type photosensitive refractive index adjusting film, method for forming refractive index adjusting pattern, and electronic component
WO2017175642A1 (en) Photosensitive refractive index modulation film, method for forming cured film pattern, cured film and electronic component
CN110462560A (en) Transfer printing type photosensitive film, the forming method for solidifying film figure, cured film and touch panel
CN110462559A (en) Transfer printing type photosensitive film, the forming method and touch panel for solidifying film figure
US10717893B2 (en) Photosensitive film, photosensitive element, cured product and touch panel
WO2019207648A1 (en) Photosensitive resin composition, transfer-type photosensitive film, substrate having cured film attached thereto, and sensing device
JP2019174604A (en) Transfer film, cured film and method for forming the same, and electronic component
JP2019215395A (en) Transfer type photosensitive film, method for forming cured film pattern, laminate and touch panel
JP2019035801A (en) Transfer photosensitive film, method of forming cured film pattern, cured film and electronic component
JP2021144723A (en) Production method of touch panel substrate with cured film, photosensitive resin composition used for the method, photosensitive element, and touch panel
WO2019224887A1 (en) Transfer type photosensitive film, electrode substrate with resin cured film, and touch panel
WO2019207677A1 (en) Photosensitive film and photosensitive refractive-index adjustment film
WO2019186802A1 (en) Transfer film, cured film and method for forming same, and electronic component
WO2019186781A1 (en) Transfer film, cured film and method for forming same, and electrical component
JP2017111245A (en) Method of manufacturing touch panel substrate with cured film, cured film forming agent, photosensitive element, and touch panel

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
CB02 Change of applicant information
CB02 Change of applicant information

Address after: Tokyo

Applicant after: Lishennoco Co.,Ltd.

Address before: Tokyo

Applicant before: HITACHI CHEMICAL Co.,Ltd.

GR01 Patent grant
GR01 Patent grant