CN107615171A - Manufacture method, circuit layout, input unit and the display device of circuit layout - Google Patents
Manufacture method, circuit layout, input unit and the display device of circuit layout Download PDFInfo
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- CN107615171A CN107615171A CN201680029450.0A CN201680029450A CN107615171A CN 107615171 A CN107615171 A CN 107615171A CN 201680029450 A CN201680029450 A CN 201680029450A CN 107615171 A CN107615171 A CN 107615171A
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- layer
- circuit layout
- light sensitivity
- positive light
- pattern
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Classifications
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- G06F3/03—Arrangements for converting the position or the displacement of a member into a coded form
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- G06F3/044—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means by capacitive means
- G06F3/0446—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means by capacitive means using a grid-like structure of electrodes in at least two directions, e.g. using row and column electrodes
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- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
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- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
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- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
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- G—PHYSICS
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- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/20—Exposure; Apparatus therefor
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/40—Treatment after imagewise removal, e.g. baking
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- 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
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- 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
- G06F3/044—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means by capacitive means
- G06F3/0445—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means by capacitive means using two or more layers of sensing electrodes, e.g. using two layers of electrodes separated by a dielectric layer
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
- H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
- H05K3/06—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding the conductive material being removed chemically or electrolytically, e.g. by photo-etch process
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- Engineering & Computer Science (AREA)
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- General Engineering & Computer Science (AREA)
- Theoretical Computer Science (AREA)
- Human Computer Interaction (AREA)
- Manufacturing & Machinery (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Computer Hardware Design (AREA)
- Power Engineering (AREA)
- Materials For Photolithography (AREA)
- Manufacturing Of Printed Circuit Boards (AREA)
- Photosensitive Polymer And Photoresist Processing (AREA)
- Position Input By Displaying (AREA)
Abstract
The present invention provides a kind of manufacture method of circuit layout, circuit layout, input unit and display device.The manufacture method of the circuit layout can form the circuit layout of the conductive layer comprising multiple patterns with the etchant resist formation of 1 time and manufacture efficiency is excellent, and not need the contraposition of the conductive layer of multiple patterns.The manufacture method of the circuit layout includes:Process (a), to, to the circuit forming board of the 1st layer of conductive layer, forming positive light sensitivity material on the 1st layer of conductive layer with base material and xth layer;Process (b), pattern exposure and development are carried out, and positive light sensitivity material is set to the 1st pattern;Process (c), the 1st layer to i-th layer of conductive layer is etched;Process (d), pattern exposure and development are carried out to residual positive light sensitivity material, so as to which positive light sensitivity material is set into the 2nd pattern;Process (e), the 1st layer of conductive layer to jth layer is etched;Process (z), remove positive light sensitivity material and form the circuit layout of the conductive layer comprising pattern of more than two kinds.
Description
Technical field
The present invention relates to a kind of manufacture method of circuit layout, circuit layout, input unit and display device.In more detail and
Speech, the circuit layout for be related to a kind of manufacture method of circuit layout, manufacturing using the manufacture method of the circuit layout, use this
The input unit of circuit layout, the display device for possessing the input unit.
Background technology
In display device (organic EL display and liquid crystal display with touch panels such as capacitive input devices
Device etc.) in, distribution of electrode pattern, peripheral distribution part and wiring lead part equivalent to the sensor of Identification Division etc. is led
Electric layer pattern is arranged on inside touch panel.
Generally, in the formation of patterned layer, because the process number for obtaining required pattern form is few, therefore profit extensively
With the following method:To the photosensitive polymer combination layer being arranged on using photosensitive transfer printing material on arbitrary base material, via tool
The mask of desired pattern is exposed, and is developed after partial curing.
As the pattern formation method for having used photosensitive polymer combination, it is known to remembered in such as patent document 1 and 2
The method of load.
Below figure case forming method is recorded in patent document 1, it is carried out successively:Lamination process, on base material interarea
Stepped construction is formed, the stepped construction includes the 2nd film of the 1st film and the films of Bi 1 on the position more by interarea side;
Mask pattern formation process, the 1st mask pattern of the film of local complexity the 1st is formed in stepped construction;
1st etching work procedure, a part for the 1st film is removed by the 1st mask pattern;
Mask pattern add process, the 1st mask pattern a part and the 2nd film a part coating organic material and shape
Into those the 2nd mask pattern of covering;
2nd etching work procedure, the 1st mask pattern and the 2nd of the 2nd film is removed by the 1st mask pattern and the 2nd mask pattern
The region being exposed independent from mask pattern;And
Mask pattern removing step, remove the 1st mask pattern and the 2nd mask pattern.
Following pattern formation method can be provided according to patent document 1:(the 1st is against corrosion for painting erosion resistant agent so on base material
Agent), after patterning, by IJ (ink-jet) and silk-screen printing etc., the 2nd resist of predetermined pattern is coated on the 1st and resisted
Lose in agent, be then etched, the stacking film figure thus configured above and below the different pattern of more than two kinds of formation form from one another
When, the number even if photo-mask process is only 1 shape that can also obtain being delimited.
Following photosensitive transfer printing material has been recorded in patent document 2:Its successively have supporter, thermoplastic resin layer and
Photosensitive polymer combination layer, photosensitive polymer combination layer include (A) component of polymer and (B) light acid producing agent, (A) polymerization
Thing composition includes the polymer with construction unit (a1), and the construction unit (a1) has what acidic group was protected by sour decomposability base
Group.In addition, photosensitive transfer printing material described in patent document 2 is chemical amplifying type and eurymeric dry type photoresistance film.
Moreover, in a kind of pattern formation method described in patent document 2, it has:Photosensitive polymer combination layer is formed
Process, at least one side of base material, photoresist group is formed using photosensitive transfer printing material described in patent document 2
Compound layer;Exposure process, photosensitive polymer combination layer is exposed;And developing procedure, to the above-mentioned photonasty being exposed
Resin composition layer is developed.
Conventional art document
Patent document
Patent document 1:Japanese Unexamined Patent Publication 2009-59834 publications
Patent document 2:Japanese Unexamined Patent Publication 2014-85643 publications
The content of the invention
The invention technical task to be solved
Here, in touch panel circuit layout, the electrode pattern equivalent to the sensor of Identification Division is drawn with periphery
The distribution in portion (peripheral distribution part and wiring lead part) is without intersecting, it is not necessary to is connected using the 3-dimensional of electric bridge etc..Cause
This, in the technical field of the manufacture method of touch panel circuit layout, expects as conventional uses photosensitive resin composition
The pattern formation method of thing pattern progress etchant resist need not be formed as desired like that, but be formed with the etchant resist of 1 time
The circuit layout of the conductive layer comprising multiple patterns is formed, so as to omit process.
However, in patent document 1, the manufacture method on touch panel circuit layout, also, the 2nd time are not recorded
Later etchant resist, which is formed, to be needed by ink-jet etc. and direct print etc., can not be so that the etchant resist of 1 time is formed and is formed comprising more
The circuit layout of the conductive layer of kind pattern.
Also, in patent document 2, the circuit layout on conductive layer pattern is on the books, but only records and pass through repetition
Carry out etchant resist formation, exposure, development, etching and sequentially form the electrode pattern (sensor) in 2 directions intersected with each other.
Moreover, in touch panel circuit layout the 3-dimensional of electric bridge etc. need not be used to connect, however, Sensor section
Attenuate with the bonding part of another electric conductivity important document (peripheral distribution part), the contraposition between a variety of conductive layer patterns be present
The problem of precision.
The present invention problem to be solved is to provide a kind of manufacture method of circuit layout, and it can be with the etchant resist of 1 time
Formed to form the circuit layout of the conductive layer comprising multiple patterns and manufacture efficiency is excellent, it is not necessary to the conductive layer of multiple patterns
Contraposition.
The present invention problem to be solved is also to provide a kind of circuit manufactured using the manufacture method of the circuit layout
Distribution, using the circuit layout input unit, possess the display device of the input unit.
For solving the means of technical task
The result by further investigation such as the present inventor, finds for that need not make as touch panel circuit layout
The distribution connected with the 3-dimensional of electric bridge etc., it is (anti-that 1 positive light sensitivity material can be used only as new circuit forming method
Erosion agent) formation uniformly form pattern.Also, pattern is uniformly formed it was found that passing through, actually need not be equivalent to Identification Division
Sensor part electrode pattern and wiring lead contraposition (alignment).
As follows for solving the preferred scope of the invention and of the invention of the specific mode of above-mentioned problem.
[1] a kind of manufacture method of circuit layout, it include following (a) process, (b) process, (c) process, (d) process,
(e) process and (z) process,
(a) process, x is set to more than 2 integer, to a surface with base material and from base material successively with xth layer
To the circuit forming board of the 1st layer of conductive layer, the position being exposed is formed on the 1st layer of conductive layer and is dissolved in developer solution
Positive light sensitivity material;
(b) process, pattern exposure and development are carried out to the circuit forming board formed with positive light sensitivity material, and will just
Type photosensitive material is set to the 1st pattern;
(c) process, i is set to more than 1 and below x integer, the 1st pattern is set to for not formed in (b) process
The 1st layer to i-th layer of the conductive layer of positive light sensitivity material area is etched;
(d) process, to the positive light sensitivity material remained in (b) process, with the positive light sensitivity material remained
Different patterns carries out pattern exposure and development, and positive light sensitivity material is set into the 2nd pattern;
(e) process, 1 integer less than i is set to by j, and the 2nd pattern is set to for not formed in (d) process
The 1st layer of the conductive layer of positive light sensitivity material area to jth layer is etched;
(z) process, all positive light sensitivity materials remained are removed, forms the conductive layer comprising at least two kinds of patterns
Circuit layout.
[2] manufacture method of the circuit layout according to [1], preferred circuit distribution are the circuit layout of input unit.
[3] manufacture method of the circuit layout of the input unit according to [2], preferably input unit is touch panel.
[4] manufacture method of the circuit layout according to any one of [1]~[3], preferred circuit distribution include only 2
The conductive layer of kind pattern.
[5] manufacture method of the circuit layout according to any one of [1]~[4], preferably also includes following (f) work
Sequence,
(f) process, to the positive light sensitivity material remained, with the pattern different from the positive light sensitivity material remained
Pattern exposure and development are carried out, after developing, to not forming the 1st layer of conductive layer of positive light sensitivity material area to being less than
J arbitrary layer is etched, and conductive layer is set into pattern.
[6] manufacture method of the circuit layout according to [5], preferably (f) process include following (f1) processes and (f2)
Process, and the conductive layer of at least three kinds of patterns is included,
(f1) process, the positive light sensitivity material that will be remained in (e) process, with the positive light sensitivity material remained
Different patterns carries out pattern exposure and development, and positive light sensitivity material is set into the 3rd pattern,
(f2) process, 1 integer less than j is set to by k, and the 3rd pattern is set to for not formed in (f1) process
The 1st layer of conductive layer of positive light sensitivity material area be etched to kth layer.
[7] manufacture method of the circuit layout according to any one of [1]~[6], is preferably being included in circuit layout
In the conductive layer with different types of pattern in, there is the conductive layer of at least one kind of pattern to include and share identical circuit diagram
More than 2 layers of conductive layer stack of case.
[8] according to the manufacture method of the circuit layout any one of [1]~[7], preferred substrates make on two surfaces
There is the conductive layer of xth layer to the 1st layer with x independently,
Base material sequentially or simultaneously forms circuit to the conductive layer for being formed at two surfaces.
[9] manufacture method of the circuit layout according to any one of [1]~[8], is preferably included:In (z) process
The process that dielectric film is formed on the circuit layout of formation;And
The process that new conductive layer is formed on dielectric film.
[10] manufacture method of the circuit layout according to any one of [1]~[9], preferably in xth layer to the 1st layer
At least one layer in conductive layer includes metal oxide.
[11] manufacture method of the circuit layout according to any one of [1]~[10], preferably includes following process:Enter
Exercise the processing that the part or all of luminous ray reflectivity of the conductive layer of xth layer to the 1st layer reduces.
[12] manufacture method of the circuit layout according to any one of [1]~[11], preferably positive light sensitivity material
For dry film photoresist.
[13] manufacture method of the circuit layout according to any one of [1]~[12], preferred substrates are sheet tree
Oil/fat composition.
[14] manufacture method of the circuit layout according to any one of [1]~[13], preferably positive light sensitivity material
Resin comprising naphthalene quinone di-azido compound and with phenolic hydroxyl group.
[15] manufacture method of the circuit layout according to any one of [1]~[13], preferably positive light sensitivity material
Comprising (A) composition and (B) light acid producing agent,
(A) composition is the polymer for the group protected with acidic group by sour decomposability base.
[16] manufacture method of the circuit layout according to [15], preferably (A) composition is the polymer comprising polymer
Composition, the polymer have carboxyl or the phenolic hydroxyl group protected sour construction unit a1 in the form of acetal.
[17] manufacture method of the circuit layout according to [15] or [16], preferably (A) composition are with by following logical
The polymer for the construction unit that formula A1 or formula A1 ' is represented,
Formula A1
[chemical formula 1]
In formula A1, R1And R2Separately represent hydrogen atom, alkyl or aryl, R1And R2In it is at least one be alkane
Base or aryl, R3Represent alkyl or aryl, R1Or R2Can be with R3Connect and form cyclic ether, R4Represent hydrogen atom or methyl;
Formula A1 '
[chemical formula 2]
In formula A1 ', R11And R12Separately represent hydrogen atom, alkyl or aryl, R11And R12In at least one be
Alkyl or aryl, R13Represent alkyl or aryl, R11Or R12Can be with R13Connect and form cyclic ether, R14Separately represent
Hydrogen atom, hydroxyl, halogen atom, alkyl, alkoxy, alkenyl, aryl, aralkyl, alkoxy carbonyl group, hydroxy alkyl, aryl carbonyl or
Cycloalkyl.
[18] manufacture method of the circuit layout according to any one of [15]~[17], preferably positive light sensitivity material
Containing two or more (A) composition, and
As (A) composition, contain the polymer with the construction unit represented by following formula A2 ';
Formula A2 '
[chemical formula 3]
In formula A2 ', R31And R32Separately represent hydrogen atom, alkyl or aryl, R31And R32In at least one be
Alkyl or aryl, R33Represent alkyl or aryl, R31Or R32Can be with R33Connect and form cyclic ether, R34Represent hydrogen atom or first
Base, X0Represent singly-bound or arlydene.
[19] manufacture method of the circuit layout according to any one of [1]~[18], preferably in positive light sensitivity material
In material, the amount with the compound of ethylenic unsaturated bond is 0 mass %.
[20] manufacture method of the circuit layout according to any one of [1]~[19], preferably positive light sensitivity material
Include the compound containing (C) miscellaneous cyclic compound.
[21] manufacture method of the circuit layout according to [20], preferably (C) miscellaneous cyclic compound are with epoxy radicals
Compound.
[22] manufacture method of the circuit layout according to any one of [1]~[21], preferably positive light sensitivity material
Also include alkali compounds.
[23] manufacture method of the circuit layout according to any one of [1]~[22], preferably positive light sensitivity material
Also include radiation absorbance agent.
[24] manufacture method of the circuit layout according to any one of [1]~[23], preferably positive light sensitivity material
Including photo-sensitive resin and contrast enhancing layer.
[25] manufacture method of the circuit layout according to any one of [1]~[24], preferably xth layer is to the 1st layer
Conductive layer includes material different from each other.
[26] a kind of circuit layout, it is made by the manufacture method of the circuit layout any one of [1]~[25]
Make.
[27] a kind of input unit, the circuit layout described in [26] is it used.
[28] input unit according to [27], is preferably capacitance type touch panel.
[29] a kind of display device, it possesses the input unit described in [27] or [28].
Invention effect
In accordance with the invention it is possible to the conductive layer comprising multiple patterns can be formed by providing a kind of formed with the etchant resist of 1 time
Circuit layout and manufacture efficiency is excellent, and do not need multiple patterns conductive layer contraposition circuit layout manufacture method.
The manufacture method of the circuit layout is particularly suitable for use in touch panel.
In accordance with the invention it is possible to a kind of manufacture method of the circuit layout excellent using above-mentioned manufacture efficiency is provided and manufactured
Circuit layout, used the input unit of the circuit layout, possessed the display device of the input unit.
Brief description of the drawings
Fig. 1 is one of the manufacture method for the touch panel circuit layout for being denoted as one of embodiments of the present invention
Schematic diagram.
Fig. 2 be as being 2 in x in the case of one of obtained embodiments of the present invention, touch panel matched somebody with somebody with circuit
The diagrammatic cross-section of one of line.
Fig. 3 be as being 2 in x in the case of one of obtained embodiments of the present invention, touch panel matched somebody with somebody with circuit
The schematic diagram of one of line.
Fig. 4 is the schematic diagram for representing pattern A.
Fig. 5 is the schematic diagram for representing pattern B.
Fig. 6 is the schematic diagram for representing pattern C.
Fig. 7 is the schematic diagram for representing pattern D.
Fig. 8 is the schematic diagram for representing pattern E.
Fig. 9 is that the section of one of the configuration for pad portion and coupling part and the insulating barrier for representing first electrode pattern shows
It is intended to.
Figure 10 is the signal of one of the configuration for pad portion and coupling part and the insulating barrier for representing first electrode pattern
Figure.
Figure 11 is one of the configuration of the pad portion and coupling part and second electrode pattern that represent first electrode pattern
Diagrammatic cross-section.
Figure 12 is one of the configuration of the pad portion and coupling part and second electrode pattern that represent first electrode pattern
Schematic diagram.
Figure 13 is the schematic diagram for representing pattern F.
Figure 14 is the schematic diagram for representing pattern G.
Figure 15 is the schematic diagram for representing pattern H.
Figure 16 is the diagrammatic cross-section for the structure of one for representing the input unit of the present invention.
Figure 17 is the schematic diagram for representing pattern I.
Figure 18 is the schematic diagram for representing pattern J.
Figure 19 is as one of embodiments of the present invention, repaired according to position with different types of metal, and
Can suppress be coated with solder when corrosion circuit layout the diagrammatic cross-section of one.
Embodiment
Hereinafter, illustrate on the manufacture method of circuit layout of the invention, circuit layout, input unit, especially close
In the input unit as touch panel and the display device of the input unit has been used to illustrate.
The explanation of described constitutive requirements is carried out according to the representative embodiments and concrete example of the present invention below
, but the present invention is not limited to the embodiment and concrete example.In addition, in this manual, the numerical value represented with "~"
Scope refer to using the numerical value being recorded in before and after "~" as lower limit and higher limit and including scope.
[manufacture method of circuit layout]
The present invention circuit layout manufacture method be include following (a) process, (b) process, (c) process, (d) process,
(e) manufacture method of the circuit layout of process and (z) process,
(a) process, x is set to more than 2 integer, to a surface with base material and from base material successively with xth layer
To the circuit forming board of the 1st layer of conductive layer, the position being exposed is formed on the 1st layer of conductive layer and is dissolved in developer solution
Positive light sensitivity material;
(b) process, pattern exposure and development are carried out to the circuit forming board formed with positive light sensitivity material, and will just
Type photosensitive material is set to the 1st pattern;
(c) process, i is set to more than 1 and below x integer, the 1st pattern is set to for not formed in (b) process
The 1st layer to i-th layer of the conductive layer of positive light sensitivity material area is etched;
(d) process, to the positive light sensitivity material remained in (b) process, with the positive light sensitivity material remained
Different patterns carries out pattern exposure and development, and positive light sensitivity material is set into the 2nd pattern;
(e) process, 1 integer less than i is set to by j, and the 2nd pattern is set to for not formed in (d) process
The 1st layer of the conductive layer of positive light sensitivity material area to jth layer is etched;
(z) process, all positive light sensitivity materials remained are removed, forms the conductive layer comprising at least two kinds of patterns
Circuit layout.
According to said structure, the manufacture method of circuit layout of the invention with the etchant resist of 1 time because can be formed to be formed
The circuit layout of conductive layer comprising multiple patterns and manufacture efficiency is excellent, and do not need multiple patterns conductive layer contraposition,
Therefore it is applied to input unit, especially touch panel.In the manufacture method of the circuit layout of the present invention, preferred circuit distribution is
The circuit layout of input unit.Moreover, in the manufacture method of the circuit layout of the input unit of the present invention, preferred input unit
For touch panel.
Hereinafter, the preferred embodiment on the manufacture method of the circuit layout of the present invention illustrates.
< entirety processes >
First, the manufacture method of the circuit layout of the present invention is illustrated.
The one of manufacture method that one of embodiments of the present invention are shown as in Fig. 1, touch panel circuit layout
Example.
In one of the manufacture method of the touch panel circuit layout shown in Fig. 1, except (a) process, (b) process,
(c) process, (d) process, (e) process and (z) process, arbitrary (f) process is also recorded.
(a) in process, positive light sensitivity material 20 is formed on the 1st layer of conductive layer.The positive light sensitivity material is at it
In (b) afterwards, (c), (d), (e) and (f) process remain at least a portion, finally in (z) process to remained it is all just
Type photosensitive material is removed, so as to form the circuit layout of the conductive layer comprising at least two kinds of patterns.That is, can be with 1 time
Etchant resist to form the circuit layout of the conductive layer comprising multiple patterns.
(b) pattern exposure and development are carried out in process, so as to which positive light sensitivity material is set into the 1st pattern.
(c) in process, the conduction for not forming the positive light sensitivity material area for being set to the 1st pattern in (b) process
The 1st layer to i-th layer of layer is etched.In Fig. 1, i=x is set in (c) process, the 1st layer to all of xth layer is led
Electric layer is etched and removed.
1st layer to i-th layer of pattern of the conductive layer obtained in (c) process, finally carry out removing institute to (z) process
Having will not remain during positive light sensitivity material, in (f) process that can be carried out by the etching in (e) process and as needed
Etch and turn into another pattern.In the construction shown in fig. 1, the 1st layer to i-th layer of the conductive layer obtained in (c) process
Pattern is recorded as 7 posts, but turns into another pattern from the etching in right the 3rd, 4 and the 5th major gene (e) process of number, from
Right the 1st, 2 and the 6th post of number also turns into another pattern because of the etching in (f) process, carries out final (z) process and removes institute
When having positive light sensitivity material, turn into only surplus from the 7th pattern of right number.
(d) in process, to the positive light sensitivity material remained in (b) process, with the positive light sensitivity material remained
Expect that different patterns carries out pattern exposure and development, so as to which positive light sensitivity material is set into the 2nd pattern.
(e) in process, the conductive layer for not forming the positive light sensitivity material area for being set to the 2nd pattern in (d) process
The 1st layer be etched to jth layer.In Fig. 1, j=x-1 and j=i-1 are set in (e) process, and to the 1st layer to
The conductive layer of x-1 layers (jth layer) is etched and removed, and only leaves xth layer.
In Fig. 1, the detailed description of (f) process is eliminated, but (f) process of required number can be repeated.
(z) in process, all positive light sensitivity materials remained are removed, so as to be formed comprising at least two kinds of figures
The circuit layout of the conductive layer of case.Show that finally positive light sensitivity material is all removed after (z) process in Fig. 1.
On the other hand, it is not seen in fig. 1, but the present invention circuit layout manufacture method, it is also preferred that base material exists
Two surfaces conductive layer with xth layer to the 1st layer using x independently, and to being formed on two surfaces of base material
Conductive layer sequentially or simultaneously form circuit.Touch panel circuit layout can be formed according to said structure, it is in base material
One surface forms first electrode pattern, and forms second electrode pattern on another surface.Also, it is also preferred that with volume to volume
Mode forms the touch panel circuit layout of said structure from the two sides of base material.
On using positive light sensitivity material to be inputted as capacitance type obtained from etching resist (etched pattern)
The situation of the conductive layer pattern of device illustrates.
Capacitive input device preferably has base material (front panel or film substrate), and in the non-contact side of base material extremely
There is the important document of following (2)~(5) less, and formed by the manufacture method of the circuit layout of the present invention in (2), (3) and (5)
At least one.
(2) multiple pad portions extend in a first direction the multiple first electrode patterns to be formed via coupling part
(3) it is electrically insulated with above-mentioned first electrode pattern, and is formed including extending along the direction intersected with above-mentioned first direction
Multiple pad portions multiple second electrode patterns
(4) insulating barrier that above-mentioned first electrode pattern and above-mentioned second electrode pattern are electrically insulated
(5) electrically connected with least one in above-mentioned first electrode pattern and above-mentioned second electrode pattern, and with above-mentioned
One electrode pattern and the different electric conductivity important document of above-mentioned second electrode pattern
Hereinafter, the detailed content on each operation illustrates.
< (a) processes >
Illustrated on (a) process:X is set to more than 2 integer, and to a surface with base material and from base material
There is xth layer successively to the circuit forming board of the 1st layer of conductive layer, the position being exposed is formed on the 1st layer of conductive layer
The positive light sensitivity material being dissolved in developer solution.
X be more than 2 integer, preferably 2 or 3, more preferably 2.
Shown in Fig. 2 x be 2 in the case of one of obtained embodiments of the present invention, touch panel circuit layout
The diagrammatic cross-section of one.In Fig. 2, formed with first electrode pattern 3 on base material 1, on first electrode pattern formed with
Another electric conductivity important document 6.The touch panel shown in Fig. 2 includes the conductive layer of following 2 kinds of patterns with circuit layout:Formed with
The conductive layer stack of one electrode pattern 3 and another electric conductivity important document;And only there is the conductive layer of first electrode pattern 3.
If such as Fig. 2 touch panel circuit layout, such as Fig. 3 from oblique upper.Touch panel electricity consumption shown in Fig. 3
In one of road distribution, Fig. 3 dotted portion is laminated formed with the conductive layer of first electrode pattern 3 and another electric conductivity important document
Body, the part that Fig. 3 quadrangle is connected is the conductive layer for only having first electrode pattern 3.Circuit thus by the present invention is matched somebody with somebody
Circuit layout obtained from the manufacture method of line preferably comprises the conduction with different types of pattern included in circuit layout
There is more than 2 layers of conductive layer stack of the shared identical circuit pattern of conductive layer of at least one kind of pattern in layer.
(base material)
Base material is preferably glass baseplate or film substrate, more preferably film substrate.In touch panel circuit layout
In the case of, in the manufacture method of the circuit layout of the present invention, particularly preferred base material is sheet resin combination.
Also, base material is preferably transparent.
In addition, transparent in this manual refer to that the average transmittance in wavelength 400nm~700nm visible ray is 80%
More than.So as to which transparent layer refers to the layer that the average transmittance in wavelength 400nm~700nm visible ray is more than 80%.Thoroughly
Bright layer is preferably more than 90% in the average transmittance of wavelength 400nm~700nm visible ray.
The refractive index of base material is especially preferably 1.50~1.52.
Base material can be made up of transparent bases such as glass baseplates.As base material, can use with Corning
Incorporated Co., Ltd. Gorilla glass are strengthened glass of representative etc..Also, as the transparent base, energy
Enough it is preferably used in Japanese Unexamined Patent Publication 2010-86684 publications, Japanese Unexamined Patent Publication 2010-152809 publications and Japanese Unexamined Patent Publication 2010-
The material used in No. 257492 publications.
In the case of using film substrate as base material, the film substrate and transparency of no optical distortion are more preferably used
High film substrate, as specific raw material, PET (polyethylene can be enumerated
terephthalate;PET), PEN, makrolon, triacetyl cellulose and cyclic olefin polymer.
(conductive layer)
As the conductive layer of xth layer to the 1st layer, common circuit layout can be enumerated and be used in touch panel distribution
Arbitrary conductive layer.
As the material of conductive layer, metal and metal oxide etc. can be enumerated.
In the manufacture method of the circuit layout of the present invention, the conductive layer of xth layer to the 1st layer can be identical material,
It can be material different from each other, but preferably comprise material different from each other.
In the manufacture method of the circuit layout of the present invention, at least one layer preferably in the conductive layer of xth layer to the 1st layer includes
Metal oxide.
As in this case used metal oxide, ITO, IZO, SiO can be enumerated2Deng metal oxide film etc..Close
It will be carried out in metal oxide aftermentioned.
As conductive layer, first electrode pattern in aftermentioned capacitive input device, second preferably can be used
Electrode pattern and aftermentioned another electric conductivity important document.
On the preferred embodiment of other conductive layers, described in the explanation of the capacitive input device below.
(positive light sensitivity material)
The positive light sensitivity material being dissolved in the present invention using the position being exposed in developer solution.In the past, because photosensitive
The difference of the photosensitive system of property resin combination and be divided into:Irradiate photoactinic part as image and the minus that remains and
The eurymeric photoactinic part will not be irradiated be set to image and remained.In eurymeric, by irradiating actinic ray, such as using
Irradiation actinic ray and produce emulsion etc. of acid to improve the dissolubility of exposure portion, therefore in pattern exposure moment exposure portion and
Unexposed portion is uncured, in the case where resulting pattern form is bad, can be reused (again by whole face exposure etc.
Processing) base material.Therefore, from the viewpoint of so-called re-workability is excellent, preferably using eurymeric.
Also, as the present invention it is main points, the resist remained be exposed again and make different patterns
Technology, if not eurymeric resist, then can not realize.
Can be the coated film or dry film photoresist of positive light sensitivity composition as positive light sensitivity material,
Known material can be used.
In the manufacture method of the circuit layout of the present invention, positive light sensitivity material is preferably dry film photoresist.Resist in dry film
Lose in agent, it is however preferred to have temporary support and the photonasty of the photosensitive polymer combination layer as positive light sensitivity material turn
Print material.
In the case where positive light sensitivity material is photosensitive transfer printing material, it is also preferred that having temporary support, heat successively
Plastic resin layers and photosensitive polymer combination layer, there can also be other layers such as cover layer.On the preferred of temporary support
Mode, record [0017]~[0018] of Japanese Unexamined Patent Publication 2014-85643 publications, the preferred side on thermoplastic resin layer
Formula, [0189]~[0193] of Japanese Unexamined Patent Publication 2014-85643 publications is recorded, on other layers of preferred embodiment, is recorded
[0194] of Japanese Unexamined Patent Publication 2014-85643 publications~[0196], the content of the publication are incorporated in this specification.
The positive light sensitivity material of photosensitive transfer printing material is preferably used as to carry out (a) process.
Photosensitive transfer printing material can be with institute in the paragraph of [0094] of Japanese Unexamined Patent Publication 2006-259138 publications~[0098]
Made on the basis of the preparation method of the photosensitive transfer printing material of record.
Specifically, in the case of the photosensitive transfer printing material in forming the present invention with intermediate layer, preferably propping up
Coating thermoplastic organic polymer and the lysate (thermoplastic resin layer coating fluid) of additive is dissolved on support body, and made it
Dry after thermoplastic resin layer is set, in the thermoplastic resin layer, be coated on the solvent of insoluble thermoplastic resin layer
Middle addition resin and additive and prepare prepare solution (intermediate layer coating fluid), and it is dried and is laminated intermediate layer.It is excellent
The photosensitive polymer combination layer coating fluid that coating is prepared using the solvent in insoluble intermediate layer again on the intermediate layer is selected,
And it is set to dry and be laminated photosensitive polymer combination layer.
In the case that positive light sensitivity material as photosensitive transfer printing material has above-mentioned cover layer, preferably have from just
Type photosensitive material removes the cover layer removing step of above-mentioned cover layer.
(a) photosensitive polymer combination for the photosensitive transfer printing material that cover layer is preferably removed by process, which is needed on, leads
Process on the 1st layer of electric layer.
Now, after preferably the photosensitive polymer combination of photosensitive transfer printing material is laminated on the 1st layer of conductive layer
The method for removing temporary support.
Photosensitive transfer printing material is to the transfer (fitting) on the 1st layer of conductive layer, preferably by by photosensitive resin composition
Thing is overlapped in the 1st layer of the conductive layer upper and method being pressurizeed and heated to carry out.Laminating machine, vacuum can be used in fitting
Laminating machine and it can further carry laminating machine known to large-duty surface trimming laminating machine etc..
As the preferred embodiment of positive light sensitivity material, can enumerate:1st preferred embodiment, include the nitrine chemical combination of naphthoquinones two
Thing and the resin with phenolic hydroxyl group;And the 2nd preferred embodiment, positive light sensitivity material includes (A) composition and (B) light acid produces
Agent, (A) composition are the polymer for the group that there is acidic group to be protected by sour decomposability base.
Hereinafter, the material on the positive light sensitivity material used in each preferred embodiment illustrates.
- the 1st preferred embodiment of positive light sensitivity material-
First, the 1st preferred embodiment on positive light sensitivity material illustrates.
The preferred positive light sensitivity material of manufacture method of the circuit layout of the present invention includes naphthalene quinone di-azido compound and tool
There is the resin of phenolic hydroxyl group.
-- resin with phenolic hydroxyl group --
As the resin with phenolic hydroxyl group, for example, novolac resin and cresol novolac resin etc.,
Wherein, from the viewpoint of development latitude is wide, particularly preferably containing cresol novolac resin and the azido derivant of naphthoquinones two this 2
Kind.
As novolac resin, the novolaks that the mol ratio preferably with respect to the formaldehyde of phenol is 0.5~1.0 or so
Resin, from the viewpoint of developability and burning are viscous, further preferred 0.8~1.0 or so novolac resin.Also, as
The weight average molecular weight of above-mentioned novolac resin, preferably 300~4000, especially preferably 400~800.
Above-mentioned novolac resin can also be their derivative.
Above-mentioned novolac resin can be used alone, can also be used in mixed way weight average molecular weight different 2 kinds with
On, in the range of the purpose of the present invention is not damaged, it can also mix and use with other resins such as cresol novolac resin.
As the content of above-mentioned novolac resin, relative to the total solid content amount in positive type light sensitive layer, preferably 40
~90 mass %, more preferably 60~80 mass %.
-- cresol novolac resin --
As above-mentioned cresol novolac resin, the mol ratio preferably with respect to the formaldehyde of cresols is 0.7~1.0 or so
Cresol novolac resin, further preferred 0.8~1.0 or so cresol novolac resin.Also, as above-mentioned cresols phenol
The weight average molecular weight of Novolac resin, preferably 800~8,000, more preferably 1000~6000.
The ratio between isomers of above-mentioned cresol novolac resin (mol ratio of ortho position body/meta body/contraposition body) has no spy
Other limitation, can suitably it be selected according to purpose, from the viewpoint of developability is improved, relative to total isomers
The ratio for aligning body is preferably 10 moles of more than %, more preferably 20 moles of more than %.Also, from raising liquid crystal panel
Can be from the viewpoint of (burn viscous prevent performance), the ratio of meta body is preferably 5 moles of more than %, more preferably 20 moles of % with
On.
Above-mentioned cresol novolac resin can be used alone, and can be used as mixture of more than two kinds and uses.
In this case, it can mix and use with other resins such as novolaks.
Also, in the present invention, it can be used and naphthalene quinone di-azide sulfonic acid ester as above-mentioned cresol novolac resin
The derivative of the cresol novolac resins such as reaction product.
As the usage amount of above-mentioned cresol novolac resin, preferably 0.1~10g/m2, more preferably 0.5~5g/m2。
-- naphthalene quinone di-azido compound --
Above-mentioned naphthalene quinone di-azido compound is not particularly limited, and can suitably be selected according to purpose, but especially
It is preferably used in combination with cresol novolac resin.Naphthalene quinone di-azido compound can be 1 functional compound or 2 officials
Compound more than energy, can also be their mixture.
As above-mentioned 1 function naphthalene quinone di-azido compound, for example, make naphthoquinones -4- sulfonic acid chlorides or naphthoquinones -5- sulphurs
Ester compounds that acyl chlorides is reacted with fortified phenol etc..
As naphthalene quinone di-azido compound more than above-mentioned 2 function, preferably for example make naphthoquinones -4- sulfonic acid chlorides or naphthoquinones -5-
The ester compounds that sulfonic acid chloride is reacted with the compound with multiple phenolic hydroxyl group.As with multiple above-mentioned phenolic hydroxyl group
Compound, for example, the Polyphenols such as bisphenols, three phenols, four phenols;The multifunctional benzene such as dihydroxy benzenes, trihydroxy benzene
Phenol;Dimorphism or three type dihydroxy benzenes or trihydroxy benzene, asymmetrical polynuclear phenol or their mixture etc..
As the compound with multiple above-mentioned phenolic hydroxyl group, for example, 4-TBP, 4- isoamyl benzenes
Phenol, 4- tert-octyl phenols, 2- isopropyl -5- methylphenols, 2- acetyl phenols, 4- dihydroxy benaophenonels, 3- chlorophenols, 4- benzyloxies
Base carbonyl phenol, 4- dodecyl phenols, resorcinol, 4- (1- methyl isophthalic acids-phenylethyl) -1,3- Benzenediols, phloroglucin,
Double (the 3- first of 4,4 '-dihydroxy benaophenonel, double (4- hydroxy phenyls) methane, 1,1-bis(4-hydroxyphenyl)-cyclohexane, 2,2-
Base -4- hydroxy phenyls) methane, 2,3,4,4 '-tetrahydroxybenzophenone, 4,4 '-[(4- hydroxy phenyls) methylene] double [2- hexamethylenes
Base -5- methylphenols] etc..
As above-mentioned naphthalene quinone di-azido compound, for example, the nitrine -4- sulfonic acid of 4 '-t-octyl phenyl naphthoquinones two
Ester, the nitrine -5- sulphonic acid esters of 4 '-t-octyl phenyl naphthoquinones two, the nitrine -5- sulphonic acid esters of 4 '-benzoylphenyl naphthoquinones two, 2,3,4,
Reactant of 4 '-tetrahydroxybenzophenone and the nitrine -5- sulfonic acid chlorides of 1,2- naphthoquinones two etc..They can be used alone, and also may be used
With and use two or more.
The addition of naphthalene quinone di-azido compound in positive light sensitivity material is relative to above-mentioned cresol novolac resin
100 mass parts, preferably 1~200 mass parts, more preferably 5~50 mass parts.
In 1st preferred embodiment of other positive light sensitivity materials, as additive, it can use in Japanese Unexamined Patent Publication 2007-
Described material, the content of the publication are incorporated into this specification in [0072] of No. 24969 publications~[0083].
Also, in the 1st preferred embodiment of positive light sensitivity material, it can also use in aftermentioned positive light sensitivity material
Described material in 2nd preferred embodiment.
- the 2nd preferred embodiment of positive light sensitivity material-
The 2nd preferred embodiment on positive light sensitivity material illustrates.
In the manufacture method of the circuit layout of the present invention, preferably positive light sensitivity material includes (A) composition and (B) light acid
Producing agent, (A) composition are the polymer for the group protected with acidic group by sour decomposability base.
< (A) composition:The polymer > for the base protected with acidic group by sour decomposability base
(A) composition is preferably the polymer for the base protected with acidic group by sour decomposability base.
Moreover, in the manufacture method of the circuit layout of the present invention, more preferably (A) composition is the polymer comprising polymer
Composition, the polymer have carboxyl or the phenolic hydroxyl group protected sour construction unit a1 in the form of acetal.
Positive light sensitivity material can also include polymer in addition.
< < construction unit (a1) > >
Above-mentioned (A) composition has the group that acidic group is protected by sour decomposability base, preferably with carboxyl or phenolic hydroxyl group to contract
The protected sour construction unit a1 of form of aldehyde, thus, it is possible to be set to extremely highly sensitive positive light sensitivity material.
As the acidic group in " group that acidic group is protected by sour decomposability base " in the present invention and sour decomposability base, can make
Be used as acidic group and sour decomposability base and known base, there is no particular limitation.As specific acidic group, carboxylic can be preferably enumerated
Base and phenolic hydroxyl group.Also, as sour decomposability base, it can use with acid compared to being easier the group of decomposition (such as by rear
State the acetals functional groups such as ester structure, oxinane ester group or the tetrahydrofuran ester group of group that formula (A1) or formula (A1 ') represent)
With the base (such as the carbonic acid trialkyl such as the tertiary alkyl such as tert-butyl ester base, t-butyl carbonate base ester) of the less susceptible decomposition compared with acid.
The construction unit (a1) for the group protected with acidic group by sour decomposability base is preferably with by sour decomposability base guarantor
The construction unit of the protection phenolic hydroxyl group of shield, or with by the construction unit of the protection carboxyl of sour decomposability base protection.
The construction unit (a1) for the group that positive light sensitivity material is more preferably protected with above-mentioned acidic group by sour decomposability base
For the construction unit with carboxyl or the phenolic hydroxyl group protected group in the form of acetal.
Hereinafter, on the construction unit with the protection phenolic hydroxyl group protected by sour decomposability base and with by sour decomposability
The construction unit of the protection carboxyl of base protection, is illustrated successively.
< < < have by the construction unit > > > of the protection phenolic hydroxyl group of sour decomposability base protection
Construction unit with the protection phenolic hydroxyl group protected by sour decomposability base refers to there is the structure list of phenolic hydroxyl group
Member is by sour decomposability base described further below and the construction unit of protected protection phenolic hydroxyl group.
As the construction unit with above-mentioned phenolic hydroxyl group, from the viewpoint of sensitivity, hydroxy benzenes second is preferably derived from
The hydroxyl of the construction unit of alkene or Alpha-Methyl hydroxy styrenes (such as construction unit in novolaks resinoid) passes through acid point
Xie Xingji and protected construction unit, from the viewpoint of further also resolution ratio is improved, more preferably have by following logical
The polymer for the construction unit that formula A1 or formula A1 ' is represented.
Formula A1
[chemical formula 4]
In formula A1, R1And R2Separately represent hydrogen atom, alkyl or aryl, R1And R2In it is at least one be alkane
Base or aryl, R3Represent alkyl or aryl, R1Or R2Can be with R3Connect and form cyclic ether, R4Represent hydrogen atom or methyl.
In above-mentioned formula A1, in R1And R2In the case of for alkyl, the preferably alkyl of carbon number 1~10.R1And R2For
In the case of aryl, preferably phenyl.R1And R2The alkyl of hydrogen atom or carbon number 1~4 is respectively preferably, more preferably at least
One is hydrogen atom.
In above-mentioned formula A1, R3Represent the alkyl of alkyl or aryl, preferably carbon number 1~10, more preferably carbon atom
The alkyl of number 1~6.
R1Or R2Can be with R3Connect and form cyclic ether, R1Or R2It is preferred that with R3Connect and form cyclic ether.Above-mentioned ring-type
First prime number of the composition ring of ether is not particularly limited, preferably 5 or 6, more preferably 5.
In above-mentioned formula A1, R4Represent hydrogen atom or methyl, preferably hydrogen atom.
Formula A1 '
[chemical formula 5]
In formula A1 ', R11And R12Separately represent hydrogen atom, at least alkyl or aryl, R11And R12In one be
Alkyl or aryl, R13Represent alkyl or aryl, R11Or R12Can be with R13Connect and form cyclic ether, R14Separately represent
Hydrogen atom, hydroxyl, halogen atom, alkyl, alkoxy, alkenyl, aryl, aralkyl, alkoxy carbonyl group, hydroxy alkyl, aryl carbonyl or
Cycloalkyl.
In above-mentioned formula A1 ', R11And R12In the case of for alkyl, preferably carbon number is 1~10 alkyl.R11And R12
In the case of for aryl, preferably phenyl.R11And R12The alkyl of hydrogen atom or carbon number 1~4 is respectively preferably, more preferably
At least one is hydrogen atom.
In above-mentioned formula A1 ', R13Represent the alkyl of alkyl or aryl, preferably carbon number 1~10, more preferably carbon original
The alkyl of subnumber 1~6.
R11Or R12Can be with R13Connect and form cyclic ether.
In above-mentioned formula A1 ', R14Represent hydrogen atom or methyl, preferably hydrogen atom.
It is upper as that can be used in by the construction unit of the protection phenolic hydroxyl group of above-mentioned sour decomposability base protection
Sour decomposability base is stated, known sour decomposability base can be used, there is no particular limitation.In sour decomposability base, from positive type light sensitive
The basic physical properties of property material, especially from sensitivity and pattern form, positive light sensitivity material storage stability from the viewpoint of,
Preferably have by the construction unit of the protection phenolic hydroxyl group of acetal protection.Moreover, from the viewpoint of sensitivity, decomposed in acid
Property base in, more preferably phenolic hydroxyl group in the form of the acetal represented by following formulas (a1-10) it is protected protection phenol hydroxyl
Base.In addition, feelings of the phenolic hydroxyl group for the protected protection phenolic hydroxyl group in the form of the acetal represented by following formulas (a1-10)
Under condition, protecting the entirety of phenolic hydroxyl group turns into-Ar-O-CR101R102(OR103) structure.In addition, Ar represents arlydene.
Formula (a1-10)
[chemical formula 6]
(in formula (a1-10), R101And R102Hydrogen atom or alkyl are separately represented, but excludes R101And R102It is hydrogen
The situation of atom.R103Represent alkyl.R101Or R102Can be with R103Connect and form cyclic ether.)
In above-mentioned formula (a1-10), R101~R103Separately represent that hydrogen atom or alkyl, abovementioned alkyl can be straight
Any of chain, branched, ring-type.Here, R101And R102Hydrogen atom, R will not be represented simultaneously101And R102In at least one
Individual expression alkyl.
In above-mentioned formula (a1-10), in R101、R102And R103In the case of representing alkyl, abovementioned alkyl can be straight chain
Any one in shape, branched or ring-type.
As the alkyl of above-mentioned straight-chain or branched, preferably carbon number is 1~12, more preferably carbon number be 1~
6, further preferred carbon number is 1~4.Specifically, methyl, ethyl, n-propyl, isopropyl, normal-butyl, different can be enumerated
It is butyl, sec-butyl, the tert-butyl group, n-pentyl, neopentyl, n-hexyl, cyclohexyl (2,3- dimethyl -2- butyl), n-heptyl, just pungent
Base, 2- ethylhexyls, n-nonyl, positive decyl etc..
As above-mentioned cyclic alkyl, preferably carbon number is 3~12, and more preferably carbon number is 4~8, further preferably
Carbon number is 4~6.As above-mentioned cyclic alkyl, such as cyclopropyl, cyclobutyl, cyclopenta, cyclohexyl, cycloheptyl can be enumerated
Base, cyclooctyl, norborny and different camphyl etc..
Abovementioned alkyl can have substituent, as substituent, can exemplify halogen atom, aryl and alkoxy.As
Substituent and with the case of halogen atom, R101、R102、R103As haloalkyl, there is aryl as substituent
Under, R101、R102、R103As aralkyl.
As above-mentioned halogen atom, fluorine atom, chlorine atom, bromine atoms and iodine atom are exemplified, wherein, preferably fluorine atom or chlorine
Atom.
Also, as above-mentioned aryl, preferably carbon number is 6~20 aryl, and more preferably carbon number is 6~12, tool
For body, benzyl, α-methylbenzyl, naphthyl etc. can be exemplified, can as the overall i.e. aralkyl of the alkyl being substituted with aryl
Illustrate benzyl, α-methylbenzyl, phenethyl and menaphthyl etc..
As above-mentioned alkoxy, preferably carbon number is 1~6 alkoxy, and more preferably carbon number is 1~4, more preferably
Methoxy or ethoxy.
Also, in the case that abovementioned alkyl is cycloalkyl, above-mentioned cycloalkyl can have carbon number 1~10 as substituent
Straight-chain or branched alkyl, in the case that alkyl is the alkyl of straight-chain or branched, can have as substituent
There is the cycloalkyl of carbon number 3~12.
These substituents can also be substituted with such substituents as described above.
In above-mentioned formula (a1-10), R101、R102And R103In the case of representing aryl, the above-mentioned preferred carbon number of aryl is
6~12, more preferably carbon number is 6~10.Above-mentioned aryl can have substituent, as above-mentioned substituent, can exemplify
Carbon number is 1~6 alkyl.As aryl, such as phenyl, tolyl, silicyl, cumenyl and 1- naphthalenes can be exemplified
Base etc..
Also, R101、R102And R103It can bond together, ring is together formed with the carbon atom that they are bonded.As R101
With R102、R101With R103Or R102With R103Ring structure in the case of bonding, such as cyclobutyl, cyclopenta, hexamethylene can be enumerated
Base, suberyl, tetrahydrofuran base, adamantyl and THP trtrahydropyranyl etc..
In addition, in above-mentioned formula (a1-10), R101And R102In one be preferably hydrogen atom or methyl.
The preference of the acetal ester structure of phenolic hydroxyl group, can exemplify R101=methyl, R102=hydrogen atom, R103=second
The situation of base;R101=methyl, R102=hydrogen atom, R103=ethyl and R101And R103Bond together and form the feelings of 5 Yuans rings
Condition;R101=R102=R103The situation of=methyl;R101=R102=methyl and R103The situation of=benzyl.
Also, as in order to formed with phenolic hydroxyl group in the form of acetal it is protected protection phenolic hydroxyl group structure list
Member and the polymerizable monomer that uses, for example, remembered in 0042 paragraph of Japanese Unexamined Patent Publication 2011-215590 publications
Polymerizable monomer of load etc..
Wherein, from the viewpoint of the transparency, the preferably 1- alkoxyalkyls protection of 4- hydroxyphenylmethyls acrylate
The oxinane protective of body and 4- hydroxyphenylmethyl acrylate.
As the concrete example of the acetal protecting group of phenolic hydroxyl group, 1- alkoxyalkyls can be enumerated, such as 1- can be enumerated
Ethoxyethyl group, 1- methoxy ethyls, 1- n-butoxyethyls, 1- isobutoxyethies, 1- (2- chloroethoxies) ethyl, 1-
(2- ethyl hexyl oxies) ethyl, 1- positive propoxies ethyl, 1- cyclohexyloxies ethyl, 1- (2- cyclohexylethoxy radicals) ethyl, 1- benzyls
Epoxide ethyl etc., they can be used alone, or combine two or more and use.
There is the polymerization used by the construction unit of the protection phenolic hydroxyl group of above-mentioned sour decomposability base protection in order to be formed
Property monomer, can use commercially available polymerizable monomer, can also be synthesized by known method.Such as acid catalyst be present
In the case of, by making to have the compound of phenolic hydroxyl group to be reacted with vinyl ethers that can be synthesized.Can in above-mentioned synthesis
So that the monomer with phenolic hydroxyl group is copolymerized in advance with other monomers, afterwards, in the case where acid catalyst be present with second
Alkene ether is reacted.
As with by the preferable concrete example of the construction unit of the protection phenolic hydroxyl group of above-mentioned sour decomposability base protection, energy
Following construction units are enough exemplified, but the present invention is not limited to this.
[chemical formula 7]
[chemical formula 8]
[chemical formula 9]
In the polymer of construction unit (a1) for possessing the group protected with acidic group by sour decomposability base, have sour
The copolymerization ratios of the construction unit of the protection phenylol of decomposability base protection, relative to comprising with by sour decomposability base protection
The polymer of construction unit of protection phenylol be preferably 10~50%, more preferably 20~40%, especially preferably 25~
40 moles of %.
Also, (above-mentioned component of polymer is the situation of the mixture of polymer of more than two kinds by all component of polymer
Under, refer to all polymer included) resolve into construction unit (monomeric unit) on the basis of, relative to all construction units
It is mol numbers, to have acidic group by the ratio of the construction unit (a1) for the protection phenylol that sour decomposability base is protected be preferably 0~40
Mole %, more preferably 10~35 moles of %, especially preferably 15~30 moles of %.
< < < have by the construction unit > > > of the protection carboxyl of sour decomposability base protection
Construction unit with the protection carboxyl protected by above-mentioned sour decomposability base is to possess the construction unit with carboxyl
Carboxyl by sour decomposability base described further below and it is protected protection carboxyl construction unit.
As can be used in by the construction unit of the protection carboxyl of above-mentioned sour decomposability base protection with upper
The construction unit of carboxyl is stated, is not particularly limited, known construction unit can be used.For example, from insatiable hunger
With the knot of the unsaturated carboxylic acid with least one carboxyl etc. in the molecule such as monocarboxylic acid, unsaturated dicarboxylic, unsaturated tricarboxylic acids
Structure unit (a1-1-1), the construction unit (a1-1-2) with the structure for deriving from olefinic unsaturated group and acid anhydrides.
Hereinafter, on being used, from the molecule with least one as the construction unit with above-mentioned carboxyl
The construction unit (a1-1-1) of the unsaturated carboxylic acid of carboxyl etc. and the knot with the structure for deriving from olefinic unsaturated group and acid anhydrides
Structure unit (a1-1-2), is illustrated successively respectively.
< < < < derive from construction unit (a1-1-1) > in molecule with the unsaturated carboxylic acid of at least one carboxyl etc.
> > >
As the construction unit (a1-1-1) from the unsaturated carboxylic acid in above-mentioned molecule with least one carboxyl etc.
And the unsaturated carboxylic acid in the present invention is used in, the following unsaturated carboxylic acid enumerated can be used.That is, as unsaturated single carboxylic
Acid, for example, acrylic acid, methacrylic acid, crotonic acid, α-chloroacrylic acid, cinnamic acid, 2- (methyl) acryloxy
Ethyl-butanedioic acid, 2- (methyl) acryloyl-oxyethyls hexahydrophthalic acid, 2- (methyl) acryloyl-oxyethyl-adjacent benzene
Dioctyl phthalate etc..Also, as unsaturated dicarboxylic, for example, maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid
Deng.Also, in order to which the unsaturated polybasic carboxylic acid for obtaining the construction unit with carboxyl and using can be its acid anhydrides.It is specific and
Speech, can enumerate maleic anhydride, itaconic anhydride and citraconic anhydride etc..Also, unsaturated polybasic carboxylic acid can be polybasic carboxylic acid
Single (2- methacryloxyalkyls) ester, for example, mono succinate (2- acryloyl-oxyethyls) ester, mono succinate
(2- methylacryoyloxyethyls) ester, phthalic acid list (2- acryloyl-oxyethyls) ester, phthalic acid list (2- methyl-props
Alkene acyloxyethyl) ester etc..In addition, unsaturated polybasic carboxylic acid can be the list (methyl) third that two end is dicarboxyl based polyalcohol
Olefin(e) acid ester, for example, ω-carboxy-polycaprolactone mono acrylic ester, ω-carboxy-polycaprolactone monomethacrylates etc..
Also, as unsaturated carboxylic acid, it can also use acrylic acid -2- carboxylics ethyl ester, methacrylic acid -2- carboxylics ethyl ester, maleic acid list alkane
Base ester, monoalkyl esters, 4- carboxyl styrenes etc..
Wherein, from the viewpoint of developability, there is at least one carboxyl not in above-mentioned molecule in order to be formed to derive from
The construction unit (a1-1-1) of saturated carboxylic acid etc., preferably using acrylic acid, methacrylic acid, 2- (methyl) acryloxy second
Base-butanedioic acid, 2- (methyl) acryloyl-oxyethyls hexahydrophthalic acid, 2- (methyl) acryloyl-oxyethyl-adjacent benzene two
Formic acid or unsaturated polybasic acid anhydride etc., more preferably using acrylic acid, methacrylic acid, 2- (methyl) acryloyl-oxyethyl six
Hydrogen phthalic acid.
, can from the construction unit (a1-1-1) of the unsaturated carboxylic acid in above-mentioned molecule with least one carboxyl etc.
Individually to be formed by a kind, can also be made up of two or more.
< < < < have olefinic unsaturated group and the construction unit of the structure from acid anhydrides (a1-1-2) > > > >
The construction unit (a1-1-2) of structure with olefinic unsaturated group and from acid anhydrides, preferably deriving from makes tool
Have the hydroxyl in the presence of the construction unit of olefinic unsaturated group reacted with acid anhydrides obtained from monomer unit.
As above-mentioned acid anhydrides, known acid anhydrides can be used, specifically, maleic anhydride, succinic anhydride, clothing can be enumerated
The dibasic acid anhydrides such as health acid anhydrides, phthalic anhydride, tetrabydrophthalic anhydride, hexahydrophthalic anhydride, chlorosulfonic acid acid anhydride;Inclined benzene
The acid anhydrides such as three acid anhydrides, pyromellitic dianhydride, benzophenone tetracarboxylic anhydride, biphenyltetracarboxyacid acid acid anhydride.Wherein, examined from the viewpoint of developability
Consider, preferably phthalic anhydride, tetrabydrophthalic anhydride or succinic anhydride.
From the viewpoint of developability, above-mentioned acid anhydrides is preferably 10~100 moles of % to the reactivity of hydroxyl, more preferably
30~100 moles of %.
As the above-mentioned acid that can be used in by the construction unit of the protection carboxyl of above-mentioned sour decomposability base protection
Decomposability base, it can use what can be used in by the construction unit of the protection phenylol of above-mentioned sour decomposability base protection
Sour decomposability base.
In these sour decomposability bases, from the basic physical properties of positive light sensitivity material, especially from sensitivity and pattern form, just
From the viewpoint of the storage stability of type photosensitive material, preferably carboxyl protected protection carboxyl in the form of acetal.And
And in sour decomposability base, from the viewpoint of sensitivity, more preferably acetal of the carboxyl to be represented by above-mentioned formula (a1-10)
The protected protection carboxyl of form.In addition, it is to be protected in the form of the acetal represented by above-mentioned formula (a1-10) in carboxyl
Protection carboxyl in the case of, protect carboxyl entirety turn into-(C=O)-O-CR101R102(OR103) structure.
The polymerism list used to form the construction unit with the protection carboxyl represented by above-mentioned formula (a1-10)
Body, commercially available polymerizable monomer can be used, also can using by known method and the polymerizable monomer that synthesizes.Such as can
It is enough to be synthesized by described synthetic method in 0037~0040 paragraph of Japanese Unexamined Patent Publication 2011-221494 publications etc..
With by the construction unit of the protection carboxyl of above-mentioned sour decomposability base protection, examined from highly sensitive viewpoint is put forward
Consider, the construction unit preferably represented by following formula A2 '.In the manufacture method of the circuit layout of the present invention, preferred positive type light sensitive
Property material contain (A) composition of more than two kinds, and (A) composition is used as, containing tool by following formula A2 ' construction units represented
Polymer.
[chemical formula 10]
Formula A2'
(in formula A2 ', R31And R32Separately represent hydrogen atom, at least alkyl or aryl, R31And R32In one
For alkyl or aryl, R33Represent alkyl or aryl, R31Or R32Can be with R33Connect and form cyclic ether, R34Represent hydrogen atom or
Methyl, X0Represent singly-bound or arlydene.)
In above-mentioned formula A2 ', R31And R32In the case of for alkyl, preferably carbon number is 1~10 alkyl.R31And R32
In the case of for aryl, preferably phenyl.R31And R32Hydrogen atom or carbon number are respectively preferably as 1~4 alkyl.
In above-mentioned formula A2 ', R33Alkyl or aryl is represented, preferably carbon number is 1~10 alkyl, more preferably carbon atom
The alkyl of number 1~6.
In above-mentioned formula A2 ', R31Or R32Can be with R33Connect and form cyclic ether, preferably R31Or R32Can be with R33Connection
And form cyclic ether.First prime number of the composition ring of above-mentioned cyclic ether is not particularly limited, but preferably 5 or 6, more preferably 5.
In above-mentioned formula A2 ', R34Represent hydrogen atom or methyl, preferably hydrogen atom.
In above-mentioned formula A2 ', X0Represent singly-bound or arlydene, preferably singly-bound.
In the construction unit represented by above-mentioned formula A2 ', from the viewpoint of further raising sensitivity, more preferably under
State the construction unit of formula A2 " expressions.
[chemical formula 11]
Formula A2 "
(in formula, R121Represent hydrogen atom or carbon number for 1~4 alkyl, R122~R128Separately represent that hydrogen is former
Son or the alkyl that carbon number is 1~4.)
In above-mentioned formula A2 ", R121Preferably hydrogen atom or methyl.
In above-mentioned formula A2 ", R122~R128Preferably hydrogen atom.
, being capable of example as the preferable concrete example of the construction unit with the protection carboxyl protected by above-mentioned sour decomposability base
Following construction units are shown.In addition, R represents hydrogen atom or methyl.
[chemical formula 12]
In the polymer of construction unit (a1) for possessing the group protected with acidic group by sour decomposability base, have sour
The copolymerization ratios of the construction unit of the protection carboxyl of decomposability base protection, relative to comprising with by sour decomposability base protection
The polymer for protecting the construction unit of carboxyl is preferably 5~60 moles of %, more preferably 10~50 moles of %, and especially preferably 30
~50 moles of %.
Also, on the basis of all component of polymer are resolved into construction unit (monomeric unit), relative to all knots
Structure unit it is mol numbers, to have acidic group by the ratio of the construction unit (a1) for the protection carboxyl that sour decomposability base is protected be preferably 0
~60 moles of %, more preferably 10~50 moles of %, especially preferably 15~25 moles of %.
< < other structures unit > >
Above-mentioned (A) composition of above-mentioned positive light sensitivity material is except the group protected with above-mentioned acidic group by sour decomposability base
Construction unit (a1) beyond, can also have other structures unit (a3) in addition.These other structures units (a3)
The polymer being used in above-mentioned (A) composition can also be included, that is, possess the group protected with acidic group by sour decomposability base
The polymer of construction unit (a1) be used as copolymer composition.Also, it is used in having in above-mentioned (A) composition different from containing
The polymer of the construction unit (a1) for the group that acidic group is protected by sour decomposability base, do not contain actually and decomposed with acidic group by acid
Property base protection group construction unit (a1) and with other structures unit polymer, it is possible to have other structures unit
(a3)。
As the monomer as other structures unit (a3), be not particularly limited, can enumerate such as phenylethylene,
(methyl) alkyl acrylate, (methyl) acrylic acid cyclic alkyl ester, (methyl) benzyl acrylate, unsaturated dicarboxylic two
Ester, bicyclic unsaturated compound class, maleimide compound class, unsaturated aromatic compound, conjugated diene compound,
Unsaturated monocarboxylic, unsaturated dicarboxylic, unsaturated dicarboxylic acid anhydride and other unsaturated compounds.Also, as it is explained in detail hereinafter,
Can possess the construction unit with acidic group.Monomer as other structures unit (a3) can be used alone or combine 2 kinds
Use above.
Specifically, construction unit (a3) can enumerate from styrene, t-butoxystyrene, methyl styrene,
Hydroxy styrenes, α-methylstyrene, acetoxy-styrene, methoxy styrene, ethoxystyrene, chlorostyrene, second
Alkenyl methyl benzoate, vinyl benzoic acid ethyl ester, 4-HBA (3- methacryloxypropyls) ester, (methyl) propylene
Acid, (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) n-propyl, (methyl) isopropyl acrylate,
(methyl) acrylic acid 2- hydroxyl ethyl esters, (methyl) acrylic acid 2- hydroxypropyl acrylates, (methyl) benzyl acrylate, (methyl) isobomyl acrylate
The construction unit of ester, acrylonitrile, ethylene glycol single acetyl acetic acid esters, single (methyl) acrylate etc..Furthermore it is possible to enumerate in Japan
Described compound in 0021~0024 paragraph of JP 2004-264623 publications.
Also, as other structures unit (a3), from the viewpoint of electrical characteristics, optimization styrene class, there is aliphatic
The group of cyclic skeleton.Specifically, can enumerate styrene, t-butoxystyrene, methyl styrene, hydroxy styrenes,
α-methylstyrene, bicyclopentyl (methyl) acrylate, cyclohexyl (methyl) acrylate, isobornyl thiocyanoacetate (methyl) acrylic acid
Ester and benzyl (methyl) acrylate etc..
Also, as other structures unit (a3), from the viewpoint of adaptation, preferred (methyl) alkyl acrylate.
Specifically, (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) propyl acrylate, (methyl) third can be enumerated
Olefin(e) acid N-butyl etc., more preferably (methyl) methyl acrylate.
In the structure for the polymer for forming the construction unit (a1) containing the group protected with acidic group by sour decomposability base
In unit, the containing ratio of said structure unit (a3) is preferably 60 moles of below %, more preferably 50 moles of below %, further
Preferably 40 moles of below %.It can be 0 mole of % as lower limit, but such as 1 mole of more than % can be set to, and then, energy
Enough it is set to 5 moles of more than %.If in the range of above-mentioned numerical value, the various characteristics of positive light sensitivity material can become good.
As other structures unit (a3), preferably there is the construction unit comprising acidic group.By with the knot comprising acidic group
Structure unit, is easily dissolved in alkaline-based developer, more effectively plays the effect of the present invention.Acidic group in the present invention refers to pKa
(power of Ka:Acidity dissociation constant;Ka is acid ionization constant) be less than 10 proton dissociation base.Acidic group is usually used
The monomer of acidic group can be formed and be incorporated into as the construction unit comprising acidic group in polymer.By in the polymer comprising acid
The construction unit of base and have the tendency of easily to be dissolved in alkaline-based developer.
As the acidic group for the construction unit comprising acidic group being used in above-mentioned other structures unit, exemplify from carboxylic
The acidic group of acidic group, the acidic group from sulfoamido, the acidic group from phosphonate group, from sulfonic acidic group, derive from
The acidic group of phenolic hydroxyl group, sulfoamido, sulfonyl imide etc., are preferably derived from the acidic group of carboxylic acid group and/or from phenol
The acidic group of property hydroxyl.
The construction unit for including acidic group being used in above-mentioned other structures unit, more preferably to from styrene
Construction unit and construction unit from vinyl compound instead of the construction unit of acidic group and from (methyl) third
The construction unit of olefin(e) acid.
Moreover, from the viewpoint of the dissolubility to developer solution, the physics physical property of optimization film, acidic group is included it is also preferred that having
The construction unit of ester.
In the present invention, from the viewpoint of sensitivity, particularly preferably containing above-mentioned as other structures unit (a3) tool
There are the construction unit of carboxyl or the construction unit with phenolic hydroxyl group.
As the construction unit (a1) for the group protected with above-mentioned acidic group by sour decomposability base, possess with by above-mentioned acid
Decomposability base protection protection phenylol construction unit polymer, preferably in above-mentioned other structures unit (a3) it is also preferred that
It is used as copolymer composition comprising the construction unit from phenolic hydroxyl group.As what is protected with above-mentioned acidic group by sour decomposability base
The construction unit (a1) of group, possess with by the polymerization of the construction unit of the protection phenylol of above-mentioned sour decomposability base protection
Thing, the copolymer composition of the construction unit from hydroxy styrenes or Alpha-Methyl hydroxy styrenes is more preferably included, particularly preferably
It is used as copolymer composition comprising the construction unit from hydroxy styrenes.
Possess in the polymer of the construction unit with the protection phenylol protected by above-mentioned sour decomposability base and include acid
The copolymerization ratios of the construction unit of base, in the case where acidic group is phenolic hydroxyl group, have relative to possessing by the sour decomposability base
The polymer of the construction unit of the protection phenylol of protection is preferably 50~90 moles of %, more preferably 60~75 moles of %.
Also, in the case where acidic group is carboxylic acid acidic group, there is the guarantor protected by the sour decomposability base relative to possessing
The polymer for protecting the construction unit of phenylol is preferably 0~30 mole of %, more preferably 5~10 moles of %.
Possess in the polymer of the construction unit with the protection phenylol protected by above-mentioned sour decomposability base and include acid
The copolymerization ratios of the construction unit of base ester, there is the structure list for protecting phenylol protected by the sour decomposability base relative to possessing
The polymer of member is preferably 0~30 mole of %, more preferably 0~10 mole of %, especially preferably 0 mole of %.
As the construction unit (a1) for the group protected with above-mentioned acidic group by sour decomposability base, possess with by above-mentioned acid
The polymer of the construction unit of the protection carboxyl of decomposability base protection, also comprising next preferably in above-mentioned other structures unit (a3)
The construction unit and/or its ester for coming from carboxylic acid group are used as copolymer composition.Protected as with above-mentioned acidic group by sour decomposability base
Group construction unit (a1), possess with by the polymer of the construction unit of the protection carboxyl of above-mentioned sour decomposability base protection
More preferably include the construction unit from (methyl) acrylic acid, (methyl) benzyl acrylate or (methyl) acrylic acid 2- hydroxyl ethyl esters
It is used as copolymer composition.
Possess in the polymer of the construction unit with the protection carboxyl protected by above-mentioned sour decomposability base and included acidic group
Construction unit copolymerization ratios, in the case where acidic group is phenolic hydroxyl group, relative to possessing with being protected by the sour decomposability base
The polymer of the construction unit of the carboxyl of shield is preferably 50~90 moles of %, more preferably 60~75 moles of %.
Also, in the case where acidic group is carboxylic acid acidic group, there is the carboxylic protected by the sour decomposability base relative to possessing
The polymer of the construction unit of base is preferably 0~30 mole of %, more preferably 5~10 moles of %.
Possess in the polymer of the construction unit with the protection carboxyl protected by above-mentioned sour decomposability base and included acidic group
The copolymerization ratios of the construction unit of ester, have relative to possessing by the construction unit of the protection carboxyl of sour decomposability base protection
Polymer is preferably 10~80 moles of %, more preferably 30~70 moles of %, especially preferably 40~60 moles of %.
The preferred embodiment > of < component of polymer
Compared with by the construction unit of the protection phenolic hydroxyl group of above-mentioned sour decomposability base protection, have by above-mentioned acid point
The development (developed speed) of the construction unit of the protection carboxyl of Xie Xingji protections is faster.Therefore by above-mentioned positive light sensitivity
Material is intended in the case of quickly being developed after being exposed, and is preferably had by the knot of the protection carboxyl of sour decomposability base protection
Structure unit.On the contrary, in the case of development to be slowed down, preferably using the knot with the protection phenolic hydroxyl group protected by sour decomposability base
Structure unit.
In positive light sensitivity material, possesses the group protected with acidic group by sour decomposability base in above-mentioned (A) composition
The polymer of construction unit (a1) can be a kind or two or more.In positive light sensitivity material, as above-mentioned polymerization
Thing composition, preferably comprise the construction unit (a1) of the group of more than two kinds for possessing and being protected with above-mentioned acidic group by sour decomposability base
Polymer.Wherein, as above-mentioned component of polymer, further preferably possess with by the protection of above-mentioned sour decomposability base protection
The polymer of the construction unit of phenolic hydroxyl group and contain with by the structure list of the protection carboxyl of above-mentioned sour decomposability base protection
The polymer of member.
From the viewpoint of sensitivity is improved, possess particularly preferably in positive light sensitivity material containing of more than two kinds
The polymer for having the construction unit (a1) for the group that above-mentioned acidic group protected by sour decomposability base is used as above-mentioned component of polymer, and
Possess the polymer of the construction unit (a1) for the group protected with above-mentioned acidic group by sour decomposability base, and containing with by above-mentioned
The polymer for the construction unit that formula A2 ' is represented.That is, in the manufacture method of the circuit layout of the present invention, preferred positive type light sensitive
Property material contain (A) composition of more than two kinds, and contain as (A) composition with the poly- of the construction unit represented by formula A2 '
Compound.
From the viewpoint of sensitivity and resolution ratio is improved simultaneously, in positive light sensitivity material, as above-mentioned polymer
Composition, the polymerization of the construction unit (a1) containing the group of more than two kinds for possessing and being protected with above-mentioned acidic group by sour decomposability base
Thing, and as the polymer for the construction unit (a1) for possessing the group protected with above-mentioned acidic group by sour decomposability base, contain tool
There is at least one in the polymer by the above-mentioned formula A1 or above-mentioned formulas A1 ' construction units represented and with by above-mentioned
The polymer for the construction unit that formula A2 ' is represented.
Contain the base of more than two kinds for possessing and being protected with above-mentioned acidic group by sour decomposability base as above-mentioned component of polymer
In the case of the polymer of the construction unit (a1) of group, possess with by the protection phenolic hydroxyl group of above-mentioned sour decomposability base protection
The polymer of construction unit and the polymer containing the construction unit with the protection carboxyl protected by above-mentioned sour decomposability base
Ratio, by quality ratio preferably 10:90~100:0, more preferably 30:70~60:40, especially preferably 1:1.
< < contain the molecular weight of the polymer of the construction unit (a1) for the group protected with acidic group by sour decomposability base
> >
The polymer of construction unit (a1) containing the group protected with above-mentioned acidic group by sour decomposability base is divided equally again
Son amount, with polystyrene convert Weight-average molecular gauge be preferably 1,000~200,000 scope, more preferably 2,000~
50,000 scope.If in the range of above-mentioned numerical value, various characteristics are good.
The ratio between number-average molecular weight and weight average molecular weight (decentralization) they are preferably 1.0~5.0, and more preferably 1.05~3.5.
The manufacture method > > of < < (A) composition
Also, on the synthetic method of (A) composition, it is also known that have various methods, if as an example, will can include in order to
The polymerizable monomer for forming the polymerizable monomer at least used by the construction unit that above-mentioned (a1) and above-mentioned (a3) is represented mixes
Thing, by being polymerize in organic solvent using polymerization initiator to synthesize.Also, it can also pass through so-called macromolecule
React and synthesize.
Above-mentioned positive light sensitivity material is relative to the mass parts of total solid content 100 preferably with the ratio of 50~99.9 mass parts
Comprising (A) composition, more preferably with the ratio of 70~98 mass parts comprising.
The other component of polymer > > of < <
Also, different from containing the group that there is acidic group to be protected by sour decomposability base being used in above-mentioned (A) composition
The polymer of construction unit (a1), it is possible to have be actually free of the structure for the group protected with acidic group by sour decomposability base
Unit (a1), and the polymer with other structures unit.Different from the use of the polymer in above-mentioned (A) composition, in reality
The construction unit (a1) of the upper group protected not comprising acidic group by sour decomposability base, and include the polymerization with other structures unit
In the case of thing, the use level of the polymer is preferably below 60 mass % in total polymeric content, more preferably 40 matter
Below % is measured, more preferably below 20 mass %.
In above-mentioned positive light sensitivity material, these do not include construction unit (a1) actually, and have other structures list
The polymer of first (a3) can, can only include a kind, two or more can also be included.
Do not include construction unit (a1) actually as these, and there is the polymer of other structures unit (a3), such as
Polycarboxylated styrene can be used, also can use commercially available SMA 1000P, SMA 2000P, SMA 3000P, SMA 1440F,
SMA 17352P, SMA 2625P, SMA 3840F (more than, Sartom er Company, Inc manufacture), ARUFON UC-
3000、ARUFON UC-3510、ARUFON UC-3900、ARUFON UC-3910、ARUFON UC-3920、ARUFON UC-
3080 (more than, TOAGOSEI CO., L TD. manufacture), Joncryl 690, Joncryl 678, Joncryl 67, Joncryl
586 (more than, BASF AG's manufacture) etc..
< (B) composition:Light acid producing agent >
Above-mentioned positive light sensitivity material preferably comprises (B) light acid producing agent.Used in the present invention light acid producing agent (
Referred to as " (B) composition ".) it is that can produce acid by irradiating the radioactive ray such as ultraviolet, far ultraviolet, X ray, charged particle beam
Compound.(B) light acid producing agent used in the present invention, preferably with more than wavelength 300nm, preferably with wavelength 300~
450nm actinic ray is sensed and produces the compound of acid.And the chemical constitution of non-limiting (B) light acid producing agent.Also,
The light acid producing agent not sensed directly on the actinic ray with more than wavelength 300nm, if by being used in combination with sensitizer
And sensed with more than wavelength 300nm actinic ray, and produce acid compound, then can be combined with sensitizer and
Suitably use.And caused sour pKa value be preferably less than 4.0 by the irradiation of radioactive ray, more preferably 3.0 with
Under.There is no particular limitation for lower limit, such as can be set to more than -10.0.
As above-mentioned (B) light acid producing agent, ionic smooth acid producing agent and nonionic light acid producing agent can be enumerated.
As the example of nonionic light acid producing agent, trichloromethyl-s-triazine, diazomethane chemical combination can be enumerated
Thing, acid imide sulfonate compound and oxime sulfonate compounds etc..Wherein, from the viewpoint of insulating properties, in positive light sensitivity
In material, above-mentioned (B) light acid producing agent is preferably oxime sulfonate compounds.These light acid producing agents can be used alone a kind, or
Person combines two or more and used.As trichloromethyl-s-triazine and the concrete example of diazomethane derivative, can exemplify
The compound described in 0083~0088 paragraph in Japanese Unexamined Patent Publication 2011-221494 publications.
As oxime sulfonate compounds, i.e. there is the compound of oxime sulfonates structure, can preferably exemplify containing under
The compound of the oxime sulfonates structure of formula (B1) expression is stated, these contents are merged in this specification.
Formula (B1)
[chemical formula 13]
(in formula (B1), R21Represent alkyl or aryl.Wave expression is bonded with other groups.)
Any group can be substituted, R21In alkyl can be straight-chain, branched and ring-type.Hereinafter, to being held
Perhaps substituent illustrates.
As R21Alkyl, preferably carbon number be 1~10 straight-chain or branched-chain alkyl.R21Alkyl can be by
The aryl of carbon number 6~11, the alkoxy of carbon number 1~10 or cycloalkyl (include 7,7- dimethyl -2- oxo norborneols
The bridge connected alcyl such as base, preferably bicyclic alkyl etc.) substitution.
As R21Aryl, preferably carbon number 6~11 aryl, more preferably phenyl or naphthyl.R21Aryl can be by
Low alkyl group, alkoxy or halogen atom substitution.
Above-claimed cpd containing the oxime sulfonates structure represented by above-mentioned formula (B1), it is also preferred that by following formulas (B2)
The oxime sulfonate compounds of expression.
[chemical formula 14]
(in formula (B2), R42Represent alkyl or aryl, X10Represent alkyl, alkoxy or halogen atom, m4 represent 0~3 it is whole
Number, when m4 is 2 or 3, multiple X10Can be with identical, can also be different.)
As X10Alkyl be preferably carbon number 1~4 straight-chain or branched-chain alkyl.
As X10Alkoxy be preferably carbon number 1~4 straight-chain or branched alkoxy.
As X10Halogen atom be preferably chlorine atom or fluorine atom.M4 is preferably 0 or 1.It is especially excellent in above-mentioned formula (B2)
Choosing, m4 1, X10For methyl, X10The position of substitution be ortho position, R42For the straight-chain alkyl of carbon number 1~10,7,7- diformazans
Base -2- oxos norbornylmethyl or the compound to toluyl groups.
Compound containing the oxime sulfonates structure represented by above-mentioned formula (B1), preferably also by following formulas (B3) table
The oxime sulfonate compounds shown.
[chemical formula 15]
(in formula (B3), R43With the R in formula (B2)42Implication is identical, X11Represent halogen atom, hydroxyl, carbon number 1~4
Alkyl, the alkoxy of carbon number 1~4, cyano group or nitro, n4 represent 0~5 integer.)
As the R in above-mentioned formula (B3)43, preferably methyl, ethyl, n-propyl, normal-butyl, n-octyl, trifluoromethyl, five
Fluoro ethyl, perfluor n-propyl, perfluoro-n-butyl group, p-methylphenyl and 4- chlorphenyls or pentafluorophenyl group, particularly preferred n-octyl.
As X1, the preferably alkoxy of carbon number 1~5, more preferably methoxyl group.
As n4, preferably 0~2, especially preferably 0~1.
As the concrete example of the compound represented by above-mentioned formula (B3), α-(methylsulfonyloxyimino) can be enumerated
Benzyl cyanide, α-(ethylsulfonyloxy imino group) benzyl cyanide, α-(n-propyl sulfonyloxyimino) benzyl cyaniding
Thing, α-(normal-butyl sulfonyloxyimino) benzyl cyanide, α-(4- tolylsulfonyl- epoxides imino group) benzyl cyanide, α-
((methylsulfonyloxyimino) -4- methoxyphenyls) acetonitrile, α-((ethylsulfonyloxy imino group) -4- methoxyphenyls)
Acetonitrile, α-((n-propyl sulfonyloxyimino) -4- methoxyphenyls) acetonitrile, α-((normal-butyl sulfonyloxyimino) -4-
Methoxyphenyl) acetonitrile and α-(4- (tolylsulfonyl- epoxide imino group) -4- methoxyphenyls) acetonitrile.
As the concrete example of preferable oxime sulfonate compounds, following compounds (i)~(viii) etc. can be enumerated, can
1 kind is used alone, or and two or more can be used.Compound (i)~(viii) can obtain as commercially available product.Also,
It can be combined and use with (B) light acid producing agent of other species.
[chemical formula 16]
As the compound containing the oxime sulfonates structure represented by above-mentioned formula (B1), also preferably by following formulas
(OS-1) compound represented.
[chemical formula 17]
Formula (OS-1)
In above-mentioned formula (OS-1), R411Represent hydrogen atom, alkyl, alkenyl, alkoxy, alkoxy carbonyl group, acyl group, amino first
Acyl group, sulfamoylamino group, sulfo group, cyano group, aryl or heteroaryl.R412Represent alkyl or aryl.
X401Expression-O- ,-S- ,-NH- ,-NR415-、-CH2-、-CR416H- or-CR415R417-, R415~R417Represent alkyl
Or aryl.
R421~R424Separately represent hydrogen atom, halogen atom, alkyl, alkenyl, alkoxy, amino, alkoxy carbonyl group, alkane
Base carbonyl, aryl carbonyl, amide groups, sulfo group, cyano group or aryl.R421~R424In 2 can bond together and form ring.
As R421~R424, preferably hydrogen atom, halogen atom and alkyl, also, it is also preferred that R421~R424Middle at least two is each other
It is bonded and forms the mode of aryl.Wherein, from the viewpoint of sensitivity, more preferably R421~R424It is the mode of hydrogen atom.
Aforementioned functional groups can also have substituent.
The compound represented by above-mentioned formula (OS-1), the compound more preferably represented by following formulas (OS-2).
[chemical formula 18]
Formula (OS-2)
In above-mentioned formula (OS-2), R401、R402、R421~R424It is identical with the implication in formula (OS-1) respectively, preference
It is identical.
Wherein, the R in more preferably above-mentioned formula (OS-1) and above-mentioned formula (OS-2)401For the mode of cyano group or aryl, most
It is preferred that the R represented in above-mentioned formula (OS-2)401For the mode of cyano group, phenyl or naphthyl.
Also, in above-mentioned oxime sulfonate compounds, the stereochemical structure (E, Z etc.) of oxime and benzothiazole ring can be respectively
One of which or mixture.
As the concrete example for the compound represented by above-mentioned formula (OS-1) that can be preferably used in the present invention, Ke Yiju
Go out compound (exemplary compounds b-1~b- described in 0128~0132 paragraph in Japanese Unexamined Patent Publication 2011-221494 publications
34), but the present invention is not limited to this.
In the present invention, as the compound containing the oxime sulfonates structure represented by above-mentioned formula (B1), preferably under
State the oxime sulfonate compounds that formula (OS-3), following formulas (OS-4) or following formulas (OS-5) represent.
[chemical formula 19]
(in formula (OS-3)~formula (OS-5), R22、R25And R28Alkyl, aryl or heteroaryl are separately represented,
R23、R26And R29Separately represent hydrogen atom, alkyl, aryl or halogen atom, R24、R27And R30Separately represent that halogen is former
Son, alkyl, alkoxy, sulfonic group, amino-sulfonyl or alkyloxysulfonyl.X1~X3Separately represent oxygen atom or sulphur
Atom, n1~n3Separately represent 1 or 2, m1~m3Separately represent 0~6 integer.)
In above-mentioned formula (OS-3)~(OS-5), R22、R25And R28In alkyl, aryl or heteroaryl can have substitution
Base.
In above-mentioned formula (OS-3)~(OS-5), as R22、R25And R28In alkyl, can preferably have substituent
Total carbon atom number is 1~30 alkyl.
Also, in above-mentioned formula (OS-3)~(OS-5), as R22、R25And R28In aryl, preferably can have take
Dai Ji total carbon atom number is 6~30 aryl.
Also, in above-mentioned formula (OS-3)~(OS-5), as R1In heteroaryl, preferably can have substituent it is total
Carbon number is 4~30 heteroaryl.
In above-mentioned formula (OS-3)~(OS-5), R22、R25And R28As long as heteroaryl at least one ring in is hetero-aromatic ring
, such as hetero-aromatic ring can be condensed with phenyl ring.
In above-mentioned formula (OS-3)~(OS-5), R23、R26And R29Preferably hydrogen atom, alkyl or aryl, more preferably hydrogen
Atom or alkyl.
In above-mentioned formula (OS-3)~(OS-5), the R of more than 2 in compound be present23、R26And R29In, preferably 1
Or 2 are alkyl, aryl or halogen atom, more preferably 1 is alkyl, aryl or halogen atom, and particularly preferred 1 is alkyl, and its
Remaining is hydrogen atom.
As R23、R26And R29In alkyl, preferably can have substituent total carbon atom number be 1~12 alkyl, more
It is preferred that the alkyl that the total carbon atom number can with substituent is 1~6.
As R23、R26And R29In aryl, preferably can have substituent total carbon atom number be 6~30 aryl.
In above-mentioned formula (OS-3)~(OS-5), X1~X3Separately represent O or S, preferably O.
In above-mentioned formula (OS-3)~(OS-5), by X1~X3As composition ring element and comprising ring be 5 Yuans rings or 6
Member's ring.
In above-mentioned formula (OS-3)~(OS-5), n1~n3Separately represent 1 or 2, X1~X3In the case of O, n1
~n3It is preferably separately 1, also, X1~X3In the case of S, n1~n3It is preferably separately 2.
In above-mentioned formula (OS-3)~(OS-5), R24、R27And R30Separately represent halogen atom, alkyl, alkoxy,
Sulfonic group, amino-sulfonyl or alkyloxysulfonyl.Wherein, R24、R27And R30It is preferably separately alkyl or alkoxy.
R24、R27And R30In alkyl, alkoxy, sulfonic group, amino-sulfonyl and alkyloxysulfonyl can have substitution
Base.
In above-mentioned formula (OS-3)~(OS-5), as R24、R27And R30In alkyl, can preferably have substituent
Total carbon atom number be 1~30 alkyl.
In above-mentioned formula (OS-3)~(OS-5), as R24、R27And R30In alkoxy, preferably can have substitution
The alkoxy of the total carbon atom number 1~30 of base.
Also, in above-mentioned formula (OS-3)~(OS-5), m1~m3The separately integer of expression 0~6, preferably 0~
2 integer, more preferably 0 or 1, especially preferably 0.
Also, on above-mentioned (OS-3)~(OS-5) each substituent, also also, it is preferred that in Japanese Unexamined Patent Publication 2011-
The preferred scope of the substituent of (OS-3)~(OS-5) described in 0092~0109 paragraph of No. 221494 publications.
Also, particularly preferably it is by following logical containing the compound of the oxime sulfonates structure represented by above-mentioned formula (B1)
Any one oxime sulfonate compounds represented in formula (OS-6)~(OS-11).
[chemical formula 20]
(in formula (OS-6)~(OS-11), R301~R306Represent alkyl, aryl or heteroaryl, R307Represent hydrogen atom or bromine
Atom, R308~R310、R313、R316And R318Separately represent hydrogen atom, the alkyl of carbon number 1~8, halogen atom, chloromethane
Base, bromomethyl, bromoethyl, methoxy, phenyl or chlorphenyl, R311And R314Separately represent hydrogen atom, halogen atom,
Methyl or methoxy, R312、R315、R317And R319Separately represent hydrogen atom or methyl.)
Preferred scope in above-mentioned formula (OS-6)~(OS-11), and in Japanese Unexamined Patent Publication 2011-221494 publications
The preferred scope of (OS-6)~(OS-11) described in 0110~0112 paragraph is identical.
, can be with as the concrete example of the oxime sulfonate compounds represented by above-mentioned formula (OS-3)~above-mentioned formula (OS-5)
The compound described in 0114~0120 paragraph in Japanese Unexamined Patent Publication 2011-221494 publications is enumerated, but it is of the invention and unlimited
Due to this.
In above-mentioned positive light sensitivity material, (B) nonionic light acid producing agent is relative in positive light sensitivity material
100 mass parts of overall resin component (total of preferably total solid content, more preferably polymer), preferably using 0.1~10 mass
Part, more preferably using 0.5~10 mass parts.Also and two or more can be used.
As the example of ionic smooth acid producing agent, Diaryl iodonium salt, triaryl matte salt, quaternary ammonium salt can be enumerated
Class etc..Wherein, preferably triaryl matte salt and Diaryl iodonium salt.
The triaryl matte salt used as ionic smooth acid producing agent is represented by following formulas (1).
Formula (1)
[chemical formula 21]
(in formula (1), R505、R506And R507Represent can there is the alkyl or aromatic series base of substituent respectively, be alkyl
In the case of, it can be connected to each other and form ring;X-Represent conjugate base.)
As R505、R506And R507In alkyl, preferably carbon number is 1~10 alkyl, and can have substituent.
As this alkyl, methyl, ethyl, propyl group, isopropyl, butyl, the tert-butyl group, amyl group, neopentyl, hexyl, hexamethylene can be enumerated
Base, heptyl and octyl group etc..Wherein, preferably methyl, ethyl, the tert-butyl group.Also, R505、R506And R507In, it is alkyl more than 2
In the case of, preferably the alkyl of more than 2 is connected to each other and forms ring, as this loop type, preferably comprises sulphur atom
5 Yuans rings (tiacyclopentane) of form and 6 Yuans rings (thia hexamethylene).
As R505、R506And R507In aromatic series base, preferably carbon number is 6~30 aromatic series base, and can be had
Substituent.As this aromatic series base, phenyl, naphthyl, 4- methoxyphenyls, 4- chlorphenyls, 4- aminomethyl phenyls, 4- can be enumerated
Tert-butyl-phenyl, 4- Phenylsulfanylphenyls, 2,4,6- trimethylphenyls, 4- methoxy-1-naphthyls, 4- (4 '-diphenyl sulphophenyl sulphur
Base) phenyl.
Also, the ionic smooth acid producing agent represented by formula (1) can be in R505~R507Any place be bonded, shape
Into polymers such as 2 polymers.Such as above-mentioned 4- (4 '-diphenyl sulfo group thiophenyl) phenyl is an example of 2 polymers, above-mentioned 4-
Counter anion and X in (4 '-diphenyl sulfo group thiophenyl) phenyl-It is identical.
As R505、R506And R507In the substituent that can have of alkyl and aromatic series base, optimization aromatic base, specifically
For, particularly preferred phenyl, 4- methoxyphenyls, 4- chlorphenyls, 4- (4 '-diphenyl sulfo group thiophenyl) phenyl.These substitutions
Base can be further substituted with by above-mentioned substituent.
As X-In conjugate base, the preferably conjugate base of alkyl sulfonic acid, the conjugate base of aryl sulfonic acid, BY4 -(Y represents that halogen is former
Son.Hereinafter, it is also identical.)、PY6 -、AsY6 -、SbY6 -Or the anion of the monovalence represented by following formulas (3) or formula (4), especially
The conjugate base of its preferred alkyl sulfonic acid, the conjugate base of aryl sulfonic acid, PY6 -Or the anion of 1 valency represented by formula (3).
As alkyl sulfonic acid and the conjugate base of aryl sulfonic acid, preferably carbon number is the conjugate base of 1~7 alkyl sulfonic acid,
And then more preferably carbon number is the conjugate base of 1~4 alkyl sulfonic acid, if representing as the acid, particularly preferred such as first
Alkyl sulfonic acid, trifluoromethayl sulfonic acid, n-propane sulfonic acid, heptanesulfonic acid.
As the conjugate base of aryl sulfonic acid, if representing as the acid, for example, benzene sulfonic acid, chlorobenzenesulfonic acid and
P-methyl benzenesulfonic acid.
X-In BY4 -、PY6 -、AsY6 -、SbY6 -In Y, preferably fluorine atom, chlorine atom, especially preferably fluorine atom.
[chemical formula 22]
(in formula (3) and formula (4), R521、R522And R523Separately represent alkyl, the carbon of carbon number 1~10
The alkyl with fluorine atom of atomicity 1~10, or R521With R522It is former each other by the alkylidene or carbon of carbon number 2~6
The alkylidene with fluorine atom of subnumber 2~6 and the ring being bonded.)
In formula (3) and formula (4), as R521、R522And R523In carbon number be 1~10 alkyl, can enumerate
Such as methyl, ethyl, butyl, the tert-butyl group, cyclohexyl and octyl group etc..Also, it is 1~10 there is fluorine atom as carbon number
Alkyl, such as trifluoromethyl, pentafluoroethyl group, heptafluoropropyl, nine fluorine butyl, 12 fluorine amyl groups and perfluoro capryl can be enumerated
Deng.Wherein, R521、R522And R523It is preferred that carbon number is 1~10 alkyl with fluorine atom, particularly preferred carbon number is 1
~6 alkyl with fluorine atom.
In formula (3) and formula (4), as R521With R522Carbon number 2~6 in the case of bonding together and forming ring
Alkylidene, vinyl, acrylic, butylidene, pentylidene and hexylidene etc. can be enumerated.Also, as carbon number 2~6
The alkylidene with fluorine atom, tetrafluoroethene base, hexafluoropropene base, octafluoro butylidene, ten fluorine pentylidene, 11 can be enumerated
Fluorine hexylidene etc..Wherein, R521With R522Bond together in the case of forming ring, be 2~6 to have preferably by carbon number
The alkylidene of fluorine atom is bonded, and is carried out particular preferably by the alkylidene with fluorine atom that carbon number is 2~4
Bonding.
Also, as the ionic smooth acid producing agent represented by formula (1), the light preferably represented by following formulas (5)
Acid producing agent.
[chemical formula 23]
(in formula, R510、R511、R512And R513Separately represent can there is the alkyl or aromatic series base of substituent,
Ar3And Ar4Separately represent can there is the aromatic series base of the divalence of substituent, X1-And X2-Separately represent conjugation
Alkali.)
R510、R511、R512And R513In alkyl and aromatic series base and formula (1) R505、R506And R507Represented alkyl
And aromatic series base implication is identical, preferred embodiment is also identical.And it is possible to the substituent having is also identical.
X1-And X2-In conjugate base and formula (1) X-Represented conjugate base implication is identical, and preferred embodiment is also identical.
As Ar3And Ar4In divalence aromatic series base, preferably phenylene or naphthylene, particularly preferred phenylene.
The concrete example of the triaryl matte salt used as ionic smooth acid producing agent, can enumerate trifluoromethanesulfonic acid three
Phenyl sulfonium, trifluoroacetic acid triphenylsulfonium, trifluoromethanesulfonic acid 4- methoxyphenyl diphenyl sulfonium, trifluoroacetic acid 4- methoxyphenyls two
Phenyl sulfonium, trifluoromethanesulfonic acid 4- phenylthiophenyl diphenyl sulfoniums or trifluoroacetic acid 4- phenylthiophenyl diphenyl sulfoniums etc..
As commercially available compound, TPS-102 can be enumerated, 103,105,106,109,300,1000, MDS-103,
105,109,205,209, BDS-109, DTS-103,105, MNPS-109, HDS-109, (more than, Midori Kagaku Co.,
Ltd. manufacture), GSID-26-1, Cyracure UVI-6976 (more than, BASF AG manufacture).
The Diaryl iodonium salt used as ionic smooth acid producing agent, represented by following formulas (2).
Formula (2)
[chemical formula 24]
(in formula (2), R508And R509Separately represent can there is the aromatic series base of substituent, X-Represent conjugation
Alkali.)
In formula (2), R508And R509In aromatic series base and formula (1) R505、R506And R507Represented aromatic series base
Implication is identical, and preferred embodiment is also identical.
In formula (2), X-In conjugate base and formula (1) X-Represented conjugate base implication is identical, preferred embodiment also phase
Together.
Also, the light acid producing agent represented by formula (2) can pass through R508~R509And be bonded, and it is more to form 2 polymers etc.
Polymers.Such as above-mentioned 4- (4 '-diphenyl sulfo group thiophenyl) phenyl is an example of 2 polymers, above-mentioned 4- (4 '-diphenyl sulphurs
Base thiophenyl) counter anion in phenyl and above-mentioned X-It is identical.
The concrete example of the Diaryl iodonium salt used as ionic smooth acid producing agent, can enumerate diphenyl iodine
Trifluoroacetate, diphenyl iodine fluoroform sulphonate, 4- methoxyphenyl phenyl-iodides fluoroform sulphonate, 4- methoxybenzenes
Base phenyl-iodide trifluoroacetate, phenyl, 4- (the carbon epoxide of 2 '-hydroxyl -1 '-ten four) phenyl-iodide fluoroform sulphonate, 4-
(the carbon epoxide of 2 '-hydroxyl -1 '-ten four) phenyl-iodide hexafluoro antimonate, phenyl, 4- (the carbon epoxide of 2 '-hydroxyl -1 '-ten four) phenyl
Iodo- tosilate etc..
As commercially available compound, DPI-105 can be enumerated, 106,109,201, BI-105, MPI-105,106,109,
BBI-102,103,105,106,109,110,201,300,301 (more than, the manufacture of Midori Kagaku Co., Ltd.s).
The concrete example of the quaternary ammonium salt used as ionic smooth acid producing agent, can enumerate tetramethyl-ammonium butyl three
(2,6- difluorophenyl) borate, tetramethyl-ammonium hexyl three (rubigan) borate, (the 3- trifluoromethyls of tetramethyl-ammonium hexyl three
Phenyl) borate, benzyl dimethyl phenyl ammonium butyl three (2,6- difluorophenyls) borate, benzyl dimethyl phenyl ammonium hexyl three
(rubigan) borate, benzyl dimethyl phenyl ammonium hexyl three (3- trifluoromethyls) borate etc..
In addition to above-mentioned concrete example, as the concrete example of (B) composition, following compound can be enumerated, but the present invention is simultaneously
It is not limited to this.
[chemical formula 25]
[chemical formula 26]
[chemical formula 27]
The content of composition B in above-mentioned positive light sensitivity material is preferably 0.1 relative to the mass of component of polymer 100, part
~10 mass parts, more preferably 0.5~5 mass parts.If composition B content is more than 0.1 mass parts, it is readily available desired
Sensitivity (high-sensitivity), also, if 10 mass parts below, then it is easy to ensure that the transparency of film.
Also, the addition of nonionic light acid producing agent is preferably below 1 mass %, preferably do not include actually it is non-from
The mode of sub- property light acid producing agent.
< solvents >
It is molten preferably as arbitrary composition is dissolved in for forming the photosensitive polymer combination of positive light sensitivity material
Solution in agent and prepare.
As the solvent used in the photosensitive polymer combination for forming positive light sensitivity material, public affairs can be used
The solvent known, can exemplify ethylene glycol monoalkyl ether class, glycol dialkyl ether class, ethylene glycol monoalkyl ether acetate class,
Propylene-glycol monoalky lether class, propane diols dialkyl ether, propylene-glycol monoalky lether acetate esters, diethylene glycol dialkyl ether class,
Diethylene glycol monoalkyl ether acetate class, dipropylene glycol monoalkylether class, DPG dialkyl ether, DPG monoalkyl
Ether acetic acid esters, esters, ketone, amide-type and lactone etc..Also, as forming the photosensitive of positive light sensitivity material
The concrete example of solvent used in property resin combination, can also be enumerated in Japanese Unexamined Patent Publication 2011-221494 publications
Solvent described in 0174~0178 paragraph, these contents are merged in this specification.
Also, in these solvents, it can also add as needed:Benzylisoeugenol, hexyl ether, ethylene glycol phenyl ether
Acetic acid esters, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, isophorone, caproic acid, octanoic acid, 1- octanols, 1 nonyl alcohol, benzylalcohol, fennel
Fragrant ether, benzyl acetate, ethyl benzoate, diethy-aceto oxalate, diethyl maleate, ethylene carbonate, propene carbonate equal solvent.
These solvents can be used alone a kind, or mix two or more and use.The solvent that can be used in the present invention is preferably single
Solely use a kind, or and with 2 kinds, it is further preferred and with propylene-glycol monoalky lether acetate esters or two more preferably and with 2 kinds
Alkyl ether, oxalic acid esters and diethylene glycol dialkyl ether class or esters and butanediol alkylether acetates class.
Also, as components D, preferably 130 DEG C of boiling point less than 160 DEG C solvent, more than 160 DEG C of boiling point it is molten
Agent or their mixture.
As 130 DEG C of boiling point less than 160 DEG C of solvent, propylene glycol methyl ether acetate (boiling point can be exemplified
146 DEG C), propylene glycol monoethyl ether acetate (158 DEG C of boiling point), propylene glycol methyl n-butyl ether (155 DEG C of boiling point), propylene glycol methyl
N-propyl ether (131 DEG C of boiling point).
As more than 160 DEG C of solvent of boiling point, 3- ethoxyl ethyl propionates (170 DEG C of boiling point), diethyl two can be exemplified
Alcohol methyl ethyl ether (176 DEG C of boiling point), propylene glycol monomethyl ether propionate (160 DEG C of boiling point), (boiling of dipropylene glycol methyl ether acetic acid esters
Point 213 DEG C), 3- methoxybutyl ether acetic acids ester (171 DEG C of boiling point), diethylene glycol diethyl ether (189 DEG C of boiling point), diethylene glycol
Dimethyl ether (162 DEG C of boiling point), propylene-glycol diacetate (190 DEG C of boiling point), diethylene glycol monoethyl ether acetic acid esters (boiling point 220
DEG C), dipropylene glycol dimethyl ether (175 DEG C of boiling point), 1,3 butylene glycol diacetate esters (232 DEG C of boiling point).
The content of the solvent in photosensitive polymer combination layer for forming positive light sensitivity material, in photoresist
Preferably 50~95 mass parts, more preferably 60~90 mass in every 100 mass parts of overall resin component in composition
Part.
< sensitizers >
In the manufacture method of the circuit layout of the present invention, preferably positive light sensitivity material also includes sensitizer.Positive type light sensitive
Property material in the combination with (B) light acid producing agent, in order to promote its decompose and preferably comprise sensitizer, especially using it is non-from
Sensitizer is preferably comprised during sub- property light acid producing agent.Sensitizer absorbs actinic ray or radioactive ray and turns into electron excitation state.
Sensitizer and light acid producing agent as electron excitation state are contacted and produce the work such as electron transfer, energy transfer, heating
With.Thus light acid producing agent causes chemical change and decomposed, and generates acid.
By further improving exposure sensitivity containing sensitizer, also, low using the absorption efficiency of visible ray
It is particularly effective in the case of hybrid ray of the situation and exposure light source of nonionic light acid producing agent for g, h ray.
As sensitizer, preferably anthracene derivant, acridone derivatives, thioxanthone derivative, cumarin derivative,
Basicity styrene radical derivative, more preferably diphenylethyllene benzene derivative, anthracene derivant.
As anthracene derivant, preferably anthracene, 9,10- dibutoxies anthracene, the chrloroanthracenes of 9,10- bis-, 2- ethyl -9,10- dimethoxys
Anthracene, 9- methylols anthracene, 9- bromines anthracene, 9- chrloroanthracenes, 9,10- dibromoanthracenes, 2- ethyl anthracenes, 9,10- dimethoxy anthracenes.
As acridone derivatives, preferably acridone, N- butyl -2- chloro-acridines ketone, N- methylacridines ketone, 2- methoxyl group a word used for translations
Pyridine ketone, N- ethyl -2- methoxyacridine ketone.
As thioxanthone derivative, preferably the chloro- 4- propoxyl group thioxanthone of thioxanthone, diethyl thioxanthone, 1-,
2- chlorothiaxanthenones.
As cumarin derivative, preferably cumarin -1, cumarin -6H, cumarin -110, oxygen
Miscellaneous naphthalene neighbour ketone -102.
As basicity styrene radical derivative, 2- (4- dimethylaminostyryls) benzoxazoles, 2- (4- can be enumerated
Dimethylaminostyryl) benzothiazole, 2- (4- dimethylaminostyryls) aphthothiazoles.
As diphenylethyllene benzene derivative, diphenylethyllene benzene, two (4- methoxyl-styrenes) benzene, two can be enumerated
(3,4,5- trimethoxies styryl) benzene.
As the concrete example of sensitizer, following sensitizers can be enumerated, but the present invention is not limited to this.It is in addition, following
In, Me represents methyl, and Et represents ethyl, and Bu represents butyl.
[chemical formula 28]
The content of sensitizer in positive light sensitivity material is preferably 0.1~10 relative to the mass parts of polymerizable component 100
Mass parts, more preferably 0.5~5 mass parts.By the way that the content of sensitizer is set to more than 0.1 mass parts wish to be readily available
The sensitivity of prestige, and by being set to below 10 mass parts and it is easy to ensure that the transparency of film.
< alkali compounds >
In the manufacture method of the circuit layout of the present invention, preferably positive light sensitivity material also includes alkali compounds.As
Alkali compounds, it can arbitrarily select and use in workable alkali compounds in chemistry amplification resist.It can lift
Go out such as aliphatic amine, aromatic amine, heterocyclic amine, quaternary ammonium hydroxide, carboxylic acid quaternary ammonium salt., can as these concrete examples
To enumerate described compound in 0204~0207 paragraph of Japanese Unexamined Patent Publication 2011-221494 publications, these content quilts
It is incorporated in this specification.
Specifically, as aliphatic amine, for example, trimethylamine, diethylamine, triethylamine, di-n-propylamine, three just
Propylamine, two n-amylamines, tri-n-amyl amine, diethanol amine, triethanolamine, dicyclohexyl amine, dicyclohexylmethylamine etc..
As aromatic amine, for example, aniline, benzylamine, DMA, diphenylamines etc..
As heterocyclic amine, for example, pyridine, 2- picolines, 4- picolines, 2- ethylpyridines, 4- ethyl pyrroles
Pyridine, 2- phenylpyridines, 4- phenylpyridines, N- methyl 4-phenyls pyridine, 4-dimethylaminopyridine, imidazoles, benzimidazole, 4-
Methylimidazole, 2-Phenylbenzimidazole, 2,4,5- triphenylimidazolyls, nicotine, nicotinic acid, niacin hydroxyacyl amine, quinoline, 8- hydroxyl quinolines
Quinoline, pyrazine, pyrazoles, pyridazine, purine, pyrrolidines, piperidines, piperazine, morpholine, 4- methyl morpholines, 1,5- diazabicyclos
[4.3.0] -5- nonenes, 1,8- diazabicyclos [5.3.0] -7- endecatylenes etc..
As quaternary ammonium hydroxide, for example, TMAH, tetraethyl ammonium hydroxide, tetra-n-butyl hydrogen
Amine-oxides, four n-hexyl ammonium hydroxide etc..
As the quaternary ammonium salt of carboxylic acid, for example, tetramethyl-ammonium acetic acid esters, tetramethyl-ammonium benzoic ether, tetra-n-butyl
Ammonium acetic acid esters, tetra-n-butyl ammonium benzoic ether etc..
Alkali compounds used in the present invention can be used alone or two or more kinds may be used.
The content of alkali compounds in positive light sensitivity material is relative to the total solid content in positive light sensitivity material
100 mass parts, preferably 0.001~3 mass parts, more preferably 0.005~1 mass parts.
< (C):Miscellaneous cyclic compound >
In the manufacture method of the circuit layout of the present invention, preferably positive light sensitivity material contains (C) heterocycle shape
The compound of compound.By adding miscellaneous cyclic compound, the cured film obtained by positive light sensitivity material can be set to more firm
Solid film.
It is just without particular limitation in addition to component of polymer as miscellaneous cyclic compound.Such as following institute can be added
That states has the compound of epoxy radicals or oxetanylmethoxy in intramolecular, has miscellaneous cyclic compound, in addition containing alkoxy methyl
The oxygen-containing monomers such as various cyclic ethers and cyclic ester (lactone), be referred to as cyclic amine Ji the nitrogen containing monomer of oxazoline, also have, silicon, sulphur and
Phosphorus etc. has heterocyclic monomer of d electronics etc..
The addition of miscellaneous cyclic compound in positive light sensitivity material relative to positive light sensitivity material total solid into
Divide 100 mass parts, more preferably preferably 0.01~50 mass parts, more preferably 0.1~10 mass parts, 1~5 mass
Part.By being added with the scope, the cured film of mechanical strength is can obtain, and can obtain the excellent solidification of chemical resistance
Film.Miscellaneous cyclic compound can and with a variety of, in this case, miscellaneous cyclic compound is all added up and calculates content.
As the concrete example of the compound in intramolecular with epoxy radicals, bisphenol A type epoxy resin, Bisphenol F can be enumerated
Type epoxy resin, phenolic resin varnish type epoxy resin, cresol novolak type epoxy resin and aliphatic epoxy resin etc..
These compounds can obtain as commercially available product.For example, JER828, JER1007, JER157S70
(Mitsubishi Chemical Corporation manufactures), JER157S65 (Mitsubishi Chemical Holdings
Corporation is manufactured) etc., commercially available product described in 0189 paragraph of Japanese Unexamined Patent Publication 2011-221494 publications etc..
Furthermore, it is possible to enumerate ADEKA RESIN EP-4000S, ADEKA RESIN EP-4003S, ADEKA RESIN
EP-4010S, ADEKA RESIN EP-4011S (more than, ADEKA CORPORATION manufacture), NC-2000, NC-3000, NC-
7300th, XD-1000, EPPN-501, EPPN-502 (more than, ADEKA CORPORATION manufacture), Denacol EX-611, EX-
612、EX-614、EX-614B、EX-622、EX-512、EX-521、EX-411、EX-421、EX-313、EX-314、EX-321、
EX-211、EX-212、EX-810、EX-811、EX-850、EX-851、EX-821、EX-830、EX-832、EX-841、EX-911、
EX-941、EX-920、EX-931、EX-212L、EX-214L、EX-216L、EX-321L、EX-850L、DLC-201、DLC-203、
DLC-204, DLC-205, DLC-206, DLC-301, DLC-402, EX-111, EX-121, EX-141, EX-145, EX-146,
EX-147, EX-171, EX-192 (more than, Nagase ChemteX Corporation manufacture), YH-300, YH-301, YH-
302nd, YH-315, YH-324, YH-325 (more than, NIPPON STEEL CHEMICAL CO., LTD. manufacture), CE LLOXIDE
2021P, 2081,2000,3000, EHPE3150, EPOLEAD GT400, SERUBINASU B0134, B0177 (more than,
Daicel Chemical Industries Ltd. are manufactured) etc..
These can be used alone a kind, or combine two or more and use.
Wherein, bisphenol A type epoxy resin, bisphenol f type epoxy resin, phenolic resin varnish type epoxy resin and fat are more preferably enumerated
Fat race epoxy resin, particularly preferably enumerates aliphatic epoxy resin.
As the concrete example of the compound in intramolecular with oxetanylmethoxy, Aron Oxetane OXT- can be used
201st, OXT-211, OXT-212, OXT-213, OXT-121, OXT-221, OX-SO, PNOX (more than, TOAGOSEI CO., LTD.
Manufacture).
Also, the compound comprising oxetanylmethoxy, is preferably individually used, or with the compound comprising epoxy radicals
Mixed and used.
Wherein, in the manufacture method of the circuit layout of the present invention, from the viewpoint of corrosion resistance and line width stability, just
Type photosensitive material preferably above-mentioned (C) miscellaneous cyclic compound is the compound with epoxy radicals.
Also, intramolecular has the compound of alkoxyl silicone alkyl structure and miscellaneous both structures of cyclic structure simultaneously, also can
It is enough to be preferably used in positive light sensitivity material.For example, γ-glycidyloxypropyl silane, γ-
Glycidoxypropyl alkyl-dialkoxysilanes, β-(3,4- epoxycyclohexyls) ethyltrialkoxysilanes.Wherein, it is more excellent
Select γ-glycidyloxypropyl silane.These can be used alone a kind, or combine two or more and use.
< surfactants >
Above-mentioned positive light sensitivity material can contain surfactant.As surfactant, can use anionic species,
Any of cationic, nonionic class or both sexes, but preferable surfactant is nonionic class surfactant.
As the example of nonionic class surfactant, can enumerate:Polyoxyethylene higher alkyl ether, polyoxyethylene are high
Level alkyl phenyl ethers, the higher aliphatic acid diesters class of polyoxyethylene glycol, silicone, fluorine class surfactant.Also, press
Following trade name can enumerate KP (Shin-Etsu Chemical Co., Ltd. manufacture), POLYFLOW (Kyoeisha
Chemical Co., Ltd. manufacture), EFTOP (manufacture of JEMCO societies), Megafac (DIC CORPORATION manufactures),
Fluorad (Sumitomo 3M Limit ed manufactures), AsahiGuard, Surflon (ASAHI GLASS CO., LTD. systems
Make), PolyFox (OMNOVA SOLUTIONS INC. manufactures), SH-8400 (Dow Corning Toray Co., Ltd silicone)
Etc. various series.
Also, as surfactant, following copolymer can be enumerated and be used as preference:It is included by following formulas
(I-1) the construction unit A and construction unit B represented, in the case where tetrahydrofuran (THF) is set into solvent, is oozed by gel
Saturating chromatography and the weight average molecular weight (Mw) of polystyrene conversion that determines is less than more than 1,000 10,000.
Formula (I-1)
[chemical formula 29]
(in formula (I-1), R401And R403Separately represent hydrogen atom or methyl, R402It is more than 1 to represent carbon number
And less than 4 straight-chain alkyl-sub, R404Represent hydrogen atom or carbon number for more than 1 and less than 4 alkyl, L expression carbon numbers
For more than 3 and less than 6 alkylidene, p and q are the mass percent for representing polymerization ratio, and p represents more than 10 mass % and 80 matter
Measure below % numerical value, q represents more than 20 mass % and below 90 mass % numerical value, r represent more than 1 and less than 18 it is whole
Number, s represent more than 1 and less than 10 integer.)
Above-mentioned L is preferably the branched alkylidene represented by following formulas (I-2).R in formula (I-2)405Represent carbon atom
Number for more than 1 and less than 4 alkyl, from the aspect of intermiscibility and wetability to being applied face, preferably carbon number be 1 with
It is upper and less than 3 alkyl, more preferably carbon number is 2 or 3 alkyl.P and q sums (p+q) are preferably p+q=100, i.e. 100
Quality %.
Formula (I-2)
[chemical formula 30]
The weight average molecular weight (Mw) of above-mentioned copolymer is more preferably more than 1,500 and less than 5,000.
It is further possible to [0017] paragraph, Japanese Unexamined Patent Publication 2009- using No. 4502784 publications of Japanese Patent No.
Surfactant described in [0060] of No. 237362 publications~[0071] paragraph.
These surfactants can be used alone, or mixes two or more and use.
The addition of surfactant in above-mentioned positive light sensitivity material it is relative with it is total in positive light sensitivity material
The mass parts of solid constituent 100 are preferably below 10 mass parts, more preferably 0.001~10 mass parts, more preferably 0.01
~3 mass parts.
< radiation absorbance agent >
Positive light sensitivity material used in the present invention further preferably includes radiation absorbance agent.As radiation absorbance
Agent, preferably ultra-violet absorber.More preferably using it is being reduced by ultraviolet radiation absorption and absorbance, show so-called photic drift
The ultra-violet absorber of white property.Specifically, the light achromicities such as the azido derivant of naphthoquinones two, nitrone and diazol can be enumerated
Material (such as Japanese Patent Publication 62-40697 publications, M.S asano et al., SPIE Symp.Proc., 631,321
(1986) compound described in).
Radiation absorbance agent is so that the light intensity distributions in resist layer used for the purpose of being averaged, by assigning
Add formula CEL (Contrast Enhancement Lithography in meaning:Contrast strengthen photoetching) effect and figure can be obtained
Squaring, edge roughness the improvement of case (refers to semiconductor technology mate and chemicals, the positive allusion quotation chief editor of slope sheet, CMC go out
Version (2006)).
The other composition > of <
In positive light sensitivity material in addition to adding mentioned component, additionally it is possible to add:Metal oxide particle, except miscellaneous
Crosslinking agent, alkoxysilane compound containing trialkylsilyl group in molecular structure, antioxidant, dispersant, sour accelerator, development accelerant beyond cyclic compound,
Conducting fibre, colouring agent, plasticizer, hot radical producing agent, thermal acid generator, ultra-violet absorber, thickener and organic
Or additive known to inorganic suspending agent etc..
On the preferred embodiment of other compositions, be recorded in respectively [0165] of Japanese Unexamined Patent Publication 2014-85643 publications~
[0184] in, the content of the publication is merged in this specification.
< has the compound > of ethylenic unsaturated bond
In the manufacture method of the circuit layout of the present invention, from the viewpoint of resolution ratio, in positive light sensitivity material,
The amount of compound with ethylenic unsaturated bond is preferably 0 mass %.In addition, also include not damage the present invention in 0 mass %
The degree of effect include the mode of micro (such as being below 1 mass % in positive light sensitivity material).
The thickness > of < positive light sensitivity materials
The thickness of positive light sensitivity material is preferably 0.5~10 μm.If the thickness of positive light sensitivity material is less than 10 μm,
Then the resolution ratio of pattern is good, is then preferable from the viewpoint of pattern linearity degree if more than 0.5 μm.
As the thickness of positive light sensitivity material, more preferably 0.8~5 μm, especially preferably 1.0~3.0 μm.
The forming method > of < positive light sensitivity materials
Each composition is mixed with defined ratio and arbitrary method, and carries out stirring and dissolving, so as to prepare
Go out the photosensitive polymer combination for forming positive light sensitivity material.Such as each composition is set as respectively to be dissolved in solvent in advance
In solution after, these solution are mixed with defined ratio, so as to can also prepare resin combination.As more than
The composition solution prepared also can be after being filtered for entering to exercise using filter that aperture is 0.2 μm etc.
With.
< contrast enhancing layers >
In the manufacture method of the circuit layout of the present invention, preferably positive light sensitivity material includes photo-sensitive resin and right
Than degree enhancement layer.On photo-sensitive resin, above-mentioned photo-sensitive resin can be used as positive light sensitivity material.
On using contrast enhancing layer (Contrast Enhancement Layer;CEL CEL methods (Contrast)
Enhancement Layer Method:Contrast enhancement process) illustrate.It is such as existed by the Griffing of G.E. companies
Nineteen eighty-three delivers (B.F.Griffing, P.R.West;IEEE E lectron Device Letters, Vol ED1-4,14,
1983), U.S. Patent No. 4,702, No. 996, disclosed in Japanese Patent Publication 62-40697 publications, main use is by passing through light
And the discoloration compound film of light that the material to be faded i.e. aryl nitrone compound and polymer bonds mixture are formed.Photic anti-
The discoloration compound film of the light is also formed on erosion film, and pattern is formed according to the process of routine.Generally, in exposure, pass through
Photomask and the irradiation of some dim lights is also seen in the part that should block light because of Gan Wataru effects, the part passes through the discoloration film of light
(CEL) light is blocked, exposure portion and the enhancing of the contrast in unexposed portion is realized, is favorably improved resolution ratio and the depth of focus.
It is also preferred that forming intermediate layer on positive light anti-etching agent, degree of being contrasted enhancement layer (below, claims on the intermediate layer
Make CEL).Intermediate layer is the layer for preventing CEL from being mixed with positive light anti-etching agent.Such as Japanese Unexamined Patent Publication 2-212851
Disclosed in publication, CEL is big containing the absorption before exposure to exposure wavelength, is absorbed with exposure and is gradually reduced i.e. light
The layer for the material (being referred to as light achromicity pigment composition) that transmissivity uprises.As light achromicity pigment composition, it is known to diazonium
Salt, stilbene azoles salt, arylnitroso salt.As overlay film forming component, phenolic resin etc. can be used.
In addition, spend enhancement layer as a comparison, can use [0004] of Japanese Unexamined Patent Publication 6-97065 publications~
[0051], [0012] of Japanese Unexamined Patent Publication 6-332167 publications~[0055], photopolymer handbook, The Technical
Association of Photopolymers, Japan write, Kogyo Chos akai Publishing Co., Ltd.s
(1989), photopolymer/technology, hillock, pine is write forever, pair described in NIK KAN KOGYO SHIMBUN, LTD. (1988)
Than degree enhancement layer.
< (b) processes >
Illustrated on (b) process:The circuit forming board formed to eurymeric photosensitive material carries out pattern exposure
And development, so as to which positive light sensitivity material is set into the 1st pattern.
, in the present invention can be preferably using Japan as the example of above-mentioned exposure process, developing procedure and other processes
Described method in [0035] of JP 2006-23696 publications~[0051] paragraph.
Specifically, following method can be enumerated:Positive light sensitivity material on being formed at the 1st layer of above-mentioned conductive layer
Top configuration as defined in mask, the light source above the rear mask, be exposed via mask (positive light sensitivity material have
In the case of having temporary support and photosensitive polymer combination layer, the light source above mask, via mask and temporary support
Body is exposed to photosensitive polymer combination layer) etc..
There is no particular limitation for the detailed configuration of pattern and specific size in the present invention.Possesses the present invention from being intended to improve
Input unit display device (such as touch panel) display quality, also, be intended to reduce wiring lead occupied area as far as possible,
Therefore at least one (the especially part of the electrode pattern of touch panel and wiring lead) of preferred pattern is less than 100 μm thin
Line, more preferably less than 70 μm.
Here, the light source as above-mentioned exposure, can preferably select the portion that positive light sensitivity material is exposed that can irradiate
Position can be dissolved in the light (such as 365nm, 405nm etc.) of the wavelength region of developer solution.Specifically, ultra high pressure mercury can be enumerated
Lamp, high-pressure sodium lamp, metal halide lamp etc..It is 5~200mJ/cm generally as light exposure2Left and right, preferably 10~
100mJ/cm2Left and right.
Also, after exposing, for the purpose of the rectangularity and the linearity that improve pattern, hot place is preferably carried out before developing
Reason.PEB (Post Exposure Bake are referred to as by so-called:Postexposure bake) the process, when can reduce exposure by
The roughness at Resist patterns edge caused by the standing wave generated in resist.
In addition, pattern exposure can be carried out after supporter is peeled off, can also be exposed before supporter is peeled off,
Supporter is peeled off afterwards.Pattern exposure can be via mask exposure or used the digit explosure of laser etc..
Above-mentioned developing procedure is the process to being developed by the positive light sensitivity material of pattern exposure.
Above-mentioned development can be carried out using developer solution.As above-mentioned developer solution, it is not particularly limited, can uses
Developer solution known to developer solution described in Japanese Unexamined Patent Publication 5-72724 publications etc..In addition, developer solution is preferably positive type light sensitive
Property material carry out the developer solution of lysotype development behavior, such as pKa=7~13 are preferably included with 0.05~5mol/L concentration
Compound, but the organic solvent that there is miscibility with water can also be added on a small quantity.As the organic solvent with water with miscibility,
Methanol, ethanol, 2- propyl alcohol, 1- propyl alcohol, butanol, DAA, glycol monoethyl ether, ethylene glycol monoethyl ether, second two can be enumerated
Alcohol list N-butyl ether, benzylalcohol, acetone, MEK, cyclohexanone, 6-caprolactone, gamma-butyrolacton, dimethylformamide, dimethyl second
Acid amides, hexamethyl phosphoramide, ethyl lactate, methyl lactate, epsilon-caprolactams, N- methylpyrrole pyridine ketone etc..The organic solvent
Concentration is preferably the mass % of 0.1 mass %~30.
Also, known surfactant can also be added in above-mentioned developer solution.The concentration of surfactant is preferably
The mass % of 0.01 mass %~10.
Can be sheathed immersion development, spray develops, spray & rotates development, dipping shows as the mode of above-mentioned development
Any of shadow etc..Here, illustrated on the development of above-mentioned spray, by passing through to the positive light sensitivity material after exposure
Spray and spray attachment developer solution and exposed portion can be removed.In addition, it is being provided with thermoplastic resin layer and intermediate layer, CEL layers etc.
In the case of, it is also preferred that before developing, by spraying etc. and the low cleaning fluid of the dissolubility of spray attachment positive light sensitivity material, go
Except thermoplastic resin layer, intermediate layer, CEL layers etc..Also, it is preferred that after developing, by spray and spray attachment cleaning agent etc., on one side
Wiped with hairbrush etc., while removing development residue.The fluid temperature of developer solution is preferably 20 DEG C~40 DEG C, also, is developed
The pH of liquid is preferably 8~13.
Furthermore, it is also possible to there is post-bake process:To including the positive light sensitivity material as obtained from above-mentioned development
Pattern is heated, more preferably including following process:In the process for removing above-mentioned thermoplastic resin layer and above-mentioned intermediate layer
Afterwards, the rear baking heated to the pattern being made up of the positive light sensitivity material as obtained from above-mentioned development is carried out
It is roasting.
By that with above-mentioned post-bake process, can promote in positive light sensitivity material using the solution of sour protection group
Inhale, therefore preferably.From the activation energy for reducing protection group desorption, from the viewpoint of avoiding the heating after exposure, preferred eurymeric
The construction unit (a1) of the group protected with above-mentioned acidic group by sour decomposability base in photosensitive material.
The heating of baking is carried out preferably in the environment of 0.08~1.2atm after above-mentioned, more preferably the ring in more than 0.5atm
Carried out under border.On the other hand, more preferably carried out under below 1.1atm environment, particularly preferably under below 1.0atm environment
Carry out.Moreover, from the viewpoint of the decompressor without using special Do can reduce manufacturing cost, particularly preferably about in 1atm
Carried out under (atmospheric pressure) environment.
The temperature of baking is preferably 110~170 DEG C after above-mentioned, more preferably 120~160 DEG C, especially preferably 130~
150℃。
The time of baking is preferably 1~30 minute after above-mentioned, more preferably 2~10 minutes, especially preferably 2~4 minutes.
Baking can be carried out under air ambient after above-mentioned, can also be carried out in the case where nitrogen substitutes environment, but from without using spy
Do decompressor and from the viewpoint of manufacturing cost being reduced, particularly preferably carried out under air ambient.
(b) process can have other processes such as post-exposure process.
< (c) processes >
Illustrated on (c) process:I is set to more than 1 and below x integer, set for not formed in (b) process
The 1st layer to i-th layer for the conductive layer of the positive light sensitivity material area of the 1st pattern is etched.
Above-mentioned etching can be applied described in [0048] of Japanese Unexamined Patent Publication 2010-152155 publications~[0054] paragraph etc.
Method etc. known to engraving method.
Such as the method as etching, the wet etching being impregnated in etching solution generally carried out can be enumerated.Use
As long as the etching solution in Wet-type etching coordinates the object of etching and properly selects acid type or the etching solution of alkaline type
.As the etching solution of acid type, can exemplify hydrochloric acid, sulfuric acid, fluoric acid, phosphoric acid etc. individually the aqueous solution of acid ingredient,
Mixed aqueous solution of salt such as acid ingredient and iron chloride, ammonium fluoride, potassium permanganate etc..Acid ingredient can use and combine a variety of acid
The material of property composition.Also, as the etching solution of alkaline type, such as sodium hydroxide, potassium hydroxide, ammonia, organic can be exemplified
The salt such as the aqueous solution, alkaline components and potassium permanganate of the independent alkaline components such as organic amine salts such as amine, TMAH mix
Heshui solution etc..Alkaline components can also use the material for combining a variety of alkaline components.
There is no particular limitation for the temperature of etching solution, but preferably less than 45 DEG C.In the present invention, as etching mask (erosion
Needle drawing case) and acidity and alkaline etching liquid in the positive light sensitivity material preferred pair said temperature region that uses play it is especially excellent
Different patience.Therefore, the stripping of positive light sensitivity material can be prevented in etching work procedure, can be etched selectively to be not present
The part of positive light sensitivity material.
After above-mentioned etching, in order to prevent producing line pollution, matting and/or back tender can be carried out as needed
Sequence.On matting, such as base material can be cleaned 10~300 seconds with pure water at normal temperatures, on drying process, use drum
Wind suitably adjusts blast pressure (0.1~5kg/cm2Left and right).
< (d) processes >
Illustrated on (d) process:For the positive light sensitivity material remained in (b) process, with being remained
The different pattern of positive light sensitivity material carries out pattern exposure and development, so as to which positive light sensitivity material is set into the 2nd pattern.
(d) pattern exposure in process and development can use and the pattern exposure in (b) process and development identical side
Method.
< (e) processes >
Illustrated on (e) process:J is set to 1 integer less than i, and set for not formed in (d) process
It is etched for the 1st layer of conductive layer of the positive light sensitivity material area of the 2nd pattern to jth layer.
(e) etching in process can use and the etching identical method in (c) process.
(e) in process, the conductive layer fewer than (c) process is preferably etched selectively to according to desired pattern.
< (f) processes >
The manufacture method of the circuit layout of the present invention preferably also includes following (f) process.
(f) process:By the positive light sensitivity material remained with the pattern different from the positive light sensitivity material remained
Pattern exposure and development are carried out, so as to after development to not forming the 1st layer of conductive layer of positive light sensitivity material area to small
It is etched in j arbitrary layer, so as to which conductive layer is set into pattern.
Hereinafter, illustrated on (f) process.
In the manufacture method of the circuit layout of the present invention, it is also preferred that without (f) process.That is, in the circuit of the present invention
In the manufacture method of distribution, preferred circuit distribution only includes the conductive layer of 2 kinds of patterns.
(f) number of repetition of process is not particularly limited, and can be repeated according to the shape of desired pattern.
Wherein, the number of repetition of (f) process is preferably 1 time.
In the manufacture method of the circuit layout of the present invention, preferably (f) process includes following (f1) processes and (f2) process, and
Include the conductive layer of at least three kinds of patterns.
(f1) process, to the positive light sensitivity material remained in (e) process, with the positive light sensitivity material remained
Different patterns carries out pattern exposure and development, so as to which positive light sensitivity material is set into the 3rd pattern;And
(f2) process, k is set to 1 integer less than j, and the 3rd figure is set to for not formed in (f1) process
The 1st layer of the conductive layer of the positive light sensitivity material area of case to kth layer is etched.
The preferred embodiment of other (f) process is identical with (d) process and (e) process.
< (z) processes >
Illustrated on (z) process:All positive light sensitivity materials remained are removed, formation includes at least two kinds of figures
The circuit layout of the conductive layer of case.
As the method for removing all positive light sensitivity materials remained after above-mentioned etching process, special limit is had no
System, the method handled by medicine to remove can be enumerated.
As the minimizing technology of positive light sensitivity material, for example, at 30~80 DEG C, preferably at 50~80 DEG C
The base material method of 5~30 minute of the dipping with positive light sensitivity material etc. in stripper in lower stirring.As etching mask
And the resin pattern used 45 DEG C it is shown below go out excellent chemical resistance, but preferably fluid temperature turn into 50 DEG C with
On, then show the property being swelled by alkaline stripper.According to above-mentioned property, if being carried out using 50~80 DEG C of stripper
Stripping process, then activity time shortening, there is the advantages of stripping residue reduction of positive light sensitivity material.That is, in above-mentioned etching
Between process and the process for removing positive light sensitivity material, by setting difference in fluid temperature, make as etching mask
Positive light sensitivity material plays good chemical resistance in etching work procedure, on the other hand, is shown in removing step
Good fissility, it thus disclosure satisfy that chemical resistance and fissility the two opposite characteristics.
As stripper, for example, by the inorganic alkaline such as sodium hydroxide, potassium hydroxide composition, tertiary amine, quaternary ammonium salt
Deng organic basic composition, the stripper being dissolved in water, dimethyl sulfoxide (DMSO), N- methylpyrrole pyridine ketone or their mixed solution.
Above-mentioned stripper can also be used, and is peeled off by spray-on process, spray process, sheathed immersion method etc..
< lowers the processing > of luminous ray reflectivity
The manufacture method of the circuit layout of the present invention can include following process:Enter to exercise the conductive layer of xth layer to the 1st layer
Part or all of luminous ray reflectivity reduce processing.
As the processing for reducing luminous ray reflectivity, oxidation processes etc. can be enumerated.Such as by carrying out oxygen to copper
Change processing and be set to cupric oxide, thus melanism and can make luminous ray reflectivity reduction.
On the preferred embodiment for the processing for making the reduction of luminous ray reflectivity, Japanese Unexamined Patent Publication 2014-150118 is recorded in
[0017] of publication~[0025] and [0041] of Japanese Unexamined Patent Publication 2013-206315 publications, [0042], [0048] and
[0058], the content of these publications is merged in this specification.
< forms the process > of new conductive layer on dielectric film
The manufacture method of the circuit layout of the present invention preferably includes:Formed on the circuit layout formed in (z) process exhausted
The process of velum;And the process that new conductive layer is formed on dielectric film.
According to said structure, aftermentioned second electrode pattern can be formed, and it is insulated with first electrode pattern.
Process on forming dielectric film, is not particularly limited, and can enumerate the known method for forming permanent film.And
And the photosensitive material with insulating properties can also be used, and the dielectric film of desired pattern is formed by photoetching.
Process on forming new conductive layer on dielectric film, is not particularly limited.Can also use has conduction
Property photosensitive material, and form by photoetching the new conductive layer of desired pattern.
[circuit layout]
The circuit layout of the present invention is the circuit layout to manufacture by the manufacture method of the circuit layout of the present invention.This hair
Bright circuit line is preferably touch panel circuit layout.On the preferred embodiment of touch panel circuit layout, below
Described in the explanation of capacitive input device.
[input unit and display device]
The input unit of the present invention is the input unit for having used the circuit layout of the present invention.The input unit of the present invention is excellent
Elect capacitance type touch panel as.
The display device of the present invention possesses the input unit of the present invention.It is preferred that the display device of the present invention is image display dress
Put.
< capacitive input devices and the image display device > for possessing capacitive input device
The present invention input unit and display device preferred embodiment capacitive input device and by the electrostatic electricity
The image display device that appearance type input unit possesses as constitutive requirements, it can apply in " newest touch panel technologies "
The chief editor of (on July 6th, 2009 distribution Techno Times Co., Ltd.), three paddy hero two, " technology of touch panel and exploitation ",
CMC publishes (2004,12), FPD Internation al 2009Forum T-11 lecture materials, Cypress
Structure disclosed in Semiconductor Corporation application manuals AN2292 etc..
First, the structure of capacitive input device is illustrated.Figure 16 is to represent capacitive input device
Structure sectional view.Capacitive input device 10 is by base material 1, mask layer 2, first electrode pattern 3, second in figure 16
Electrode pattern 4, insulating barrier 5, another electric conductivity important document 6 and protective clear layer 7 are formed.
In figure 16, the side for being provided with each important document of base material 1 is referred to as non-contact face.Inputted in above-mentioned capacitance type
In device 10, make the contact surface (opposing face in non-contact face) of the contact base material 1 such as finger and inputted.
Also, it is provided with mask layer 2 on the non-contact face of base material 1.Mask layer 2 is in (such as the touch panel of base material 1
Front panel) the viewing area that is formed of non-contact side around frame-shaped pattern, in order that winding distribution etc. is not visible and shape
Into.
, can also be to be set in a manner of a part of region for covering base material 1 on above-mentioned capacitive input device 10
There is mask layer 2.Moreover, can opening portion be locally also set on base material 1.On opening portion, it can also set by by being pressed into
The mechanical switch of row operation.
Formed on the non-contact face of base material 1:Multiple first electrode patterns 3, multiple pad portions are via coupling part edge
First direction extends to be formed;Multiple second electrode patterns 4, are electrically insulated with electrode pattern 3, and the direction by intersecting in the first direction
Multiple pad portions that extension is formed are formed;And insulating barrier 5, first electrode pattern 3 and second electrode pattern 4 are carried out electric exhausted
Edge.Above-mentioned first electrode pattern 3, second electrode pattern 4 and aftermentioned another electric conductivity important document 6 are preferably transparent.Transparent first
Electrode pattern 3, second electrode pattern 4 and another electric conductivity important document 6 are preferably conductive film, can be for example, by ITO (Indium
Tin Oxide:Tin indium oxide) and IZO (Indium Zinc Oxide:Indium zinc oxide) etc. transparent conductive metal oxide
Film and make.As conductive film, the metal films such as Al, Zn, Cu, Fe, Ni, Cr, Mo can be enumerated;ITO、IZO、SiO2Deng metal
Oxidation film etc..Now, the thickness of each important document can be set to 10~200nm.Also, amorphous state ito film is set to by calcining
Poly-ITO film and resistance can be reduced.
Also, above-mentioned first electrode pattern 3 and second electrode pattern 4 are against corrosion by the way that positive light sensitivity material is used as into etching
Agent (etched pattern) and formed.In the formation of the second electrode lay for forming second electrode pattern, except with the present invention
Outside the photoetching of resist headed by used positive light sensitivity material, additionally it is possible to method known to utilization.It is further possible to
Manufactured using the photosensitive transfer printing material with the photosensitive polymer combination for having used conducting fibre.Passing through
ITO etc. and in the case of forming first conductive pattern etc., can refer to [0014] of No. 4506785 publications of Japanese Patent No.~
[0016] paragraph etc..
Also, it is at least one in first electrode pattern 3 and second electrode pattern 4, can be across the non-contact face of base material 1
And mask layer 2 is set with the two regions of face of 1 opposite side of base material.Figure 16 illustrates shown across second electrode pattern
The figure set with the two regions of face of 1 opposite side of base material of the non-contact face of base material 1 and mask layer 2.
Illustrated using Figure 11 and 12 pair of first electrode pattern and second electrode pattern 4.Figure 11 and 12 and represent the
The explanation figure of one of one electrode pattern and second electrode pattern.As shown in Figure 11 and 12, pad portion in first electrode pattern
3a is extended in a first direction and formed via coupling part 3b.Also, second electrode pattern 4 by insulating barrier 5 and with first electricity
Pole figure case is electrically insulated, by extending the multiple welding disks formed along the direction (second direction in Fig. 3) intersected with first direction
Divide and form.Here, in the case where forming first electrode pattern 3, can be by above-mentioned pad portion 3a and coupling part 3b systems
Make integrally, can also only make coupling part 3b, pad portion 3a and second electrode pattern 4 are made into (formation pattern) into one
Body.In the case that pad portion 3a and second electrode pattern 4 are made into (formation pattern) integrally, as shown in Figure 11 and 12, respectively
Layer is formed as:A coupling part 3b part and pad portion 3a part connection, and first electrode pattern 3 and second
Electrode pattern 4 is electrically insulated by insulating barrier 5.
In figure 16, the surface side of 1 opposite side of base material is provided with another electric conductivity important document 6 in mask layer 2.Another conduction
Property important document 6 electrically connects with least one in first electrode pattern 3 and second electrode pattern 4, and with first electrode pattern 3 and
Two electrode patterns 4 are different important documents.In figure 16, show that another electric conductivity important document 6 is connected to second electrode pattern 4
Figure.
Also, in figure 16, it is provided with protective clear layer 7 in a manner of covering each constitutive requirements entirety.Protective clear layer 7
Can also be to be formed in a manner of only covering a part for each constitutive requirements.Insulating barrier 5 and protective clear layer 7 can be identical materials
Material, also can be able to be different materials.As the material for forming insulating barrier 5 and protective clear layer 7, preferred case hardness, heat-resisting
Property high material, known photo-sensitive siloxane resin material, acrylic materials etc. can be used, these materials are for this
It is known for the practitioner of field.
The formation patterning method of insulating barrier can also be utilized known to ink-jet, silk-screen printing etc. in addition to photolithographicallpatterned
Method.
In the manufacture method of above-mentioned capacitive input device, preferably above-mentioned first electrode pattern 3, second electrode figure
Positive light sensitivity material is used as etching resist (etched pattern) and carried out by least one in case 4 and another electric conductivity important document 6
Etching process and formed.Also, the mask layer 2 and insulating barrier 5 of black, as needed, in protective clear layer 7 it is at least one will
Part, it is also preferred that using successively have temporary support, thermoplastic resin layer and light-cured resin layer photosensitive film and shape
Into.
At least one in above-mentioned first electrode pattern 3, second electrode pattern 4 and another electric conductivity important document 6, preferably will just
Type photosensitive material is used as etching resist (etched pattern) and is etched and is formed.
Above-mentioned first electrode pattern 3, second electrode pattern 4 and another electric conductivity important document 6 are formed by etching process
In the case of, first, on the non-contact face of the base material 1 formed with black mask layer 2, in the part provided with black mask layer 2 extremely
Inorganic insulation layer is set less, the transparency electrodes such as ITO are formed by sputtering on the non-contact face of base material 1 or on inorganic insulation layer
Layer.Then, on above-mentioned transparent electrode layer, there is etching light-cured resin using as above-mentioned light-cured resin layer
The positive light sensitivity material of layer, and form etched pattern by exposed and developed.Afterwards, transparent electrode layer is etched and
Pattern is carried out to transparency electrode to be formed, and first electrode pattern 3 etc. can be formed by removing etched pattern.
Above-mentioned the is being formed using the above-mentioned photosensitive film with the light-cured resin layer comprising conductive material
, can be by the surface of above-mentioned base material 1 in the case of one electrode pattern 3, second electrode pattern 4 and another electric conductivity important document 6
On be provided with the part of black mask layer 2 at least provided with inorganic insulation layer, on the non-contact face of base material 1 or on inorganic insulation layer
Transfer the light-cured resin layer comprising above-mentioned conductive material and formed.
Aforementioned mask layer 2, insulating barrier 5 and protective clear layer 7 can be by using photosensitive films by light-cured resin
Layer is transferred to base material 1 and formed.Such as in the case where forming black mask layer 2, can be by using as photo-curable tree
Lipid layer and with black light-cured resin layer above-mentioned photosensitive film, in the above-mentioned black light of surface transfer of above-mentioned base material 1
Curable resin layer and formed., can be by using as the above-mentioned light-cured resin of use in the case where forming insulating barrier 5
Layer and with insulating properties light-cured resin layer above-mentioned photosensitive film, formed with first electrode pattern or second electrode figure
The above-mentioned light-cured resin layer of surface transfer of the above-mentioned base material 1 of case and formed.In the case where forming protective clear layer 7, energy
It is enough that there is the above-mentioned photosensitive film of transparent light-cured resin layer by using as above-mentioned light-cured resin layer,
The above-mentioned light-cured resin layer of surface transfer of above-mentioned base material 1 formed with each important document and formed.
Embodiment
Hereinafter, embodiment is enumerated to the present invention and then is specifically illustrated.The material that is shown in following examples, use
Amount, ratio, process content, processing sequence etc., just can suitably it be changed without departing from the purport of the present invention.So as to,
The scope of the present invention is not limited to concrete example as shown below.In addition, as long as no special explanation, " part ", " % " are matter
Measure benchmark.
[embodiment 1]
< (a) processes >
In the PET base material of 100 μm of thickness, as the 2nd layer of conductive layer, ITO is carried out by sputtering with 150nm thickness
Film forming, thereon, as the 1st layer of conductive layer, copper is subjected to film forming by vacuum vapour deposition with 200nm thickness, and be set to electricity
Road forms substrate.
Moreover, make the dry film photoresist used as positive light sensitivity material by the following method.Use
The eurymeric resist FH2405 of FUJIFILM Electronic Materials Co., Ltd.s manufacture, passes through Japanese Unexamined Patent Publication
Method described in 2007-24969 [0278] paragraph is made, in 75 μm of polyethylene terephthalate thin film of thickness
On supporter (temporary support), eurymeric resist is coated with a manner of dry film thickness turns into 2.0 μm using slit-shaped nozzle.
Afterwards, using 100 DEG C of stream oven drying 2 minutes, finally, as diaphragm by polyethylene film (Tredegar
Corporation is manufactured, OSM-N) crimped and produce dry film photoresist.The dry film photoresist is to include the nitrine of naphthoquinones two
Compound and with phenolic hydroxyl group resin positive light sensitivity material.
Above-mentioned dry film photoresist is laminated in the 1st layer (layers of copper) of conductive layer, foring positive light sensitivity material, (eurymeric resists
Lose oxidant layer).
< (b) processes >
By the positive light sensitivity material (eurymeric resist layer), using with the structure that conductive welding disk is connected with along a direction
The light shielding part for being provided with pattern A shown in Fig. 4 and the photomask of opening portion carry out pattern exposure, carry out having used tetramethyl hydrogen
The mass % of amine-oxides (TMAH) aqueous solution 2.38 development and washing, so as to obtain the 1st pattern (pattern A light shielding part region shape
The pattern of shape).
Solid line portion and grey portion are light shielding part in pattern A shown in Fig. 4, and other parts are opening portion, and dotted line part is virtually
The part of the frame of alignment is shown.Also, solid line portion is set as less than 70 μm of fine rule.Hereinafter, in other embodiments and comparative example
It is also formed with identical fine rule.
< (c) processes >
Then, the 1st layer (layers of copper) is entered using copper etchant solution (Cu-02 of KANTO CHEMICAL CO., INC. manufactures)
After row etching, the 2nd layer (ITO layer) is entered using ITO etching solutions (ITO-02 of KANTO CHEMICAL CO., INC. manufactures)
Etching is gone.By being so etched, the 1st layer to the 2nd of above-mentioned conductive layer to not forming positive light sensitivity material area
Layer be etched, do not formed the positive light sensitivity material area for being set to the 1st pattern the 1st layer (layers of copper) and the 2nd layer
(ITO layer) is depicted as the substrate of the 1st pattern (pattern of pattern A light shielding part region shape).
< (d) processes >
Then, the state for using to be aligned is provided with the pattern B opening portion shown in Fig. 5 and the photomask of light shielding part enters
Row pattern exposure, used the TMAH aqueous solution 2.38% development and washing and obtain the 2nd pattern (pattern A light shielding part
And the pattern of pattern B light shielding part lap).
Grey portion is light shielding part in the pattern B shown in Fig. 5, and other parts are opening portions, and dotted line part is virtually to show
The part of the frame of alignment.
< (e) processes >
Afterwards, only the 1st layer (layers of copper) is etched using Cu-02, is thus etched to not formed and is being set to the 2nd pattern just
The 1st layer of the above-mentioned conductive layer in type photosensitive material region.Obtain only including the conduction of 2 kinds of patterns by being so etched
The substrate of layer.Resulting conductive layer, specifically, it is set to the 1st layer of the positive light sensitivity material institute forming region of the 2nd pattern
(layers of copper) and the 2nd layer (ITO layer) is depicted as pattern A (pattern of the light shielding part region shape of the 1st pattern), and is not formed and set
For the positive light sensitivity material area of the 2nd pattern the 2nd layer (ITO layer) be depicted as the 2nd pattern light shielding part region shape
Pattern.
< (z) processes >
The positive light sensitivity material that will be remained, by using stripper (KANTO CHEMICAL CO., INC. manufacture
KP-301) removed being peeled off, obtained circuit layout, real formed with the conductive layer comprising 2 kinds of patterns on base material
Apply the touch panel circuit layout of example 1.
The touch panel circuit layout of embodiment 1 has the circuit layout of pattern C shown in Fig. 6.Fig. 6 grey area
Wiring part included in domain is divided into the state that the 2nd layer (ITO distributions) exposes.Fig. 6 dotted line part Virtual table shows alignment
Frame.Part in addition equivalent to peripheral distribution part, turn into be laminated the 1st layer (copper wiring) on the 2nd layer (ITO distributions) and
The structure of more than 2 layers of the conductive layer stack comprising shared identical circuit pattern.On including shared identical circuit diagram
The structure of more than 2 layers of conductive layer stack of case, figure 3 illustrates schematic diagram.The touch panel circuit layout of embodiment 1
In, Fig. 3 dotted portion is overlapped with the 1st layer (copper wiring) on the 2nd layer (ITO distributions).
[embodiment 2]
In following synthesis example, following symbol represents following compound respectively.
MATHF:2- tetrahydrofuran methyls acrylate (synthetic)
MAEVE:1- ethoxyethyl methacrylates (Wako Pure Chemical Industries, Ltd. systems
Make)
PHS:4-Vinyl phenol
PHS-EVE:The 1- ethoxyethyl group protectives of 4-Vinyl phenol
PHS-THF:The 2- tetrahydrofuran protectives of 4-Vinyl phenol
PGMEA:Propylene glycol methyl ether acetate
< synthesis examples 1:PHS-EVE synthesis >
By alkali soluble resins (VP-8000NIPPON SODA CO., LTD. manufacture) 20g and propylene glycol methyl ether acetate
(PGMEA) 320g is dissolved in flask and is evaporated under reduced pressure, and water and PGMEA have been carried out into azeotropic distillation.Confirming aqueous quantitative change
After low situation, ethyl vinyl ether 24g and p-methyl benzenesulfonic acid 0.35g is added, has been stirred at room temperature 1 small
When.Triethylamine 0.28g is added to it and it is stopped reaction.Ethyl acetate is added in reaction solution, and then after being washed, is led to
The PGMEA for being evaporated under reduced pressure and removing ethyl acetate, water and azeotropic component is crossed, is obtained by the alkali soluble resins of sour decomposability base protection i.e.
PHS-EVE.The weight average molecular weight of resulting resin is 11,000.Also, polydispersity is 1.13.
Polymer P HS-EVE structure is as follows, is the 1- ethoxyethyl groups protective/to hydroxyl of 4-Vinyl phenol
Styrol copolymer (30 moles of %/70 mole %).
[chemical formula 31]
Positive light sensitivity composition is produced using synthesized PHS-EVE, and by formula as below.
·PHS-EVE:95.8 parts
Light acid producing agent (following PAG-1):2 parts
Sensitizer:(following sensitizers 1):2 parts
Alkali compounds (following alkali compounds 1):0.1 part
Surfactant (following surfactants 1):0.1 part
·PGMEA:900 parts
PAG-1:According under method synthesis described in [0108] paragraph of Japanese Unexamined Patent Application Publication 2002-528451 publications
State the compound of structure (Ts parts represent p-toluenesulfonyl).
[chemical formula 32]
Sensitizer 1:Dibutoxy anthracene (the manufacturer of following structures:Kawasaki Kasei Chemicals Ltd. systems
Make, goods number:9,10- dibutoxies anthracene)
[chemical formula 33]
Alkali compounds 1:Compound (the manufacturer of following structures:Toyo Kasei Co., Ltd.s manufacture, goods number:
CMTU)
[chemical formula 34]
Surfactant 1:F-554, the nonionic class surfactant containing perfluoroalkyl represented by following structural formula
(DIC Corporation are manufactured.Weight % is identical with quality % implications)
[chemical formula 35]
Following (a) process is carried out:By above-mentioned positive light sensitivity composition, the circuit used in embodiment 1 forms base
On plate, slot coated is carried out with 1.2 μm of thickness, is dried 2 minutes in 100 DEG C of stream baking oven, forms positive light sensitivity material
Expect (resist layer).
Afterwards, with order same as Example 1, the touch panel circuit layout of embodiment 2 is produced.
[embodiment 3]
The positive light sensitivity composition that will be produced in example 2, in 75 μm of PET of thickness
On film support (temporary support), it is coated using slit-shaped nozzle in a manner of dry film thickness turns into 2.0 μm,
Dried 2 minutes in 100 DEG C of stream baking oven, finally, using as the polyethylene film of diaphragm (Tredegar Corporation systems
Make, OSM-N) crimped, so as to produce dry film photoresist.
Following (a) process is carried out:After using the dry film photoresist, diaphragm is peeled off, institute in embodiment 1
The desciccator diaphragm of positive light sensitivity composition is transferred on the circuit forming board used, temporary support is peeled off and formed just
Type photosensitive material (resist layer).
Afterwards, the touch panel circuit layout of embodiment 3 is gone out with sequentially built same as Example 1.
[embodiment 4]
< synthesis examples 2:PHS-THF synthesis >
By alkali soluble resins (VP-8000NIPPON SODA CO., LTD. manufacture) 15.6g and propylene glycol monomethyl ether acetic acid
Ester (PGMEA) 100g is dissolved in bottle and is evaporated under reduced pressure, and water and PGMEA have been carried out into azeotropic distillation.Confirming aqueous quantitative change
After low situation, DHF 2.7g and p-methyl benzenesulfonic acid 0.015g is added, has been stirred at room temperature 2 small
When.Triethylamine 0.090g is added to it and it is stopped reaction.Ethyl acetate is added in reaction solution, and then carries out washing it
Afterwards, ethyl acetate, water are distilled by vacuum distillation, it is i.e. poly- for 25 moles of % soluble resin has obtained protective rate
Compound PHS-THF.The weight average molecular weight of resulting resin is 12,000.Also, polydispersity is 1.13.
Polymer P HS-THF structure is as follows, is 2- tetrahydrofurans protective/para hydroxybenzene of 4-Vinyl phenol
Ethylene copolymer (30 moles of %/70 mole %).
[chemical formula 36]
Positive light sensitivity composition is produced using synthesized PHS-THF, and by formula as below.
·PHS-THF:95.8 parts
Light acid producing agent (PAG-1):2 parts
Sensitizer:(sensitizer 1):2 parts
Alkali compounds (alkali compounds 1):0.1 part
Surfactant (surfactant 1):0.1 part
·PGMEA:900 parts
Using produced positive light sensitivity composition, made in a manner of same as Example 3 dry film photoresist it
Afterwards, the touch panel circuit layout of embodiment 4 is gone out with sequentially built same as Example 3.
[embodiment 5]
< synthesis examples 3:Polymer novolaks-EVE (1- ethoxyethyl groups protective) synthesis >
By polymer novolaks-EVE (the 1- ethoxyethyl group protectives of following structures.Construction unit ratio is mole
Than), synthesized in the identical method of embodiment 1 with Japanese Unexamined Patent Publication 2003-98671 publications.Resulting novolac resin
Weight average molecular weight be 5,000.Also, polydispersity is 7.0.
[chemical formula 37]
Positive light sensitivity composition is produced using synthesized novolac resin, and by formula as below.
Polymer novolaks-EVE (1- ethoxyethyl groups protective):95.8 parts
Light acid producing agent (PAG-1):2 parts
Sensitizer:(sensitizer 1):2 parts
Alkali compounds (alkali compounds 1):0.1 part
Surfactant (surfactant 1):0.1 part
·PGMEA:900 parts
Using produced positive light sensitivity composition, made in a manner of same as Example 3 dry film photoresist it
Afterwards, the touch panel circuit layout of embodiment 5 is gone out with sequentially built same as Example 3.
[embodiment 6]
< synthesis examples 4:The synthesis > of MATHF copolymers
Methacrylic acid (86g, 1mol) is cooled down at 15 DEG C, and with the addition of camphorsulfonic acid (4.6g,
0.02mol).2- dihydrofuran (71g, 1mol, 1.0 equivalents) is added dropwise in the solution.After stirring 1 hour, saturated carbon is added
Sour hydrogen sodium (500mL), is extracted with ethyl acetate (500mL), and after being dried using magnesium sulfate, insoluble matter is entered
Row filtering, then, is concentrated under reduced pressure with less than 40 DEG C of temperature, the yellow oil of residue is evaporated under reduced pressure, as
Colorless oil and the methacrylic acid tetrahydrochysene -2H- furans -2- bases for having obtained boiling point (bp.) 54~56 DEG C/3.5mmHg cuts
(MATHF) 125g and (yield 80%).
Methacrylic acid 1- ethoxyethyl groups are replaced using resulting methacrylic acid tetrahydrochysene -2H- furans -2- bases,
In addition, MATHF copolymers have been synthesized in a manner of with the synthesis identical of the MAEVE copolymers of synthesis example 4.
Resulting MATHF copolymers by gel permeation chromatography (GPC) and determine weight average molecular weight be 14,
000。
Hereinafter, the structure of the MATHF copolymers obtained by showing (construction unit ratio is mol ratio).
[chemical formula 38]
Positive light sensitivity composition is produced using synthesized MATHF copolymers, and by formula as below.
·PHS-EVE:47.9 parts
MATHF copolymers:47.9 parts
Light acid producing agent (PAG-1):2 parts
Sensitizer:(sensitizer 1):2 parts
Alkali compounds (alkali compounds 1):0.1 part
Surfactant (surfactant 1):0.1 part
·PGMEA:900 parts
Using produced positive light sensitivity composition, made in a manner of same as Example 3 dry film photoresist it
Afterwards, the touch panel circuit layout of embodiment 6 is produced by order same as Example 3.
[embodiment 7]
Positive light sensitivity composition is produced by formula as below.
·PHS-EVE:91.2 parts
Light acid producing agent (PAG-1):1.9 part
Sensitizer:(sensitizer 1):1.9 part
Alkali compounds (alkali compounds 1):0.105 part
Surfactant (surfactant 1):0.095 part
Miscellaneous cyclic compound (Denacol EX-321L (Nagase ChemteX Corporation manufactures)):4.8 part
·PGMEA:900 parts
Using produced positive light sensitivity composition, made in a manner of same as Example 3 dry film photoresist it
Afterwards, the touch panel circuit layout of embodiment 7 is produced by order same as Example 3.
[embodiment 8]
Positive light sensitivity composition is produced by formula as below.
·PHS-EVE:91.2 parts
Light acid producing agent (PAG-1):1.9 part
Sensitizer:(sensitizer 1):1.9 portion
Alkali compounds (alkali compounds 1):0.105 part
Surfactant (surfactant 1):0.095 part
Miscellaneous cyclic compound (3- glycidoxypropyltrimewasxysilanes (KBM-403 Shin-Etsu
Chemical Co., Ltd. manufacture)):4.8 part
·PGMEA:900 parts
Using produced positive light sensitivity composition, made in a manner of same as Example 3 dry film photoresist it
Afterwards, the touch panel circuit layout of embodiment 8 is gone out by sequentially built same as Example 3.
[embodiment 9]
Positive light sensitivity composition is produced by formula as below.
MATHF copolymers:94.9 parts
Light acid producing agent (PAG-1):1.98 part
Sensitizer:(sensitizer 1):1.98 part
Alkali compounds (alkali compounds 1):0.099 part
Surfactant (surfactant 1):0.099 part
Radiation absorbance agent (DAITO CHEMIX Co., Ltd.s manufacture, DTEP-250):0.94 part
·PGMEA:900 parts
Using produced positive light sensitivity composition, made in a manner of same as Example 3 dry film photoresist it
Afterwards, the touch panel circuit layout of embodiment 9 is produced by order same as Example 3.
[embodiment 10]
Positive light sensitivity composition is produced by formula as below.
MATHF copolymers:95.3 parts
Light acid producing agent (PAG-1):1.98 part
Sensitizer:(sensitizer 1):1.98 part
Alkali compounds (alkali compounds 1):0.099 part
Surfactant (surfactant 1):0.099 part
Radiation absorbance agent (following radiation absorbance agent 1):0.54 part
·PGMEA:900 parts
Radiation absorbance agent 1:The compound of following structures
[chemical formula 39]
Using produced positive light sensitivity composition, made in a manner of same as Example 3 dry film photoresist it
Afterwards, the touch panel of embodiment 10 circuit layout is produced by order same as Example 3.
[embodiment 11]
According to the record of Japanese Unexamined Patent Publication 6-332167 [0053] paragraph, increased by consisting of to prepare contrast
Strong layer (following CEL) composition.
α-[to (lignocaine) styryl]-N- (2- methyl -4- carboxyl phenyls) nitrone:45 parts
Three (methylol) aminomethanes:20 parts
The mass % of polyvinylpyrrolidone 60 and the mass % of polyacrylic acid 40 copolymer polymer:35 parts
Pure water:900 parts
On the polyethylene terephthalate thin film supporter (temporary support) of 75 μm of thickness, sprayed using slit-shaped
Mouth, the CEL compositions are coated with a manner of dry film thickness turns into 0.2 μm, and have been dried 5 minutes in 100 DEG C of stream baking oven.
Then, on CEL layers, using slit-shaped nozzle, with coating of the dry film thickness as 2.0 μm and institute in embodiment 2
The identical positive light sensitivity composition of making, and dried 2 minutes in 100 DEG C of stream baking oven, finally, using as diaphragm
Polyethylene film (Tredegar Corporation are manufactured, OSM-N) is crimped, so as to produce dry film photoresist.
Used using the dry film photoresist as positive light sensitivity material, after the pattern exposure of (b) process and (d) process
Positive light sensitivity material development before, carried out CEL layer lift-off processings with pure water to remove CEL layers, in addition,
The touch panel circuit layout of embodiment 11 is produced by order same as Example 1.
[embodiment 12]
< (a) processes >
Two sides in the PET base material of 100 μm of thickness, as the 2nd layer of conductive layer, by ITO by sputtering the film with 150nm
Thickness carries out film forming, thereon, as the 1st layer of conductive layer, copper is carried out into film forming with 200nm thickness by sputtering, so as to produce
Circuit forming board of the two sides formed with ITO and layers of copper on base material.
The dry film photoresist produced in method same as Example 3 is used, in the 1st layer (layers of copper) of conductive layer
Above-mentioned dry film photoresist is laminated, forms positive light sensitivity material.
< (b) processes >
Pattern A photomask is provided with using the one side to the positive light sensitivity material, and use is provided with another side
The pattern D shown in Fig. 7 photomask, is aligned, and has been carried out two sides while has been exposed.Carried out using the TMAH aqueous solution 2.38%
Development and washing, having obtained one side description has pattern A, and another side describes the substrate for having pattern D.
In pattern D shown in Fig. 7, solid line portion and grey portion are light shielding part, and other parts are opening portion, and dotted line part is virtually
The frame of alignment is shown.Also, solid line portion is set as less than 70 μm of fine rule.
< (c) processes >
Then, the 1st layer (layers of copper) is entered using copper etchant solution (Cu-02 of KANTO CHEMICAL CO., INC. manufactures)
After row etching, the 2nd layer (ITO layer) is entered using ITO etching solutions (ITO-02 of KANTO CHEMICAL CO., INC. manufactures)
Etching is gone.By being so etched, the 1st layer to the 2nd of above-mentioned conductive layer to not forming positive light sensitivity material area
Layer be etched, do not formed the positive light sensitivity material area for being set to the 1st pattern the 1st layer (layers of copper) and the 2nd layer
(ITO layer) its one side is depicted as the 1st pattern (pattern of pattern A light shielding part region shape), and another side is depicted as
The substrate of another pattern (pattern of pattern D light shielding part region shape).
< (d) processes, (e), (z) >
Pattern exposure, development, washing are carried out to the two sides of the substrate, in addition, in the same manner as example 1,
With being provided with pattern B opening portion and after the photomask of light shielding part is exposed and develops, only the 1st layer (copper wiring) carried out
Etch and form circuit, carried out resist stripping.
Thus, obtained formed with the pattern C that the one side on base material is the conductive layer comprising 2 kinds of patterns, and another side is
Circuit layout, embodiment 12 the touch panel of pattern E described in Fig. 8 of conductive layer comprising 2 kinds of patterns is matched somebody with somebody with circuit
Line.
Wiring part included in Fig. 8 gray area is divided into the state that the 2nd layer (ITO distributions) exposes.Fig. 8 dotted line
Portion virtually shows the frame of alignment.Part in addition is formed on the 2nd layer (ITO distributions) equivalent to peripheral distribution part
It is laminated the structure of the 1st layer (copper wiring) and more than 2 layers of the conductive layer stack comprising shared identical circuit pattern.
[embodiment 13]
On glass baseplate (EagleXG of Corning Incorporated Co., Ltd.s manufacture), as the 2nd layer of conduction
Layer, ITO is subjected to film forming by sputtering with 150nm thickness, thereon, as the 1st layer of conductive layer, by copper by sputter with
200nm thickness carries out film forming, and is set to circuit forming board.
The dry film photoresist produced in embodiment 3 is laminated to it, afterwards, is obtained in the same manner as example 1
Copper and ITO are depicted as pattern A circuit layout substrate.
Then, to depicting pattern A circuit layout substrate as, to coat pattern A conductive pad portion 3a and conductive weld
The coupling part 3b (connecting portion) of disk mode forms insulating barrier 5.The section signal of substrate obtained by being shown in Fig. 9 and Figure 10
Figure and schematic top plan view.
Moreover, on the substrate formed with the insulating barrier 5, as the 2nd electrode layer, ITO is sputtered, formd and the
The 2nd electrode that one electrode pattern 3, the pad portion 3a of first electrode pattern, coupling part 3b insulate, that there is different patterns
Layer.Afterwards, the dry film photoresist applied and produced in example 3 is pressed in the 2nd electrode layer, uses the light of described pattern D in Fig. 7
Mask carries out pattern exposure, is developed and is washed using the TMAH aqueous solution 2.38%, and uses ITO etching solutions (KANTO
The ITO-02 of CHEMICAL CO., INC. manufactures) it is etched, so as to form pattern D second electrode pattern 4.Such
The touch panel circuit layout of embodiment 13 is arrived.
On the touch panel circuit layout of resulting embodiment 13, first electrode pattern is shown in Figure 11 and Figure 12
Pad portion 3a, coupling part 3b and second electrode pattern 4 diagrammatic cross-section, schematic top plan view.
[embodiment 14]
In the PET base material of 100 μm of thickness, as the 2nd layer of conductive layer, by MAM (molybdenum/aluminium/molybdenum) layers by sputter with
250nm thickness carries out film forming, thereon, as the 1st layer of conductive layer, by layers of copper by vacuum vapour deposition with 200nm thickness
Film forming is carried out.Moreover, on the 1st layer of conductive layer (layers of copper), cupric oxide is subjected to film forming with 50nm thickness by sputtering, entered
The processing (Darkening process) for reducing the luminous ray reflectivity of the 1st layer of conductive layer (layers of copper) is gone.
The dry film photoresist produced in embodiment 3 is laminated on the circuit forming board, forms positive light sensitivity
Material.
To the positive light sensitivity material, Fig. 4 institutes are provided with using with the structure that conductive welding disk is connected with along a direction
Diagram case A photomask carries out pattern exposure, has been come in development, washing using the TMAH aqueous solution 2.38%.
Then, using Cu etching solutions (Cu-02 of KANTO CHEMICAL CO., INC. manufactures) to copper oxide/1st layer
After conductive layer (layers of copper) is etched, MAM layers are lost using MAM etching solutions (phosphoric acid/nitric acid/acetic acid mixed aqueous solution)
Carve, resulting in copper oxide and the 1st layer of conductive layer (layers of copper) and the 2nd layer of conductive layer (MAM layers) is depicted as pattern A's
Substrate.
Afterwards, pattern exposure is carried out using the photomask for the opening portion and light shielding part for being provided with pattern F shown in Figure 13, used
After the TMAH aqueous solution 2.38% is developed and washed, copper oxide/1st layer conductive layer (layers of copper) is entered using Cu etching solutions
Etching is gone.
In the pattern F shown in Figure 13, grey portion is light shielding part, and other parts are opening portions, and dotted line part is virtually shown
The frame of alignment.
Finally, the positive light sensitivity material of residual is peeled off, has obtained being depicted as the implementation of pattern C shown in Fig. 6
The touch panel circuit layout of example 14.However, different from embodiment 1, the touch panel of embodiment 14 is wrapped with circuit layout
Include the wiring part in Fig. 6 gray area and be divided into and be laminated with the 1st layer of conductive layer on the 2nd layer of conductive layer (MAM distributions)
(Cu) state of/CuO distributions.Part in addition turns into only by the 2nd layer of conductive layer (MAM equivalent to peripheral distribution part
Distribution) and the state of distribution.
[embodiment 15]
On glass epoxide base material, layers of copper is formed with 10 μm of thickness by vacuum vapour deposition, afterwards, with 5 μm of thickness
Layer gold is formed, and is set to circuit forming board.
It is laminated by embodiment 3 and the dry film photoresist produced, uses the opening portion and shading for being provided with pattern I
The photomask in portion carries out pattern exposure, is developed and is washed using the TMAH aqueous solution 2.38%, so as to obtain pattern I shading
The pattern of portion's shape.In the pattern I shown in Figure 17, grey portion is light shielding part, and other parts are opening portions, and dotted line part is virtually
The frame of alignment is shown.
Then, using golden etching solution (AURUM-100 of KANTO CHEMICAL CO., INC. manufactures) to the 1st layer of (gold
Layer) be etched after, using copper etchant solution (Cu-02 of KANTO CHEMICAL CO., INC. manufacture) to the 2nd layer (layers of copper)
It is etched, is thus etched place to the 1st layer to the 2nd layer of the above-mentioned conductive layer that does not form positive light sensitivity material area
Reason, has obtained gold and copper is depicted as the circuit of the 1st pattern (pattern I light shielding part shape).
Then, pattern exposure is carried out using the photomask for the opening portion and light shielding part that pattern J is provided with the state being aligned,
And developed and washed using the TMAH aqueous solution 2.38%, so as to obtain (the screening of pattern I light shielding part and pattern J of the 2nd pattern
The pattern of light portion lap).Figure 18 illustrates pattern J in, grey portion is light shielding part, and other parts are opening portions, empty
Line portion virtually shows the frame of alignment.
Afterwards, only the 1st layer (layer gold) is etched using AURUM-100, is thus etched to not formed and is set to the 2nd pattern
The 1st layer of above-mentioned conductive layer of positive light sensitivity material area.Obtained by being so etched only comprising 2 kinds of patterns
The substrate of conductive layer.Specifically, in resulting conductive layer, the positive light sensitivity material for being set to the 2nd pattern forms area
1st layer (layer gold) in domain and the 2nd layer (layers of copper) is depicted as pattern I (pattern of the light shielding part region shape of the 1st pattern), and
The 2nd layer (layers of copper) for not forming the positive light sensitivity material area for being set to the 2nd pattern is depicted as the light shielding part region of the 2nd pattern
Shape pattern.Resulting circuit layout is set to the circuit layout of embodiment 15.Formed circuit is shown in Figure 19
The diagrammatic cross-section of distribution.
As shown in Figure 19 diagrammatic cross-section, a part of copper circuit (layers of copper 11) on base material 1 is laminated with gold on circuit
Layer 12, a part turn into the state of only copper circuit (layers of copper 11).Thus, being laminated with the circuit of the part of gold can suppress to weld
Material is coated on corrosion when on circuit.According to circumstances, repaired with different types of metal, by using with can press down
The making of circuit layout in the purposes such as substrate, spaceship of corrosion during system coating solder becomes easily (special with reference to Japan
Open flat 11-312862 publications etc.).
[comparative example 1]
In the PET base material of 100 μm of thickness, as the 2nd layer of conductive layer, ITO is carried out by sputtering with 150nm thickness
Film forming, thereon, as the 1st layer of conductive layer, copper is subjected to film forming by vacuum vapour deposition with 200nm thickness, and be set to electricity
Road forms substrate.
On the 1st layer of conductive layer (layers of copper) of circuit forming board, what lamination was produced in the same manner as example 1
Dry film photoresist, form positive light sensitivity material.
By the positive light sensitivity material, pattern exposure is carried out using the photomask for being provided with pattern A, and it is water-soluble using TMAH
Liquid 2.38% is developed and washed.
Then, after being etched using copper etchant solution to the 1st layer of conductive layer (layers of copper), using ITO etching solutions to the 1st layer
Conductive layer (ITO layer) is etched and forms pattern A.
Afterwards, positive light sensitivity material is all peeled off.
Then, the dry film photoresist that will be produced in the same manner as example 1, it is laminated to again formed with pattern A
Circuit forming board on, and exposed using the photomask for being provided with pattern B.
After being developed and being washed and obtain pattern, the 1st layer of conductive layer (layers of copper) is lost using copper etchant solution
Carve.
Finally, positive light sensitivity material resist is all peeled off again, the touch panel for having obtained comparative example 1 is used
Circuit layout.
[comparative example 2]
In the PET base material of 100 μm of thickness, as the 1st layer of conductive layer, ITO is carried out by sputtering with 150nm thickness
Film forming.
The dry film photoresist produced in the same manner as example 1 is laminated, forms positive light sensitivity material.
By the positive light sensitivity material, pattern exposure is carried out using the photomask for being provided with pattern G shown in Figure 14, and make
Developed and washed with the TMAH aqueous solution 2.38%.
Then, the 1st layer of conductive layer (ITO layer) is etched using ITO etching solutions and forms pattern G.In Figure 14 institutes
In diagram case G, solid line portion and grey portion are light shielding parts, and other parts are opening portions, and dotted line part virtually shows the frame of alignment.
Then, on the substrate formed with pattern G, by the 2nd layer of conductive layer (layers of copper) by vacuum vapour deposition with 150nm's
Thickness has carried out film forming.
Afterwards, there is the substrate of the 2nd layer of conductive layer from film forming, positive light sensitivity material is all once peeled off.
The dry film photoresist that will be produced in the same manner as example 1, being laminated to film forming again has the 2nd layer of conductive layer
Substrate on, carried out pattern exposure using the photomask for being provided with pattern H shown in Figure 15.In pattern H shown in Figure 15, solid line
Portion is light shielding part, and other parts are opening portions, and dotted line part virtually shows the frame of alignment.
After develop and having washed, the 2nd layer of conductive layer (layers of copper) is etched using copper etchant solution.Most
Afterwards, resist is all peeled off, obtains the touch panel circuit layout of comparative example 2.
[evaluation]
On various embodiments above and the circuit layout of comparative example manufacture method and resulting each embodiment and compare
The circuit layout of example is evaluated.
Understand the manufacture method of the circuit layout of the present invention because can be formed with the etchant resist formation of 1 time and include a variety of figures
The circuit layout of the conductive layer of case and manufacture efficiency is excellent, it is not necessary to the contraposition of the conductive layer of multiple patterns.Moreover, understand basis
The preferred embodiment of the manufacture method of the circuit layout of the present invention, also being capable of the generation open circuit of suppression circuit distribution.
In circuit layout of the invention obtained by each embodiment, the first of the shape of the grey parts equivalent to Fig. 4
The bonding part and another electric conductivity of (conduction) pad portion of electrode pattern and another electric conductivity important document (peripheral distribution part)
The peripheral distribution part of important document also will not be breaking, and circuit layout is good.
Although being not bound to any theory, deducibility is due to by the positive light sensitivity material formed in (a) process
It is used directly in (d) process in the 2nd pattern exposure, therefore even if fine patterns, by by pattern is differential will not also being caused
Influence, and positive light sensitivity material can follow completely (that is, it is seamlessly differential according to pattern and formed with positive light sensitivity
Material), this is the reason to form good circuit layout.It is believed that the sky between positive light sensitivity material and circuit layout
The generation of gap is inhibited, and causes etching solution to be not easily accessible, and makes the pattern to be remained be difficult to be etched.
And, it is believed that according to the manufacture method of the circuit layout of the present invention, first electrode figure can be carried out with high accuracy
The contraposition of the pattern of (conduction) pad portion of case and the pattern of another electric conductivity important document (peripheral distribution part), even if especially electric
Road distribution is touch panel thread pattern, it is also difficult to causes the mismatch of position.
On the other hand, in the manufacture method for the touch panel circuit layout for having carried out the comparative example 1 that 2 etchant resists are formed
In obtained by touch panel circuit Wiring pattern, seem at first sight identical shape with what is produced in embodiment 1, still
In (conduction) pad portion of first electrode pattern and bonding part, the Yi Ji of another electric conductivity important document (peripheral distribution part)
The peripheral existing loose contact as caused by open circuit of wiring part distribution.Can estimate the reason be after pattern is formed to be laminated again it is dry
During film resist, because of fine patterns, positive light sensitivity material (dry film photoresist) fails to follow pattern completely differential.Therefore, recognize
For because producing space between circuit layout in positive light sensitivity material (dry film photoresist) and etching solution enters, the figure to be remained
A part for case is etched and breaking.
Obtained by having carried out in the manufacture method of touch panel circuit layout for the comparative example 2 that 2 etchant resists are formed
Touch panel with circuit Wiring pattern in the case of, will in (conduction) pad portion and another electric conductivity of first electrode pattern
The bonding part of part (peripheral distribution part) is found that open circuit.It is believed that, it is necessary to enter exactly in the manufacture method of comparative example 2
Pair of the pattern of (conduction) pad portion of row first electrode pattern and the pattern of another electric conductivity important document (peripheral distribution part)
Position, the mismatch of position caused by thread pattern easily occurs.
Symbol description
1- base materials, 2- mask layers, 3- first electrode patterns, 3a- pad portions, 3b- coupling parts, 4- second electrode figures
Case, 5- insulating barriers, another electric conductivity important documents of 6- (peripheral distribution part and wiring lead part), 7- protective clear layers, 10- electrostatic
Capacitor type input unit, 11- layers of copper, 12- layer gold, 20- positive light sensitivity materials.
Claims (29)
1. a kind of manufacture method of circuit layout, it includes following (a) process, (b) process, (c) process, (d) process, (e) work
Sequence and (z) process,
(a) process, x is set to more than 2 integer, to a surface with base material and from the base material successively with xth layer
To the circuit forming board of the 1st layer of conductive layer, the position being exposed is formed on the 1st layer of the conductive layer and is dissolved in development
Positive light sensitivity material in liquid;
(b) process, pattern exposure and development are carried out to the circuit forming board formed with the positive light sensitivity material, and
Positive light sensitivity material is set to the 1st pattern;
(c) process, i is set to more than 1 and below x integer, the 1st pattern is set to for not formed in (b) process
The 1st layer to i-th layer of the conductive layer of positive light sensitivity material area is etched;
(d) process, to the positive light sensitivity material remained in (b) process, with the positive light sensitivity material remained
Different patterns carries out pattern exposure and development, and positive light sensitivity material is set into the 2nd pattern;
(e) process, 1 integer less than i is set to by j, and the 2nd pattern is set to for not formed in (d) process
The 1st layer of the conductive layer of positive light sensitivity material area to jth layer is etched;
(z) process, all positive light sensitivity materials remained are removed, forms the circuit of the conductive layer comprising at least two kinds of patterns
Distribution.
2. the manufacture method of circuit layout according to claim 1, wherein,
The circuit layout is the circuit layout of input unit.
3. the manufacture method of the circuit layout of input unit according to claim 2, wherein,
The input unit is touch panel.
4. the manufacture method of circuit layout according to any one of claim 1 to 3, wherein,
The circuit layout includes the conductive layer of only 2 kinds patterns.
5. the manufacture method of circuit layout according to any one of claim 1 to 4, it also includes following (f) process,
(f) process, to the positive light sensitivity material remained, carried out with the pattern different from the positive light sensitivity material remained
Pattern exposure and development, after developing, to not forming the 1st layer of the conductive layer of positive light sensitivity material area to being less than
J arbitrary layer is etched, and conductive layer is set into pattern.
6. the manufacture method of circuit layout according to claim 5, (f) process includes following (f1) processes and (f2)
Process, and the conductive layer of at least three kinds of patterns is included,
(f1) process, to the positive light sensitivity material remained in (e) process, with the positive light sensitivity material remained
Different patterns carries out pattern exposure and development, and positive light sensitivity material is set into the 3rd pattern,
(f2) process, k is set to 1 integer less than j, the 3rd pattern is set to for not formed in (f1) process
The 1st layer of the conductive layer of positive light sensitivity material area be etched to kth layer.
7. the manufacture method of circuit layout according to any one of claim 1 to 6, wherein,
In the conductive layer with different types of pattern being included in the circuit layout, there is leading at least one kind of pattern
Electric layer includes more than 2 layers of conductive layer stack for sharing identical circuit pattern.
8. the manufacture method of circuit layout according to any one of claim 1 to 7, wherein,
The base material has the conductive layer of xth layer to the 1st layer using x independently on two surfaces,
The base material sequentially or simultaneously forms circuit to the conductive layer for being formed at two surfaces.
9. the manufacture method of circuit layout according to any one of claim 1 to 8, it includes:
The process that dielectric film is formed on the circuit layout formed in (z) process;And
The process that new conductive layer is formed on the dielectric film.
10. the manufacture method of circuit layout according to any one of claim 1 to 9, wherein,
At least one layer in the xth layer to the 1st layer of conductive layer includes metal oxide.
11. the manufacture method of circuit layout according to any one of claim 1 to 10, it includes following process:
Enter the processing that the part or all of luminous ray reflectivity for the conductive layer for exercising the xth layer to the 1st layer reduces.
12. the manufacture method of the circuit layout according to any one of claim 1 to 11, wherein, the positive light sensitivity
Material is dry film photoresist.
13. the manufacture method of the circuit layout according to any one of claim 1 to 12, wherein, the base material is sheet material
Shape resin combination.
14. the manufacture method of the circuit layout according to any one of claim 1 to 13, wherein,
The positive light sensitivity material includes naphthalene quinone di-azido compound and the resin with phenolic hydroxyl group.
15. the manufacture method of the circuit layout according to any one of claim 1 to 13, wherein,
The positive light sensitivity material includes (A) composition and (B) light acid producing agent,
(A) composition is the polymer for the group protected with acidic group by sour decomposability base.
16. the manufacture method of circuit layout according to claim 15, wherein,
(A) composition is the component of polymer comprising polymer, and the polymer has carboxyl or phenolic hydroxyl group with acetal
The protected sour construction unit a1 of form.
17. the manufacture method of the circuit layout according to claim 15 or 16, wherein,
(A) composition is the polymer with the construction unit by following formula A1 or formula A1 ' expressions,
Formula A1
In formula A1, R1And R2Separately represent hydrogen atom, alkyl or aryl, R1And R2In it is at least one be alkyl or virtue
Base, R3Represent alkyl or aryl, R1Or R2Can be with R3Connect and form cyclic ether, R4Represent hydrogen atom or methyl;
Formula A1 '
In formula A1 ', R11And R12Separately represent hydrogen atom, alkyl or aryl, R11And R12In it is at least one be alkyl
Or aryl, R13Represent alkyl or aryl, R11Or R12Can be with R13Connect and form cyclic ether, R14Separately represent that hydrogen is former
Son, hydroxyl, halogen atom, alkyl, alkoxy, alkenyl, aryl, aralkyl, alkoxy carbonyl group, hydroxy alkyl, aryl carbonyl or cycloalkanes
Base.
18. the manufacture method of the circuit layout according to any one of claim 15 to 17, wherein,
The positive light sensitivity material contains described (A) composition of more than two kinds, and
As (A) composition, contain the polymer with the construction unit represented by following formula A2 ';
Formula A2 '
In formula A2 ', R31And R32Separately represent hydrogen atom, alkyl or aryl, R31And R32In it is at least one be alkyl
Or aryl, R33Represent alkyl or aryl, R31Or R32Can be with R33Connect and form cyclic ether, R34Represent hydrogen atom or methyl, X0
Represent singly-bound or arlydene.
19. the manufacture method of the circuit layout according to any one of claim 1 to 18, wherein,
In the positive light sensitivity material, the amount with the compound of ethylenic unsaturated bond is 0 mass %.
20. the manufacture method of the circuit layout according to any one of claim 1 to 19, wherein,
The positive light sensitivity material includes the compound containing (C) miscellaneous cyclic compound.
21. the manufacture method of circuit layout according to claim 20, wherein,
(C) the miscellaneous cyclic compound is the compound with epoxy radicals.
22. the manufacture method of the circuit layout according to any one of claim 1 to 21, wherein,
The positive light sensitivity material also includes alkali compounds.
23. the manufacture method of the circuit layout according to any one of claim 1 to 22, wherein,
The positive light sensitivity material also includes radiation absorbance agent.
24. the manufacture method of the circuit layout according to any one of claim 1 to 23, wherein,
The positive light sensitivity material includes photo-sensitive resin and contrast enhancing layer.
25. the manufacture method of the circuit layout according to any one of claim 1 to 24, wherein,
The conductive layer of the xth layer to the 1st layer includes material different from each other.
26. a kind of circuit layout, it is made by the manufacture method of the circuit layout any one of claim 1 to 25
Make.
27. a kind of input unit, it use the circuit layout described in claim 26.
28. input unit according to claim 27, it is capacitance type touch panel.
29. a kind of display device, it possesses the input unit described in claim 27 or 28.
Applications Claiming Priority (3)
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JP2015-109163 | 2015-05-28 | ||
JP2015109163 | 2015-05-28 | ||
PCT/JP2016/065654 WO2016190405A1 (en) | 2015-05-28 | 2016-05-27 | Circuit wiring manufacturing method, circuit wiring, input device and display device |
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CN109216206A (en) * | 2018-08-23 | 2019-01-15 | 江苏中科智芯集成科技有限公司 | A kind of wafer scale is fanned out to packaging method and encapsulating structure |
CN110908245A (en) * | 2019-11-13 | 2020-03-24 | Tcl华星光电技术有限公司 | Patterning method, glass substrate manufacturing method and display panel |
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JP6685460B2 (en) * | 2017-02-22 | 2020-04-22 | 富士フイルム株式会社 | Photosensitive transfer material, method for manufacturing circuit wiring, and method for manufacturing touch panel |
CN110325917A (en) * | 2017-02-22 | 2019-10-11 | 富士胶片株式会社 | The manufacturing method of photosensitive transfer printing material, the manufacturing method of circuit layout and touch panel |
CN107783697A (en) * | 2017-11-03 | 2018-03-09 | 业成科技(成都)有限公司 | The method of circuit and bendable contactor control device are formed on conducting polymer |
CN111651099A (en) | 2020-04-28 | 2020-09-11 | 北京载诚科技有限公司 | Touch device |
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WO2016190405A1 (en) | 2016-12-01 |
JPWO2016190405A1 (en) | 2018-03-22 |
JP6507239B2 (en) | 2019-04-24 |
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