CN113946103B - Dry film resist, method for manufacturing circuit wiring, input device, and display device - Google Patents

Dry film resist, method for manufacturing circuit wiring, input device, and display device Download PDF

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Publication number
CN113946103B
CN113946103B CN202111230313.2A CN202111230313A CN113946103B CN 113946103 B CN113946103 B CN 113946103B CN 202111230313 A CN202111230313 A CN 202111230313A CN 113946103 B CN113946103 B CN 113946103B
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pattern
group
acid
dry film
resist
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CN113946103A (en
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片山晃男
长田崇一郎
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Fujifilm Corp
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Fujifilm Corp
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
    • G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
    • G—PHYSICS
    • G06—COMPUTING; CALCULATING OR COUNTING
    • G06F—ELECTRIC DIGITAL DATA PROCESSING
    • G06F3/00—Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
    • G06F3/01—Input arrangements or combined input and output arrangements for interaction between user and computer
    • G06F3/03—Arrangements for converting the position or the displacement of a member into a coded form
    • G06F3/041—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means
    • G06F3/0412—Digitisers structurally integrated in a display

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • General Engineering & Computer Science (AREA)
  • Theoretical Computer Science (AREA)
  • Human Computer Interaction (AREA)
  • Materials For Photolithography (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Manufacturing Of Printed Circuit Boards (AREA)
  • Photosensitive Polymer And Photoresist Processing (AREA)
  • Phenolic Resins Or Amino Resins (AREA)

Abstract

The invention relates to a dry film resist, a method for manufacturing a circuit wiring, an input device, and a display device. Provided is a dry film resist which enables the production of circuit wiring having high pattern linearity. A dry film resist, a method for manufacturing a circuit wiring, an input device, and a display device, wherein the dry film resist is a positive dry film resist having a resist layer on a temporary support, and the total light haze of the temporary support is 0.3% or less.

Description

Dry film resist, method for manufacturing circuit wiring, input device, and display device
The present application is a divisional application of the application having the application date of 2016, 10 and 21, the application number of 201610919906.2, the application name of Fuji film Co., ltd., the application name of "dry film resist, method for manufacturing circuit wiring, input device, and display device".
Technical Field
The invention relates to a dry film resist, a method for manufacturing a circuit wiring, an input device and a display device.
Background
In a display device (an organic Electro Luminescence (EL) display device, a liquid crystal display device, or the like) including a touch panel such as a capacitive input device, a conductive pattern such as an electrode pattern of a sensor corresponding to a recognition portion, a peripheral wiring portion, or a wiring of a take-out wiring portion is provided inside the touch panel.
Generally, for the purpose of forming a patterned conductive layer, the following methods are widely used for the reason of the small number of steps for obtaining a necessary pattern shape: a resist layer (layer of a photosensitive resin composition) provided on an arbitrary circuit-forming substrate using a dry film resist as a photosensitive transfer material is exposed to light through a mask having a desired pattern, and the resist layer is partially cured or dissolved and then developed to obtain a circuit pattern, and then the circuit pattern is transferred onto a conductive layer by etching.
Here, the resist layer is roughly classified into a negative type and a positive type according to a reaction method with light or electron beam. When the negative resist layer is exposed, the solubility in a developer decreases, and an exposed portion remains after development. When the positive resist layer is exposed, the solubility in a developer increases, and the exposed portion is removed after development. A positive dry film resist is required because it has an advantage of easy formation of a pattern of high resolution as compared with a negative resist.
As a positive dry film resist, for example, those described in patent documents 1 and 2 are known.
Patent document 1 discloses a multilayer resist in which an intermediate layer having photobleaching and/or light absorbing properties is provided between a lower photoresist layer and an upper photoresist layer. Patent document 1 also describes: a multilayer resist having improved controllability of multiple contrast exposure and improved multiple contrast exposure effect is provided.
Patent document 2 describes a film-type photodegradable transfer material comprising: a support film, a photodegradable photoresist layer, and a reflection suppressing layer formed on a surface laminated on the circuit forming substrate.
Prior art literature
Patent literature
Patent document 1: japanese patent laid-open No. 5-66568
Patent document 2: japanese patent laid-open No. 2009-282522
Disclosure of Invention
Problems to be solved by the invention
The present inventors have studied a circuit formed using the positive dry film resist described in patent documents 1 and 2, and as a result, have found that: when pattern exposure is performed without peeling off the temporary support, the exposure light is diffused due to light diffusion of the temporary support, and thus the linearity of the obtained pattern is lowered. Since the positive dry film resist is a mask image formed by dissolution of the exposed portion, peeling is particularly likely to occur in a thin line pattern in a state where the remaining pattern portion is not cured and the pattern linearity is lowered. Therefore, degradation of circuit quality, circuit disconnection, and short circuit may be caused. Therefore, it is found that the decrease in pattern linearity is a significant problem when forming a high resolution pattern with a positive dry film resist, as compared with the case of forming a high resolution pattern with a negative resist.
The invention provides a dry film resist which is positive type and can manufacture circuit wiring with high pattern linearity, wherein high resolution patterns are easy to form.
Further, the present invention provides a circuit wiring and a method for manufacturing the circuit wiring, which are positive and have high linearity for easily forming a pattern with high resolution.
Further, an object of the present invention is to provide an input device using the circuit wiring and a display device including the input device.
Means for solving the problems
The present inventors have conducted intensive studies and as a result, have found that the above problems can be solved by using a temporary support having low haze.
It has also been found that the above problems can be solved by using a resist layer containing a binder having a specific constituent unit.
On the other hand, patent document 1 does not describe transparency and haze of a support of a multilayer resist, and a commercially available adhesive made of a novolac resin is used as an adhesive for a resist layer. Patent document 2 discloses only a support film as a film transfer material, but is not particularly limited as long as transparency that does not inhibit light transmittance is satisfied, and the haze is not described, and the use of a novolak resin as an alkali-soluble resin is described in the binder of the resist layer.
The present invention, which is a specific means for solving the above problems, and preferred ranges of the present invention are as follows.
[1] A dry film resist is a positive dry film resist having a resist layer on a temporary support,
The temporary support has a total light haze of 0.3% or less.
[2] A dry film resist is a positive dry film resist having a resist layer on a temporary support,
The resist layer contains a component (A) and a photoacid generator (B),
(A) The component (a) is a polymer having an acid constituent unit a0 in which an acid group is protected by an acid-decomposable group,
The acid constituent unit a0 has a constituent unit represented by the following formula A3,
General formula A3:
[ chemical formula 1]
In the general formula A3, R 31 and R 32 each independently represent a hydrogen atom, an alkyl group or an aryl group, at least any one of R 31 and R 32 is an alkyl group or an aryl group, R 33 represents an alkyl group or an aryl group, R 31 and R 33 or R 32 are optionally linked to R 33 to form a cyclic ether, R 34 represents a hydrogen atom or a methyl group, X 0 represents a single bond or an arylene group, and Y represents a nitrogen atom, a sulfur atom or an oxygen atom.
[3] The dry film resist according to [1], preferably:
The resist layer contains a component (A) and a photoacid generator (B),
(A) The component (a) is a polymer having an acid constituent unit a0 in which an acid group is protected by an acid-decomposable group,
The acid constituent unit a0 has a constituent unit represented by the following formula A3,
General formula A3:
[ chemical formula 2]
In the general formula A3, R 31 and R 32 each independently represent a hydrogen atom, an alkyl group or an aryl group, at least any one of R 31 and R 32 is an alkyl group or an aryl group, R 33 represents an alkyl group or an aryl group, R 31 and R 33 or R 32 are optionally linked to R 33 to form a cyclic ether, R 34 represents a hydrogen atom or a methyl group, X 0 represents a single bond or an arylene group, and Y represents a nitrogen atom, a sulfur atom or an oxygen atom.
[4] The dry film resist according to [2] or [3], preferably: in the general formula A3, X 0 is a single bond.
[5] The dry film resist according to any one of [2] to [4], preferably: in the general formula A3, Y is an oxygen atom.
[6] The dry film resist according to [1], preferably: the resist layer contains a component (A) and a photoacid generator (B),
(A) The component (a) is a polymer having an acid constituent unit a0 in which an acid group is protected by an acid-decomposable group,
The acid constituent unit a0 is an acid constituent unit a1 in which a carboxyl group or a phenolic hydroxyl group is protected as an acetal.
[7] The dry film resist according to [6], preferably: the acid constituent unit A1 has a constituent unit represented by the following formula A1,
The general formula A1:
[ chemical 3]
In the general formula A1, R 1 and R 2 each independently represent a hydrogen atom, an alkyl group or an aryl group, at least any one of R 1 and R 2 is an alkyl group or an aryl group, R 3 represents an alkyl group or an aryl group, R 1 and R 3 or R 2 and R 3 are optionally connected to form a cyclic ether, and R 4 represents a hydrogen atom or a methyl group.
[8] The dry film resist according to [6], preferably: the acid constituent unit a1 has a constituent unit represented by the following formula A2,
General formula A2:
[ chemical formula 4]
In the general formula A2, R 11 and R 12 each independently represent a hydrogen atom, an alkyl group or an aryl group, at least any one of R 11 and R 12 is an alkyl group or an aryl group, R 13 represents an alkyl group or an aryl group, R 11 and R 13 or R 12 are optionally linked to R 13 to form a cyclic ether, and R 14 each independently represents a hydrogen atom, a hydroxyl group, a halogen atom, an alkyl group, an alkoxy group, an alkenyl group, an aryl group, an aralkyl group, an alkoxycarbonyl group, a hydroxyalkyl group, an arylcarbonyl group or a cycloalkyl group.
[9] The dry film resist according to any one of [1] and [3] to [8], preferably: the resist layer contains 2 or more polymers having an acid constituent unit a0 in which an acid group is protected with an acid-decomposable group.
[10] The dry film resist according to [1], preferably: the resist layer contains a naphthoquinone diazide compound and a resin having a phenolic hydroxyl group.
[11] The dry film resist according to any one of [1] to [10], preferably: the resist layer further contains a heterocyclic compound.
[12] The dry film resist according to any one of [1] to [11], preferably: the resist layer further contains an alkaline compound.
[13] The dry film resist according to any one of [1] to [12], preferably: the resist layer further contains a radiation absorber.
[14] The dry film resist according to any one of [1] to [13], preferably: at least one of the following conditions (1) and (2) is satisfied,
Condition (1): the temporary support has a transmittance of 80% or less for the exposure dominant wavelength of the resist layer;
Condition (2): a light absorbing layer having a transmittance of 80% or less with respect to the exposure dominant wavelength of the resist layer is provided between the temporary support and the resist layer.
[15] A method for manufacturing a circuit wiring, comprising the following steps (a), (b), (c) and (d),
(A) A lamination step of laminating the dry film resist described in any one of [1] to [14] on a circuit forming substrate having a base material and a conductive layer;
(b) A pattern exposure step of exposing the contact pattern with a pattern for pattern exposure without peeling off the temporary support of the dry film resist;
(c) A developing step of developing the temporary support after the temporary support is peeled off to form a pattern for pattern exposure on the resist layer;
(d) An etching step of forming a pattern for pattern exposure on the circuit forming substrate by etching.
[16] The method for manufacturing a circuit wiring according to [15], preferably:
(b) The step (b 1) is as follows,
(C) The step (c 1) is as follows,
(D) The step (d 1) is as follows,
Further comprising the following step (e 1), step (f 1) and step (g),
(B1) A pattern exposure step of exposing the contact pattern with the 1 st pattern without peeling off the temporary support of the dry film resist;
(c1) A developing step of developing the temporary support after the temporary support is peeled off to form a1 st pattern on the resist layer;
(d1) An etching step of forming a1 st pattern on the circuit forming substrate by etching;
(e1) A pattern exposure step of performing contact pattern exposure with the 2 nd pattern without peeling the resist layer having the 1 st pattern formed in the step (c 1);
(f1) A developing step of developing the resist layer to form a2 nd pattern different from the 1 st pattern;
(g) And an etching step of forming a2 nd pattern on the circuit forming substrate by etching.
[17] The method for manufacturing a circuit wiring according to [15], preferably:
(b) The step (b 1) is as follows,
(C) The step (c 1) is as follows,
(D) The step (d 2) is as follows,
Further comprising a step (e 2), a step (f 2) and a step (g),
(B1) A pattern exposure step of exposing the contact pattern with the 1 st pattern without peeling off the temporary support of the dry film resist;
(c1) A developing step of developing the temporary support after the temporary support is peeled off to form a1 st pattern on the resist layer;
(d2) An etching step of forming a1 st pattern on the circuit forming substrate by etching, and then bonding a cover film to the remaining resist layer without peeling the resist layer having the 1 st pattern formed in the step (c 1);
(e2) A pattern exposure step of performing contact pattern exposure with the 2 nd pattern without peeling the cover film bonded in the step (d 2);
(f2) A developing step of peeling off the cover film bonded in the (d 2) step, and then developing the cover film to form a2 nd pattern different from the 1 st pattern on the resist layer;
(g) And an etching step of forming a2 nd pattern on the circuit forming substrate by etching.
[18] The method for manufacturing a circuit wiring according to any one of [15] to [17], preferably: the pH of the developer used in the developing step is 12.5 or less.
[19] A circuit wiring manufactured by the method of manufacturing a circuit wiring described in any one of [15] to [18 ].
[20] An input device using the circuit wiring described in [19 ].
[21] The input device according to [20], preferably: the input device is a capacitive touch panel.
[22] A display device comprising the input device of [20] or [21 ].
Effects of the invention
According to the present invention, a dry film resist that can easily form a positive pattern of a high resolution pattern and can produce a circuit wiring having high pattern linearity can be provided.
Further, according to the present invention, a circuit wiring which is positive and has high pattern linearity and is easy to form a pattern with high resolution, and a method for manufacturing the circuit wiring can be provided.
Further, according to the present invention, an input device using the circuit wiring and a display device including the input device can be provided.
Drawings
Fig. 1 is a schematic diagram showing an example of a method of manufacturing a circuit wiring.
Fig. 2 is a schematic cross-sectional view of an example of a circuit wiring of an embodiment of the present invention obtained when x is 2.
Fig. 3 is a schematic diagram of an example of the circuit wiring of the embodiment of the present invention obtained when x is 2.
Fig. 4 is a schematic diagram showing a pattern a.
Fig. 5 is a schematic diagram showing a pattern B.
Fig. 6 is a schematic diagram showing a pattern C.
Fig. 7 is a schematic cross-sectional view showing an example of the arrangement of the connection portion of the first electrode pattern and the second electrode pattern.
Fig. 8 is a schematic view showing an example of the arrangement of the pad portion and the connection portion of the first electrode pattern, and the second electrode pattern.
Fig. 9 is a schematic cross-sectional view showing a configuration of an example of an input device of the present invention.
Detailed Description
The dry film resist, the method for manufacturing a circuit wiring, the input device, in particular, the input device as a touch panel of the present invention, and the display device using the input device will be described below.
The following description of the constituent elements is made based on the representative embodiments and specific examples of the present invention, but the present invention is not limited to the embodiments and specific examples. In the present specification, the numerical range indicated by "to" means a range including numerical values described before and after "to" as a lower limit value and an upper limit value.
[ Dry film resist ]
The 1 st aspect of the dry film resist of the present invention is a positive dry film resist having a resist layer on a temporary support,
The temporary support has a total light haze of 0.3% or less.
The 2 nd aspect of the dry film resist of the present invention is a positive dry film resist having a resist layer on a temporary support,
The resist layer contains a component (A) and a photoacid generator (B),
(A) The component (a) is a polymer having an acid constituent unit a0 in which an acid group is protected by an acid-decomposable group,
The acid constituent unit a0 has a constituent unit represented by the following formula A3.
General formula A3:
[ chemical 5]
In the general formula A3, R 31 and R 32 each independently represent a hydrogen atom, an alkyl group or an aryl group, at least any one of R 31 and R 32 is an alkyl group or an aryl group, R 33 represents an alkyl group or an aryl group, R 31 and R 33 or R 32 are optionally linked to R 33 to form a cyclic ether, R 34 represents a hydrogen atom or a methyl group, X 0 represents a single bond or an arylene group, and Y represents a nitrogen atom, a sulfur atom or an oxygen atom.
With the above configuration, the dry film resist of the present invention is a positive type which can easily form a pattern with high resolution, and can produce a circuit wiring with high pattern linearity. Here, in the dry film resist, when exposure is performed through the temporary support, pattern linearity is reduced due to light diffusion caused by exposure light of the temporary support. While not being bound by any theory, the reason for the problem of reduced linearity of the estimated pattern is mainly: the filler or other temporary support present in and/or on the temporary support causes light diffusion of the exposure light. When the energy of the exposure light diffused by the temporary support exceeds the resist sensitivity (activation energy of the sensitizer of the resist layer, that is, the necessary exposure amount), a portion which should become an unexposed portion in the desired pattern is exposed by the diffused light, and the pattern linearity is lowered. On the other hand, when the diffused exposure light energy does not exceed the resist sensitivity (necessary exposure amount), the portion of the desired pattern that should be the unexposed portion is not exposed to light by the diffused light in fact, and the decrease in the linearity of the pattern can be suppressed.
In order to avoid a decrease in pattern linearity due to light diffusion of exposure light in the temporary support, the following method may be considered: (i) For example, suppression of light diffusion in the temporary support due to suppression of haze or the like of the temporary support; (ii) Absorbing the diffused light passing through the temporary support with other members disposed in the temporary support or before the resist layer; (iii) lowering sensitivity of the resist layer, and the like.
In the 1 st aspect of the dry film resist of the present invention, the above (i) is focused on the constitution of the method of suppressing light diffusion in the temporary support, for example, due to suppressing haze of the temporary support, whereby a decrease in pattern linearity can be suppressed.
In embodiment 2 of the dry film resist of the present invention, the alkali dissolution rate can be further improved, and particularly, when the developer used in the developing step is a weak base having pH (power of Hydrogen) of 12.5 or less, the pattern linearity is preferable.
It should be noted that a combination of the above-described aspects (i) to (iii) can be used as a preferable means to suppress the decrease in linearity.
< Constitution >
The film resist of the present invention has at least a resist layer on a temporary support. The dry film resist of the present invention preferably further comprises a light-absorbing layer between the temporary support and the resist layer, wherein the light-absorbing layer has a transmittance of 80% or less with respect to the exposure dominant wavelength of the resist layer.
The dry film resist of the present invention preferably further comprises a temporary support, a thermoplastic resin layer, and a resist layer in this order, and may further comprise other layers such as a protective film and an intermediate layer. The dry film resist of the present invention also preferably has a temporary support, a thermoplastic resin, an intermediate layer, and a resist layer in this order. The preferable modes of the thermoplastic resin layer are described in [0189] to [0193] of Japanese unexamined patent application publication No. 2014-85643, and the preferable modes of the other layers are described in [0194] to [0196] of Japanese unexamined patent application publication No. 2014-85643, the contents of which are incorporated into the present specification.
The dry film resist of the present invention is a positive dry film resist in which the exposed portions are dissolved in a developer. The positive dry film resist has an advantage of easy formation of a pattern of high resolution as compared with the negative resist.
In the positive type, since the solubility of the exposed portion is improved by irradiation with an active light, for example, by using a sensitizer or the like which generates an acid upon irradiation with the active light, neither the exposed portion nor the unexposed portion is cured at the time of pattern exposure, and the circuit forming substrate can be reused (reworked) by a blanket exposure or the like when the obtained pattern shape is defective. Therefore, from the viewpoint of excellent reworkability, a positive type is preferably used.
In addition, the technique of re-exposing the remaining resist to light to create a different pattern cannot be realized in the case of non-positive type.
The dry film resist of the present invention preferably satisfies at least one of the following conditions (1) and (2).
Condition (1): the temporary support has a transmittance of 80% or less for the exposure dominant wavelength of the resist layer;
Condition (2): a light absorbing layer having a transmittance of 80% or less with respect to the exposure dominant wavelength of the resist layer is provided between the temporary support and the resist layer.
When the condition (1) is satisfied, the following condition (1A) is particularly preferably satisfied.
Condition (1A): the temporary support has a transmittance of more than 10% and 80% or less for the exposure dominant wavelength of the resist layer.
When the condition (2) is satisfied, the following condition (2A) is particularly preferably satisfied.
Condition (2A): a light absorbing layer having a transmittance of more than 10% and 80% or less with respect to the exposure dominant wavelength of the resist layer is provided between the temporary support and the resist layer.
When the condition (2) or the condition (2A) is satisfied, the film may include a temporary support, a light absorbing layer, and a resist layer in this order from the opposite side of the lamination surface that contacts the target substrate when the dry film resist is laminated (for example, transferred) to the target substrate.
Here, japanese patent application laid-open No. 2009-282522 describes as a preferable embodiment: the reflection-suppressing layer has an absorptivity of 90% or more with respect to light in the wavelength range of 200nm to 700 nm. In the temporary support or the light-absorbing layer, when the light absorption of the exposure dominant wavelength of the resist layer is excessive, there is a pressure for designing the resist due to the large amount of the photosensitive agent contained in the resist layer, and even productivity is deteriorated due to the need for a large amount of exposure, so that it is practically preferable to use the temporary support or the light-absorbing layer having a transmittance exceeding 10% and 80% or less with respect to the exposure dominant wavelength of the resist layer.
(Temporary support)
The dry film resist of the present invention has a temporary support.
In embodiment 1 of the dry film resist of the present invention, the total light haze (also referred to as haze) of the temporary support is 0.3% or less, preferably 0.20% or less, more preferably 0.18% or less, and particularly preferably 0.16% or less. In embodiment 2 of the dry film resist of the present invention, the total light haze of the temporary support is preferably 0.3% or less, more preferably 0.20% or less, particularly preferably 0.18% or less, and even more preferably 0.16% or less. The lower limit of the total light haze of the temporary support is not particularly limited, and for example, in the case of a PET film, a filler added to the film or coated on the film surface is a main haze source, and when the amount of the filler is too small, problems such as deterioration in handleability and blocking during storage are caused. Therefore, considering that a minimum amount of filler is required, it is practical that the total light haze of the temporary support is 0.05% or more. Of course, the practically lowest total haze may be different in films other than PET, and thus the value of 0.05% or more is not limited in general meaning.
As means for reducing the haze of the temporary support, in addition to selecting the polymer type of the temporary support, there are exemplified reduction of the amount of filler such as silica particles used as a lubricant, reduction of surface irregularities, addition of a refractive index adjusting layer, and the like. In particular, when the temporary support is polyethylene terephthalate (PET), reduction of the filler amount is an effective means. However, when the amount of the filler as the lubricant is too small, the above-mentioned problems such as deterioration of handling property and storage property and generation of static electricity occur, and therefore, adjustment is desired to avoid these problems. In addition, the above filler may be added and dispersed in the temporary support during film formation, or a functional layer containing the filler may be applied to the surface of the temporary support after film formation, and in any case, the haze reducing effect due to the reduction of the amount of the filler may be obtained.
As the temporary support, a material having good solvent coatability, being able to transmit ultraviolet light to perform ultraviolet exposure, and having little abnormal birefringence, in addition to low haze, can be preferably used. In the present invention, a film that is not normally used as a temporary support for a dry film resist can be used as the temporary support. In the present invention, a film having a haze lower than that of a film for general optical use may be used as the temporary support.
The temporary support preferably has a transmittance of 80% or less, more preferably 60% or less, and particularly preferably 50% or less with respect to the exposure dominant wavelength of the resist layer. However, in the present invention, if the haze is within the above range, the pattern linearity is good even if the exposure dominant wavelength for the resist layer has a transmittance exceeding 80%.
Examples of such temporary supports include polyethylene terephthalate films, cellulose acetate films, and polypropylene films, and among these, polyethylene terephthalate films having reduced haze are particularly preferable.
A preferred embodiment of the other temporary support is described in japanese patent application laid-open nos. 2014-85643 [0017] to [0018], the contents of which are incorporated into the present specification.
(Resist layer)
The dry film resist of the present invention has a resist layer.
In embodiment 1 of the dry film resist, the resist layer preferably contains a photosensitive agent.
In embodiment 2 of the dry film resist of the present invention, the resist layer contains (B) a photoacid generator as a photosensitive agent.
Examples of the sensitizer include naphthoquinone diazide compounds described later and photoacid generators described later.
Preferable examples of the resist layer in the 1 st aspect of the dry film resist of the present invention include the 1 st preferable aspect of the resin containing a naphthoquinone diazide compound and having a phenolic hydroxyl group, and the 2 nd preferable aspect described below: the resist layer contains a component (A) which is a polymer having a group in which an acid group is protected by an acid-decomposable group, and a photoacid generator (B). In the 2 nd preferred embodiment, the solubility of the resist layer is improved by chemical amplification, and thus the pattern linearity can be improved, as compared with the 1 st preferred embodiment, and in this respect, the 2 nd preferred embodiment is preferred.
On the other hand, the resist layer in the 2 nd aspect of the dry film resist of the present invention is as follows: in a preferred embodiment 2 of the resist layer in embodiment 1 of the dry film resist of the present invention, the component (a) is a polymer having an acid constituent unit a0 in which an acid group is protected with an acid-decomposable group, and the acid constituent unit a0 has a constituent unit represented by the general formula A3.
The resist layer materials used in the preferred embodiments will be described below. A preferred embodiment of the resist layer in the 2 nd aspect of the dry film resist of the present invention is described together with one of the 2 nd preferred aspects of the resist layer in the 1 st aspect of the dry film resist of the present invention.
Preferred mode for the resist layer 1
First, a preferred embodiment 1 of the resist layer will be described.
In embodiment 1 of the dry film resist of the present invention, the resist layer preferably contains a naphthoquinone diazide compound and a resin having a phenolic hydroxyl group. Among them, from the viewpoint of wide development latitude, it is particularly preferable that the resist layer contains both of a cresol novolac resin and a naphthoquinone diazide derivative.
Resins having phenolic hydroxyl groups
Examples of the resin having phenolic hydroxyl groups include phenol novolac resins and cresol novolac resins.
The phenol novolac resin is preferably a resin having a molar ratio of formaldehyde content to phenol of about 0.5 to 1.0, and more preferably about 0.8 to 1.0 from the viewpoints of developability and residual image. The weight average molecular weight of the phenol novolac resin is preferably 300 to 4000, and particularly preferably 400 to 800.
The phenol novolac resin may also use derivatives of these.
The phenol novolac resin may be used alone or in combination of 1 or more of 2 or more kinds of different weight average molecular weights, or may be used in combination with other resins such as cresol novolac resin within a range that does not impair the object of the present invention.
The content of the phenol novolac resin is preferably 40 to 90 mass%, more preferably 60 to 80 mass% with respect to the total solid content in the positive resist layer.
The cresol novolac resin is preferably a resin having a molar ratio of formaldehyde content to cresol of about 0.7 to 1.0, and more preferably about 0.8 to 1.0. The weight average molecular weight of the cresol novolac resin is preferably 800 to 8,000, more preferably 1000 to 6000.
The isomer ratio (molar ratio of ortho-isomer/meta-isomer/para-isomer) of the cresol novolac resin is not particularly limited, and may be appropriately selected according to the purpose, and from the viewpoint of improving the developability, the ratio of para-isomer to all isomers is preferably 10 mol% or more, and more preferably 20 mol% or more.
The cresol novolac resin may be used alone or in a mixture of 2 or more. In this case, the resin may be used in combination with other resins such as phenol novolac.
In the present invention, as the cresol novolak resin, a derivative of cresol novolak resin such as a reaction product with naphthoquinone diazide sulfonate may be used.
The amount of the cresol novolac resin used is preferably 0.1 to 10g/m 2, more preferably 0.5 to 5g/m 2.
Naphthoquinone diazide compound
The naphthoquinone diazide compound is not particularly limited, and may be appropriately selected according to the purpose, and is particularly preferably used in combination with a cresol novolac resin. The naphthoquinone diazide compound may be a 1-functional compound, a 2-functional compound or more, or a mixture thereof.
Examples of the 1-functional naphthoquinone diazide compound include ester compounds obtained by reacting naphthoquinone-4-sulfonyl chloride or naphthoquinone-5-sulfonyl chloride with a substituted phenol.
As the naphthoquinone diazide compound having the 2-or more functions, for example, an ester compound obtained by reacting naphthoquinone-4-sulfonyl chloride or naphthoquinone-5-sulfonyl chloride with a compound having a plurality of phenolic hydroxyl groups is preferable. Examples of the compound having a plurality of phenolic hydroxyl groups include polyphenols such as bisphenols, triphenols, and tetraphenols; polyfunctional phenols such as dihydroxybenzene and trihydroxybenzene; di-or tri-form dihydroxybenzene or trihydroxybenzene, asymmetric polynuclear phenols, or mixtures of these, and the like.
Examples of the compound having a plurality of phenolic hydroxyl groups include 4-t-butylphenol, 4-isopentylphenol, 4-t-octylphenol, 2-isopropyl-5-methylphenol, 2-acetylphenol, 4-hydroxybenzophenone, 3-chlorophenol, 4-benzyloxycarbonyl phenol, 4-dodecylphenol, resorcinol, 4- (1-methyl-1-phenylethyl) -1, 3-benzenediol, phloroglucinol, 4' -dihydroxybenzophenone, bis (4-hydroxyphenyl) methane, 1-bis (4-hydroxyphenyl) cyclohexane, 2-bis (3-methyl-4-hydroxyphenyl) methane, 2,3, 4' -tetrahydroxybenzophenone, 4' - [ (4-hydroxyphenyl) methylene ] bis [ 2-cyclohexyl-5-methylphenol ], and the like.
Examples of the naphthoquinone diazide compound include 4 '-tert-octylphenyl naphthoquinone diazide-4-sulfonate, 4' -tert-octylphenyl naphthoquinone diazide-5-sulfonate, 4 '-benzoylphenyl naphthoquinone diazide-5-sulfonate, and a reaction product of 2,3, 4' -tetrahydroxybenzophenone and 1, 2-naphthoquinone diazide-5-sulfonyl chloride. These may be used alone or in combination of 1 or more than 2. The naphthoquinone diazide compound described in Japanese patent application laid-open No. 4-22955 may also be used, and the content of the publication is incorporated into the present specification.
The amount of naphthoquinone diazide compound added to the resist layer is preferably 1 to 200 parts by mass, more preferably 5 to 50 parts by mass, based on 100 parts by mass of the cresol novolac resin.
In a preferred embodiment 1 of the other resist layer, as the additive, materials described in [0072] to [0083] of JP-A2007-24969 can be used, and the content of the publication is incorporated into the present specification.
In addition, in the 1 st preferred embodiment of the resist layer, a material described in the 2 nd preferred embodiment of the resist layer described later may be used.
Preferred mode for the resist layer 2
A preferred embodiment of the resist layer 2 will be described.
In embodiment 1 of the dry film resist of the present invention, the resist layer preferably contains a component (a) and a photoacid generator (B), and the component (a) is preferably a polymer having a group in which an acid group is protected with an acid-decomposable group.
In the 2 nd aspect of the dry film resist of the present invention, the resist layer contains a component (a) and a photoacid generator (B), the component (a) is a polymer having an acid constituent unit a0 in which an acid group is protected with an acid-decomposable group, and the acid constituent unit a0 has a constituent unit represented by the above general formula A3.
Component (A): polymer having acid constituent unit a0 in which acid group is protected with acid-decomposable group >
(A) The component (a) is preferably a polymer having an acid constituent unit a0 in which an acid group is protected with an acid-decomposable group.
Further, the dry film resist of the present invention is more preferably one wherein the component (a) is a polymer component containing a polymer having an acid constituent unit a1 in which a carboxyl group or a phenolic hydroxyl group is protected as an acetal, or a polymer component containing a polymer having a constituent unit represented by the general formula A3. The constituent unit represented by the general formula A3 is an acid constituent unit in which the carboxyl group is protected in the form of an acetal (when Y described below is an oxygen atom) or in another form (when Y described below is a nitrogen atom or a sulfur atom), and therefore has a portion in which the acid constituent unit a1 is contained in the carboxyl group or the phenolic hydroxyl group and is protected in the form of an acetal, and a portion not contained therein.
The resist layer may further contain polymers other than these.
Groups in which the acid group is protected with an acid-decomposable group
The component (a) can form a resist layer having extremely high sensitivity by containing a polymer having an acid constituent unit a0 in which an acid group is protected with an acid-decomposable group, preferably a polymer having an acid constituent unit a1 in which a carboxyl group or a phenolic hydroxyl group is protected as an acetal, or a polymer having a constituent unit represented by the general formula A3.
The acid group and the acid-decomposable group in the acid constituent unit a0 in which the acid group is protected with the acid-decomposable group in the present invention may be any known acid group and acid-decomposable group, and are not particularly limited. Specific examples of the acid group include a carboxyl group and a phenolic hydroxyl group. As the acid-decomposable group, a group which is relatively easily decomposed by an acid (for example, an ester structure of a group represented by the general formula A1, the general formula A2 or the general formula A3, which will be described later, an acetal-based functional group such as a tetrahydropyran ester group or a tetrahydrofuran ester group), a group which is relatively hardly decomposed by an acid (for example, a tertiary alkyl group such as a tertiary butyl ester group, a tertiary alkyl carbonate group such as a tertiary butyl carbonate group, or the like) may be used.
The acid constituent unit a0 having an acid group protected with an acid-decomposable group is preferably a constituent unit having a phenolic hydroxyl group protected with an acid-decomposable group or a constituent unit having a carboxyl group protected with an acid-decomposable group.
The acid constituent unit a0 in which the acid group is protected with an acid-decomposable group is more preferably an acid constituent unit a1 in which a carboxyl group or a phenolic hydroxyl group is protected as an acetal, or a constituent unit represented by the general formula A3.
The constituent unit having a phenolic hydroxyl group protected by an acid-decomposable group and the constituent unit having a carboxyl group protected by an acid-decomposable group will be described below in order.
Structural unit having a phenolic hydroxyl group protected with an acid-decomposable group
The constituent unit having a phenolic hydroxyl group protected by an acid-decomposable group means: the structural unit having a phenolic hydroxyl group is a structural unit having a protective phenolic hydroxyl group protected with an acid-decomposable group described in detail below.
As the above-mentioned constituent unit having a phenolic hydroxyl group, a constituent unit in which a hydroxyl group derived from a hydroxystyrene or α -methylhydroxystyrene (for example, a constituent unit in a novolak resin) is protected with an acid-decomposable group is preferable from the viewpoint of sensitivity; from the viewpoint of further high resolution, a polymer having a constituent unit represented by the following general formula A1 or a general formula A2 is more preferable; particularly preferred are polymers having constituent units represented by the following formula A1. In other words, in embodiment 1 of the dry film resist of the present invention, the acid constituent unit A1 preferably has a constituent unit represented by the following formula A1. In the dry film resist according to embodiment 1 of the present invention, the acid constituent unit a1 preferably has a constituent unit represented by the following formula A2.
The general formula A1:
[ 6] A method for producing a polypeptide
In the general formula A1, R 1 and R 2 each independently represent a hydrogen atom, an alkyl group or an aryl group, at least any one of R 1 and R 2 is an alkyl group or an aryl group, R 3 represents an alkyl group or an aryl group, R 1 and R 3 or R 2 and R 3 are optionally connected to form a cyclic ether, and R 4 represents a hydrogen atom or a methyl group.
In the general formula A1, when R 1 and R 2 are alkyl groups, alkyl groups having 1 to 10 carbon atoms are preferable. When R 1 and R 2 are aryl groups, phenyl groups are preferred. R 1 and R 2 are each preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably at least one of them is a hydrogen atom.
In the above formula A1, R 3 represents an alkyl group or an aryl group, preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms.
R 1 and R 3 or R 2 and R 3 are optionally linked to form a cyclic ether, preferably R 1 and R 3 or R 2 and R 3 are linked to form a cyclic ether. The number of ring members of the cyclic ether is not particularly limited, and is preferably 5 or 6, more preferably 5.
In the above formula A1, R4 represents a hydrogen atom or a methyl group, preferably a hydrogen atom.
General formula A2:
[ chemical 7]
In the general formula A2, R 11 and R 12 each independently represent a hydrogen atom, an alkyl group or an aryl group, at least any one of R 11 and R 12 is an alkyl group or an aryl group, R 13 represents an alkyl group or an aryl group, R 11 and R 13 or R 12 are optionally linked to R 13 to form a cyclic ether, and R 14 each independently represents a hydrogen atom, a hydroxyl group, a halogen atom, an alkyl group, an alkoxy group, an alkenyl group, an aryl group, an aralkyl group, an alkoxycarbonyl group, a hydroxyalkyl group, an arylcarbonyl group or a cycloalkyl group.
In the general formula A2, when R 11 and R 12 are alkyl groups, alkyl groups having 1 to 10 carbon atoms are preferable. When R 11 and R 12 are aryl groups, phenyl groups are preferred. R 11 and R 12 are each preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably at least one of them is a hydrogen atom.
In the above formula A2, R 13 represents an alkyl group or an aryl group, preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms.
R 11 and R 13 or R 12 and R 13 are optionally linked to form a cyclic ether.
In the above formula A2, R 14 represents a hydrogen atom or a methyl group, preferably a hydrogen atom.
The acid-decomposable group that can be used in the constituent unit having a phenolic hydroxyl group protected with an acid-decomposable group is not particularly limited, and any known acid-decomposable group can be used. From the viewpoints of basic physical properties of the resist layer, particularly sensitivity and pattern shape, and storage stability of the resist layer, it is preferable that the resist layer has a structural unit having a phenolic hydroxyl group protected by an acetal in an acid-decomposable group. Further, from the viewpoint of sensitivity, it is more preferable that the phenolic hydroxyl group is protected with a protective phenolic hydroxyl group in the form of an acetal represented by the following general formula (a 1-10) among the acid-decomposable groups. When the phenolic hydroxyl group is a protected phenolic hydroxyl group which is protected in the form of an acetal represented by the following general formula (a 1-10), the structure of-Ar-O-CR 101R102(OR103) is formed as a whole to protect the phenolic hydroxyl group. Ar represents an arylene group.
General formula (a 1-10):
[ chemical formula 8]
( In the general formulae (a 1 to 10), R 101 and R 102 each independently represent a hydrogen atom or an alkyl group, but excluding the case where R 101 and R 102 are both hydrogen atoms. R 103 represents an alkyl group. R 101 and R 103 or R 102 and R 103 are optionally linked to form a cyclic ether. )
In the general formulae (a 1 to 10), R 101 and R 102 each independently represent a hydrogen atom or an alkyl group, and R 103 represents an alkyl group. The alkyl group may be any of linear, branched, and cyclic. Here, not both R 101 and R 102 represent a hydrogen atom, but at least one of R 101 and R 102 represents an alkyl group.
In the general formulae (a 1-10), when R 101、R102 and R 103 represent an alkyl group, the alkyl group may be any of a linear, branched or cyclic alkyl group.
The linear or branched alkyl group is preferably a carbon number of 1 to 12, more preferably a carbon number of 1 to 6, and still more preferably a carbon number of 1 to 4. Specifically, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, neopentyl, n-hexyl, 2, 3-dimethyl-2-butyl (the xyl), n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl and the like are exemplified.
The cyclic alkyl group is preferably a cyclic alkyl group having 3 to 12 carbon atoms, more preferably a cyclic alkyl group having 4 to 8 carbon atoms, and still more preferably a cyclic alkyl group having 4 to 6 carbon atoms. Examples of the cyclic alkyl group include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, norbornyl, and isobornyl.
The alkyl group may have a substituent, and examples of the substituent include a halogen atom, an aryl group, and an alkoxy group. When a halogen atom is used as a substituent, R 101、R102、R103 is a haloalkyl group, and when an aryl group is used as a substituent, R 101、R102、R103 is an aralkyl group. Aralkyl is all alkyl groups substituted with aryl groups. Examples of the aralkyl group include benzyl, α -methylbenzyl, phenethyl, naphthylmethyl and the like.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and among these, a fluorine atom or a chlorine atom is preferable.
The aryl group is preferably an aryl group having 6 to 20 carbon atoms, and more preferably an aryl group having 6 to 12 carbon atoms. Specifically, phenyl, < -methylphenyl, naphthyl, and the like can be exemplified.
The above-mentioned alkoxy group is preferably an alkoxy group having 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms, and still more preferably a methoxy group or an ethoxy group.
Further, when the alkyl group is a cycloalkyl group, the cycloalkyl group may have a linear or branched alkyl group having 1 to 10 carbon atoms as a substituent, and when the alkyl group is a linear or branched alkyl group, the cycloalkyl group may have a cycloalkyl group having 3 to 12 carbon atoms as a substituent.
These substituents may be further substituted with the above substituents.
In addition, R 101、R102 and R 103 may be linked to each other to form a ring together with the carbon atoms to which they are bonded. Examples of the ring structure when R 101 and R 102、R101 and R 103 or R 102 and R 103 are bonded include cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, tetrahydrofuranyl, adamantyl and tetrahydropyranyl.
In the general formulae (a 1 to 10), it is preferable that any one of R 101 and R 102 is a hydrogen atom or a methyl group.
As preferable examples of the acetal ester structure of the phenolic hydroxyl group, there may be exemplified a case where R 101 =methyl group, R 102 =hydrogen atom, R 103 =ethyl group, and R 101 and R 103 are connected to each other to form a 5-membered ring; r 101＝R102＝R103 = methyl; and the case of R 101＝R102 =methyl, R 103 =benzyl.
Examples of the polymerizable monomer used for forming a structural unit having a phenolic hydroxyl group protected in the form of an acetal include those described in paragraph 0042 of JP-A2011-215590.
Among these, from the viewpoint of transparency, a 1-alkoxyalkyl protector of 4-hydroxyphenyl methacrylate and a tetrahydropyranyl protector of 4-hydroxyphenyl methacrylate are preferable.
Specific examples of the acetal protecting group for a phenolic hydroxyl group include 1-alkoxyalkyl groups, for example, 1-ethoxyethyl, 1-methoxyethyl, 1-n-butoxyethyl, 1-isobutoxyethyl, 1- (2-chloroethoxy) ethyl, 1- (2-ethylhexyloxy) ethyl, 1-n-propoxyethyl, 1-cyclohexyloxyethyl, 1- (2-cyclohexylethoxy) ethyl, and 1-benzyloxyethyl. These may be used alone or in combination of 2 or more.
The polymerizable monomer used for forming the above-mentioned constituent unit having a phenolic hydroxyl group protected with an acid-decomposable group may be a commercially available monomer or a monomer synthesized by a known method. For example, a compound having a phenolic hydroxyl group can be synthesized by reacting a vinyl ether with an acid catalyst. In the above synthesis, a monomer having a phenolic hydroxyl group may be copolymerized with another monomer in advance and then reacted with a vinyl ether in the presence of an acid catalyst.
The following structural units may be exemplified as preferable specific examples of the structural unit having a phenolic hydroxyl group protected with an acid-decomposable group, and the present invention is not limited to these examples.
[ Chemical formula 9]
[ Chemical formula 10]
[ Chemical formula 11]
The copolymerization ratio of the constituent unit having the protective phenol group protected by the acid-decomposable group in the polymer having the acid constituent unit a0 in which the acid group is protected by the acid-decomposable group is preferably 10 to 50 mol%, more preferably 20 to 40 mol%, particularly preferably 25 to 40 mol% with respect to the polymer having the constituent unit having the protective phenol group protected by the acid-decomposable group.
In addition, when the total polymer component (when the polymer component is a mixture of 2 or more polymers, all the polymers contained therein) is decomposed into constituent units (monomer units), the proportion of the constituent units having the protecting phenol groups whose acid groups are protected by the acid-decomposable groups to the number of moles of the total constituent units is preferably 0 to 40 mol%, more preferably 10 to 35 mol%, and particularly preferably 15 to 30 mol%.
Constituent Unit having protected carboxyl group protected with acid-decomposable group
The constituent unit having a carboxyl group protected with an acid-decomposable group means: the carboxyl group containing a carboxyl group-containing constituent unit is a carboxyl group-protecting constituent unit protected with an acid-decomposable group described in detail below.
The constituent unit having a carboxyl group that can be used as the constituent unit having a protected carboxyl group protected with an acid-decomposable group is not particularly limited, and known constituent units can be used. Examples thereof include constituent units (a 1-1-1) derived from unsaturated carboxylic acids having at least 1 carboxyl group in the molecule, such as unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, and unsaturated tricarboxylic acids; constituent units (a 1-1-2) having both an ethylenically unsaturated group and a structure derived from an acid anhydride; a constituent unit represented by the general formula A3.
The constituent unit (a 1-1-1) derived from an unsaturated carboxylic acid having at least 1 carboxyl group in the molecule, the constituent unit (a 1-1-2) having both an ethylenically unsaturated group and an acid anhydride-derived structure, and the constituent unit represented by the general formula A3, which are used as the constituent units having carboxyl groups, will be described in order.
The constituent unit (a 1-1-1) derived from an unsaturated carboxylic acid or the like having at least 1 carboxyl group in the molecule
As the constituent unit (a 1-1-1) derived from the unsaturated carboxylic acid having at least 1 carboxyl group in the molecule, the unsaturated carboxylic acid used in the present invention may be exemplified as follows. That is, examples of the unsaturated monocarboxylic acid include acrylic acid, methacrylic acid, crotonic acid, α -chloroacrylic acid, cinnamic acid, 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxyethyl hexahydrophthalic acid, and 2- (meth) acryloyloxyethyl phthalic acid. Examples of the unsaturated dicarboxylic acid include maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, and the like. The unsaturated polycarboxylic acid used to obtain the constituent unit having a carboxyl group may be an acid anhydride thereof. Specifically, maleic anhydride, itaconic anhydride, citraconic anhydride, and the like can be cited. The unsaturated polycarboxylic acid may be a mono (2-methacryloxyalkyl) ester of a polycarboxylic acid, and examples thereof include succinic acid mono (2-acryloxyethyl ester), succinic acid mono (2-methacryloxyethyl ester), phthalic acid mono (2-acryloxyethyl ester), phthalic acid mono (2-methacryloxyethyl ester), and the like. Further, the unsaturated polycarboxylic acid may be a mono (meth) acrylate of a dicarboxylic polymer at both ends thereof, and examples thereof include ω -carboxyl polycaprolactone monoacrylate, ω -carboxyl polycaprolactone monomethacrylate, and the like. Further, as the unsaturated carboxylic acid, 2-carboxyethyl acrylate, 2-carboxyethyl methacrylate, monoalkyl maleate, monoalkyl fumarate, 4-carboxystyrene, and the like can be used.
Among them, in order to form the above-mentioned constituent unit (a 1-1-1) derived from an unsaturated carboxylic acid having at least 1 carboxyl group in the molecule, etc., acrylic acid, methacrylic acid, 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxyethyl hexahydrophthalic acid, 2- (meth) acryloyloxyethyl phthalic acid, or an acid anhydride of an unsaturated polycarboxylic acid, etc., are preferably used, and acrylic acid, methacrylic acid, 2- (meth) acryloyloxyethyl hexahydrophthalic acid, etc., are more preferably used.
The constituent unit (a 1-1-1) derived from an unsaturated carboxylic acid having at least 1 carboxyl group in the molecule may be used alone or in combination of at least 2 kinds.
The structural unit (a 1-1-2) having both an ethylenically unsaturated group and a structure derived from an acid anhydride
The constituent unit (a 1-1-2) having both an ethylenically unsaturated group and a structure derived from an acid anhydride is preferably a unit derived from a monomer obtained by reacting a hydroxyl group present in the constituent unit having an ethylenically unsaturated group with an acid anhydride.
The acid anhydride may be any known acid anhydride, and specifically, acid anhydrides of dibasic acids such as maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, and chlorendic anhydride; anhydride such as trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic anhydride, and biphenyl tetracarboxylic anhydride. Among these, phthalic anhydride, tetrahydrophthalic anhydride and succinic anhydride are preferable from the viewpoint of developability.
From the viewpoint of developability, the reaction rate of the acid anhydride with respect to the hydroxyl group is preferably 10 to 100 mol%, more preferably 30 to 100 mol%.
As the acid-decomposable group that can be used in the constituent unit having a protected carboxyl group protected with an acid-decomposable group, an acid-decomposable group that can be used in the constituent unit having a protected phenol group protected with an acid-decomposable group can be used.
Among these acid-decomposable groups, a protected carboxyl group in which a carboxyl group is protected as an acetal is preferable from the viewpoints of basic physical properties of a resist layer, particularly sensitivity and pattern shape, and storage stability of the resist layer. Further, from the viewpoint of sensitivity, a protected carboxyl group in which the carboxyl group is protected in the form of an acetal represented by the above general formula (a 1-10) in an acid-decomposable group is more preferable. When the carboxyl group is a protected carboxyl group protected in the form of an acetal represented by the general formula (a 1-10), the whole protected carboxyl group has a structure of- (C=O) -O-CR 101R102(OR103).
The polymerizable monomer used for forming the constituent unit having the protected carboxyl group represented by the above general formula (a 1 to 10) may be a commercially available monomer or a monomer synthesized by a known method. For example, the synthesis method described in Japanese patent application laid-open No. 2011-221494, paragraph nos. 0037 to 0040, and the like can be used.
Structural unit represented by general formula A3
Among the acid constituent units a0 in which the acid groups are protected with acid-decomposable groups, the acid constituent unit a0 having the constituent unit represented by the following formula A3 is preferable because the alkali dissolution rate in the developing step can be further improved.
In addition, when the acid constituent unit a0 in which the acid group is protected with the acid-decomposable group is an acid constituent unit in which the carboxyl group is protected with the acid-decomposable group (the constituent unit having a protected carboxyl group protected with the acid-decomposable group described above), the constituent unit represented by the following general formula A3 is preferable from the viewpoint of improving sensitivity. The dry film resist of the present invention is preferably: the resist layer contains 2 or more kinds of component (a), and contains a polymer having a constituent unit represented by the following general formula A3 as component (a).
[ Chemical formula 12]
General formula A3:
In the general formula A3, R 31 and R 32 each independently represent a hydrogen atom, an alkyl group or an aryl group, at least any one of R 31 and R 32 is an alkyl group or an aryl group, R 33 represents an alkyl group or an aryl group, R 31 and R 33 or R 32 are optionally linked to R 33 to form a cyclic ether, R 34 represents a hydrogen atom or a methyl group, X 0 represents a single bond or an arylene group, and Y represents a nitrogen atom, a sulfur atom or an oxygen atom.
In the above formula A3, when R 31 and R 32 are alkyl groups, alkyl groups having 1 to 10 carbon atoms are preferable. When R 31 and R 32 are aryl groups, phenyl groups are preferred. R 31 and R 32 are preferably each a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
In the above formula A3, R 33 represents an alkyl group or an aryl group, preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms.
In the above formula A3, R 31 and R 33 or R 32 and R 33 are optionally linked to form a cyclic ether, preferably R 31 and R 33 or R 32 and R 33 are linked to form a cyclic ether. The number of ring members of the cyclic ether is not particularly limited, and is preferably 5 or 6, more preferably 5.
In the above formula A3, R 34 represents a hydrogen atom or a methyl group, preferably a hydrogen atom.
In the above formula A3, X 0 represents a single bond or arylene group, and in the dry film resist of the present invention, X 0 is preferably a single bond in the formula A3.
In the above formula A3, Y represents a nitrogen atom, a sulfur atom or an oxygen atom, and in the dry film resist of the present invention, Y is preferably an oxygen atom in the formula A3.
Among the constituent units represented by the above general formula A3, the constituent unit represented by the following general formula A3-1 is more preferable from the viewpoint of further improving sensitivity.
[ Chemical formula 13]
General formula A3-1:
(wherein R 121 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R 122～R128 each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.)
In the above formula A3-1, R 121 is preferably a hydrogen atom or a methyl group.
In the above formula A3-1, R 122～R128 is preferably a hydrogen atom.
The following structural units may be exemplified as preferable specific examples of the structural unit having a carboxyl group protected with an acid-decomposable group. R represents a hydrogen atom or a methyl group.
[ Chemical formula 14]
The copolymerization ratio of the acid constituent unit a0 having an acid group and a carboxyl group-protected constituent unit having an acid-decomposable group in the polymer having the acid constituent unit a0 having an acid-decomposable group is preferably 5 to 60 mol%, more preferably 10 to 50 mol%, particularly preferably 30 to 50 mol% with respect to the polymer having the carboxyl group-protected constituent unit having an acid-decomposable group.
The proportion of the constituent unit having a protected carboxyl group in which an acid group is protected with an acid-decomposable group to the number of moles of all constituent units is preferably 0 to 60 mol%, more preferably 10 to 50 mol%, particularly preferably 15 to 25 mol%, in addition to the decomposition of all polymer components into constituent units (monomer units).
Other constituent Unit (a 3)
The component (a) of the resist layer may contain other constituent units (a 3) than the acid constituent unit a0 in which the acid group is protected with an acid-decomposable group. These other constituent units (a 3) may contain, as a copolymerization component, a polymer used in the above-mentioned component (a), that is, a polymer having an acid constituent unit a0 in which an acid group is protected with an acid-decomposable group. In addition to the polymer containing the acid constituent unit a0 in which the acid group is protected with the acid-decomposable group used in the component (a), a polymer containing the acid constituent unit a0 in which the acid group is substantially not protected with the acid-decomposable group and having other constituent units may be used as the other constituent unit (a 3).
The monomer forming the other constituent unit (a 3) is not particularly limited, and examples thereof include styrenes, alkyl (meth) acrylates, cyclic alkyl (meth) acrylates, aryl (meth) acrylates, unsaturated dicarboxylic acid diesters, bicyclic unsaturated compounds, maleimide compounds, unsaturated aromatic compounds, conjugated diene compounds, unsaturated monocarboxylic acids, unsaturated dicarboxylic anhydrides, and other unsaturated compounds. As described later, the resin composition may further contain a constituent unit having an acid group. The monomers constituting the other constituent unit (a 3) may be used alone or in combination of 2 or more.
Specific examples of the constituent unit (a 3) include constituent units derived from styrene, t-butoxystyrene, methylstyrene, hydroxystyrene, α -methylstyrene, acetoxystyrene, methoxystyrene, ethoxystyrene, chlorostyrene, methyl vinylbenzoate, ethyl vinylbenzoate, 3-methacryloxypropyl 4-hydroxybenzoate, (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, acrylonitrile, ethylene glycol monoacetoacetate mono (meth) acrylate, and the like. Further, the compounds described in paragraphs 0021 to 0024 of Japanese patent application laid-open No. 2004-264623 are exemplified.
Further, as the other constituent unit (a 3), from the viewpoint of electrical characteristics, styrene and a group having an aliphatic cyclic skeleton are preferable. Specifically, styrene, t-butoxystyrene, methylstyrene, hydroxystyrene, α -methylstyrene, dicyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, benzyl (meth) acrylate, and the like can be cited.
Further, as the other constituent unit (a 3), alkyl (meth) acrylate is preferable from the viewpoint of adhesion. Specifically, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, and the like are cited, and methyl (meth) acrylate is more preferable.
The content of the constituent unit (a 3) in the constituent unit constituting the polymer containing the acid constituent unit a0 in which the acid group is protected with the acid-decomposable group is preferably 60 mol% or less, more preferably 50 mol% or less, and still more preferably 40 mol% or less. The lower limit may be 0 mol% or more, for example, 1 mol% or more, and further 5 mol% or more. Within the above numerical range, the properties of the resist layer become good.
The other constituent unit (a 3) preferably has an acid group-containing constituent unit. The effect of the present invention can be more effectively exhibited by providing the component (a) with an acid group-containing constituent unit, and making the component (a) readily soluble in an alkaline developer. The acid group in the present invention means a proton dissociable group having a pKa (power of Ka; ka is an acid dissociation constant) of 10 or less. Acid groups are generally monomers which form acid groups and are introduced into the polymer in the form of acid group-containing constituent units. The polymer contains an acid group-containing constituent unit, which tends to cause the component (a) to be easily dissolved in an alkaline developer.
Examples of the acid group-containing constituent unit used in the other constituent unit include an acid group derived from a carboxylic acid group, an acid group derived from a sulfonamide group, an acid group derived from a phosphonic acid group, an acid group derived from a sulfonic acid group, an acid group derived from a phenolic hydroxyl group, a sulfonamide group, a sulfonylimide group, and the like, and an acid group derived from a carboxylic acid group and/or an acid group derived from a phenolic hydroxyl group is preferable.
The acid group-containing constituent unit used in the other constituent units is more preferably: the constituent unit derived from styrene, the constituent unit derived from a vinyl compound in which an acid group is substituted, and the constituent unit derived from (meth) acrylic acid.
Further, from the viewpoints of solubility in a developer and optimization of physical properties of a film, it is preferable to have a constituent unit of an ester containing an acid group.
In the present invention, it is particularly preferable that the constituent unit (a 3) contains a constituent unit having a carboxyl group or a constituent unit having a phenolic hydroxyl group as the other constituent unit from the viewpoint of sensitivity.
In the polymer containing the above-mentioned constituent unit having a protective phenol group protected with an acid-decomposable group as the acid constituent unit a0 having the above-mentioned acid group protected with an acid-decomposable group, the constituent unit derived from a phenolic hydroxyl group in the above-mentioned other constituent unit (a 3) is preferably contained as a copolymerization component. The polymer containing the above-mentioned constituent unit having a protective phenol group protected with an acid-decomposable group as the acid constituent unit a0 having the above-mentioned acid group protected with an acid-decomposable group is more preferably a polymer containing a constituent unit derived from hydroxystyrene or α -methylhydroxystyrene as a copolymerization component, and particularly preferably a polymer containing a constituent unit derived from hydroxystyrene as a copolymerization component.
The copolymerization ratio of the acid group-containing constituent unit in the polymer having the constituent unit of the protective phenol group protected with the acid-decomposable group is preferably 50 to 90 mol%, more preferably 60 to 75 mol% with respect to the polymer having the constituent unit of the protective phenol group protected with the acid-decomposable group when the acid group is a phenolic hydroxyl group.
When the acid group is a carboxylic acid group, the amount of the acid group is preferably 0 to 30 mol%, more preferably 5 to 10 mol%, based on the polymer having a constituent unit having a protective phenol group protected with an acid-decomposable group.
The copolymerization ratio of the acid group-containing ester constituent unit in the polymer containing the constituent unit having the protective phenol group protected with the acid-decomposable group is preferably 0 to 30 mol%, more preferably 0 to 10 mol%, and particularly preferably 0 mol% with respect to the polymer containing the constituent unit having the protective phenol group protected with the acid-decomposable group.
The polymer containing the acid constituent unit a0 having the acid-decomposable group-protected carboxyl group, preferably contains a constituent unit of a carboxylic acid group and/or an ester thereof in the other constituent unit (a 3) as a copolymerization component. The polymer containing the above-mentioned constituent unit having a protected carboxyl group protected with an acid-decomposable group as the acid constituent unit a0 having the acid group protected with an acid-decomposable group more preferably contains a constituent unit derived from (meth) acrylic acid, benzyl (meth) acrylate or 2-hydroxyethyl (meth) acrylate as a copolymerization component.
The copolymerization ratio of the acid group-containing constituent unit in the polymer having the constituent unit having a carboxyl group protected with an acid-decomposable group is preferably 50 to 90 mol%, more preferably 60 to 75 mol% with respect to the polymer having the constituent unit having a carboxyl group protected with an acid-decomposable group when the acid group is a phenolic hydroxyl group.
When the acid group is a carboxylic acid group, the amount of the carboxylic acid group is preferably 0to 30 mol%, more preferably 5 to 10 mol% based on the polymer having a constituent unit having a carboxyl group protected with an acid-decomposable group.
The copolymerization ratio of the acid group-containing ester constituent unit in the polymer having the carboxyl group-protected constituent unit protected with the acid-decomposable group is preferably 10 to 80 mol%, more preferably 30 to 70 mol%, and particularly preferably 40 to 60 mol% with respect to the polymer having the carboxyl group-protected constituent unit protected with the acid-decomposable group.
< Preferred modes of Polymer Components >
The constituent unit having the protected carboxyl group protected with the acid-decomposable group is developed (developed at a higher rate) than the constituent unit having the protected phenolic hydroxyl group protected with the acid-decomposable group. Therefore, when the resist layer is to be developed rapidly after exposure, it is preferable to use a constituent unit having a protected carboxyl group protected by an acid-decomposable group. In contrast, when slower development is desired, it is preferable to use a constituent unit having a phenolic hydroxyl group protected by an acid-decomposable group.
In the resist layer, the polymer having an acid constituent unit a0 in which an acid group is protected with an acid-decomposable group in the component (a) may be 1 kind or 2 kinds or more.
First, a case will be described in which the resist layer of the dry film resist contains 1 polymer having an acid constituent unit a0 in which an acid group is protected by an acid-decomposable group. When the resist layer contains 1 kind of the polymer having the acid constituent unit a0 in which the acid group is protected by the acid-decomposable group as the polymer component, the component (a) is preferably a polymer component containing the acid constituent unit a0 in which the acid group is protected by the acid-decomposable group, the acid constituent unit a0 having a constituent unit represented by the general formula A3, from the viewpoint of improving the linearity of the pattern, particularly, from the viewpoint of improving the linearity of the pattern when the pH of the developer used in the developing step is 12.5 or less.
When the resist layer contains 1 polymer having an acid constituent unit a0 in which an acid group is protected with an acid-decomposable group, 60 to 100 mol% of the acid constituent unit a0 in which an acid group is protected with an acid-decomposable group is preferably a constituent unit represented by the general formula A3, more preferably 70 to 100 mol% is a constituent unit represented by the general formula A3, and particularly preferably 100 mol% is a constituent unit represented by the general formula A3.
When the resist layer contains 1 kind of polymer having an acid constituent unit a0 in which an acid group is protected by an acid-decomposable group, the polymer component having a constituent unit represented by the general formula A3 is preferably 70 to 100% by mass, more preferably 90 to 100% by mass, and particularly preferably 100% by mass (i.e., no polymer component other than the polymer having a constituent unit represented by the general formula A3) among the polymers having a group in which an acid group is protected by an acid-decomposable group contained in the resist layer.
Next, in the dry film resist of the present invention, the resist layer may contain 2 or more polymers having an acid constituent unit a0 in which an acid group is protected with an acid-decomposable group. When the resist layer contains 2 or more polymers each having an acid constituent unit a0 in which an acid group is protected with an acid-decomposable group, the polymer component having an acid constituent unit a0 in which an acid group is protected with an acid-decomposable group is more preferably a polymer containing the above-mentioned constituent unit having a phenolic hydroxyl group protected with an acid-decomposable group and a polymer containing the above-mentioned constituent unit having a carboxyl group protected with an acid-decomposable group.
When the resist layer contains 2 or more polymers having an acid constituent unit a0 in which an acid group is protected with an acid-decomposable group, particularly preferred are polymers containing the polymer having a constituent unit represented by the general formula A3 as the acid constituent unit a0 in which the acid group is protected with an acid-decomposable group, from the viewpoint of improving sensitivity. That is, the dry film resist of the present invention is preferably: the resist layer contains 2 or more kinds of component (A) and contains a polymer having a constituent unit represented by the general formula A3 as component (A).
When the resist layer contains 2 or more polymers having an acid constituent unit a0 in which an acid group is protected with an acid-decomposable group, it is more particularly preferable that the polymer having at least one of the polymers having a constituent unit represented by the general formula A1 or the general formula A2 and the polymer having a constituent unit represented by the general formula A3 be contained as the polymer having the acid constituent unit a0 in which an acid group is protected with an acid-decomposable group, from the viewpoint of improving both sensitivity and resolution. From the viewpoint of improving both sensitivity and resolution, more particularly, a polymer containing at least one of the polymers having the constituent unit represented by the general formula A1 and the constituent unit represented by the general formula A3 is preferable.
When the resist layer contains 2 or more kinds of polymers having an acid constituent unit a0 in which an acid group is protected with an acid-decomposable group, the ratio of the polymer having a constituent unit in which a protective phenolic hydroxyl group is protected with an acid-decomposable group to the polymer having a constituent unit in which a protective carboxyl group is protected with an acid-decomposable group is preferably 10:90 to 100:0, more preferably 30:70 to 60:40, and particularly preferably 1:1 in terms of mass ratio.
Molecular weight of Polymer containing acid constituent Unit a0 in which an acid group is protected with an acid-decomposable group
The weight average molecular weight of the polymer containing the acid constituent unit a0 in which the acid group is protected with the acid-decomposable group is preferably 1,000 ～ 200,000, more preferably in the range of 2,000 to 50,000 in terms of polystyrene. Within the above numerical range, various characteristics are good.
The ratio (dispersity) of the number average molecular weight to the weight average molecular weight is preferably 1.0 to 5.0, more preferably 1.05 to 3.5.
Process for producing component (A)
In addition, various methods are known for synthesizing the component (a). If one example is listed, it can be synthesized by the following method: a polymerizable monomer mixture containing at least a polymerizable monomer used for forming the acid constituent unit a0 in which the acid group is protected by an acid-decomposable group and the constituent unit shown in (a 3) is polymerized in an organic solvent using a polymerization initiator. Furthermore, the synthesis can be carried out by a so-called polymer reaction.
The resist layer preferably contains the component (a) in an amount of 50 to 99.9 parts by mass, more preferably 70 to 98 parts by mass, based on 100 parts by mass of the total solid content.
< Other Polymer component >
In addition to the polymer containing the acid constituent unit a0 in which the acid group is protected with the acid-decomposable group, which is used in the component (a), a polymer containing the acid constituent unit a0 in which the acid group is substantially not protected with the acid-decomposable group and having other constituent units may be contained. When the polymer having other constituent units, in addition to the polymer used in the component (a), substantially no acid constituent unit a0 having an acid group protected by an acid-decomposable group is contained, the blending amount of the polymer is preferably 60% by mass or less, more preferably 40% by mass or less, particularly preferably 20% by mass or less, and even more preferably 3% by mass or less, based on the total polymer components. Most preferably 0 mass%.
In the resist layer, the polymer having the acid constituent unit a0 substantially free of the acid group and the other constituent unit (a 3) protected by the acid-decomposable group may contain only 1 kind or may contain 2 or more kinds.
As these polymers having other constituent units (a 3) substantially free of acid constituent unit a0 having an acid group protected by an acid-decomposable group, for example, polyhydroxystyrene may be used, and commercially available SMA 1000P, SMA 2000P, SMA 3000P, SMA 1440F, SMA 17352P, SMA P, SMA F (manufactured by SARTOMER Co., ltd., above), ARUFON UC-3000, ARUFON UC-3510, ARUFON UC-3900, ARUFON UC-3910, ARUFON UC-3920, ARUFON UC-3080 (manufactured by Tolyene Synthesis Co., ltd.), joncryl 690, joncryl 678, joncryl 67, joncryl 586 (manufactured by BASF, above) and the like may be used.
Component (B): photoacid generator)
The resist layer preferably contains (B) a photoacid generator. The photoacid generator (also referred to as a "(B) component") used in the present invention is a compound capable of generating an acid by irradiation with radiation such as ultraviolet rays, far ultraviolet rays, X-rays, charged particle rays, and the like. The photoacid generator (B) used in the present invention is preferably a compound that generates an acid by sensing an active light having a wavelength of 300nm or more, preferably 300 to 450 nm. The chemical structure of the photoacid generator (B) is not limited. The photoacid generator that does not directly sense the active light having a wavelength of 300nm or more may be preferably used in combination with a sensitizer as long as it is a compound that senses the active light having a wavelength of 300nm or more and generates an acid when used in combination with a sensitizer. The pKa value of the acid generated by irradiation with the radiation is preferably 4.0 or less, more preferably 3.0 or less. The lower limit is not particularly limited, and may be, for example, -10.0 or more.
Examples of the photoacid generator (B) include an ionic photoacid generator and a nonionic photoacid generator.
Examples of the nonionic photoacid generator include trichloromethyl s-triazines, diazomethane compounds, imide sulfonate compounds, oxime sulfonate compounds, and the like. Among these, the resist layer is preferably one in which the above (B) photoacid generator is an oxime sulfonate compound from the viewpoint of insulation. These photoacid generators may be used singly or in combination of 2 or more. Specific examples of trichloromethyl s-triazines and diazomethane derivatives include compounds described in paragraphs 0083 to 0088 of Japanese patent application laid-open No. 2011-221494, which are incorporated herein by reference.
As the oxime sulfonate compound, that is, a compound having an oxime sulfonate structure, a compound containing an oxime sulfonate structure represented by the following general formula (B1) can be preferably exemplified.
General formula (B1):
[ 15] A method of producing a polypeptide
( In the general formula (B1), R 21 represents an alkyl group or an aryl group. Wavy lines indicate bonds of other groups. )
Any of the groups may be substituted, and the alkyl group in R 21 may be linear, branched, or cyclic. Acceptable substituents will be described below.
As the alkyl group of R 21, a linear or branched alkyl group having 1 to 10 carbon atoms is preferable. The alkyl group of R 21 may be substituted with an aryl group having 6 to 11 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a cycloalkyl group (including a bridged alicyclic group such as a 7, 7-dimethyl-2-oxo-norbornyl group, preferably a bicycloalkyl group).
The aryl group of R 21 is preferably an aryl group having 6 to 11 carbon atoms, and more preferably a phenyl group or a naphthyl group. The aryl group of R 21 may be substituted by a lower alkyl group, an alkoxy group, or a halogen atom.
The above compound containing an oxime sulfonate structure represented by the above general formula (B1) is also preferably an oxime sulfonate compound represented by the following general formula (B2).
[ 16] The preparation method
(In the general formula (B2), R 42 represents an alkyl group or an aryl group, X 10 represents an alkyl group, an alkoxy group, or a halogen atom, m4 represents an integer of 0 to 3, and when m4 is 2 or 3, a plurality of X 10 may be the same or different.)
The alkyl group of X 10 is preferably a linear or branched alkyl group having 1 to 4 carbon atoms.
The alkoxy group of X 10 is preferably a linear or branched alkoxy group having 1 to 4 carbon atoms.
The halogen atom of X 10 is preferably a chlorine atom or a fluorine atom. m4 is preferably 0 or 1. Particularly preferred are compounds of the general formula (B2) wherein m4 is 1, X 10 is methyl, the substitution position of X 10 is ortho, R 42 is a linear alkyl group having 1 to 10 carbon atoms, 7-dimethyl-2-oxonorbornylmethyl group or p-tolyl group.
The compound containing an oxime sulfonate structure represented by the above general formula (B1) is also preferably an oxime sulfonate compound represented by the following general formula (B3).
[ Chemical formula 17]
(In the general formula (B3), R 43 has the same meaning as R 42 in the general formula (B2), X 11 represents a halogen atom, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a cyano group or a nitro group, and n4 represents an integer of 0 to 5.)
R 43 in the above general formula (B3) is preferably methyl, ethyl, n-propyl, n-butyl, n-octyl, trifluoromethyl, pentafluoroethyl, perfluoro-n-propyl, perfluoro-n-butyl, p-tolyl, 4-chlorophenyl or pentafluorophenyl, particularly preferably n-octyl.
As X 11, an alkoxy group having 1 to 5 carbon atoms is preferable, and a methoxy group is more preferable.
N4 is preferably 0 to 2, particularly preferably 0 to 1.
Specific examples of the compound represented by the above general formula (B3) include α - (methylsulfonyloxyimino) benzyl cyanide, α - (ethylsulfonyloxy-imino) benzyl cyanide, α - (n-propylsulfonyloxy-imino) benzyl cyanide, α - (n-butylsulfonyloxy-imino) benzyl cyanide, α - (4-toluenesulfonyloxy-imino) benzyl cyanide, α - [ (methylsulfonyloxy) -4-methoxyphenyl ] acetonitrile, α - [ (ethylsulfonyloxy-imino) -4-methoxyphenyl ] acetonitrile, α - [ (n-propylsulfonyloxy-imino) -4-methoxyphenyl ] acetonitrile, α - [ (n-butylsulfonyloxy-imino) -4-methoxyphenyl ] acetonitrile, and α - [ 4-toluenesulfonyloxy-imino ] -4-methoxyphenyl ] acetonitrile.
Specific examples of the preferable oxime sulfonate compound include the following compounds (i) to (viii), and 1 or 2 or more compounds may be used singly or in combination. The compounds (i) to (viii) can be obtained in the form of commercial products. In addition, it is also possible to use the photoacid generator (B) in combination with other kinds of photoacid generator (B).
[ Chemical formula 18]
As the compound containing the oxime sulfonate structure represented by the above general formula (B1), a compound represented by the following general formula (OS-1) is also preferable.
[ Chemical formula 19]
General formula (OS-1)
In the above general formula (OS-1), R 411 represents a hydrogen atom, an alkyl group, an alkenyl group, an alkoxy group, an alkoxycarbonyl group, an acyl group, a carbamoyl group, an aminosulfonyl group, a sulfo group, a cyano group, an aryl group, or a heteroaryl group. R 412 represents an alkyl group, or an aryl group.
X 401 represents-O-, -S-; -NH-, -NR 415-、-CH2-、-CR416 H-; or-CR 415R417-,R415～R417 represents an alkyl group, or an aryl group.
R 421～R424 each independently represents a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an amino group, an alkoxycarbonyl group, an alkylcarbonyl group, an arylcarbonyl group, an amide group, a sulfo group, a cyano group, or an aryl group. 2 of R 421～R424 may be respectively linked to each other to form a ring.
As R 421～R424, a hydrogen atom, a halogen atom, and an alkyl group are preferable, and a mode in which at least 2 of R 421～R424 are connected to each other to form an aryl group is also preferable. Among them, from the viewpoint of sensitivity, the system in which R 421～R424 is a hydrogen atom is preferable.
The functional groups may each have a further substituent.
The compound represented by the general formula (OS-1) is more preferably a compound represented by the following general formula (OS-2).
[ Chemical formula 20]
General formula (OS-2):
In the general formula (OS-2), R 411、R412 and R 421～R424 have the same meanings as R 411、R412 and R 421～R424 in the general formula (OS-1), respectively, and preferable examples are the same.
Of these, more preferable is a system in which R 411 in the above general formula (OS-1) and the above general formula (OS-2) is cyano or aryl, and most preferable is a system in which R 411 is cyano, phenyl or naphthyl, which is represented by the above general formula (OS-2).
In the oxime sulfonate compound, the steric structures (E, Z, etc.) of the oxime and benzothiazole rings may be either one or a mixture.
Specific examples of the compounds represented by the general formula (OS-1) which can be preferably used in the present invention include the compounds described in paragraphs 0128 to 0132 of Japanese patent application laid-open No. 2011-221494 (exemplified by compounds b-1 to b-34), but the present invention is not limited thereto.
In the present invention, the compound containing an oxime sulfonate structure represented by the above general formula (B1) is preferably an oxime sulfonate compound represented by the following general formula (OS-3), the following general formula (OS-4) or the following general formula (OS-5).
[ Chemical formula 21]
(Formula (OS-3) to formula (OS-5), R 22、R25 and R 28 each independently represent an alkyl group, an aryl group or a heteroaryl group, R 23、R26 and R 29 each independently represent a hydrogen atom, an alkyl group, an aryl group or a halogen atom, R 24、R27 and R 30 each independently represent a halogen atom, an alkyl group, an alkoxy group, a sulfonic acid group, an aminosulfonyl group or an alkoxysulfonyl group, X 1～X3 each independently represent an oxygen atom or a sulfur atom, n 1～n3 each independently represents 1 or 2, and m 1～m3 each independently represents an integer of 0 to 6.)
In the general formulae (OS-3) to (OS-5), the alkyl group, aryl group or heteroaryl group in R 22、R25 and R 28 may have a substituent.
In the above formulae (OS-3) to (OS-5), the alkyl group in R 22、R25 and R 28 is preferably an alkyl group having 1 to 30 total carbon atoms which may have a substituent.
In the general formulae (OS-3) to (OS-5), the aryl group in R 22、R25 and R 28 is preferably an aryl group having 6 to 30 total carbon atoms which may have a substituent.
In the general formulae (OS-3) to (OS-5), the heteroaryl group in R 1 is preferably a heteroaryl group having 4 to 30 total carbon atoms which may have a substituent.
In the general formulae (OS-3) to (OS-5), at least 1 ring of the heteroaryl group in R 22、R25 and R 28 may be a heteroaromatic ring, and for example, the heteroaromatic ring and the benzene ring may be condensed.
In the general formulae (OS-3) to (OS-5), R 23、R26 and R 29 are preferably a hydrogen atom, an alkyl group or an aryl group, and more preferably a hydrogen atom or an alkyl group.
In the general formulae (OS-3) to (OS-5), 2 or more of R 23、R26 and R 29 are present in the compound, preferably 1 or 2 are an alkyl group, an aryl group or a halogen atom, more preferably 1 is an alkyl group, an aryl group or a halogen atom, particularly preferably 1 is an alkyl group and the remainder are hydrogen atoms.
The alkyl group in R 23、R26 and R 29 is preferably an alkyl group having 1 to 12 total carbon atoms which may be substituted, and more preferably an alkyl group having 1 to 6 total carbon atoms which may be substituted.
The aryl group in R 23、R26 and R 29 is preferably an aryl group having 6 to 30 total carbon atoms and optionally having a substituent.
In the general formulae (OS-3) to (OS-5), X 1～X3 independently represents O or S, preferably O.
In the general formulae (OS-3) to (OS-5), the ring containing X 1～X3 as a ring member is a 5-membered ring or a 6-membered ring.
In the general formulae (OS-3) to (OS-5), n 1～n3 independently represents 1 or 2, n 1～n3 independently represents 1 when X 1～X3 is O, and n 1～n3 independently represents 2 when X 1～X3 is S.
In the general formulae (OS-3) to (OS-5), R 24、R27 and R 30 each independently represent a halogen atom, an alkyl group, an alkoxy group, a sulfonic group, an aminosulfonyl group or an alkoxysulfonyl group. Wherein R 24、R27 and R 30 are each independently preferably alkyl or alkoxy.
The alkyl group, alkoxy group, sulfonic group, sulfamoyl group, and alkoxysulfonyl group in R 24、R27 and R 30 may have a substituent.
In the general formulae (OS-3) to (OS-5), the alkyl group in R 24、R27 and R 30 is preferably an alkyl group optionally having 1 to 30 total carbon atoms as a substituent.
In the general formulae (OS-3) to (OS-5), the alkoxy group in R 24、R27 and R 30 is preferably an alkoxy group having 1 to 30 total carbon atoms, which may have a substituent.
In the general formulae (OS-3) to (OS-5), m 1～m3 independently represents an integer of 0 to 6, preferably an integer of 0 to 2, more preferably 0 or 1, and particularly preferably 0.
In addition, regarding each substituent of the above-mentioned (OS-3) to (OS-5), the preferable range of the substituents of (OS-3) to (OS-5) described in paragraphs 0092 to 0109 of Japanese unexamined patent publication No. 2011-221494 is also preferable.
Specific examples of the oxime sulfonate compounds represented by the general formulae (OS-3) to (OS-5) include compounds described in paragraphs 0114 to 0120 of Japanese patent application laid-open No. 2011-221494, but the present invention is not limited to these examples.
The compound containing an oxime sulfonate structure represented by the above general formula (B1) is particularly preferably an oxime sulfonate compound represented by any one of the following general formulae (OS-6) to (OS-11).
[ Chemical formula 22]
(In the general formulae (OS-6) to (OS-11), R 301～R306 represents an alkyl group, an aryl group or a heteroaryl group, R 307 represents a hydrogen atom or a bromine atom, R 308～R310、R313、R316 and R 318 each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a halogen atom, a chloromethyl group, a bromomethyl group, a bromoethyl group, a methoxymethyl group, a phenyl group or a chlorophenyl group, R 311 and R 314 each independently represent a hydrogen atom, a halogen atom, a methyl group or a methoxy group, and R 312、R315、R317 and R 319 each independently represent a hydrogen atom or a methyl group.)
The preferable ranges of the general formulae (OS-6) to (OS-11) are the same as those of (OS-6) to (OS-11) described in paragraphs 0110 to 0112 of Japanese unexamined patent publication No. 2011-221494.
In the resist layer, the photoacid generator (B) is preferably used in an amount of 0.1 to 10 parts by mass, more preferably 0.5 to 10 parts by mass, based on 100 parts by mass of the total resin components (preferably the total solid components, more preferably the total of the polymers) in the resist layer. More than 2 kinds may be used in combination.
Examples of the ionic photoacid generator include diaryliodonium salts, triarylsulfonium salts, and quaternary ammonium salts. Among these, triarylsulfonium salts and diaryl iodonium salts are preferable.
Triarylsulfonium salts used as the ionic photoacid generator are represented by the following general formula (1).
General formula (1):
[ chemical formula 23]
( In the general formula (1), R 505、R506 and R 507 each represent an alkyl group or an aromatic group which may have a substituent, and when the alkyl group is an alkyl group, they may be bonded to each other to form a ring; x-represents a conjugated salt group. )
The alkyl group in R 505、R506 and R 507 is preferably an alkyl group having 1 to 10 carbon atoms, and may have a substituent. Examples of the alkyl group having 1 to 10 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, pentyl, neopentyl, hexyl, cyclohexyl, heptyl, octyl and the like. Among them, methyl, ethyl and tert-butyl are preferable. When 2 or more of R 505、R506 and R 507 are alkyl groups, the 2 or more alkyl groups are preferably linked to each other to form a ring, and the ring is preferably a 5-membered ring (thiocyclopentane) or a 6-membered ring (thiocyclohexane) containing a sulfur atom.
The aromatic group in R 505、R506 and R 507 is preferably an aromatic group having 6 to 30 carbon atoms, and may have a substituent. Examples of the aromatic group having 6 to 30 carbon atoms include phenyl, naphthyl, 4-methoxyphenyl, 4-chlorophenyl, 4-methylphenyl, 4-tert-butylphenyl, 4-phenylthiophenyl, 2,4, 6-trimethylphenyl, 4-methoxy-1-naphthyl and 4- (4' -diphenylsulfonium phenylthio) phenyl.
In addition, any of R 505～R307 in the ionic photoacid generator represented by the general formula (1) may be bonded to each other to form a polymer such as a 2-mer. For example, the 4- (4 '-diphenylsulfonium phenylthio) phenyl group is an example of a 2-mer, and the counter anion in the 4- (4' -diphenylsulfonium phenylthio) phenyl group is the same as X -.
The substituents which the alkyl groups and aromatic groups in R 505、R506 and R 507 may have are preferably aromatic groups, and specifically, phenyl, 4-methoxyphenyl, 4-chlorophenyl, and 4- (4' -diphenylsulfonium phenylthio) phenyl are particularly preferable. These substituents may be further substituted with the above substituents.
As the conjugated salt group represented BY X -, preferred are the conjugated salt group of an alkylsulfonic acid, the conjugated salt group of an arylsulfonic acid, BY 4 - (Y represents a halogen atom. The same applies hereinafter), PY 6 -、AsY6 -、SbY6 -, or a monovalent anion represented BY the following general formula (3) or general formula (4), and particularly preferred is the conjugated salt group of an alkylsulfonic acid, the conjugated salt group of an arylsulfonic acid, PY 6 -, or a 1-valent anion represented BY the following general formula (3).
The conjugated salt groups of the alkylsulfonic acid and the arylsulfonic acid are preferably conjugated salt groups of the alkylsulfonic acid having 1 to 7 carbon atoms, and more preferably conjugated salt groups of the alkylsulfonic acid having 1 to 4 carbon atoms, and when expressed in the form of an acid, methanesulfonic acid, trifluoromethanesulfonic acid, n-propanesulfonic acid, and heptanesulfonic acid are particularly preferred.
Examples of the conjugated salt group of the aryl sulfonic acid include benzenesulfonic acid, chlorobenzenesulfonic acid and p-toluenesulfonic acid when expressed in the form of an acid.
Y in BY 4 -、PY6 -、AsY6 -、SbY6 - in X - is preferably a fluorine atom or a chlorine atom, and particularly preferably a fluorine atom.
[ Chemical 24]
(In the general formulae (3) and (4), R 521、R522 and R 523 each independently represent an alkyl group having 1 to 10 carbon atoms, an alkyl group having 1 to 10 carbon atoms and a fluorine atom, or a ring in which R 521 and R 522 are bonded to each other through an alkylene group having 2 to 6 carbon atoms or an alkylene group having 2 to 6 carbon atoms and a fluorine atom.)
In the general formulae (3) and (4), examples of the alkyl group having 1 to 10 carbon atoms in R 521、R522 and R 523 include methyl, ethyl, butyl, t-butyl, cyclohexyl, and octyl. Examples of the alkyl group having a fluorine atom of 1 to 10 carbon atoms include trifluoromethyl, pentafluoroethyl, heptafluoropropyl, nonafluorobutyl, dodecafluoropentyl, and perfluorooctyl. Of these, R 521、R522 and R 523 are preferably an alkyl group having a fluorine atom and having 1 to 10 carbon atoms, and particularly preferably an alkyl group having a fluorine atom and having 1 to 6 carbon atoms.
In the general formulae (3) and (4), examples of the alkylene group having 2 to 6 carbon atoms when R 521 and R 522 are connected to each other to form a ring include ethylene, propylene, butylene, pentylene, and hexylene. Examples of the alkylene group having a fluorine atom of 2 to 6 carbon atoms include tetrafluoroethylene group, hexafluoropropylene group, octafluorobutylene group, decafluoropentylene group, undecanohexylene group, and the like. Among these, when R 521 and R 522 are connected to each other to form a ring, the bonding is preferably performed through an alkylene group having a fluorine atom of 2 to 6 carbon atoms, and particularly preferably through an alkylene group having a fluorine atom of 2 to 4 carbon atoms.
The ionic photoacid generator represented by the general formula (1) is preferably a photoacid generator represented by the following general formula (5).
[ Chemical 25]
(In the general formula (5), R 510、R511、R512 and R 513 each independently represent an alkyl group or an aromatic group which may have a substituent, ar 3 and Ar 4 each independently represent a divalent aromatic group which may have a substituent, and X 1- and X 2- each independently represent a conjugated salt group.)
The alkyl and aromatic groups in R 510、R511、R512 and R 513 have the same meaning as the alkyl and aromatic groups represented by R 505、R506 and R 507 in the general formula (1), and the preferable mode is the same. The substituents may be the same.
The conjugated salt groups represented by X 1- and X 2- have the same meaning as the conjugated salt group represented by X-of the general formula (1), and the preferable mode is the same.
The divalent aromatic group in Ar 3 and Ar 4 is preferably phenylene or naphthylene, and particularly preferably phenylene.
As specific examples of triarylsulfonium salts used as the ionic photoacid generator, triphenylsulfonium triflate, triphenylsulfonium trifluoroacetate, 4-methoxyphenyl diphenylsulfonium triflate, 4-methoxyphenyl diphenylsulfonium trifluoroacetate, 4-thiophenyl diphenylsulfonium triflate, 4-thiophenyl diphenylsulfonium trifluoroacetate and the like can be given.
Examples of commercially available compounds include TPS-102, 103, 105, 106, 109, 300, and 1000; MDS-103, 105, 109, 205, 209; BDS-109; DTS-103, 105; MNPS-109; HDS-109, (manufactured by Midori Kagaku Co., ltd.), GSID-26-1, cyracure UVI-6976 (manufactured by BASF Co., ltd.).
The diaryliodonium salts used as the ionic photoacid generator are represented by the following general formula (2).
General formula (2):
[ chemical 26]
(In the general formula (2), R 508 and R 509 each independently represent an aromatic group which may have a substituent, and X - represents a conjugated salt group.)
In the general formula (2), the aromatic groups represented by R 508 and R 509 have the same meaning as the aromatic groups represented by R 505、R506 and R 507 in the general formula (1), and the preferable mode is the same.
In the general formula (2), the conjugate base represented by X - has the same meaning as the conjugate base represented by X - of the general formula (1), and the preferable mode is the same.
In addition, in the photoacid generator represented by the general formula (2), R 508 and R 509 may be bonded to each other to form a polymer such as a 2-mer. For example, the 4- (4 '-diphenylsulfonium phenylthio) phenyl group is an example of a 2-mer, and the counter anion in the 4- (4' -diphenylsulfonium phenylthio) phenyl group is the same as that in X -.
Specific examples of the diaryliodonium salts used as the ionic photoacid generator include diphenyliodonium trifluoroacetate, diphenyliodonium trifluoromethanesulfonate, 4-methoxyphenylphenyl iodonium trifluoroacetate, phenyl-4- (2 '-hydroxy-1' -tetradecyloxy) phenyliodonium trifluoromethanesulfonate, 4- (2 '-hydroxy-1' -tetradecyloxy) phenyliodonium hexafluoroantimonate, phenyl-4- (2 '-hydroxy-1' -tetradecyloxy) phenyliodonium-p-toluenesulfonate, and the like.
As commercially available compounds DPI-105, 106, 109, 201; BI-105; MPI-105, 106, 109; BBI-102, 103, 105, 106, 109, 110, 201, 300;301 (the above is manufactured by Midori Kagaku Co., ltd.).
Specific examples of quaternary ammonium salts used as the ionic photoacid generator include tetramethylammonium butyltris (2, 6-difluorophenyl) borate, tetramethylammonium hexyltris (p-chlorophenyl) borate, tetramethylammonium hexyltris (3-trifluoromethylphenyl) borate, benzyldimethylanilinium butyltris (2, 6-difluorophenyl) borate, benzyldimethylanilinium hexyltris (p-chlorophenyl) borate, benzyldimethylanilinium hexyltris (3-trifluoromethylphenyl) borate, and the like.
In addition to the above specific examples, the following compounds may be mentioned as specific examples of the component (B), but the present invention is not limited to these compounds.
[ Chemical formula 27]
[ Chemical 28]
[ Chemical 29]
The content of the component B in the resist layer is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass, relative to 100 parts by mass of the polymer component. When the content of the component B is 0.1 part by mass or more, a desired sensitivity (increased sensitivity) is easily obtained, and when it is 10 parts by mass or less, the transparency of the coating film is easily ensured.
The amount of the nonionic photoacid generator to be added is preferably 1% by mass or less, and is preferably substantially free of the nonionic photoacid generator.
< Solvent >
The photosensitive resin composition for forming the resist layer is preferably prepared in the form of a solution in which a predetermined component is dissolved in a solvent (component (D)).
As the solvent used in the photosensitive resin composition for forming the resist layer, a known solvent may be used, and examples thereof include ethylene glycol monoalkyl ethers, ethylene glycol dialkyl ethers, ethylene glycol monoalkyl ether acetates, propylene glycol monoalkyl ethers, propylene glycol dialkyl ethers, propylene glycol monoalkyl ether acetates, diethylene glycol dialkyl ethers, diethylene glycol monoalkyl ether acetates, dipropylene glycol monoalkyl ethers, dipropylene glycol dialkyl ethers, dipropylene glycol monoalkyl ether acetates, esters, ketones, amides, lactones, and the like. Further, specific examples of the solvent used in the photosensitive resin composition for forming the resist layer include solvents described in paragraphs 0174 to 0178 of Japanese patent application laid-open No. 2011-221494, which are incorporated herein by reference.
Further, to these solvents, a solvent such as benzyl ethyl ether, dihexyl ether, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, anisole, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, ethylene carbonate, propylene carbonate, and the like may be further added as necessary. These solvents may be used singly or in combination of 2 or more. As the solvent which can be used in the present invention, 2 kinds of solvents are more preferably used in combination, and propylene glycol monoalkyl ether acetates or dialkyl ethers, diacetates and diethylene glycol dialkyl ethers are further preferably used in combination; or esters with butanediol alkyl ether acetates.
Further, as component D, a solvent having a boiling point of 130℃or more and less than 160℃or a solvent having a boiling point of 160℃or more, or a mixture thereof is preferable.
Examples of the solvent having a boiling point of 130℃or more and less than 160℃include propylene glycol monomethyl ether acetate (boiling point 146 ℃), propylene glycol monoethyl ether acetate (boiling point 158 ℃), propylene glycol methyl n-butyl ether (boiling point 155 ℃) and propylene glycol methyl n-propyl ether (boiling point 131 ℃).
Examples of the solvent having a boiling point of 160℃or higher include ethyl 3-ethoxypropionate (boiling point 170 ℃), diethylene glycol methyl ethyl ether (boiling point 176 ℃), propylene glycol monomethyl ether propionate (boiling point 160 ℃), dipropylene glycol methyl ether acetate (boiling point 213 ℃), 3-methoxybutyl ether acetate (boiling point 171 ℃), diethylene glycol diethyl ether (boiling point 189 ℃), diethylene glycol dimethyl ether (boiling point 162 ℃), propylene glycol diacetate (boiling point 190 ℃), diethylene glycol monoethyl ether acetate (boiling point 220 ℃), dipropylene glycol dimethyl ether (boiling point 175 ℃), and 1, 3-butanediol diacetate (boiling point 232 ℃).
The content of the solvent in the resist layer for forming the resist layer is preferably 50 to 95 parts by mass, more preferably 60 to 90 parts by mass, relative to 100 parts by mass of the total resin components in the photosensitive resin composition.
< Sensitizer >
The resist layer preferably further contains a sensitizer. The resist layer may contain a sensitizer in order to promote decomposition thereof in combination with the photoacid generator (B), and particularly preferably contains a sensitizer when a nonionic photoacid generator is used. The sensitizer absorbs active light or radiation and becomes an electron-excited state. The sensitizer which becomes in an electron excited state contacts with the photoacid generator to cause electron transfer, energy transfer, heat release and the like. Thus, the photoacid generator is chemically changed and decomposed to generate an acid.
The inclusion of the sensitizer greatly improves the exposure sensitivity, and is particularly effective when a nonionic photoacid generator having low absorptivity of visible light is used, and the exposure light source is a mixed line of g-line and h-line.
As the sensitizer, anthracene derivatives, acridone derivatives, thioxanthone derivatives, coumarin derivatives, base styryl (base stylyl) derivatives, distyrylbenzene derivatives are preferable, and anthracene derivatives are more preferable.
As the anthracene derivative, anthracene, 9, 10-dibutoxyanthracene, 9, 10-dichloro anthracene, 2-ethyl-9, 10-dimethoxy anthracene, 9-hydroxymethyl anthracene, 9-bromo anthracene, 9-chloro anthracene, 9, 10-dibromoanthracene, 2-ethyl anthracene, 9, 10-dimethoxy anthracene are preferable.
As the acridone derivative, acridone, N-butyl-2-chloroacridone, N-methylacridone, 2-methoxyacridone, N-ethyl-2-methoxyacridone are preferable.
As thioxanthone derivatives, preference is given to thioxanthone, diethylthioxanthone, 1-chloro-4-propoxythioxanthone, 2-chlorothioxanthone. .
As coumarin derivatives, coumarin-1, coumarin-6H, coumarin-110, and coumarin-102 are preferred.
Examples of the alkali styryl derivative include 2- (4-dimethylaminostyryl) benzoxazole, 2- (4-dimethylaminostyryl) benzothiazole, and 2- (4-dimethylaminostyryl) naphthothiazole.
Examples of the distyrylbenzene derivative include distyrylbenzene, bis (4-methoxystyryl) benzene, and bis (3, 4, 5-trimethoxystyryl) benzene.
Specific examples of the sensitizer include the following, but the present invention is not limited to these examples. In the following, me represents methyl, et represents ethyl, and Bu represents butyl.
[ Chemical formula 30]
The content of the sensitizer in the resist layer is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass, relative to 100 parts by mass of the polymerizable component. When the content of the sensitizer is 0.1 part by mass or more, a desired sensitivity can be easily obtained, and when it is 10 parts by mass or less, transparency of the coating film can be easily ensured.
< Basic Compound >
The dry film resist of the present invention preferably further contains an alkaline compound in the resist layer. The basic compound may be arbitrarily selected from basic compounds used in chemically amplified resists. Examples thereof include aliphatic amines, aromatic amines, heterocyclic amines, quaternary ammonium hydroxides, quaternary ammonium salts of carboxylic acids, and the like. Specific examples of these include compounds described in paragraphs 0204 to 0207 of Japanese patent application laid-open No. 2011-221494, which are incorporated herein by reference.
Specifically, examples of the aliphatic amine include trimethylamine, diethylamine, triethylamine, di-N-propylamine, tri-N-propylamine, di-N-pentylamine, tri-N-pentylamine, diethanolamine, triethanolamine, dicyclohexylamine, dicyclohexylmethylamine, and N-cyclohexyl-N' - [2- (4-morpholinyl) ethyl ] thiourea (CHMETU).
Examples of the aromatic amine include aniline, benzylamine, N-dimethylaniline, and diphenylamine.
Examples of the heterocyclic amine include pyridine, 2-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, N-methyl-4-phenylpyridine, 4-dimethylaminopyridine, imidazole, benzimidazole, 4-methylimidazole, 2-phenylbenzimidazole, 2,4, 5-triphenylimidazole, nicotine, nicotinic acid, nicotinamide, quinoline, 8-hydroxyquinoline, pyrazine, pyrazole, pyridazine, purine, pyrrolidine, piperidine, piperazine, morpholine, 4-methylmorpholine, 1, 5-diazabicyclo [4.3.0] -5-nonene (DBN), and 1, 8-diazabicyclo [5.3.0] -7-undecene.
Examples of the quaternary ammonium hydroxide include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetra-n-butylammonium hydroxide, tetra-n-hexylammonium hydroxide, and the like.
Examples of the quaternary ammonium salt of carboxylic acid include tetramethylammonium acetate, tetramethylammonium benzoate, tetra-n-butylammonium acetate, tetra-n-butylammonium benzoate, and the like.
The alkali compound used in the present invention may be used alone or in combination of 1 or more than 2 kinds.
The content of the basic compound in the resist layer is preferably 0.001 to 3 parts by mass, more preferably 0.005 to 1 part by mass, relative to 100 parts by mass of the total solid content in the resist layer.
< (C): heterocyclic Compound ]
The dry film resist of the present invention preferably contains (C) a heterocyclic compound in the resist layer. By adding the heterocyclic compound, a cured film obtained from the resist layer can be made stronger.
The heterocyclic compound is not particularly limited except for the polymer component. Examples of the compound include a compound having an epoxy group or an oxetane group in the molecule, a heterocyclic compound containing an alkoxymethyl group, various oxygen-containing monomers such as a cyclic ether and a cyclic ester (lactone), nitrogen-containing monomers such as a cyclic amine and an oxazoline, and heterocyclic monomers having d-electrons such as silicon, sulfur and phosphorus, which are described below.
The amount of the heterocyclic compound added to the resist layer is preferably 0.01 to 50 parts by mass, more preferably 0.1 to 10 parts by mass, and even more preferably 1 to 5 parts by mass, based on 100 parts by mass of the total solid content of the resist layer. By adding in this range, a cured film excellent in mechanical strength can be obtained, and a cured film excellent in chemical resistance can be obtained. The heterocyclic compounds may be used in combination, and in this case, the total content of all heterocyclic compounds may be calculated.
Specific examples of the compound having an epoxy group in a molecule include bisphenol a type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, aliphatic epoxy resin, and the like.
These are available in the form of commercial products. Examples thereof include JER828, JER1007, JER S157S 70 (manufactured by mitsubishi chemical Co., ltd.), JER S157S 65 (manufactured by Mitsubishi Chemical Holdings Corporation), and commercially available products described in paragraph 0189 of Japanese patent application laid-open No. 2011-221494.
Examples of the "main component" include ADEKA RESIN EP-4000S, ADEKA EP-4003S, ADEKA EP-4010S, ADEKA EP-4011S (manufactured by ADEKA, incorporated herein by reference), NC-2000, NC-3000, NC-7300, XD-1000, EPPN-501, EPPN-502 (manufactured by incorporated herein by reference) and )、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( (manufactured by incorporated herein by reference) and NagaseChemtex (manufactured by incorporated herein by reference), YH-300, YH-301, YH-302, YH-315, YH-324, YH-325 (manufactured by incorporated herein by reference), CELLOXIDE 2021P, 2081, 2000, 3000, EHPE3150, EPOLEAD GT400, serubinasu B0134, and B0177 (manufactured by incorporated herein by reference).
These may be used singly or in combination of 2 or more.
Among these, bisphenol a type epoxy resins, bisphenol F type epoxy resins, phenol novolac type epoxy resins, aliphatic epoxy resins, and aliphatic epoxy resins are more preferable, and aliphatic epoxy resins are particularly preferable.
As specific examples of the compound having an oxetanyl group in the molecule, ARONOXETANE OXT-201, OXT-211, OXT-212, OXT-213, OXT-121, OXT-221, OX-SQ and PNOX (manufactured by Tokyo Co., ltd.) can be used.
In addition, the oxetanyl group-containing compound is preferably used alone or in combination with an epoxy group-containing compound.
Among these, the heterocyclic compound (C) is preferably a compound having an epoxy group from the viewpoints of etching resistance and line width stability.
In addition, a compound having both an alkoxysilane structure and a heterocyclic structure in the molecule can also be suitably used in the resist layer. Examples thereof include gamma-glycidoxypropyl trialkoxysilane, gamma-glycidoxypropyl alkyl dialkoxysilane and beta- (3, 4-epoxycyclohexyl) ethyl trialkoxysilane. Of these, gamma-glycidoxypropyl trialkoxysilane is more preferable. These may be used singly or in combination of 2 or more.
< Surfactant >
The resist layer may further contain a surfactant. As the surfactant, any of anionic, cationic, nonionic, or amphoteric surfactants may be used, and a preferable surfactant is a nonionic surfactant.
Examples of the nonionic surfactant include polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkylphenyl ethers, higher fatty acid diesters of polyoxyethylene glycol, silicone-based surfactants, and fluorine-based surfactants. Further, the following trade names may be cited: KP (manufactured by singe chemical industry, inc.), POLYFLOW (manufactured by co-Rong chemical Co., ltd.), F-top (manufactured by JEMCO), MEGAFAC (manufactured by DIC, inc.), FLUORADE (manufactured by sumitomo 3M, inc.), asahiGuard, surfion (manufactured by asahi nitro, inc.), polyFox (manufactured by OMNOVA), SH-8400 (Toray Dowcorning Silicone), and the like.
The surfactant may be a copolymer containing a constituent unit A and a constituent unit B represented by the following general formula (I-1) and having a weight average molecular weight of 1,000 to 10,000 as measured by gel permeation chromatography in the presence of Tetrahydrofuran (THF) as a solvent.
General formula (I-1):
[ chemical 31]
(In the formula (I-1), R 401 and R 403 each independently represent a hydrogen atom or a methyl group, R 402 represents a linear alkylene group having 1 to 4 carbon atoms, R 404 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, L represents an alkylene group having 3 to 6 carbon atoms, p and q are mass percentages representing a polymerization ratio, p represents a value of 10 to 80 mass%, q represents a value of 20 to 90 mass%, R represents an integer of 1 to 18, s represents an integer of 1 to 10, and the like.)
The above-mentioned L is preferably a branched alkylene group represented by the following general formula (I-2). R 405 in the general formula (I-2) represents an alkyl group having 1 to 4 carbon atoms, preferably an alkyl group having 1 to 3 carbon atoms, more preferably an alkyl group having 2 or 3 carbon atoms, from the viewpoints of compatibility and wettability to a surface to be coated. The sum of p and q (p+q) is p+q=100, i.e., preferably 100 mass%.
General formula (I-2):
[ chemical formula 32]
The weight average molecular weight (Mw) of the copolymer is more preferably 1,500 or more and 5,000 or less.
Further, surfactants described in paragraphs [0017] of Japanese patent No. 4502784 and paragraphs [0060] to [0071] of Japanese patent application laid-open No. 2009-237362 may be used.
These surfactants may be used singly or in combination of 2 or more.
The amount of the surfactant added to the resist layer is preferably 10 parts by mass or less, more preferably 0.001 to 10 parts by mass, and still more preferably 0.01 to 3 parts by mass, based on 100 parts by mass of the total solid content in the resist layer.
< Radiation absorber >
The resist layer also preferably contains a radiation absorber. As the radiation absorber, an ultraviolet absorber is preferable. More preferably, the ultraviolet absorber exhibits so-called photobleaching property, which is reduced in absorbance by absorption of ultraviolet light. Specifically, examples of the photobleaching materials include naphthoquinone diazide derivatives, nitrones, and diazonium salts (for example, compounds described in Japanese patent publication (Kokai) No. 62-40697, M.Sasano et al, SPIE Symp.Proc.,631, 321 (1986)).
The radiation absorber is used for the purpose of equalizing the light intensity distribution in the resist layer, and thus, by providing a so-called additive CEL (Contrast Enhancement Lithography) effect, it is possible to obtain an effect of improving the rectangularity of the pattern and the linearity of the pattern (line edge roughness) (refer to "semiconductor process materials and chemicals", sakagu n lien-creditor, CMC publication (2006)).
< Other ingredients >
In addition to the above components, known additives such as metal oxide particles, a crosslinking agent other than a heterocyclic compound, an alkoxysilane compound, an antioxidant, a dispersant, an acid multiplier, a development accelerator, conductive fibers, a colorant, a plasticizer, a thermal radical generator, a thermal acid generator, a thickener, and an organic or inorganic deposition inhibitor may be further added to the resist layer.
A preferred embodiment of the other components is described in [0165] to [0184] of japanese patent application laid-open publication No. 2014-85643, respectively, the contents of which are incorporated into the present specification.
< Compound having an ethylenically unsaturated bond >
From the viewpoint of resolution, the dry film resist preferably has an amount of the compound having an ethylenically unsaturated bond in the resist layer of 0 mass%. The term "0 mass% includes a form in which a minute amount (for example, 1 mass% or less in the resist layer) is contained so as not to hinder the resolution effect.
< Film thickness of resist layer >
The thickness of the resist layer is preferably 0.5 to 10. Mu.m. When the film thickness of the resist layer is 10 μm or less, the resolution of the pattern is good, and when it is 0.5 μm or more, it is preferable from the viewpoint of the straightness of the pattern.
The thickness of the resist layer is more preferably 0.8 to 5. Mu.m, particularly preferably 1.0 to 3.0. Mu.m.
< Method for Forming resist layer >
The components are mixed in a predetermined ratio by an arbitrary method and dissolved by stirring, whereby a photosensitive resin composition for forming a resist layer can be prepared. For example, the components may be dissolved in a solvent to form a solution, and then these components may be mixed at a predetermined ratio to prepare a resin composition. The composition solution prepared as described above may be used after being filtered by a filter having a pore size of 0.2. Mu.m.
(Light absorbing layer)
The dry film resist may contain a light absorbing layer having a transmittance of 80% or less with respect to the exposure dominant wavelength of the resist layer between the temporary support and the resist layer.
The light absorbing layer preferably has a transmittance of 60% or less, more preferably 55% or less.
The light absorbing layer is described. The light absorbing layer absorbs unnecessary light in the exposure light diffused by the temporary support to suppress the photosensitivity of the resist, and is therefore preferably provided between the resist layer and the temporary support.
The light absorbing layer preferably contains a light absorber and a resin.
The light absorber may be a substance selected from ultraviolet absorbers, dyes, and the like, with or without photobleaching. Photobleaching is a property of absorbing exposure light to reduce absorbance.
Examples of the photobleaching materials include photobleaching materials such as naphthoquinone diazide derivatives, nitrones, and diazonium salts (for example, compounds described in japanese patent publication No. 62-40697, m.sasano et al, SPIE symp. Proc.,631, 321 (1986)), salts of organic pyridines (stilbazolium), aryl nitroso salts, formazan pigments, and oxonol pigments. As more specific examples, formazan pigments such as nitro blue tetrazolium, MTT formazan, 1,3, 5-triphenylformazan, INT formazan, and the like can be cited; oxonol pigments such as oxonol yellow K and oxonol 805 blue.
As the light absorber which does not cause photobleaching, a known ultraviolet absorber or the like can be used. Typical examples of the structure of the photobleaching-free light absorber include benzotriazole-based, benzophenone-based, triazine-based, cyanoacrylate-based, oxanilide-based, and formamidine-based. More specific examples of the photobleaching-free light absorber include benzotriazole compounds such as TINUVIN384, 900 and 928 (all manufactured by BASF corporation), adekastab LA to 29 and LA to 36 (all manufactured by ADEKA corporation), triazine compounds such as TINUVIN400 and 460 (all manufactured by BASF corporation), adekastabLA to 46 (manufactured by ADEKA corporation) and benzophenone compounds such as Adekastab 1413 (manufactured by ADEKA corporation).
The resin constituting the light absorbing layer needs to disappear by alkali development together with the resist layer, and thus alkali-soluble resins are preferable. The alkali-soluble resin is preferably a linear organic polymer, which is soluble in an organic solvent and developable with a weak alkali aqueous solution. Examples of the linear organic polymer include polymers having carboxylic acids in the side chains, for example, JP-A-59-44615, JP-B-54-34327, JP-B-58-12577, JP-B-54-25957, JP-A-59-53836, and JP-A-59-71048, and the like, and acid cellulose derivatives having carboxylic acids in the side chains are also useful.
In addition to the above, as an alkali-soluble resin, a product of adding an acid anhydride to a polymer having a hydroxyl group, or the like, a polyhydroxystyrene resin, a polysiloxane resin, poly (2-hydroxyethyl (meth) acrylate), polyvinylpyrrolidone, polyethylene oxide, polyvinyl alcohol, or the like is also useful. The linear organic high molecular polymer may be obtained by copolymerizing a monomer having hydrophilicity. Examples thereof include alkoxyalkyl (meth) acrylates, hydroxyalkyl (meth) acrylates, glycerol (meth) acrylates, acrylamide, N-methylolacrylamide, secondary or tertiary alkylacrylamide, dialkylaminoalkyl (meth) acrylate, morpholino (meth) acrylate, N-vinylpyrrolidone, N-vinylcaprolactam, vinylimidazole, vinyltriazole, methyl (meth) acrylate, ethyl (meth) acrylate, branched or linear propyl (meth) acrylate, branched or linear butyl (meth) acrylate, and phenoxyhydroxypropyl (meth) acrylate.
In addition to the above, a surfactant, an antioxidant, an antifoaming agent, a development accelerator, a plasticizer, and the like may be added to the light absorbing layer to improve characteristics.
< Method for producing Dry film resist >
The dry film resist can be produced by a method for producing a photosensitive transfer material described in paragraphs [0094] to [0098] of JP 2006-259138A. The resist layer is preferably formed using a positive photosensitive resin composition.
In embodiment 1 of the dry film resist of the present invention, a temporary support having a low haze, in which the total light haze is 0.3% or less, is used. When a dry film resist is produced using such a low-haze temporary support, it is preferable that the step of forming a resist layer includes a step of removing the temporary support from electricity. That is, the dry film resist of the present invention is preferably formed with a resist layer on the temporary support after the removal of the electricity. When the low-haze temporary support is a temporary support having a small filler content in the interior or on the surface of the temporary support, static electricity is likely to be generated when the temporary support is unwound from the rolled temporary support. The removal of electricity from the temporary support is preferably performed for the purpose of removing static electricity from the temporary support. When a resist layer is formed by applying a resist layer coating liquid, electrostatic energy is removed to improve the coatability of the resist layer. In addition, when a resist layer is formed by applying a solvent-based coating liquid for a resist layer, the safety of the coating process in a solvent atmosphere can be improved by removing static electricity. The step of removing the temporary support may be included in any of before, during, and after the formation of the resist layer. From the viewpoint of the improvement of the coatability and the safety, it is preferable to include at least 1 time of the removal step before the formation of the resist layer.
Specifically, when forming a dry film resist having an intermediate layer, a solution in which an additive is dissolved simultaneously with a thermoplastic organic polymer (a coating solution for a thermoplastic resin layer) is applied to a temporary support, and the solution is dried to provide a thermoplastic resin layer, and then a preparation solution (a coating solution for an intermediate layer) prepared by adding a resin and an additive to a solvent in which the thermoplastic resin layer is not dissolved is applied to the thermoplastic resin layer, and then the solution is dried to laminate the intermediate layer, and then a coating solution for a resist layer prepared by a solvent in which the intermediate layer is not dissolved is further applied to the intermediate layer, and then the solution is dried to laminate the resist layer, thereby producing the dry film resist.
[ Method of manufacturing Circuit Wiring ]
The method for manufacturing a circuit wiring according to the present invention is a method for manufacturing a circuit wiring including the following steps (a), (b), (c), and (d).
(A) A lamination step of laminating the dry film resist of the present invention on a circuit forming substrate having a base material and a conductive layer;
(b) A pattern exposure step of performing contact pattern exposure with a pattern exposure pattern (preferably, a photomask having a shape of the pattern exposure pattern) without peeling off the temporary support of the dry film resist;
(c) A developing step of developing the temporary support after the temporary support is peeled off to form a pattern for pattern exposure (preferably a resist pattern having a shape of the pattern for pattern exposure) on the resist layer;
(d) An etching step of forming a pattern for pattern exposure (preferably, a conductive layer pattern (circuit wiring) having a shape of the pattern for pattern exposure) on the circuit forming substrate by etching.
In the present specification, unless otherwise specified, the term "pattern exposure pattern" refers to "shape of pattern exposure pattern". The development after the pattern exposure is performed, and when the resist layer is formed into a pattern for pattern exposure, it means that a resist pattern having the same shape as the "shape of the pattern for pattern exposure" used in the pattern exposure is formed. When a pattern for pattern exposure is formed on a circuit forming substrate by etching, it means that a conductive layer pattern having the same shape as the "shape of the pattern for pattern exposure" used in pattern exposure is formed.
The circuit wiring of the present invention is suitable for use in input devices, particularly touch panels. In the method for manufacturing a circuit wiring of the present invention, the circuit wiring is preferably a circuit wiring of an input device. Further, in the method for manufacturing a circuit wiring of an input device of the present invention, the input device is preferably a touch panel.
A preferred embodiment of the method for manufacturing a circuit wiring of the present invention will be described below.
From the viewpoint of forming a circuit wiring including a conductive layer of 2 patterns, the method for manufacturing a circuit wiring of the present invention is preferably:
(b) The step (b 1) is as follows,
(C) The step (c 1) is as follows,
(D) The step (d 1) is as follows,
Further comprising the following step (e 1), step (f 1) and step (g),
(B1) A pattern exposure step of exposing the contact pattern with the 1 st pattern without peeling off the temporary support of the dry film resist;
(c1) A developing step of developing the temporary support after the temporary support is peeled off to form a1 st pattern on the resist layer;
(d1) An etching step of forming a1 st pattern on a circuit forming substrate (substantially a conductive layer of the circuit forming substrate) by etching;
(e1) A pattern exposure step of exposing the 2 nd pattern to a contact pattern without peeling the resist layer on which the 1 st pattern was transferred in the (c 1) step;
(f1) A developing step of developing the resist layer to form a 2 nd pattern different from the 1 st pattern;
(g) And an etching step of forming a2 nd pattern on the circuit forming substrate (substantially the conductive layer of the circuit forming substrate) by etching.
The method for manufacturing a circuit wiring according to the present invention is preferable from the viewpoint of forming a circuit wiring including a conductive layer having 2 patterns and more easily suppressing process contamination:
(b) The step (b 1) is as follows,
(C) The step (c 1) is as follows,
(D) The step (d 2) is as follows,
Further comprising a step (e 2), a step (f 2) and a step (g),
(B1) A pattern exposure step of exposing the contact pattern with the 1 st pattern without peeling off the temporary support of the dry film resist;
(c1) A developing step of developing the temporary support after the temporary support is peeled off to form a1 st pattern on the resist layer;
(d2) An etching step of transferring the 1 st pattern on the circuit forming substrate (substantially the conductive layer of the circuit forming substrate) by etching, and then bonding a cover film to the remaining resist layer without peeling the resist layer having the 1 st pattern formed in the step (c 1);
(e2) A pattern exposure step of exposing the contact pattern with the 2 nd pattern without peeling the cover film bonded in the step (d 2);
(f2) A developing step of peeling off the cover film bonded in the (d 2) step and developing the cover film to form a 2 nd pattern different from the 1 st pattern on the resist layer;
(g) And an etching step of forming a2 nd pattern on the circuit forming substrate (substantially the conductive layer of the circuit forming substrate) by etching.
In the method for manufacturing the circuit wiring, it is preferable that the conductive layers are provided on both surfaces of the base material, and the circuit is formed sequentially or simultaneously on the conductive layers formed on both surfaces of the base material. With this configuration, a circuit wiring for a touch panel in which the first electrode pattern is formed on one surface of the base material and the second electrode pattern is formed on the other surface can be formed. Further, it is preferable to form the circuit wiring for the touch panel having such a configuration from both surfaces of the base material by a roll-to-roll method.
A case where a conductive pattern of a capacitive input device is obtained by using a resist layer as an etching resist (etching pattern) will be described.
The electrostatic capacity type input device includes a base material (also referred to as a front panel) and at least the following elements (2) to (5) on the non-contact surface side of the base material, and preferably at least 1 of (2), (3) and (5) is formed by the circuit wiring manufacturing method of the present invention.
(2) A plurality of first electrode patterns formed along a first direction by the plurality of pad portions via the connection portion
(3) A plurality of second electrode patterns electrically insulated from the first electrode patterns and including a plurality of pad portions and connection portions formed along a direction crossing the first direction
(4) An insulating layer electrically insulating the first electrode pattern from the second electrode pattern
(5) Conductive elements electrically connected to at least one of the first electrode pattern and the second electrode pattern and different from the first electrode pattern and the second electrode pattern
Details of each step are described below.
Step (a)
A lamination step of (a) laminating the dry film resist of the present invention on a circuit-forming substrate having a base material and a conductive layer will be described.
Lamination (transfer and lamination) of the dry film resist onto the circuit forming substrate is preferably performed by a method of laminating a resist layer on the circuit forming substrate (preferably, on the conductive layer, on the 1 st layer of the conductive layer when the conductive layer is 2 or more), pressurizing, and heating. For lamination, a known lamination apparatus such as a lamination apparatus, a vacuum lamination apparatus, and an automatic cutting lamination apparatus capable of further improving productivity can be used.
(Substrate)
The substrate is preferably a glass substrate or a film substrate, more preferably a film substrate. In the method for producing a circuit wiring of the present invention, the substrate is preferably a sheet-like resin composition particularly when the circuit wiring is used for a touch panel.
Furthermore, it is preferred that the substrate is transparent.
In the present specification, transparent means that the average transmittance of visible light having a wavelength of 400nm to 700nm is 80% or more. Thus, the transparent layer is a layer having an average transmittance of 80% or more of visible light having a wavelength of 400nm to 700 nm. The transparent layer preferably has an average transmittance of 90% or more of visible light having a wavelength of 400nm to 700 nm.
The refractive index of the substrate is particularly preferably 1.50 to 1.52.
The substrate may be composed of a transparent substrate such as a glass substrate. As the base material, strengthened glass typified by gorilla glass of Corning inc. As the transparent substrate, materials used in japanese patent application laid-open publication nos. 2010-86684 and 2010-152809 and 2010-257492 can be preferably used.
When a film substrate is used as the substrate, a substrate having no optical distortion and a substrate having high transparency is more preferably used, and specific materials include polyethylene terephthalate (polyethylene terephthalate; PET), polyethylene naphthalate, polycarbonate, triacetylcellulose, and cycloolefin polymer.
(Conductive layer)
The conductive layer may be any conductive layer used for a normal circuit wiring or a touch panel wiring.
As a material of the conductive layer, a metal oxide, or the like can be cited.
The plurality of conductive layers may be made of the same material or different materials, and preferably contain different materials.
Preferably at least one of the multiple conductive layers contains a metal oxide.
Examples of the metal Oxide used in this case include a metal Oxide film such as ITO (Indium Tin Oxide), IZO (Indium zinc Oxide ), or SiO 2. The metal oxide will be described later.
The conductive layer is preferably a material of a first electrode pattern, a second electrode pattern, and another conductive element, which will be described later, used in a capacitance type input device.
A preferred embodiment of the other conductive layer will be described below with reference to the capacitive input device.
Step (b)
The pattern exposure step (b) of performing contact pattern exposure with the pattern exposure pattern without peeling off the temporary support of the dry film resist will be described below.
(B) The step (b 1) is preferably a pattern exposure step of exposing the contact pattern with the 1 st pattern without peeling off the temporary support of the dry film resist.
As examples of the exposure step, the development step of the step (c) described later, and other steps, the methods described in paragraphs [0035] to [0051] of japanese patent application laid-open No. 2006-23696 can be suitably used in the present invention.
Specifically, the following methods and the like can be mentioned: a predetermined mask is disposed above a resist layer formed on a circuit forming substrate (preferably, on the 1 st layer of the conductive layer when the conductive layer is 2 or more layers) and in direct contact with a temporary support, and then contact pattern exposure is performed from a light source above the mask through the mask and the temporary support.
In the present invention, the specific arrangement and specific size of the pattern are not particularly limited. In order to improve the display quality of a display device (e.g., a touch panel) including the input device of the present invention and to minimize the area occupied by the extraction wiring, at least a part of the pattern (particularly, the electrode pattern of the touch panel and the part of the extraction wiring) is preferably a thin line of 100 μm or less, more preferably 70 μm or less, and particularly preferably 10 μm or less.
Here, as the light source for the exposure, a light source capable of irradiating light (for example, 365nm, 405nm, etc.) in a wavelength range in which the exposure position of the etchant layer is soluble in the developer can be appropriately selected and used. Specifically, an ultrahigh-pressure mercury lamp, a high-pressure mercury lamp, a metal halide lamp, and the like are cited. The exposure amount is usually about 5 to 200mJ/cm 2, preferably about 10 to 100mJ/cm 2.
Further, after exposure, it is preferable to perform heat treatment before development for the purpose of improving the rectangularity of the pattern and the straightness of the pattern. By this step called PEB (Post Exposure Bake), the roughness of the resist pattern edge due to standing waves generated in the resist layer at the time of exposure can be reduced.
The pattern exposure is performed before the temporary support is peeled off. The support may then be peeled off. The exposure may be performed through a mask, or may be performed digitally using a laser or the like. The pattern exposure is preferably exposure through a mask. In the case of performing exposure through a mask, the pattern for pattern exposure is also referred to as a mask pattern.
Step (c)
A development step of forming a pattern for pattern exposure on the resist layer by developing after peeling off the temporary support will be described.
(C) The step (c 1) is preferably a development step of forming the 1 st pattern on the resist layer by performing development after the temporary support is peeled off.
The developing step is a step of developing the resist layer subjected to the pattern exposure.
The development may be performed using a developer. The developer is not particularly limited, and a known developer such as the developer described in JP-A-5-72724 can be used. The developer preferably undergoes a development action in which the resist layer is dissolved, and preferably contains a compound having pka=7 to 13 at a concentration of, for example, 0.05 to 5mol/L, and further an organic solvent having miscibility with water may be added in a small amount. Examples of the organic solvent having miscibility with water include methanol, ethanol, 2-propanol, 1-propanol, butanol, diacetone alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-N-butyl ether, benzyl alcohol, acetone, methyl ethyl ketone, cyclohexanone, epsilon-caprolactone, gamma-butyrolactone, dimethylformamide, dimethylacetamide, hexamethylphosphoramide, ethyl lactate, methyl lactate, epsilon-caprolactam, and N-methylpyrrolidone. The concentration of the organic solvent is preferably 0.1 to 30 mass%.
In addition, a known surfactant may be further added to the developer. The concentration of the surfactant is preferably 0.01 to 10 mass%.
The development may be performed by any of pit (puddle) development, shower & spin development, immersion development, and the like. Here, in the description of the development by showering, the developing solution is sprayed onto the resist layer after exposure, and the exposed portion is removed. When the thermoplastic resin layer, the intermediate layer, or the like is provided, it is also preferable to remove the thermoplastic resin layer, the intermediate layer, or the like in advance by blowing a washing liquid having low solubility of the resist layer by spraying or the like before development. Further, it is preferable to remove the development residues by spraying and blowing a detergent or the like after development, and wiping with a brush or the like. The temperature of the developer is preferably 20 to 40 ℃.
The pH of the developer may be selected from, for example, more than 7 and 13.5 or less, and by using the dry film resist of the present invention, the pattern linearity is also improved when the pH of the developer used in the developing step is 12.5 or less. In particular, in the dry film resist, when the component (a) is a polymer component containing a polymer having an acid constituent unit a1 in which a carboxyl group or a phenolic hydroxyl group is protected as an acetal, and the acid constituent unit a1 has a constituent unit represented by the general formula A3, the pattern linearity is more excellent when the pH of a developer used in a developing step is 12.5 or less. Thus, by using the dry film resist of the present invention, there can be obtained advantages such as: weak base developer with small process load and environment load can be used, and the selectivity of the developer is widened.
Further, the method may further include a post-baking step of heat-treating the pattern containing the resist layer obtained by the development, and the method may include a step of performing a post-baking step of: after the step of removing the thermoplastic resin layer and the intermediate layer, the development is performed, and the obtained pattern containing the resist layer is subjected to a heat treatment.
By the post baking step, the removal of the protecting group using an acid in the resist layer can be promoted. The acid constituent unit a0 in which the acid group is protected with an acid-decomposable group in the resist layer is preferably an acetal to protect the carboxyl group from the viewpoints of reducing the activation energy for protecting the protecting group from detachment and avoiding heat treatment after exposure.
(C) Other processes such as a post exposure process may be provided before or after the process.
Step (d)
An etching step of forming a pattern for pattern exposure on the circuit forming substrate by etching will be described.
(D) The step (d 1) is preferably an etching step of forming the 1 st pattern on the circuit forming substrate by etching or (d 2) is preferably an etching step of forming the 1 st pattern on the circuit forming substrate by etching and then bonding a cover film to the remaining resist layer.
(D2) After the 1 st pattern is formed on the circuit forming substrate by etching, the resist layer having the 1 st pattern formed in the step (c 1) is not peeled off, and the temporary support temporarily peeled off in the step (c) is preferably used as a cover film in the etching step of bonding the cover film to the remaining resist layer.
The etching may be performed by a known etching method such as the methods described in paragraphs [0048] to [0054] of JP-A2010-152155.
For example, a wet etching method in which the etching is performed in a liquid etchant is generally used. The etching liquid used in the wet etching may be an acidic etching liquid or an alkaline etching liquid, as appropriate, depending on the etching object. Examples of the acidic etching solution include aqueous solutions of only acidic components such as hydrochloric acid, sulfuric acid, hydrofluoric acid, and phosphoric acid; and mixed aqueous solutions of acidic components and salts such as ferric chloride, ammonium fluoride, potassium permanganate, etc. The acidic component may also be used in combination of a plurality of acidic components. Examples of the alkaline etching solution include aqueous solutions of only an alkali component such as salts of organic amines including sodium hydroxide, potassium hydroxide, ammonia, organic amines, and tetramethylammonium hydroxide; and mixed aqueous solutions of alkali components and salts such as potassium permanganate. The alkali component may be used in combination of a plurality of alkali components.
The temperature of the etching solution is not particularly limited, but is preferably 45 ℃ or lower. The resist layer used as an etching mask (etching pattern) in the present invention preferably exhibits particularly excellent resistance to an acidic and alkaline etching solution in the above temperature range. Thus, the resist layer is prevented from peeling in the etching process, and the portion where the resist layer is not present is selectively etched.
After the etching, a washing step and/or a drying step may be performed as needed to prevent contamination of the production line. In the washing step, for example, the substrate is washed with pure water at room temperature for 10 to 300 seconds; the drying step may be performed by using air blowing and appropriately adjusting the air blowing pressure (about 0.1 to 5kg/cm 2).
Step (e 1) and step (e 2)
The following description will be given of (e 1) a pattern exposure step of performing contact pattern exposure with the 2 nd pattern without peeling the resist layer having the 1 st pattern formed in the (c 1) step, and (e 2) a pattern exposure step of performing contact pattern exposure with the 2 nd pattern without peeling the cover film bonded in the (d 2) step.
(E1) The contact pattern exposure in the step (e 2) and the step (b) may be performed by the same method as the contact pattern exposure in the step (b).
Step (f 1) and step (f 2)
The development step (f 1) of forming a 2 nd pattern different from the 1 st pattern on the resist layer, and the development step (f 2) of removing the cover film bonded in the step (d 2) and then developing the cover film to form a 2 nd pattern different from the 1 st pattern on the resist layer are described below.
(F1) The development in the step (f 2) may be performed by the same method as the development in the step (c).
Working procedure (g)
An etching step (g) of forming the 2 nd pattern on the circuit forming substrate by etching will be described.
(G) The etching in the step (d) may be performed by the same method as that used in the step (d).
(G) In the step (d), the conductive layer is preferably selectively etched according to a desired pattern, which is smaller than that in the step (d).
< Method of Forming Circuit Wiring containing conductive layer of 2 patterns >
In forming a circuit wiring including at least 2 conductive layers having patterns, the following steps (Xa), (Xb), (Xc), (Xd), (Xe), and (Xz) are preferably combined with the steps of the method for manufacturing a circuit wiring according to the present invention.
(Xa) a lamination step of forming a resist layer having an exposure position dissolved in a developer on the 1 st layer of the conductive layer, on a circuit forming substrate having a base material and the x 1 st conductive layer in this order from one surface of the base material, wherein x is an integer of 2 or more;
(Xb) a pattern exposure and development step of performing pattern exposure and development on the circuit-forming substrate on which the resist layer is formed to form the 1 st pattern on the resist layer;
(Xc) an etching step of etching the 1 st to i th conductive layers in the region where the 1 st pattern resist layer is not formed in the (Xb) step, with i being an integer of 1 to x;
(Xd) a pattern exposure and development step of exposing and developing the resist layer remaining in the (Xb) step to a pattern different from the pattern of the remaining resist layer to form a 2 nd pattern on the resist layer;
(Xe) an etching step of etching the 1 st to j th conductive layers in the region where the resist layer to be the 2 nd pattern is not formed in the step (Xd), with j being an integer of 1 or more and less than i;
(Xz) a resist layer removing step of removing all the remaining resist layers to form a circuit wiring including at least 2 kinds of conductive layers.
Fig. 1 shows an example of a method for manufacturing a circuit wiring for a touch panel, in which the circuit wiring includes at least 2 kinds of conductive layers.
In one example of the method for manufacturing the circuit wiring for the touch panel shown in fig. 1, an optional (Xf) step is described in addition to the (Xa) step, (Xb) step, (Xc) step, (Xd) step, (Xe) step, and (Xz) step.
In the step (Xa), a resist layer is formed on the 1 st layer of the conductive layer. The resist layer is at least partially left in the subsequent step (Xa), (Xb), (Xc), (Xd), (Xe) and (Xf), and finally the entire resist layer left is removed in the step (Xz) to form a circuit wiring including at least 2 kinds of conductive layers in a pattern. That is, a circuit wiring including conductive layers of various patterns can be formed by 1 resist formation.
In the (Xb) step, pattern exposure and development are performed to form the 1 st pattern on the resist layer.
In the step (Xc), the 1 st to i st conductive layers in the region where the 1 st pattern resist layer is not formed in the step (Xb) are subjected to etching treatment. In fig. 1, (Xc) step, i=x, and all of the conductive layers of the 1 st to x-th layers are etched and removed.
The pattern of the 1 st to i st conductive layers obtained in the (Xc) step is not left after the final step of removing all the resist layers in the (Xz) step, and is changed to another pattern by etching in the (Xe) step and etching in the (Xf) step, which may be performed as needed. In the configuration shown in fig. 1, the pattern of the 1 st to i th conductive layers obtained by the (Xc) step is described as 7-column pattern, and the 3 rd, 4 th and 5 th columns from the right are changed to another pattern by etching in the (Xe) step, and the 1 st, 2 nd and 6 th columns from the right are also changed to another pattern by etching in the (Xf) step, and when all resist layers are removed in the final (Xz) step, only the 7 th column from the right is changed to the pattern of the 1 st to i th conductive layers.
In the step (Xd), the resist layer remaining in the step (Xb) is subjected to pattern exposure and development in a pattern different from that of the remaining resist layer, whereby the resist layer is formed into the 2 nd pattern.
In the (Xe) step, the 1 st to j th conductive layers in the region where the resist layer to be the 2 nd pattern is not formed in the (Xd) step are subjected to etching treatment. In fig. 1, (Xe) step, j=x-1 and j=i-1, the conductive layers of the 1 st to x-1 st layers (j-th layers) are etched and removed, and only the x-th layer remains.
Details of the (Xf) process are omitted in fig. 1, and the (Xf) process may be repeated as many times as necessary.
In the (Xz) step, all the remaining resist layers are removed to form a circuit wiring including at least 2 kinds of conductive layers. In fig. 1, it is shown that eventually the resist layer is completely removed after the (Xz) process.
((Xa) procedure)
The following describes the (Xa) process: and a lamination step of laminating a resist layer, in which an exposure position is dissolved in a developer, on the 1 st layer of the electroconductive layer, in a circuit forming substrate having a base material and electroconductive layers, which are the x-th layer to the 1 st layer in this order from one surface of the base material, by setting x to an integer of 2 or more.
The (Xa) step is preferably a step of laminating a resist layer of the dry film resist from which the protective film is removed on the 1 st layer of the conductive layer.
X is an integer of 2 or more, preferably 2 or 3, more preferably 2.
Fig. 2 is a schematic cross-sectional view showing an example of a circuit wiring for a touch panel according to one embodiment of the present invention obtained when x is 2. In fig. 2, a first electrode pattern 3 is formed on a substrate 1, and an additional conductive element 6 is formed on the first electrode pattern. The circuit wiring for the touch panel shown in fig. 2 is a circuit wiring including a conductive layer of the following 2 patterns: a conductive layer laminate having conductive elements different from those of the first electrode pattern 3, and a conductive layer having only the first electrode pattern 3.
The circuit wiring for the touch panel of fig. 2 is shown in fig. 3 when viewed from obliquely above. In an example of the circuit wiring for a touch panel shown in fig. 3, the dotted line portion in fig. 3 is a conductive layer laminate in which conductive elements different from those of the first electrode pattern 3 are formed, and the portion where the quadrangles in fig. 3 are connected is a conductive layer having only the first electrode pattern 3. As shown in fig. 3, among the conductive layers having different types of patterns included in the circuit wiring, the conductive layer having at least 1 type of pattern preferably includes a laminate of 2 or more conductive layers sharing the same circuit pattern.
((Xb) step)
The following describes the (Xb) step: and a pattern exposure and development step of exposing and developing the pattern of the resist layer to form the 1 st pattern on the circuit forming substrate on which the resist layer is formed.
The pattern exposure and development in the (Xd) step may be performed by the same method as the pattern exposure and development in the (b) step and the (c) step.
((Xc) procedure)
The following describes the step (Xc): and an etching step of performing etching treatment on the 1 st to i st conductive layers in the region where the 1 st pattern resist layer is not formed in the (Xb) step, with i being an integer of 1 to x.
The etching treatment in the step (Xc) may be performed by the same method as that in the step (d).
((Xd) Process)
The following description (Xd) step: and a pattern exposure and development step of exposing and developing the resist layer remaining in the (Xb) step to a pattern different from the pattern of the remaining resist layer to form a2 nd pattern on the resist layer.
The pattern exposure and development in the (Xd) step may be performed by the same method as the pattern exposure and development in the (Xb) step.
((Xe) procedure)
The following description (Xe) process: and an etching step of performing etching treatment on the 1 st to j th conductive layers in the region where the resist layer to be the 2 nd pattern is not formed in the step (Xd) by setting j to an integer of 1 or more and less than i.
The etching in the (Xe) step may be performed by the same method as that in the (Xc) step.
In the (Xe) step, the conductive layer is preferably selectively etched less than in the (Xc) step according to a desired pattern.
((Xf) procedure)
The method for manufacturing a circuit wiring preferably further includes the following (Xf) step.
(Xf) step: and a pattern exposure and development step of exposing and developing the remaining resist layer to a pattern different from the pattern of the remaining resist layer, and then etching any one of the 1 st to j-smaller conductive layers in the region where the resist layer is not formed, to pattern the conductive layer.
The step (Xf) is described below.
The method for manufacturing a circuit wiring of the present invention is also preferably not performed in the (Xf) step. That is, in the method for manufacturing a circuit wiring of the present invention, the circuit wiring preferably includes a conductive layer having only 2 patterns.
The number of the steps (Xf) is not particularly limited, and may be repeated according to a desired pattern shape. Among them, the number of (Xf) steps is preferably 1.
The method for manufacturing a circuit wiring of the present invention is preferably: the (Xf) step includes the following (Xf 1) step and (Xf 2) step, and includes a conductive layer having at least 3 patterns.
(Xf 1) a pattern exposure and development step of exposing and developing the resist layer remaining in the step (Xe) to a pattern different from the pattern of the remaining resist layer to form a3 rd pattern on the resist layer;
(Xf 2) a pattern exposure and development step of etching the conductive layers of the 1 st to k rd layers in the region where the resist layer of the 3 rd pattern is not formed in the step (f 1), with k being an integer of 1 or more and less than j.
The preferred mode of the (Xf) step is the same as the (Xd) step and the (Xe) step.
((Xz) procedure)
The following description (Xz) process: and a residual resist layer removing step of removing all the residual resist layer to form a circuit wiring including at least 2 pattern conductive layers.
The method for removing all the resist layer remaining after the etching treatment is not particularly limited, and a method for removing the resist layer by a chemical treatment may be mentioned.
Examples of the method for removing the resist layer include a method in which a substrate having a resist layer or the like is immersed in a stripping solution under stirring at 30 to 80 ℃, preferably 50 to 80 ℃ for 5 to 30 minutes. The resin pattern used as the etching mask may be a resin pattern exhibiting excellent chemical resistance at 45 ℃ or lower, and preferably exhibits a property of swelling due to an alkaline stripping liquid when the chemical temperature reaches 50 ℃ or higher. By utilizing the above properties, when the stripping step is performed using a stripping liquid at 50 to 80 ℃, there are advantages in that the step time is shortened and the stripping residue of the resist layer is reduced. That is, by providing a difference in chemical solution temperature between the etching step and the step of removing the resist layer, the resist layer used as an etching mask exhibits good chemical solution resistance in the etching step and good peelability in the removing step, and thus, contradictory properties of chemical solution resistance and peelability can be satisfied.
Examples of the stripping liquid include a liquid obtained by dissolving an inorganic base component such as sodium hydroxide or potassium hydroxide, an organic base component such as a tertiary amine or a quaternary ammonium salt in water, dimethyl sulfoxide, N-methylpyrrolidone, or a mixed solution of these. The stripping may be performed by spraying, pit method, or the like using the stripping liquid.
[ Circuit Wiring ]
The circuit wiring of the present invention is a circuit wiring manufactured by the circuit wiring manufacturing method of the present invention. The circuit wiring of the present invention is preferably a circuit wiring for a touch panel. A preferred embodiment of the circuit wiring for the touch panel will be described in the end of the description of the capacitive input device.
[ Input device and display device ]
The input device of the present invention is an input device using the circuit wiring of the present invention. In the present invention, the input device is preferably a capacitive touch panel.
The display device of the present invention includes the input device of the present invention. The display device of the present invention is preferably an image display device.
< Capacitive input device, and image display device Provided with capacitive input device >
The input device and the capacitive input device as a preferred embodiment of the display device of the present invention, and the image display device including the capacitive input device as a constituent element can be configured as disclosed in "latest touch panel technology" (release (ed) Technotimes of 7/6/2009), three Gu Xionger, male and female plate, technology and development of touch panels (CMC publications, 2004, 12), FPD International Forum T-11 lecture set, cypress Semiconductor Corporation application note AN2292, and the like.
First, the configuration of the capacitive input device will be described. Fig. 9 is a cross-sectional view showing the configuration of the capacitive input device. In fig. 9, the capacitive input device 10 is composed of a substrate 1, a mask layer 2, a first electrode pattern 3, a second electrode pattern 4, an insulating layer 5, another conductive element 6, and a transparent protective layer 7.
In fig. 9, the side of the substrate 1 on which the elements are provided is referred to as a non-contact surface. In the capacitive input device 10, input is performed by touching a contact surface (surface opposite to a non-contact surface) of the substrate 1 with a finger or the like. Hereinafter, the substrate may be referred to as a "front panel".
Further, a mask layer 2 is provided on the non-contact surface of the substrate 1. The mask layer 2 is a frame-like pattern formed around the display region on the non-contact surface side of the substrate 1 (for example, the front panel of the touch panel), and is formed to conceal routing lines and the like.
The capacitive input device 10 may be provided with a mask layer 2 so as to cover a partial region of the substrate 1. Furthermore, an opening may be provided in a part of the base material 1. The opening may be provided with a switch that operates the machine by pressing.
The contact surface of the substrate 1 is formed with: a plurality of first electrode patterns 3 formed along a first direction by the plurality of pad portions via the connection portion; a plurality of second electrode patterns 4 electrically insulated from the first electrode patterns 3 and including a plurality of pad portions and connection portions formed along a direction crossing the first direction; and an insulating layer 5 electrically insulating the first electrode pattern 3 from the second electrode pattern 4. The first electrode pattern 3, the second electrode pattern 4, and the additional conductive element 6 described later can be made of, for example, a transparent conductive film. Examples of the conductive film include a metal film such as Al, zn, cu, fe, ni, cr, mo; metal oxide films such as ITO, IZO, and SiO 2. In this case, the film thickness of each element may be 10 to 200nm. In addition, the resistance can be reduced by firing to convert an amorphous ITO film into a polycrystalline ITO film.
The first electrode pattern 3 and the second electrode pattern 4 are preferably formed using a resist layer as an etching resist (etching pattern). In the formation of the second electrode layer for forming the second electrode pattern, a known method may be used in addition to photolithography using a resist typified by a resist layer used in the present invention. The photosensitive transfer material can be produced using a photosensitive resin composition using conductive fibers. For the formation of the first electrode pattern or the like from ITO or the like, refer to paragraphs [0014] to [0016] of japanese patent No. 4506785.
At least one of the first electrode pattern 3 and the second electrode pattern 4 may be provided across the non-contact surface of the substrate 1 and two regions of the surface of the mask layer 2 opposite to the substrate 1. Fig. 9 shows a manner in which the second electrode pattern 4 is provided across two regions of the non-contact surface of the substrate 1 and the surface of the mask layer 2 opposite to the substrate 1.
The first electrode pattern and the second electrode pattern 4 will be described with reference to fig. 7 and 8. Fig. 7 and 8 are explanatory views showing an example of the first electrode pattern and the second electrode pattern. As shown in fig. 8, the first electrode pattern is formed by the pad portion 3a along the first direction via the connection portion 3 b. Further, the second electrode pattern 4 is electrically insulated from the first electrode pattern by the insulating layer 5, and is constituted by a plurality of pad portions formed along a direction (second direction) intersecting the first direction. Here, when the first electrode pattern 3 is formed, the pad portion 3a and the connection portion 3b may be integrally formed, or only the connection portion 3b may be integrally formed, and the pad portion 3a and the second electrode pattern 4 may be integrally formed (patterned). When the pad portion 3a and the second electrode pattern 4 are integrally formed (patterned), as shown in fig. 7 and 8, each layer is formed as follows: a part of the connection portion 3b is connected to a part of the pad portion 3a (not shown in fig. 7), and the first electrode pattern 3 and the second electrode pattern 4 are electrically insulated by the insulating layer 5.
In fig. 9, another conductive element 6 is provided on the surface of the mask layer 2 opposite to the substrate 1. The other conductive element 6 is electrically connected to at least one of the first electrode pattern 3 and the second electrode pattern 4, and is an element different from the first electrode pattern 3 and the second electrode pattern 4. Fig. 9 shows a connection of the other conductive element 6 to the second electrode pattern 4.
In fig. 9, an overall transparent protective layer 7 is provided to cover the respective components. The transparent protective layer 7 may be configured to cover only a part of each component. The insulating layer 5 and the transparent protective layer 7 may be the same material or different materials. As the material constituting the insulating layer 5 and the transparent protective layer 7, a material having high surface hardness and heat resistance is preferable, and a known photosensitive silicone resin material, an acrylic resin material, or the like, which is known to those skilled in the art, can be used.
The insulating layer may be patterned by a known method such as ink jet or screen printing, in addition to the photolithography method.
In the method for manufacturing the capacitive input device, it is preferable that at least 1 of the first electrode pattern 3, the second electrode pattern 4, and the additional conductive element 6 is formed by etching using a resist layer as an etching resist (etching pattern). At least one element of the black mask layer 2, the insulating layer 5, and the transparent protective layer 7 as needed is also preferably formed using a photosensitive film having a temporary support, a thermoplastic resin layer, and a photocurable resin layer in this order.
Preferably, at least 1 of the first electrode pattern 3, the second electrode pattern 4, and the additional conductive element 6 is formed by etching using a resist layer as an etching resist (etching pattern).
When the first electrode pattern 3, the second electrode pattern 4, and the other conductive element 6 are formed by etching, first, at least an inorganic insulating layer is provided on the non-contact surface of the substrate 1 on which the black mask layer 2 is formed, and a transparent electrode layer such as ITO is formed by sputtering on the non-contact surface of the substrate 1 or on the inorganic insulating layer, on the portion on which the black mask layer 2 is provided. Then, an etching pattern is formed on the transparent electrode layer by exposure and development using a resist layer having an etching photocurable resin layer as the photocurable resin layer. Then, the transparent electrode layer is etched, the transparent electrode is patterned, and the etched pattern is removed, whereby the first electrode pattern 3 and the like can be formed.
When the first electrode pattern 3, the second electrode pattern 4, and the other conductive element 6 are formed using a photosensitive film having a photocurable resin layer containing a conductive material, the following method can be used to form: at least an inorganic insulating layer is provided on the surface of the substrate 1 at a portion where the black mask layer 2 is provided, and a photocurable resin layer (laminate) containing a conductive material is transferred onto the non-contact surface of the substrate 1 or onto the inorganic insulating layer.
The mask layer 2, the insulating layer 5, and the transparent protective layer 7 may be formed by transferring a photocurable resin layer to the substrate 1 using a photosensitive film. For example, when forming the black mask layer 2, a photosensitive film having a black photocurable resin layer may be used as the photocurable resin layer, and the black photocurable resin layer may be transferred onto the surface of the substrate 1. In forming the insulating layer 5, a photosensitive film having an insulating photocurable resin layer may be used as the photocurable resin layer, and the photocurable resin layer may be transferred onto the surface of the substrate 1 on which the first or second electrode pattern is formed. In forming the transparent protective layer 7, a photosensitive film having a transparent photocurable resin layer may be used as the photocurable resin layer, and the photocurable resin layer may be transferred onto the surface of the substrate 1 on which each element is formed.
Examples
The present invention will be described in more detail with reference to the following examples. The materials, amounts used, proportions, contents of processing, order of processing, and the like shown in the following examples may be appropriately changed within the scope not departing from the gist of the present invention. Therefore, the scope of the present invention is not limited by the specific examples shown below. Unless otherwise specified, "parts" and "%" are mass references.
The following symbols represent the following compounds, respectively.
MATHF: 2-Tetrahydrofurane methacrylate
MAEVE: 1-ethoxyethyl methacrylate (manufactured by Heguang Chun medicine industry Co., ltd.)
PHS: para-hydroxystyrene
PHS-EVE: 1-ethoxyethyl protective body of p-hydroxystyrene
PHS-THF: 2-tetrahydrofuran protecting body of p-hydroxystyrene
PGMEA: propylene glycol monomethyl ether acetate
[ Evaluation method of Material Properties ]
The method for evaluating the material properties is described below.
< Total light haze of temporary support >
The total light haze (%) of the small pieces of temporary support was determined based on JIS (Japanese Industrial Standards) K7136 using Suga Test Instruments co., ltd.
< Transmittance of temporary support or light absorbing layer >
The transmittance at 365nm, which is the same as the main wavelength of exposure of the resist layer, was obtained by measuring the transmission spectrum of a sample of a small piece of the temporary support or a sample of the light-absorbing layer prepared by peeling off the temporary support from a laminate having the light-absorbing layer formed on the temporary support using a 8453 ultraviolet-visible spectrophotometer (Agilent Technologies, manufactured by the company).
Example 1
A positive photosensitive resin composition was prepared according to the following formulation.
Novolak resin (m-cresol: p-cresol=30:70, molecular weight 5,500): 79.9 parts
Sensitizer: naphthoquinone diazide (hereinafter also referred to as NQD) compound (1) described in japanese patent laid-open No. 4-22955, page 4: 20 parts of
Surfactant (surfactant 1 below): 0.1 part
PGMEA:900 parts
Surfactant 1: f-554, perfluoroalkyl group-containing nonionic surfactant (DIC)
[ Chemical formula 33]
Weight average molecular weight 1500
The photosensitive resin composition was applied to a polyethylene terephthalate film (hereinafter referred to as PET (A)) having a film thickness of 100 μm as a temporary support by a slit nozzle so as to dry the film thickness and further to have a film thickness of 2.0. Mu.m. Then, the film was dried in a convection oven at 100℃for 2 minutes, and finally, a polyethylene film (manufactured by Tredegar Corporation. Mu. OSM-N) was pressure-bonded as a protective film to prepare a dry film resist. The dry film resist obtained was used as the dry film resist of example 1.
The PET (A) contained no filler as a lubricant, and had a total haze of 0.3%.
Then, a copper film was formed as a conductive layer on a PET substrate having a film thickness of 100 μm by vacuum vapor deposition to have a film thickness of 200nm, and the conductive layer was used as a circuit-forming substrate.
After the protective film was peeled from the dry film resist of example 1, a lamination step (a) described below was performed. The dry film resist of example 1 was laminated and transferred onto the copper layer to prepare a positive resist layer, that is, a lamination step was performed.
The resist layer was exposed to a contact pattern, that is, a pattern exposure step (b) was performed using a photomask provided with a line having a line width of 4 μm and a blank wiring pattern (the width ratio of the opening to the light shielding portion is 1:1) without peeling the temporary support. In the exposure, a high-pressure mercury lamp having an i-line (365 nm) as an exposure main wavelength was used.
After the temporary support was peeled off from the circuit-forming substrate after exposure, development using a 2.38 mass% aqueous solution of tetramethylammonium hydroxide (TMAH) was performed, and water washing was performed to obtain a resist layer on which a wiring pattern was formed, that is, a development step (c) was performed. The pH of the TMAH 2.38 mass% aqueous solution was 13.3.
Then, the copper layer was etched using a copper etching solution (Cu-02 manufactured by kanto chemical corporation) to form a pattern for pattern exposure on the circuit forming substrate, that is, an etching (d) step was performed, thereby obtaining a copper wiring substrate. The obtained circuit wiring was taken as the circuit wiring of example 1.
Example 2
A dry film resist of example 2 was produced in the same manner as in example 1, except that the temporary support used was PET (hereinafter referred to as PET (B)) having a film thickness of 75 μm and a total light haze of 0.16%. Further, a copper wiring substrate as a circuit wiring of example 2 was obtained in the same manner as in example 1 except that the dry film resist of example 2 was used as a dry film resist.
Example 3
A dry film resist of example 3 was produced in the same manner as in example 1, except that the temporary support used was a polypropylene film (hereinafter referred to as PP (a)) having a film thickness of 25 μm and a total light haze of 0.20%. Further, a copper wiring substrate as a circuit wiring of example 3 was obtained in the same manner as in example 1 except that the dry film resist of example 3 was used as a dry film resist.
Example 4
A dry film resist of example 4 was produced in the same manner as in example 1, except that the temporary support used was a cellulose triacetate film (hereinafter TAC) having a film thickness of 40 μm and a total light haze of 0.30%. Further, a copper wiring substrate as a circuit wiring of example 4 was obtained in the same manner as in example 1 except that the dry film resist of example 4 was used as a dry film resist.
Example 5
Synthesis example 1: synthesis of PHS-EVE ]
20G of an alkali-soluble resin (VP-8000 manufactured by Caon, japan) and 320g of Propylene Glycol Monomethyl Ether Acetate (PGMEA) were dissolved in a flask, and distilled under reduced pressure to azeotropically distill off water and PGMEA. After confirming that the water content was sufficiently reduced, 24g of ethyl vinyl ether and 0.35g of p-toluenesulfonic acid were added, and the mixture was stirred at room temperature for 1 hour. To this was added 0.28g of triethylamine, and the reaction was stopped. Ethyl acetate was added to the reaction solution, followed by washing with water, and then ethyl acetate, water and PGMEA, which are azeotropic components, were distilled off by distillation under reduced pressure to obtain an alkali-soluble resin PHS-EVE protected with an acid-decomposable group. The weight average molecular weight of the obtained resin was 12,000. In addition, the polydispersity was 1.21.
The structure of PHS-EVE is shown below, which is a 1-ethoxyethyl protector of p-hydroxystyrene/p-hydroxystyrene copolymer (30 mol%/70 mol%).
[ Chemical 34]
Using the synthesized PHS-EVE, a positive photosensitive composition was prepared according to the following formulation.
PHS-EVE:97.9 parts of
Photoacid generator (PAG-1 below): 2 parts of
Surfactant (surfactant 1 above): 0.1 part
PGMEA:900 parts
PAG-1: compound B-9 described in WO 2014/020984.
The positive photosensitive composition was slit-coated on PET (a) as a temporary support so that the dry film thickness was 2.0 μm, dried in a convection oven at 100 ℃ for 2 minutes, and finally a polyethylene film (manufactured by Tredegar Corporation, OSM-N) was pressure-bonded as a protective film to prepare a dry film resist. The dry film resist obtained was used as the dry film resist of example 5.
A copper wiring substrate as a circuit wiring of example 5 was produced in the same manner as in example 1 except that the dry film resist of example 5 was used as the dry film resist.
Example 6
A dry film resist of example 6 was produced in the same manner as in example 5, except that PET (B) was used as a temporary support. A copper wiring board as a circuit wiring of example 6 was produced in the same manner as in example 1, except that the dry film resist of example 6 was used as a dry film resist.
Example 7
A dry film resist of example 7 was produced in the same manner as in example 5, except that PP (a) was used as a temporary support. A copper wiring substrate as a circuit wiring of example 7 was produced in the same manner as in example 1, except that the dry film resist of example 7 was used as a dry film resist.
Example 8
A dry film resist of example 8 was produced in the same manner as in example 5, except that TAC was used as a temporary support. A copper wiring board as a circuit wiring of example 8 was produced in the same manner as in example 1, except that the dry film resist of example 8 was used as a dry film resist.
Example 9
< Synthetic example 2: synthesis of PHS-THF
15.6G of an alkali-soluble resin (VP-8000 Seto Co., ltd.) and 100g of Propylene Glycol Monomethyl Ether Acetate (PGMEA) were dissolved in a flask, and distilled under reduced pressure to azeotropically distill off water and PGMEA. After confirming that the water content was sufficiently lowered, 2.7g of 2, 3-dihydrofuran and 0.015g of p-toluenesulfonic acid were added, and the mixture was stirred at room temperature for 2 hours. To this was added 0.090g of triethylamine to stop the reaction. Ethyl acetate was added to the reaction solution, followed by washing with water, and then ethyl acetate and water were distilled off by distillation under reduced pressure to obtain a soluble resin PHS-THF having a protection ratio of 25 mol%. The weight average molecular weight of the obtained resin was 12,000. In addition, the polydispersity was 1.13.
The structure of PHS-THF is shown below, which is a 2-tetrahydrofuran protector of p-hydroxystyrene/p-hydroxystyrene copolymer (30 mol%/70 mol%).
[ 35]
Using the synthesized PHS-THF, a positive photosensitive composition was prepared according to the following formulation.
PHS-THF:97.9 parts of
Photoacid generator (PAG-2 below): 2 parts of
Surfactant (surfactant 1 above): 0.1 part
PGMEA:900 parts
PAG-2: compound A-1 described in [0227] of Japanese patent application laid-open No. 2013-047765
The positive photosensitive composition was slit-coated on PET (a) as a temporary support so that the dry film thickness became 2.0 μm, dried in a convection oven at 100 ℃ for 2 minutes, and finally a polyethylene film (manufactured by Tredegar Corporation, OSM-N) was pressure-bonded as a protective film to prepare a dry film resist. The dry film resist obtained was used as the dry film resist of example 9.
A copper wiring substrate as a circuit wiring of example 9 was produced in the same manner as in example 5 except that the dry film resist of example 9 was used as the dry film resist.
Example 10
A dry film resist of example 10 was produced in the same manner as in example 9, except that PET (B) was used as a temporary support. A copper wiring board as a circuit wiring of example 10 was produced in the same manner as in example 9, except that the dry film resist of example 10 was used as the dry film resist.
Example 11
A dry film resist of example 11 was produced in the same manner as in example 9, except that PP (a) was used as a temporary support. A copper wiring board as a circuit wiring of example 11 was produced in the same manner as in example 9, except that the dry film resist of example 11 was used as the dry film resist.
Example 12
A dry film resist of example 12 was produced in the same manner as in example 9, except that TAC was used as a temporary support. A copper wiring board as a circuit wiring of example 12 was produced in the same manner as in example 9, except that the dry film resist of example 12 was used as a dry film resist.
Example 13
< Synthesis example 3: synthesis of Polymer novolak-EVE (1-ethoxyethyl protector)
The polymer novolak-EVE (1-ethoxyethyl protector) was synthesized by the same method as in example 1 of japanese patent laid-open publication No. 2003-98671. The weight average molecular weight of the obtained resin was 5,000. In addition, the polydispersity was 7.0. The structure of the polymer novolak-EVE (1-ethoxyethyl protector) is shown below (the numerical values in the structural formulae are molar ratios).
[ Chemical formula 36]
Using the synthetic polymer novolak-EVE, a positive photosensitive composition was prepared according to the following formulation.
Polymer novolac-EVE: 97.9 parts of
Photoacid generator (PAG-2 above): 2 parts of
Surfactant (surfactant 1 above): 0.1 part
PGMEA:900 parts
The positive photosensitive composition was slit-coated on PET (a) as a temporary support so that the dry film thickness became 2.0 μm, dried in a convection oven at 100 ℃ for 2 minutes, and finally a polyethylene film (manufactured by Tredegar Corporation, OSM-N) was pressure-bonded as a protective film to prepare a dry film resist. The dry film resist obtained was used as the dry film resist of example 13.
A copper wiring substrate as a circuit wiring of example 13 was produced in the same manner as example 5 except that the dry film resist of example 13 was used as the dry film resist.
Example 14
A dry film resist of example 14 was produced in the same manner as in example 13, except that PET (B) was used as a temporary support. A copper wiring substrate as a circuit wiring of example 14 was produced in the same manner as in example 13, except that the dry film resist of example 14 was used as the dry film resist.
Example 15
A dry film resist of example 15 was produced in the same manner as in example 13, except that PP (a) was used as a temporary support. A copper wiring substrate as a circuit wiring of example 15 was produced in the same manner as in example 13, except that the dry film resist of example 15 was used as a dry film resist.
Example 16
A dry film resist of example 16 was produced in the same manner as in example 13, except that TAC was used as a temporary support. A copper wiring substrate as a circuit wiring of example 16 was produced in the same manner as in example 13, except that the dry film resist of example 16 was used as a dry film resist.
Example 17
< Synthetic example 4: MATHF Synthesis of copolymer ]
Methacrylic acid (86 g,1 mol) was cooled to 15℃in advance, and camphorsulfonic acid (4.6 g, 0.02 mol) was added. To this solution was added dropwise 2, 3-dihydrofuran (71 g,1 mol, 1.0 eq). After stirring for 1 hour, saturated sodium hydrogencarbonate (500 mL) was added, followed by extraction with ethyl acetate (500 mL), drying over magnesium sulfate, filtration of insoluble matter and concentration under reduced pressure at 40℃or below, and the yellow oil as a residue was distilled under reduced pressure to obtain 125g (yield 80 mol%) of tetrahydro-2H-furan-2-yl Methacrylate (MATHF) having a boiling point (bp.) of 54 to 56℃and a 3.5mmHg fraction as a colorless oil.
Using this material, the following MATHF copolymer was synthesized by the method described in [0248] to [0249] of JP-A2013-61616. The weight average molecular weight of the MATHF copolymer obtained, as determined by Gel Permeation Chromatography (GPC), was 14,000. The structure of MATHF copolymers is shown below (the values in the formulae are molar ratios). Of the acid constituent unit A1 in which the carboxyl group or phenolic hydroxyl group contained in the MATHF copolymer is protected as an acetal, 100 mol% is a constituent unit represented by the general formula A3, and the constituent unit represented by the general formula A1 is 0 mol%.
[ FORMS 37]
Using the synthesized MATHF copolymer, a positive photosensitive composition was prepared according to the following formulation. In the polymer (a) having a group in which an acid group is protected by an acid-decomposable group, the polymer component having a structural unit represented by the general formula A3 as an acid structural unit a1 in which a carboxyl group or a phenolic hydroxyl group is protected as an acetal is 100% by mass.
MATHF copolymer above: 97.9 parts of
Photoacid generator (PAG-2 above): 2 parts of
Surfactant (surfactant 1 above): 0.1 part
PGMEA:900 parts
The positive photosensitive composition was slit-coated on PET (a) as a temporary support so that the dry film thickness became 2.0 μm, dried in a convection oven at 100 ℃ for 2 minutes, and finally a polyethylene film (manufactured by Tredegar Corporation, OSM-N) was pressure-bonded as a protective film to prepare a dry film resist. The dry film resist obtained was used as the dry film resist of example 17.
A copper wiring substrate as a circuit wiring of example 17 was produced in the same manner as in example 5, except that the dry film resist of example 17 was used as a dry film resist, and development using 1.0 mass% aqueous solution of sodium carbonate as a developer with a pH of 11.2 was performed instead of development using 2.38 mass% aqueous solution of TMAH.
Example 18
A dry film resist of example 18 was produced in the same manner as in example 17, except that PET (B) was used as a temporary support. A copper wiring board as a circuit wiring of example 18 was produced in the same manner as in example 17, except that the dry film resist of example 18 was used as the dry film resist.
Example 19
A dry film resist of example 19 was produced in the same manner as in example 17, except that PP (a) was used as a temporary support. A copper wiring board as a circuit wiring of example 19 was produced in the same manner as example 17, except that the dry film resist of example 19 was used as the dry film resist.
Example 20
A dry film resist of example 20 was produced in the same manner as in example 17, except that TAC was used as a temporary support. A copper wiring substrate as a circuit wiring of example 20 was produced in the same manner as in example 17, except that the dry film resist of example 20 was used as a dry film resist.
Example 21
Positive photosensitive compositions were prepared according to the following formulations.
MATHF copolymer above: 69.1 parts
PHS-THF described above: 28.8 parts of
Photoacid generator (PAG-2 above): 2 parts of
Surfactant (surfactant 1 above): 0.1 part
PGMEA:900 parts
The positive photosensitive composition was slit-coated on PET (a) as a temporary support so that the dry film thickness became 2.0 μm, dried in a convection oven at 100 ℃ for 2 minutes, and finally a polyethylene film (manufactured by Tredegar Corporation, OSM-N) was pressure-bonded as a protective film to prepare a dry film resist. The dry film resist obtained was used as the dry film resist of example 21.
A copper wiring substrate as a circuit wiring of example 21 was produced in the same manner as in example 5, except that the dry film resist of example 21 was used as the dry film resist.
Example 22
A dry film resist of example 22 was produced in the same manner as in example 21, except that PET (B) was used as a temporary support. A copper wiring board as a circuit wiring of example 22 was produced in the same manner as in example 21, except that the dry film resist of example 22 was used as a dry film resist.
Example 23
A dry film resist of example 23 was produced in the same manner as in example 21, except that PP (a) was used as a temporary support. A copper wiring substrate as a circuit wiring of example 23 was produced in the same manner as in example 21, except that the dry film resist of example 23 was used as the dry film resist.
Example 24
A dry film resist of example 24 was produced in the same manner as in example 21, except that TAC was used as a temporary support. A copper wiring substrate as a circuit wiring of example 24 was produced in the same manner as in example 21, except that the dry film resist of example 24 was used as a dry film resist.
Example 25
Positive photosensitive compositions were prepared according to the following formulations.
MATHF copolymer above: 97.7 parts
Photoacid generator (PAG-2 above): 2 parts of
Basic compound (N-cyclohexyl-N' - [2- (4-morpholinyl) ethyl ] thiourea abbreviation CHMETU): 0.2 part
Surfactant (surfactant 1 above): 0.1 part
PGMEA:900 parts
The positive photosensitive composition was slit-coated on PET (B) as a temporary support so that the dry film thickness became 2.0 μm, dried in a convection oven at 100 ℃ for 2 minutes, and finally a polyethylene film (manufactured by Tredegar Corporation, OSM-N) was pressure-bonded as a protective film to prepare a dry film resist. The dry film resist obtained was used as the dry film resist of example 25.
A copper wiring substrate as a circuit wiring of example 25 was produced in the same manner as example 17, except that the dry film resist of example 25 was used as the dry film resist.
Example 26
Positive photosensitive compositions were prepared according to the following formulations.
MATHF copolymer above: 97.8 parts of
Photoacid generator (PAG-2 above): 2 parts of
Basic compound (1, 5-diazabicyclo [4.3.0] -5-nonene abbreviated DBN): 0.1 part
Surfactant (surfactant 1 above): 0.1 part
PGMEA:900 parts
The positive photosensitive composition was slit-coated on PET (B) as a temporary support so that the dry film thickness became 2.0 μm, dried in a convection oven at 100 ℃ for 2 minutes, and finally a polyethylene film (manufactured by Tredegar Corporation, OSM-N) was pressure-bonded as a protective film to prepare a dry film resist. The dry film resist obtained was used as the dry film resist of example 26.
A copper wiring substrate as a circuit wiring of example 26 was produced in the same manner as in example 17, except that the dry film resist of example 26 was used as the dry film resist.
Example 27
Positive photosensitive compositions were prepared according to the following formulations.
MATHF copolymer above: 93.1 parts
Photoacid generator (PAG-2 above): 2 parts of
Surfactant (surfactant 1 above): 0.1 part
Heterocyclic Compound (Denacol EX-321L (Nagase Chemtex)): 4.8 parts of
PGMEA:900 parts
The positive photosensitive composition was slit-coated on PET (B) as a temporary support so that the dry film thickness became 2.0 μm, dried in a convection oven at 100 ℃ for 2 minutes, and finally a polyethylene film (manufactured by Tredegar Corporation, OSM-N) was pressure-bonded as a protective film to prepare a dry film resist.
A copper wiring board was produced in the same manner as in example 5 except that the dry film resist was used. The dry film resist obtained was used as the dry film resist of example 27.
A copper wiring substrate as a circuit wiring of example 27 was produced in the same manner as example 17, except that the dry film resist of example 27 was used as the dry film resist.
Example 28
Positive photosensitive compositions were prepared according to the following formulations.
MATHF copolymer above: 93.0 parts of
Photoacid generator (PAG-2 above): 2 parts of
Surfactant (surfactant 1 above): 0.1 part
Heterocyclic compound (3-glycidoxypropyl trimethoxysilane (KBM-403, manufactured by Sitting chemical Co., ltd.)): 4.8 parts of
PGMEA:900 parts
The positive photosensitive composition was slit-coated on PET (B) as a temporary support so that the dry film thickness became 2.0 μm, dried in a convection oven at 100 ℃ for 2 minutes, and finally a polyethylene film (manufactured by Tredegar Corporation, OSM-N) was pressure-bonded as a protective film to prepare a dry film resist. The dry film resist obtained was used as the dry film resist of example 28.
A copper wiring substrate as a circuit wiring of example 28 was produced in the same manner as in example 17, except that the dry film resist of example 28 was used as a dry film resist.
Example 29
Positive photosensitive compositions were prepared according to the following formulations.
MATHF copolymer above: 97.8 parts of
Photoacid generator (PAG-2 above): 2 parts of
Ultraviolet absorber (ultraviolet absorber 1 having the following structure): 0.1 part
Surfactant (surfactant 1 above): 0.1 part
PGMEA:900 parts
Ultraviolet absorber 1
[ Chemical 38]
The positive photosensitive composition was slit-coated on PET (B) as a temporary support so that the dry film thickness became 2.0 μm, dried in a convection oven at 100 ℃ for 2 minutes, and finally a polyethylene film (manufactured by Tredegar Corporation, OSM-N) was pressure-bonded as a protective film to prepare a dry film resist. The dry film resist obtained was used as the dry film resist of example 29.
A copper wiring substrate as a circuit wiring of example 29 was produced in the same manner as example 17, except that the dry film resist of example 29 was used as the dry film resist.
Example 30
A dry film resist was produced in the same manner as in example 17, except that PET (C) having a haze of 0.16% and a light transmittance of 70% at 365nm was used as a temporary support. The dry film resist obtained was used as the dry film resist of example 30.
A copper wiring substrate as a circuit wiring of example 30 was produced in the same manner as example 17, except that the dry film resist of example 30 was used as the dry film resist.
The PET (C) was prepared by adding a UV absorbing dye to PET (B).
Example 31
A composition for a light-absorbing layer was prepared according to the following composition.
1,3, 5-Triphenylformazan: 12 parts of
Copolymer of polyvinylpyrrolidone 60 mol% and polyacrylic acid 40 mol%: 88 parts of
Pure water: 900 parts
The composition for a light-absorbing layer was slit-coated on PET (B) so that the dry film thickness became 1.0. Mu.m, and dried in a convection oven at 100℃for 5 minutes to prepare a light-absorbing layer. The transmittance of the produced light absorbing layer to light having a wavelength of 365nm was 70%.
The positive photosensitive composition used in example 17 was slit-coated on the light absorbing layer so that the dry film thickness became 2.0 μm, and dried in a convection oven at 100℃for 5 minutes. Finally, a polyethylene film (Tredegar Corporation, OSM-N) was bonded as a protective film to prepare a dry film resist. The dry film resist obtained was used as the dry film resist of example 31.
A copper wiring substrate as a circuit wiring of example 31 was produced in the same manner as in example 17, except that the dry film resist of example 31 was used as the dry film resist.
Example 32
An ITO film was formed as a conductive layer of layer 2 by sputtering at a film thickness of 150nm on a PET substrate having a film thickness of 100. Mu.m, and a copper film was formed as a conductive layer of layer 1 by vacuum vapor deposition at a film thickness of 200nm thereon to form a circuit-forming substrate.
After the protective film was peeled off from the dry film resist of example 18, the dry film resist of example 18 was laminated on the copper layer to produce a positive resist layer, that is, the lamination step (a) was performed.
The resist layer is exposed to a contact pattern, that is, a pattern exposure step (b 1) is performed by using a photomask having a pattern a (1 st pattern) shown in fig. 4, in which the shapes of pad portions having electrode patterns are connected in one direction, without peeling off the temporary support. In the pattern a shown in fig. 4, solid line portions and gray portions are light shielding portions, other portions are opening portions, and broken line portions virtually show aligned frames. In the exposure, a high-pressure mercury lamp having an i-line (365 nm) as an exposure main wavelength was used.
Then, the temporary support was peeled off, and the resist layer on which the pattern a was formed was obtained by development with a 1.0 mass% aqueous solution of sodium carbonate as a developer having a pH of 11.2 and washing with water, that is, the development step (c 1) was performed.
Then, after the 1 st layer (copper layer) was etched with a copper etching solution (Cu-02 manufactured by kanto chemical corporation), the 2 nd layer (ITO layer) was etched with an ITO etching solution (ITO-02 manufactured by kanto chemical corporation), thereby forming the 1 st pattern on the circuit forming substrate, that is, the (d 1) etching step was performed. By performing etching in this manner, the 1 st to 2 nd layers of the conductive layer in the region where the resist layer is not formed are subjected to etching treatment, and a circuit forming substrate in which the 1 st layer (copper layer) and the 2 nd layer (ITO layer) which are regions where the resist layer is not formed in the 1 st pattern are each drawn in the 1 st pattern (pattern which is a shape of the region (negative) where the pattern a does not exist) is obtained.
Then, in the aligned state, pattern exposure is performed using a photomask provided with an opening of the pattern B (pattern 2) shown in fig. 5, that is, the pattern exposure step (e 1) is performed. In the pattern B shown in fig. 5, gray portions are light shielding portions, other portions are opening portions, and broken line portions virtually show aligned frames. In the exposure, a high-pressure mercury lamp having an i-line (365 nm) as an exposure main wavelength was used.
Then, development and water washing were performed using 1.0 mass% aqueous solution of sodium carbonate as a developing solution having a pH of 11.2 to obtain a resist layer transferred with a 2 nd pattern (pattern where the light shielding portion of pattern a and the light shielding portion of pattern B overlap) different from the 1 st pattern, that is, a (f 1) development step was performed.
Then, using Cu-02, only the wiring of the 1 st layer (copper layer) is etched, and the etching is performed to the 1 st layer of the conductive layer which is the region where the resist layer is not formed in the 2 nd pattern, thereby forming a pattern for pattern exposure on the circuit forming substrate, that is, the etching step (g) is performed. By doing so, a circuit forming substrate including a conductive layer of only 2 patterns is obtained. In detail, regarding the obtained conductive layer, the 1 st layer (copper layer) and the 2 nd layer (ITO layer) which become the region of the 2 nd pattern where the resist layer is formed are each drawn in a pattern a (a pattern which is a shape of the region (negative) where the 1 st pattern is not present), and the 2 nd layer (ITO layer) which becomes the region of the 2 nd pattern where the resist layer is not formed is drawn in a pattern which is a shape of the region (negative) where the 2 nd pattern is not present.
The remaining resist layer was peeled off with a peeling liquid (KP-301 manufactured by kanto chemical corporation) and removed, and a circuit wiring including a conductive layer of 2 patterns was formed on a substrate, to obtain a circuit wiring of example 32. The circuit wiring of embodiment 32 has the circuit wiring of pattern C shown in fig. 6. The wiring portion included in the gray area of fig. 6 is in a state where the 2 nd layer (ITO wiring) is exposed. The dashed line portion of fig. 6 virtually shows the aligned frames. The other parts correspond to peripheral wiring parts, and have a structure including a conductive layer laminate of 2 or more layers (copper wiring) having the same circuit pattern in common, and the 1 st layer (copper wiring) is laminated on the 2 nd layer (ITO wiring). Fig. 2 and 3 show a structure of a conductive layer laminate including 2 or more layers sharing the same circuit pattern. In the circuit wiring of example 32, the dotted line portion of fig. 3 overlaps the layer 1 (copper wiring) on the layer 2 (ITO wiring).
Example 33
An ITO film was formed as a2 nd conductive layer with a film thickness of 150nm by sputtering on a PET substrate with a film thickness of 100 μm, and a copper film was formed as a1 st conductive layer with a film thickness of 200nm by vacuum vapor deposition thereon as a circuit forming substrate.
After the protective film was peeled off from the dry film resist of example 18, the dry film resist used in example 18 was laminated on the copper layer to produce a positive resist layer, that is, the lamination step (a) was performed.
The resist layer is exposed to a contact pattern, that is, (b 1) a pattern exposure step, by using a photomask having a pattern a (1 st pattern) in which shapes of pad portions having electrode patterns are connected in one direction, and the photomask is brought into contact with the temporary support without peeling the temporary support. In the exposure, a high-pressure mercury lamp having an i-line (365 nm) as an exposure main wavelength was used.
Then, the temporary support was peeled off, and the resist layer on which the pattern a was formed was obtained by development with a 1.0 mass% aqueous solution of sodium carbonate as a developer having a pH of 11.2 and washing with water, that is, the development step (c 1) was performed.
Then, after the 1 st layer (copper layer) was etched with a copper etching solution (Cu-02 manufactured by kanto chemical corporation), the 2 nd layer (ITO layer) was etched with an ITO etching solution (ITO-02 manufactured by kanto chemical corporation), whereby a pattern for pattern exposure was transferred onto the circuit forming substrate. By performing etching in this manner, the 1 st to 2 nd layers of the conductive layer in the region where the resist layer is not formed are subjected to etching treatment, and a circuit forming substrate in which the 1 st layer (copper layer) and the 2 nd layer (ITO layer) which are regions where the resist layer is not formed in the 1 st pattern are each drawn in the 1 st pattern (pattern which is a shape of the region (negative) where the pattern a does not exist) is obtained. Then, PET (B) used for the temporary support is laminated again as a cover film on the remaining resist, that is, the etching step (d 2) is performed.
In a state where the cover film bonded in the step (d 2) is not peeled off, the photomask provided with the opening of the pattern B (pattern 2) is used in an aligned state, and the pattern exposure is performed by bringing the photomask into contact with the cover film, that is, the step (e 2) of pattern exposure is performed. In the exposure, a high-pressure mercury lamp having an i-line (365 nm) as an exposure main wavelength was used.
After the cover film bonded by the etching step (d 2) is peeled off, development with a 1.0 mass% aqueous solution of sodium carbonate as a developer having a pH of 11.2 and water washing are performed to obtain a resist layer transferred with a 2 nd pattern (pattern where the light shielding portion of pattern a and the light shielding portion of pattern B overlap) different from the 1 st pattern, that is, the developing step (f 2) is performed.
Then, only the wiring of the 1 st layer (copper layer) is etched using Cu-02, and the 1 st layer of the conductive layer, which is the region where the resist layer is not formed in the 2 nd pattern, is etched, whereby a pattern for pattern exposure is formed on the circuit forming substrate, that is, a (g) etching step is performed.
The remaining resist layer was peeled off with a peeling liquid (KP-301 manufactured by kanto chemical corporation) and removed, to obtain a circuit wiring of example 33 in which a circuit wiring including 2 kinds of conductive layers was formed on a substrate. The circuit wiring of embodiment 33 has the circuit wiring of pattern C shown in fig. 6.
Example 34
< Preparation of composition for thermoplastic resin layer >
The composition for thermoplastic resin layer was prepared according to the following formulation.
Methyl ethyl ketone: 82.0 parts
PGMEA:12.8 parts of
Methyl methacrylate/2-ethylhexyl acrylate/benzyl methacrylate/methacrylic acid copolymer (copolymerization composition ratio (molar ratio) =55/11.7/4.5/28.8, weight average molecular weight=10ten thousand, glass transition temperature (Tg) ≡70 ℃). 3.5 parts
Monomer (trade name: BPE-500, manufactured by Xinzhou chemical Co., ltd.): 1.5 parts by weight
Fluorine-based polymer: 0.2 part
The fluorine-containing polymer was a 30 mass% solution of methyl ethyl ketone (trade name: MEGAFAC F780F, DIC Co., ltd.) and was C 6F13CH2CH2OCOCH＝CH2 parts and H (a copolymer of CH 3)CH2)7OCOCH＝CH2 parts and H (OCHCH 2)7OCOCH＝CH2 parts) having a weight average molecular weight of 3 ten thousand
< Preparation of composition for intermediate layer >
The composition for the intermediate layer was prepared according to the following formulation.
Distilled water: 39.0 parts
Methanol: 58.0 parts
Polyvinyl alcohol (trade name: PVA205, (co.) colali, saponification degree=88%, polymerization degree 550): 1.5 parts by weight
Hydroxypropyl methylcellulose (trade name: TC-5, manufactured by Xinyue chemical Co., ltd.): 1.5 parts by weight
< Preparation of Positive photosensitive composition >
A positive photosensitive composition was prepared according to the following formulation.
MATHF copolymer: 97.9 parts of
Photoacid generator (PAG-2 above): 2 parts of
Surfactant (surfactant 1 above): 0.1 part
PGMEA:900 parts
The composition for thermoplastic resin layer was slit-coated on PET (A) as a temporary support so that the dry film thickness became 1.0. Mu.m, and dried in a convection oven at 100℃for 2 minutes. Then, the composition for an intermediate layer was slit-coated on the thermoplastic resin layer so that the dry film thickness became 0.5. Mu.m, and dried in a convection oven at 100℃for 2 minutes. Finally, the positive photosensitive composition was slit coated so that the dry film thickness became 3.0 μm, and then dried in a convection oven at 100℃for 2 minutes, followed by press-bonding a polyethylene film (manufactured by Tredegar Corporation. Mu.m, OSM-N) as a protective film, to prepare a dry film resist.
A copper wiring board as a circuit wiring of example 34 was produced in the same manner as in example 5 except that the dry film resist was used.
Example 35
A copper wiring board as a circuit wiring of example 35 was produced in the same manner as in example 34 except that PET (B) was used as a temporary support.
Comparative example 1
The positive photosensitive resin composition prepared in the same manner as in example 5 was applied to PET (hereinafter referred to as PET (D)) having a film thickness of 25 μm as a temporary support using a slit nozzle so that the dry film thickness became 2.0 μm. Then, the film was dried in a convection oven at 100℃for 2 minutes, and finally, a polyethylene film (manufactured by Tredegar Corporation. Mu. OSM-N) was pressure-bonded as a protective film to prepare a dry film resist. The dry film resist obtained was used as the dry film resist of comparative example 1. The total haze of PET (D) with a film thickness of 25 μm was 0.48%.
A copper wiring substrate as a circuit wiring of comparative example 1 was produced in the same manner as in example 5, except that the dry film resist of comparative example 1 was used as the dry film resist.
Comparative example 2
A dry film resist of comparative example 2 was produced in the same manner as in comparative example 1 except that the temporary support used was PET (hereinafter referred to as PET (E)) having a film thickness of 40 μm and a total light haze of 1.10%. Further, a copper wiring substrate as a circuit wiring of comparative example 2 was obtained in the same manner as in comparative example 1 except that the dry film resist of comparative example 2 was used as a dry film resist.
Comparative example 3
A dry film resist of comparative example 3 was produced in the same manner as in comparative example 1 except that the temporary support used was PP (hereinafter referred to as PP (b)) having a film thickness of 50 μm and a total light haze of 0.50%. Further, a copper wiring substrate as a circuit wiring of comparative example 3 was obtained in the same manner as in comparative example 1 except that the dry film resist of comparative example 3 was used as a dry film resist.
Comparative example 4
A copper wiring substrate as a circuit wiring of comparative example 4 was obtained in the same manner as in comparative example 1 except that the temporary support was peeled off and the photomask was brought into contact with the resist layer to perform contact pattern exposure.
[ Evaluation ]
< Pattern Linearity (LWR) >)
Positions were randomly selected from the line and blank patterns of the circuit wiring substrates having the obtained circuit wirings of each example and comparative example, and the pattern widths of 20 positions were measured. Based on the obtained line width data, a value of the standard deviation σ multiplied by 3 is defined as LWR (LINE WIDTH Roughness) on the basis of the standard deviation σ, as an index of pattern linearity.
By definition, the smaller the LWR, the smaller the line width variation, and more preferable. For a pattern of 4 μm line width, the values of LWR were used for evaluation as follows.
Evaluation of D1.0. Ltoreq. LWR: the large line width variation causes circuit defects, and cannot be used as a circuit wiring board.
Evaluating that LWR is less than or equal to C0.5 and less than 1.0: although it can be used as a circuit wiring board, it is not preferable because it may cause defects.
Evaluating B0.3 to LWR < 0.5: the circuit wiring board is preferable.
Evaluation a LWR < 0.3: the circuit wiring board is very preferable.
Among the above evaluations, the evaluation a is preferable because the evaluation a and the evaluation B are necessary for obtaining a circuit wiring board having good performance in practical use.
The evaluation results are shown in table 1 below.
< Process contamination >
Whether or not an attached matter was observed on the photomask after the exposure treatment was visually judged, and the process contamination related to the photomask contamination caused by the transfer of the resist to the photomask at the time of exposure was evaluated based on the following criteria.
A: no deposit was observed on the photomask after the exposure treatment.
B: after the exposure treatment, an attached matter was observed on the photomask.
The evaluation results are shown in table 1 below.
TABLE 1
As is clear from table 1, the dry film resist of the present invention can provide a dry film resist which can easily form a positive pattern with high resolution and can produce a circuit wiring with high pattern linearity. The circuit wiring having high pattern linearity is suitable as a circuit wiring of an input device or a display device. Further, according to the method for manufacturing a circuit wiring of the present invention, it is possible to manufacture a circuit wiring having high pattern linearity without any process contamination.
As shown in comparative examples 1 to 3, when pattern exposure is performed via a temporary support having a haze of more than 0.3%, linearity tends to decrease with the haze value, and the product is not preferable quality, or cannot be used at all, although the product can be used as a circuit wiring board.
Further, as shown in comparative example 4, exposure to peel off the temporary support is not preferable in terms of the process because mask contamination occurs and process contamination occurs because the photomask and the resist are in direct contact, although high pattern linearity can be obtained.
Symbol description
1: Substrate material
2: Mask layer
3: First electrode pattern
3A: pad portion
3B: connection part
4: Second electrode pattern
5: Insulating layer
6: Additional conductive elements (peripheral wiring portion and extraction wiring portion)
7: Transparent protective layer
10: Capacitive input device

Claims (16)

1. A dry film resist is a positive dry film resist having a resist layer on a temporary support,
The temporary support has a total light haze of 0.3% or less,
Which satisfies the following condition (1) and condition (2) or satisfies only condition (2),
Condition (1): the temporary support has a transmittance of 80% or less for an exposure dominant wavelength of the resist layer;
Condition (2): a light absorbing layer having a transmittance of 80% or less with respect to an exposure dominant wavelength of the resist layer is provided between the temporary support and the resist layer,
The resist layer contains a component (A) and a photoacid generator (B),
The component (A) is a polymer having an acid constituent unit a0 in which an acid group is protected with an acid-decomposable group,
The acid constituent unit a0 has a constituent unit represented by the following general formula A3 or A1,
General formula A3:
In the general formula A3, R 31 and R 32 respectively and independently represent a hydrogen atom, an alkyl group or an aryl group, at least any one of R 31 and R 32 is an alkyl group or an aryl group, R 33 represents an alkyl group or an aryl group, R 31 and R 33 or R 32 are optionally connected with R 33 to form a cyclic ether, R 34 represents a hydrogen atom or a methyl group, X 0 represents a single bond or an arylene group, Y represents a nitrogen atom, a sulfur atom or an oxygen atom,
The general formula A1:
In the general formula A1, R 1 and R 2 respectively and independently represent a hydrogen atom, an alkyl group or an aryl group, at least any one of R 1 and R 2 is an alkyl group or an aryl group, R 3 represents an alkyl group or an aryl group, R 1 and R 3 or R 2 and R 3 are optionally connected to form a cyclic ether, and R 4 represents a hydrogen atom or a methyl group.
2. The dry film resist according to claim 1, wherein in the general formula A3, X 0 is a single bond.
3. The dry film resist according to claim 1 or 2, wherein in the general formula A3, Y is an oxygen atom.
4. The dry film resist according to claim 1 or 2, wherein the resist layer contains 2 or more kinds of polymers having an acid constituent unit a0 in which an acid group is protected with an acid-decomposable group.
5. The dry film resist according to claim 1, wherein the resist layer contains a naphthoquinone diazide compound and a resin having a phenolic hydroxyl group.
6. The dry film resist according to claim 1 or 2, wherein the resist layer further contains a heterocyclic compound.
7. The dry film resist according to claim 1 or 2, wherein the resist layer further contains an alkaline compound.
8. The dry film resist of claim 1 or 2, wherein the resist layer further contains a radiation absorber.
9. A method for manufacturing a circuit wiring, comprising the following steps (a), (b), (c) and (d),
(A) A lamination step of laminating the dry film resist according to any one of claims 1 to 8 on a circuit forming substrate having a base material and a conductive layer;
(b) A pattern exposure step of performing contact pattern exposure with a pattern for pattern exposure without peeling the temporary support of the dry film resist;
(c) A developing step of developing the temporary support after the temporary support is peeled off, and forming the pattern for pattern exposure on the resist layer;
(d) And an etching step of forming the pattern for pattern exposure on the circuit forming substrate by etching.
10. The method for manufacturing a circuit wiring according to claim 9, wherein,
The step (b) is a step (b 1) described below,
The step (c) is a step (c 1) described below,
The step (d) is a step (d 1) described below,
Further comprising the following step (e 1), step (f 1) and step (g),
(B1) A pattern exposure step of performing contact pattern exposure in a1 st pattern without peeling the temporary support of the dry film resist;
(c1) A developing step of developing the temporary support after the temporary support is peeled off to form the 1 st pattern on the resist layer;
(d1) An etching step of forming the 1 st pattern on the circuit forming substrate by etching;
(e1) A pattern exposure step of performing contact pattern exposure with a2 nd pattern without peeling the resist layer on which the 1 st pattern is formed in the (c 1) step;
(f1) A developing step of developing the resist layer to form a2 nd pattern different from the 1 st pattern;
(g) And an etching step of forming the 2 nd pattern on the circuit forming substrate by etching.
11. The method for manufacturing a circuit wiring according to claim 9, wherein,
The step (b) is a step (b 1) described below,
The step (c) is a step (c 1) described below,
The step (d) is a step (d 2) described below,
Further comprising a step (e 2), a step (f 2) and a step (g),
(B1) A pattern exposure step of performing contact pattern exposure in a1 st pattern without peeling the temporary support of the dry film resist;
(c1) A developing step of developing the temporary support after the temporary support is peeled off to form the 1 st pattern on the resist layer;
(d2) An etching step of forming the 1 st pattern on the circuit forming substrate by etching, and then bonding a cover film to the remaining resist layer without peeling the resist layer on which the 1 st pattern was formed in the (c 1) step;
(e2) A pattern exposure step of performing contact pattern exposure with a2 nd pattern without peeling the cover film bonded in the step (d 2);
(f2) A developing step of peeling off the cover film bonded in the (d 2) step, and then developing the cover film to form a 2 nd pattern different from the 1 st pattern on the resist layer;
(g) And an etching step of forming the 2 nd pattern on the circuit forming substrate by etching.
12. The method for manufacturing a circuit wiring according to claim 9 or 10, wherein a pH of a developer used in the developing step is 12.5 or less.
13. A circuit wiring manufactured by the manufacturing method of the circuit wiring according to any one of claims 9 to 12.
14. An input device using the circuit wiring of claim 13.
15. The input device of claim 14, wherein the input device is an electrostatic capacitive touch panel.
16. A display device provided with the input device of claim 14 or 15.
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CN108255018B (en) * 2018-01-05 2020-12-11 湖北固润科技股份有限公司 Photoresist composition comprising poly (p-hydroxystyrene) epoxy resin as film-forming resin
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CN113166323A (en) * 2018-12-04 2021-07-23 富士胶片株式会社 Transfer material, method for manufacturing resin pattern, method for manufacturing circuit wiring, and method for manufacturing touch panel
JP7410053B2 (en) * 2018-12-18 2024-01-09 三菱製紙株式会社 Positive dry film resist and etching method
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102331684A (en) * 2010-07-13 2012-01-25 日立化成工业株式会社 Photosensitive element, formation method of corrosion-resisting pattern, manufacture method of printing circuit wiring board and printing circuit wiring board
JP2012181488A (en) * 2010-11-02 2012-09-20 Fujifilm Corp Photosensitive resin composition for etching resist, method of manufacturing pattern, mems structure and method of manufacturing the same, dry etching method, wet etching method, mems shutter device, and image display device
JP2013037038A (en) * 2011-08-03 2013-02-21 Asahi Kasei E-Materials Corp Photopolymerizable resin composition, photopolymerizable resin laminate, method for forming resist pattern, and method for manufacturing circuit board, lead frame and semiconductor package
JP2014010382A (en) * 2012-07-02 2014-01-20 Fujifilm Corp Photosensitive transfer material, cured film and production method of the same, organic electroluminescence (el) display device, liquid crystal display device and electrostatic capacitance type input device
CN104871088A (en) * 2012-12-12 2015-08-26 日立化成株式会社 Photosensitive resin composition and photosensitive film using same

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4761909B2 (en) * 2005-10-05 2011-08-31 旭化成イーマテリアルズ株式会社 Photosensitive resin composition and laminate
JP2011017976A (en) * 2009-07-10 2011-01-27 Hitachi Chem Co Ltd Method for forming light shielding film
JP6149266B2 (en) * 2011-12-07 2017-06-21 東レ株式会社 Microporous membrane wound body and method for producing the same
JP5865851B2 (en) * 2012-03-23 2016-02-17 富士フイルム株式会社 Manufacturing method of conductive member, conductive member, and touch panel using the same
TWI585522B (en) * 2012-08-31 2017-06-01 富士軟片股份有限公司 Photosensitive resin composition, cured product and method for manufacturing the same, method for manufacturing resin pattern, cured film, liquid crystal display apparatus, organic electroluminescent apparatus and touch panel apparatus
JP6267951B2 (en) * 2013-12-18 2018-01-24 富士フイルム株式会社 Photosensitive transfer material, pattern forming method and etching method
WO2017018053A1 (en) * 2015-07-29 2017-02-02 日立化成株式会社 Photosensitive resin composition, photosensitive element, method for forming resist pattern and method for producing printed wiring board

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102331684A (en) * 2010-07-13 2012-01-25 日立化成工业株式会社 Photosensitive element, formation method of corrosion-resisting pattern, manufacture method of printing circuit wiring board and printing circuit wiring board
JP2012181488A (en) * 2010-11-02 2012-09-20 Fujifilm Corp Photosensitive resin composition for etching resist, method of manufacturing pattern, mems structure and method of manufacturing the same, dry etching method, wet etching method, mems shutter device, and image display device
JP2013037038A (en) * 2011-08-03 2013-02-21 Asahi Kasei E-Materials Corp Photopolymerizable resin composition, photopolymerizable resin laminate, method for forming resist pattern, and method for manufacturing circuit board, lead frame and semiconductor package
JP2014010382A (en) * 2012-07-02 2014-01-20 Fujifilm Corp Photosensitive transfer material, cured film and production method of the same, organic electroluminescence (el) display device, liquid crystal display device and electrostatic capacitance type input device
CN104871088A (en) * 2012-12-12 2015-08-26 日立化成株式会社 Photosensitive resin composition and photosensitive film using same

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