CN106918995B - Photosensitive resin composition, photosensitive resin laminate, method for producing resin pattern and cured film pattern, and display device - Google Patents

Photosensitive resin composition, photosensitive resin laminate, method for producing resin pattern and cured film pattern, and display device Download PDF

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CN106918995B
CN106918995B CN201611208215.8A CN201611208215A CN106918995B CN 106918995 B CN106918995 B CN 106918995B CN 201611208215 A CN201611208215 A CN 201611208215A CN 106918995 B CN106918995 B CN 106918995B
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photosensitive resin
resin composition
protective film
group
forming
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CN106918995A (en
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吉田真由纪
渋井智史
下田浩一朗
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Asahi Kasei 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
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/0035—Multiple processes, e.g. applying a further resist layer on an already in a previously step, processed pattern or textured surface
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/031—Organic compounds not covered by group G03F7/029
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers

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  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
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  • Materials For Photolithography (AREA)

Abstract

The invention provides a photosensitive resin composition, a photosensitive resin laminate, a resin pattern manufacturing method, a cured film pattern manufacturing method, and a display device. [ problem ] to provide a photosensitive resin composition which has excellent balance between rust resistance, bendability, and releasability of various patterns such as round holes and sensitivity, and is suitable for protecting conductor sections such as wiring and electrodes. The photosensitive resin composition for forming a protective film of a conductor part comprises (A) an alkali-soluble resin; (B) a compound having an ethylenically unsaturated double bond; (C) a photopolymerization initiator; and (D) a rust preventive, wherein the component (C) contains an oxime compound having an absorption coefficient at a wavelength of 365nm of 17mL/(mg cm) to 60mL/(mg cm) in an ethanol solution.

Description

Photosensitive resin composition, photosensitive resin laminate, method for producing resin pattern and cured film pattern, and display device
Technical Field
The present invention relates to a photosensitive resin composition, a photosensitive resin laminate, a method for producing a resin pattern using a photosensitive resin laminate, a method for producing a cured film pattern, a display device, and the like.
Background
In recent years, with the progress of high performance, diversification, and reduction in size and weight of electronic devices, devices in which a transparent touch panel (touch sensor) is mounted on the entire surface of a display element such as a liquid crystal have been increasing. The transparent touch panel is used to visually confirm and select characters, symbols, patterns, and the like displayed on the display element, and switching between functions of the device by operating the transparent touch panel is increasing. Touch panels are used not only for large electronic devices such as personal computers and televisions, but also for small electronic devices such as car navigation systems, cellular phones, and electronic dictionaries, and display devices such as OA and FA devices. As transparent conductive electrode materials, ITO (Indium-Tin-Oxide), Indium Oxide, and Tin Oxide are known, and these materials are mainly used as electrode materials for substrates for liquid crystal display elements and the like because of their high visible light transmittance.
As conventional touch panel systems, resistive film systems, optical systems, pressure systems, electrostatic capacitance systems, electromagnetic induction systems, image recognition systems, vibration detection systems, ultrasonic wave systems, and the like are cited, and various systems have been put into practical use. In the capacitive touch panel, when a fingertip, which is a conductive body, contacts a touch input surface, capacitive coupling occurs between the fingertip and a conductive film, thereby forming a capacitor. Therefore, the electrostatic capacitance type touch panel detects coordinates of a contact position by capturing a change in charge of the contact position of a fingertip. In particular, a projection-type capacitance touch panel has excellent operability for detecting multiple points of a fingertip, and thus can perform complicated instructions, and is widely used as an input device on a display surface of a device having a small display device such as a mobile phone or a portable music player. In general, in a projection type capacitance touch panel, in order to express two-dimensional coordinates by using X-axis and Y-axis, a plurality of X electrodes and a plurality of Y electrodes perpendicular to the plurality of X electrodes are formed in a 2-layer structure, and ITO is used as an electrode material.
However, since the edge region of the touch panel is a region where the touch position cannot be detected, reducing the area of the edge region is an important factor for improving the product value. In the fringe area, a metal wiring is required to conduct a detection signal of a touched position, and the width of the metal wiring is required to be reduced in order to reduce the fringe area. Since ITO is not sufficiently high in conductivity, copper is generally used for the metal wiring.
However, in the touch panel as described above, corrosive components such as moisture and salt may enter the inside from the sensing region when the finger tip is in contact with the touch panel. If a corrosive component enters the inside of the touch panel, there is a fear that the metal wiring is corroded, and the resistance between the electrode and the driving circuit is increased or the wiring is broken.
Further, the metal wiring for conducting the detection signal needs to be connected to other components by the terminal portion to ensure conduction, and the terminal portion needs to be removed from the protective film. Therefore, the protective film is required to have good developability or good releasability of various patterns such as round holes.
In addition, in the manufacturing process of the touch panel, a highly sensitive protective film that can be exposed in a short time is desired for improving productivity. Further, when the protective film is provided on the flexible display substrate, the load on the protective film increases as the substrate bends, and cracks are likely to occur, and therefore, a high adhesion property to the substrate and a bending property capable of withstanding the substrate bending are required.
From the viewpoint of the shape, transparency, moisture permeability, rust prevention, or alkali developability of the protective film, a method for producing a substrate for a touch panel with a cured film has been proposed (patent documents 1 and 2).
In the field of photosensitive colored resin compositions or photosensitive resin compositions used for forming color filters and organic EL liquid crystal display devices, the absorption coefficient of an initiator contained in a resin composition is studied from the viewpoint of solvent resistance or resolution of the photosensitive resin layer (patent documents 3 and 4).
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open publication No. 2015-121929
Patent document 2: japanese laid-open patent publication No. 2015-108881
Patent document 3: international publication No. 2015/025689
Patent document 4: international publication No. 2015/060240
Disclosure of Invention
Problems to be solved by the invention
The method for producing a substrate for a touch panel with a cured film described in patent document 1 is for suppressing corrosion of copper wiring used for conducting a detection signal of a touched position, and is not described in relation to bendability. Patent document 2 also does not mention suppression of corrosion or developability, and naturally does not describe bendability. Patent documents 3 and 4 describe that a composition having good solvent resistance and resolution can be obtained by using an initiator having a specific absorption coefficient, but do not describe rust resistance and bendability.
Accordingly, an object of the present invention is to provide a photosensitive resin composition which is excellent in a balance between rust resistance, flexibility, and releasability (hereinafter referred to as "resolution") of various patterns such as round holes and sensitivity, and which is suitable for protecting conductor portions such as wiring and electrodes.
Means for solving the problems
The present inventors have conducted intensive studies to solve the above problems, and as a result, have found that: the present inventors have found that a photosensitive resin composition which comprises (a) an alkali-soluble resin, (B) a compound having an ethylenically unsaturated double bond, (C) a photopolymerization initiator, and (D) a rust inhibitor, and further comprises an oxime compound having a specific absorption coefficient as component (C) can be excellent in the balance among rust inhibition, flexibility, resolution, and sensitivity, and is suitable for protecting conductor parts such as wiring and electrodes, and have completed the present invention.
That is, the present invention is as follows.
[1] A photosensitive resin composition for forming a protective film of a conductor part, comprising the following components:
(A) an alkali-soluble resin;
(B) a compound having an ethylenically unsaturated double bond;
(C) a photopolymerization initiator; and
(D) a rust-proof agent, a corrosion inhibitor,
further, the component (C) includes an oxime compound having an absorption coefficient at 365nm in an ethanol solution of 17mL/(mg cm) to 60mL/(mg cm).
[2] The photosensitive resin composition according to [1], wherein the photosensitive resin composition for forming a protective film of the conductor part comprises the following compound as a component (D),
the compound has a heterocyclic ring composed of a carbon (C) atom and a nitrogen (N) atom and/or a sulfur (S) atom, and the number of N atoms is 3 or less, or the number of S atoms is 3 or less, or the total number of N atoms and S atoms is 3 or less in the same heterocyclic ring.
[3] The photosensitive resin composition according to [1] or [2], wherein the photosensitive resin composition for forming a protective film of the conductor part contains at least 1 compound selected from the group consisting of benzotriazole, benzotriazole derivatives, imidazole and imidazole derivatives as the component (D).
[4] The photosensitive resin composition according to [3], wherein the photosensitive resin composition for forming a protective film of the conductor part contains benzotriazole or a benzotriazole derivative as the component (D).
[5] The photosensitive resin composition according to [1] or [2], wherein the photosensitive resin composition for forming a protective film of the conductor part contains at least 1 compound selected from the group consisting of triazole, triazole derivatives, tetrazole derivatives, thiadiazole derivatives, indazole, and indazole derivatives as the component (D).
[6] The photosensitive resin composition according to [5], wherein the photosensitive resin composition for forming a protective film of the conductor part contains triazole or a triazole derivative as the component (D).
[7] The photosensitive resin composition according to [5], wherein the photosensitive resin composition for forming a protective film of the conductor part contains tetrazole or a tetrazole derivative as the component (D).
[8] The photosensitive resin composition according to [5], wherein the photosensitive resin composition for forming a protective film of the conductor part contains thiadiazole or a thiadiazole derivative as the component (D).
[9] The photosensitive resin composition according to [5], wherein the photosensitive resin composition for forming a protective film of the conductor part contains indazole or an indazole derivative as the component (D).
[10] The photosensitive resin composition according to any one of [1] to [9], wherein the photosensitive resin composition for forming a protective film of the conductor part contains a compound represented by the following formula (4) as a component (C).
Formula (4)
Figure BDA0001190434340000051
{ in formula (II), X4And X5Each independently represents a monovalent organic group, at least one of which has a structure represented by the following formula (5), and Y4Represents H or a 1-valent organic group. }
Formula (5)
Figure BDA0001190434340000052
[11] The photosensitive resin composition according to [10], wherein the photosensitive resin composition for forming a protective film of the conductor part comprises a compound represented by the following formula (6) as a component (C),
formula (6)
Figure BDA0001190434340000053
{ in formula, Y5Is H, -CH3An aliphatic hydrocarbon group having 2 or more carbon atoms, or an alicyclic hydrocarbon group having 3 or more carbon atoms and optionally substituted with a hetero atom or/and a halogen atom; n is an integer of 0 or 1; y is5Is H or-CH3When n is 0; y is5When the alkyl group is an aliphatic hydrocarbon group having 2 or more carbon atoms or an alicyclic hydrocarbon group having 3 or more carbon atoms and optionally having a heteroatom or/and a halogen atom, n is 1; and Y is6Represents H or a 1-valent organic group. }.
[12] The photosensitive resin composition according to any one of [1] to [9], wherein the photosensitive resin composition for forming a protective film of the conductor part contains a compound represented by the following formula (1) and/or a compound represented by the following formula (2) as a component (C),
Figure BDA0001190434340000061
{ in formula (II), X1Represents a 1-valent group containing a heterocyclic ring optionally having a substituent; y is1Represents a substituent selected from the group consisting of an alkyl group having 1 to 8 carbon atoms which optionally forms a branched structure or a ring structure, and a phenyl group which optionally has a substituent; and Z is1Represents a 1-valent organic group. }
Figure BDA0001190434340000062
{ in formula (II), X2And X3Represent the same or different electron withdrawing groups; y is2And Y3Identical or different, Y2And Y3Represents a substituent selected from the group consisting of an alkyl group having 1 to 10 carbon atoms which optionally forms a branched structure or a ring structure, and a phenyl group which optionally has a substituent; and Z is2Represents a 2-valent group selected from the group consisting of an alkylene group having 1 to 16 carbon atoms and an optionally substituted phenylene group. }.
[13]According to [12]]The photosensitive resin composition, wherein the photosensitive resin composition for forming a protective film of the conductor part comprises X in the formula (1)1A compound having a 1-valent group represented by the following formula (3) as the component (C),
Figure BDA0001190434340000071
{ wherein A represents an oxygen (O) atom or an S atom. }.
[14] The photosensitive resin composition according to any one of [1] to [13], wherein the photosensitive resin composition for forming a protective film of the conductor part contains an alkali-soluble resin having an aromatic group in a side chain as the component (A).
[15] The photosensitive resin composition according to any one of [1] to [14], wherein the photosensitive resin composition for forming a protective film of the conductor part contains (E) a silane coupling agent.
[16] The photosensitive resin composition according to any one of [1] to [15], wherein the photosensitive resin composition for forming a protective film of the conductor part comprises (F) an amine compound.
[17] A photosensitive resin laminate comprising: and a photosensitive resin layer formed of the photosensitive resin composition for a protective film of a conductor part according to any one of [1] to [16] provided on the support film.
[18] The photosensitive resin laminate according to [17], wherein the thickness of the photosensitive resin layer is 15 μm or less, and the absorbance of the photosensitive resin layer at a wavelength of 365nm is 0.01 to 0.05 per 1 μm of thickness.
[19] A method for producing a pattern, comprising the step of forming a pattern by laminating the photosensitive resin laminate according to [17] or [18] on a substrate, exposing the laminate to light, and developing the exposed laminate.
[20] A cured film pattern manufacturing method, comprising:
a step of forming a pattern by laminating the photosensitive resin laminate according to [17] or [18] on a substrate, exposing the laminate, and developing the exposed laminate; and
and a step of subjecting the pattern to post-exposure treatment and/or heat treatment to cure the pattern.
[21] A cured film produced by the cured film pattern production method of [20 ].
[22] A touch panel display device, a device having a touch sensor, or a device having a pressure sensor, which is provided with a cured film produced by the cured film pattern production method of [20 ].
ADVANTAGEOUS EFFECTS OF INVENTION
The present invention can provide a photosensitive resin composition and a photosensitive resin laminate which are excellent in a balance among rust resistance, flexibility, resolution, and sensitivity and suitable for protecting a conductor section such as a wiring or an electrode.
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FIG. 1 is a diagram for explaining a method of bending resistance test in examples.
Description of the reference numerals
1 sample of
2 cylindrical core rod with arbitrary diameter phi
Detailed Description
Hereinafter, specific embodiments of the present invention (hereinafter, abbreviated as "embodiments") will be described in detail. The present invention is not limited to the following embodiments, and various modifications can be made within the scope of the present invention.
[ photosensitive resin composition and photosensitive resin laminate ]
In an embodiment of the present invention, a photosensitive resin laminate includes a support film and a photosensitive resin layer formed of a photosensitive resin composition, the photosensitive resin composition including the following components: (A) an alkali-soluble resin, (B) a compound having an ethylenically unsaturated double bond, (C) a photopolymerization initiator, and (D) a rust inhibitor. The photosensitive resin composition may contain (E) a silane coupling agent, (F) an amine compound, and other components as desired. The components constituting the photosensitive resin composition will be specifically described below.
< A) alkali-soluble resin >
The alkali-soluble resin in the present embodiment is a polymer having a carboxyl group, and is preferably obtained by polymerizing at least 1 kind of first monomer having a carboxyl group in the molecule, as described later. The alkali-soluble resin is more preferably obtained by copolymerizing at least 1 kind of first monomer and at least 1 kind of second monomer described later.
Examples of the first monomer include (meth) acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, maleic anhydride, and maleic ester. Here, (meth) acryloyl represents acryloyl and/or methacryloyl, and the same applies to (meth) acrylate.
The second monomer is a monomer that is non-acidic and has at least 1 polymerizable unsaturated group in the molecule. Examples of the second monomer include vinyl alcohol esters such as methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, meth) acrylonitrile, and vinyl acetate; aromatic (meth) acrylates such as benzyl (meth) acrylate; styrene and its polymerizable derivatives, and the like.
Among these copolymers, a copolymer containing a structural unit derived from (meth) acrylic acid and a structural unit derived from an aromatic ester of (meth) acrylic acid or styrene is preferable from the viewpoint of rust prevention of a wiring or an electrode formed on a substrate. Further, from the viewpoint of flexibility, a copolymer containing a structural unit derived from (meth) acrylic acid and a structural unit derived from an aromatic ester of (meth) acrylic acid is more preferable.
By copolymerizing a unit having an aromatic group with another unit, the hydrophobicity of the alkali-soluble resin and the film density of the photosensitive resin laminate after curing are increased, and the rust-proofing property is improved, while when the hydrophobicity is too high, the developability is deteriorated. Therefore, the content of the unit having an aromatic group in the alkali-soluble resin is preferably 20 to 90% by mass, more preferably 50 to 85% by mass, with respect to the mass of the alkali-soluble resin. The aromatic group may be, for example, a phenyl group optionally having a substituent.
The alkali-soluble resin preferably has an acid equivalent (g/mol) of 430 to 860. The acid equivalent is preferably 430 or more from the viewpoint of improving rust prevention, and preferably 860 or less from the viewpoint of improving developability. From the viewpoint of balance between rust prevention and developability, the acid equivalent is more preferably 430 to 570, and still more preferably 430 to 510.
The acid equivalent was measured by a potentiometric titration method using an automatic titration apparatus (COM-555) manufactured by Pouzolk industries, Ltd., and 0.1mol/L sodium hydroxide. When a plurality of (a) alkali-soluble resins are contained in the composition, the acid equivalent thereof means the acid equivalent of the entire alkali-soluble resin.
The weight average molecular weight of the alkali-soluble resin is not particularly limited, and is preferably 5,000 or more and 500,000 or less in general from the viewpoint of coatability, coating film strength and developability. The weight average molecular weight of the alkali-soluble resin is preferably 5,000 or more from the viewpoint of the properties of development aggregates and the properties of an unexposed film such as edge fusibility and chipping property of the photosensitive resin laminate, and is preferably 500,000 or less from the viewpoint of improvement of developability. Here, the edge fusibility means: when the photosensitive resin laminate is wound in a roll form, the photosensitive resin composition layer is exposed from the end face of the roll. The swarf property is: when the unexposed film is cut by a cutter, the fragments are scattered. The scattered debris adheres to the upper surface of the photosensitive resin laminate, and is transferred to the mask in a subsequent exposure step or the like, causing a failure. The weight average molecular weight of the alkali-soluble resin is more preferably 5,000 or more and 300,000 or less, and still more preferably 10,000 or more and 200,000 or less. The weight average molecular weight was measured using a Gel Permeation Chromatograph (GPC) manufactured by japan spectrography, inc. The obtained weight average molecular weight is a polystyrene equivalent.
A pump: gulliver, PU-1580 type
Column: shodex (registered trademark) (KF-807, KF-806M, KF-806M, KF-802.5) 4-series-connected, manufactured by Showa Denko K.K.,
Fluidized bed solvent: tetrahydrofuran (THF)
Standard curve: standard curve specified using polystyrene Standard sample { Standard curve based on polystyrene Standard sample (Shodex STANDARD SM-105, manufactured by Showa Denko K.K. }) }
The content of the alkali-soluble resin in the photosensitive resin composition is 30 to 70% by mass based on the mass of the photosensitive resin composition, and is preferably 40 to 65% by mass, and more preferably 50 to 65% by mass, from the viewpoint of rust prevention and bendability.
< Compound having an ethylenically unsaturated double bond >
The compound having an ethylenically unsaturated double bond described in this embodiment is a compound having polymerizability by having an ethylenically unsaturated group in its structure.
Examples of the compound having an ethylenically unsaturated double bond include: a compound obtained by adding (meth) acrylic acid to one end of a polyoxyalkylene, a compound obtained by adding (meth) acrylic acid to one end and alkyl-etherifying or allyl-etherifying the other end, and the like.
Further, as the compound having an ethylenically unsaturated double bond, for example: a compound having (meth) acryloyl groups at both ends of a polyoxyalkylene chain, a compound having (meth) acryloyl groups at both ends of an oxyalkylene chain obtained by randomly or blockwise bonding a polyoxyethylene chain and a polyoxypropylene chain, a compound having (meth) acryloyl groups at both ends of bisphenol a modified with an oxyalkylene.
In addition, examples of the compound having an ethylenically unsaturated double bond include a urethane compound which is a reaction product of a diisocyanate compound and a compound having a hydroxyl group and a (meth) acryloyl group in one molecule.
Further, as the compound having an ethylenically unsaturated double bond, a compound having more than 2 (meth) acryloyl groups in one molecule may also be used. Such a compound can be obtained by converting the following alcohol as a central skeleton, which is referred to as a (meth) acrylate: having 3 moles or more of a group capable of adding an oxyalkylene group in the molecule, and an oxyalkylene group such as an oxyethylene group, an oxypropylene group or an oxybutylene group is added to the group. In addition, the central skeleton may be directly reacted with (meth) acrylic acid without modifying the central skeleton with an oxyalkylene group. Examples of the compound capable of forming the central skeleton include glycerin, trimethylolpropane, pentaerythritol, diglycerin, ditrimethylolpropane, dipentaerythritol, and isocyanurate rings. The compound having an ethylenically unsaturated double bond preferably contains a compound having 3 or more (meth) acryloyl groups in one molecule, and more preferably contains dipentaerythritol hexa (meth) acrylate, trimethylolpropane tri (meth) acrylate, or ditrimethylolpropane tri (meth) acrylate, from the viewpoint of rust prevention.
The content of the compound having an ethylenically unsaturated double bond in the photosensitive resin composition is preferably 20 to 60 mass%, more preferably 35 to 50 mass%, based on the mass of the photosensitive resin composition, from the viewpoints of resolution, adhesion, and rust prevention.
[ C ] photopolymerization initiator
The photopolymerization initiator according to the present embodiment is an oxime compound, and is characterized in that the absorbance coefficient at a wavelength of 365nm in an ethanol solution is 17mL/(mg cm) to 60mL/(mg cm). From the viewpoint of surface curability and sensitivity of the protective film, the absorption coefficient at a wavelength of 365nm in an ethanol solution of an oxime compound is preferably 17mL/(mg · cm) or more, and particularly preferably 26mL/(mg · cm) or more. From the viewpoint of curability of the bottom of the protective film, it is preferably 60mL/(mg · cm) or less. For the same reason, the above-mentioned absorption coefficient is more preferably from 35 mL/(mg. cm) to 55 mL/(mg. cm).
By using an oxime initiator having a high absorption coefficient at a wavelength of 365nm, a protective film with high sensitivity under i-ray exposure can be obtained. Further, it can be considered that: in the development process using an aqueous sodium carbonate solution, when sodium ions permeate into the surface of the cured protective film to form a sodium salt with a carboxylic acid of the alkali-soluble resin, water easily permeates into the protective film, and rust resistance is deteriorated. Here, it can be assumed that: when an oxime initiator having a high absorption coefficient is used, absorption at the surface of the protective film during exposure becomes large, so that high surface curability can be obtained, and intrusion of sodium ions during development can be suppressed, as a result, high rust resistance can be obtained. In this case, since the surface curing is further promoted, the bottom portion of the protective film is not cured excessively, and good bendability can be obtained. On the other hand, if the absorption coefficient is too high, the reaction proceeds only on the surface of the protective film, and the bottom of the protective film is insufficiently cured, resulting in poor adhesion to the substrate and poor flexibility. In order to well balance these ranges, the absorbance coefficient at a wavelength of 365nm in an ethanol solution of an oxime compound is from 17 mL/(mg. cm) to 60 mL/(mg. cm). Examples of the oxime compound include carbazole and derivatives thereof, and oxime compounds having a fluorene structure, and the like, and are preferable in the present embodiment.
Specific examples of oxime initiators having an absorption coefficient at 365nm wavelength in ethanol of 17mL/(mg cm) to 60mL/(mg cm) include compounds 2, D-1, D-3, D-4, D-9, D-12, D-14, D-15, D-20, C-2 described in Japanese patent No. 5682094, and commercially available products include (7-nitro-9, 9-dipropyl-9H-fluoren-2-yl) (O-tolyl) methanone O-acetyloxime (DFI-020 produced by ダイトーケミックス Co., Ltd.), 1, 2-propanedione, 3-cyclohexyl-1- [ 9-ethyl-6- (2-furylcarbonyl) -9H-carbazol-3-yl ] -,2- (O-acetyloxime) (TR-PBG-326, product name of Nisshin ケムテック Co.), 1, 8-octanedione, 1, 8-bis [9- (2-ethylhexyl) -6-nitro-9H-carbazol-3-yl ] -,1, 8-bis (O-acetyloxime) (アデカアークルズ NCI-831, product name of ADEKA Co., Ltd.), 3-cyclohexyl-1- (6- (2- (benzoyloxyimino) octanoyl) -9-ethyl-9H-carbazol-3-yl) -propane-1, 2-dione-2- (O-benzoyloxime) (TR-PBG-371, product name of Nisshin ケムテック Co., Ltd.), product name), etc., can be easily obtained. From the viewpoint of rust prevention, bendability and resolution, TR-PBG-326, NCI-831 and TR-PBG-371 are more preferable, and from the viewpoint of rust prevention, bendability, resolution and storage stability TR-PBG-371 is particularly preferable.
Further, as the photopolymerization initiator, a compound represented by the following general formula (1) and/or a compound represented by the following general formula (2) is excellent in terms of high surface curability, sensitivity, rust prevention, and flexibility.
Figure BDA0001190434340000131
{ in formula (II), X1Represents a 1-valent group containing a heterocyclic ring optionally having a substituent; y is1Representing a group selected from optionally forming branchesA substituent selected from the group consisting of an alkyl group having 1 to 8 carbon atoms and optionally substituted phenyl groups; and Z is1Represents a 1-valent organic group. }
Figure BDA0001190434340000141
{ in formula (II), X2And X3Represent the same or different electron withdrawing groups; y is2And Y3Identical or different, Y2And Y3Represents a substituent selected from the group consisting of an alkyl group having 1 to 10 carbon atoms which optionally forms a branched structure or a ring structure, and a phenyl group which optionally has a substituent; and Z is2Represents a 2-valent group selected from the group consisting of an alkylene group having 1 to 16 carbon atoms and an optionally substituted phenylene group. }
The 1-valent organic group means a hydrocarbon group (which may be saturated or unsaturated, linear or branched, or may have a cyclic structure in the structure), and may contain a heteroatom or a halogen atom.
The compound represented by formula (1) is more preferably X in formula (1) from the viewpoints of sensitivity, rust prevention and bendability1Is a compound having a 1-valent group represented by the following general formula (3).
Figure BDA0001190434340000142
{ wherein A represents an oxygen (O) atom or an S atom. }.
Examples of the compound represented by the formula (1) include 1, 2-propanedione, 3-cyclohexyl-1- [ 9-ethyl-6- (2-furylcarbonyl) -9H-carbazol-3-yl ] -,2- (O-acetyloxime) (TR-PBG-326, product name, manufactured by hitachi ケムテック co., ltd.).
For the compound of formula (2) as a compound with X2Or X3Examples of the electron-withdrawing group include a halogen group, a nitro group, a carbonyl group, and a cyano group, and a nitro group is preferable.
Specific examples of the compound represented by the formula (2) include 1, 7-heptanedione, 1, 7-bis [ 9-ethyl-6-nitro-9H-carbazol-3-yl ] -,1, 7-bis (O-acetyl oxime), 1, 7-heptanedione, 1, 7-bis [9- (2-ethylhexyl) -6-nitro-9H-carbazol-3-yl ] -,1, 7-bis (O-acetyl oxime), and 1, 8-octanedione, 1, 8-bis [9- (2-ethylhexyl) -6-nitro-9H-carbazol-3-yl ] -,1, 8-bis (O-acetyl oxime) (アデカアークルズ NCI-831, manufactured by ADEKA Co., Ltd.) (アデカアークルズ NCI-831), Product name), etc.
Further, as the photopolymerization initiator, a compound represented by the following formula (4) is particularly preferable from the viewpoints of sensitivity, rust prevention, flexibility, resolution, and storage stability.
Formula (4)
Figure BDA0001190434340000151
{ in formula (II), X4And X5Each independently represents a monovalent organic group, at least one of which has a structure represented by the following formula (5), and Y4Represents H or a 1-valent organic group. }
Formula (5)
Figure BDA0001190434340000152
The storage stability is as follows: the photosensitive resin laminate maintains stable performance without changing its various properties such as sensitivity over a long period of time. When a photosensitive resin laminate is applied to industry, deterioration of storage stability leads to shortening of the life span and increase of management effort and management cost, and therefore, storage stability is an important performance of the photosensitive resin laminate.
Further, as the photopolymerization initiator, a compound represented by the following formula (6) is particularly preferable from the viewpoints of sensitivity, rust prevention, flexibility, resolution, and storage stability.
Formula (6)
Figure BDA0001190434340000153
{ in formula, Y5Is H, -CH3An aliphatic hydrocarbon group having 2 or more carbon atoms, or an aliphatic hydrocarbon group having 3 or more carbon atomsAn alicyclic hydrocarbon group optionally substituted with a hetero atom or/and a halogen atom; n is an integer of 0 or 1; y is5Is H or-CH3When n is 0; y is5When the alkyl group is an aliphatic hydrocarbon group having 2 or more carbon atoms or an alicyclic hydrocarbon group having 3 or more carbon atoms and optionally having a heteroatom or/and a halogen atom, n is 1; and Y is6Represents H or a 1-valent organic group. }
An oxime compound as a photopolymerization initiator is easily deteriorated in function by hydrolysis of an oxime group in the presence of an acid. Therefore, in a photosensitive resin composition or a photosensitive resin laminate containing an alkali-soluble resin having a carboxyl group, there is a problem that sensitivity is lowered or various performances are deteriorated due to deactivation of an initiator by long-term storage. The photopolymerization initiators represented by the formulae (4) and (6) have a benzoyloxime group, and therefore it can be considered that: when hydrolysis is performed in the presence of an acidic compound, a phenyl radical is generated, but the phenyl radical is less mobile than a methyl radical or the like, and is therefore less likely to be inactivated. Further, the photopolymerization initiators represented by the formulae (4) and (6) have high absorption coefficients and therefore exhibit high reactivity, and sensitivity, rust prevention, flexibility, resolution and storage stability can be obtained at a practically satisfactory level and in a well-balanced manner.
Further, when a group having a strong electron-withdrawing property is bonded to the carbazole skeleton, the charge of — C ═ N — of the oxime group involved in the conjugation with the carbazole skeleton is biased toward the C side, and therefore, it is presumed that the N — O bond of the oxime group is easily broken, and the storage stability is deteriorated. Therefore, the group bonded to the carbazole skeleton is preferably a group having a weak electron-withdrawing property. Therefore, from the viewpoint of storage stability, the group Y of the formula (4)4Preferably a group having a weak electron-withdrawing property, more preferably-Y of the formula (6)5-(Y6)nThe groups shown. Examples of the group having a low electron-withdrawing property include an alkyl group, a hydroxyl group, and an amino group. Specific examples of the compound represented by the formula (4) or (6) include 3-cyclohexyl-1- (6- (2- (benzoyloxyimino) octanoyl) -9-ethyl-9H-carbazol-3-yl) -propane-1, 2-dione-2- (O-benzoyl oxime) (TR-PBG-371 manufactured by Nikken ケムテック, product name), and the like.
The content of the oxime compound having an absorption coefficient at 365nm in the ethanol solution of 17mL/(mg · cm) to 60mL/(mg · cm) in the photosensitive resin composition is preferably 0.05 to 5% by mass, more preferably 0.1 to 3% by mass, and even more preferably 0.1 to 1% by mass, based on the mass of the photosensitive resin composition, from the viewpoint of the balance among rust resistance, flexibility, resolution, and sensitivity.
In the present embodiment, the photosensitive resin composition may contain, if necessary, an oxime compound having an absorption coefficient at a wavelength of 365nm of 17mL/(mg · cm) to 60mL/(mg · cm) in an ethanol solution, an oxime compound having an absorption coefficient at a wavelength of 365nm of less than 17mL/(mg · cm) or more than 60mL/(mg · cm) in an ethanol solution, or a photopolymerization initiator other than an oxime compound.
The total content of all photopolymerization initiators in the photosensitive resin composition is preferably 0.1 to 10% by mass based on the mass of the photosensitive resin composition, and more preferably 0.3 to 5% by mass from the viewpoint of sensitivity and resolution. When the content of the photopolymerization initiator is in the range of 0.1 to 10% by mass, the photosensitivity becomes sufficient, and the absorption of the surface of the composition increases when the actinic ray is irradiated, so that it is possible to suppress problems such as insufficient internal photocuring.
[ anti-rust agent (D) ]
The rust inhibitor according to the present embodiment is a compound having a rust-preventing effect, and is, for example, a substance that prevents corrosion or rust of a metal by forming a coating on the surface of the metal.
As the rust inhibitor, from the viewpoint of compatibility and sensitivity in the photosensitive resin composition described in the present embodiment, a heterocyclic compound containing N, S, O or the like is preferable, and examples thereof include tetrazole and a derivative thereof, triazole and a derivative thereof, imidazole and a derivative thereof, indazole and a derivative thereof, pyrazole and a derivative thereof, imidazoline and a derivative thereof, oxazole and a derivative thereof, isoxazole and a derivative thereof, oxadiazole and a derivative thereof, thiazole and a derivative thereof, isothiazole and a derivative thereof, thiadiazole and a derivative thereof, thiophene and a derivative thereof, and the like. The derivatives described herein include compounds obtained by introducing a substituent into the parent structure. For example, the tetrazole derivative includes a compound having a substituent introduced into tetrazole. The substituent is not particularly limited, and examples thereof include substituents containing one or more functional groups having hetero atoms such as a hydrocarbon group (which may be saturated or unsaturated, linear or branched, and may have a cyclic structure) or a hydroxyl group, a carbonyl group, a carboxyl group, an amino group, an amide group, a nitro group, a cyano group, a thiol group, and a halogen (e.g., fluorine, chlorine, bromine, and iodine) group.
Further, from the viewpoint of rust prevention, the heterocyclic compound is preferably a compound having a heterocyclic ring composed of C and N and/or S, and the number of N atoms in the same heterocyclic ring is 3 or less, or the number of S atoms is 3 or less, or the total number of N atoms and S atoms is 3 or less, more preferably triazole and its derivative, imidazole and its derivative, imidazoline and its derivative, thiazole and its derivative, isothiazole and its derivative, thiadiazole and its derivative, thiophene and its derivative, and the like, and further preferably benzotriazole and its derivative, and imidazole and its derivative, from the viewpoint of rust prevention and developability. The use of the component (D) having good developability reduces the sagging of the formed pattern, and the application of the protective film of the present invention to the terminal portion is more preferable in terms of securing conduction.
Specific examples of compounds having a heterocyclic ring composed of C and N and/or S, in which the number of N atoms in the same heterocyclic ring is 3 or less, or the number of S atoms is 3 or less, or the total number of N atoms and S atoms is 3 or less are shown below:
triazole: for example, 1,2, 3-triazole, 1,2, 4-triazole, etc.;
triazole derivatives: for example, 3-mercaptotriazole, 3-amino-5-mercaptotriazole, benzotriazole, 1H-benzotriazole-1-acetonitrile, 1- [ N, N-bis (2-ethylhexyl) aminomethyl ] benzotriazole, 1- (2-di-N-butylaminomethyl) -5-carboxybenzotriazole, 1- (2-di-N-butylaminomethyl) -6-carboxybenzotriazole, 1H-benzotriazole-1-methanol, 5-methyl-1H-benzotriazole, 5-carboxybenzotriazole, 1-hydroxybenzotriazole, 5-chlorobenzotriazole, 5-nitrobenzotriazole and the like;
imidazole;
imidazole derivatives: such as undecylimidazole, benzimidazole, 5-carboxybenzimidazole, 6-bromobenzimidazole, 5-chlorobenzimidazole, 2-hydroxybenzimidazole, 2- (1-hydroxymethyl) benzimidazole, 2-methylbenzimidazole, 5-nitrobenzimidazole, 2-phenylbenzimidazole, 2-aminobenzimidazole, 5-amino-2-mercaptobenzimidazole, etc.;
imidazoline;
imidazoline derivatives: such as 2-undecylimidazoline, 2-propyl-2-imidazoline, 2-phenylimidazoline, etc.;
a thiazole;
thiazole derivatives: for example, 2-amino-4-methylthiazole, 5- (2-hydroxyethyl) -4-methylthiazole, benzothiazole, 2-mercaptobenzothiazole, 2-aminobenzothiazole, 2-amino-6-methylbenzothiazole, (2-benzothiazolylthio) acetic acid, 3- (2-benzothiazolylthio) propionic acid, etc.;
isothiazole;
isothiazole derivatives: such as 3-chloro-1, 2-benzisothiazole, etc.;
thiadiazole: such as 1,2, 3-thiadiazole, 1,2, 5-thiadiazole, 1,3, 4-thiadiazole, and the like;
thiadiazole derivatives: such as 4-amino-2, 1, 3-benzothiadiazole, 2-amino-5-mercapto-1, 3, 4-thiadiazole, 2-amino-5-methyl-1, 3, 4-thiadiazole, 2-amino-1, 3, 4-thiadiazole, 5-amino-1, 2, 3-thiadiazole, 2-mercapto-5-methyl-1, 3, 4-thiadiazole and the like;
thiophene;
thiophene derivatives: such as 2-thiophenecarboxylic acid, methyl 3-amino-2-thiophenecarboxylate, 3-methylbenzothiophene, and the like.
Among the above rust inhibitors, benzotriazole, 5-carboxybenzotriazole, 1-hydroxybenzotriazole and 5-chlorobenzotriazole are particularly preferable from the viewpoint of rust inhibition and developability.
On the other hand, as the component (D), tetrazole and its derivative, triazole and its derivative, indazole and its derivative, and thiadiazole and its derivative are preferable from the viewpoint of rust prevention and adhesion.
Specific examples of the tetrazole include 1H-tetrazole.
Specific examples of the tetrazole derivative include 5-amino-1H-tetrazole, 5-methyl-1H-tetrazole, 1-methyl-5-ethyl-1H-tetrazole, 1-methyl-5-mercapto-1H-tetrazole, 1-phenyl-5-mercapto-1H-tetrazole, 1- (dimethylaminoethyl) -5-mercapto-1H-tetrazole, and 5-phenyl-1H-tetrazole.
Specific examples of indazoles include 1H-indazole.
Examples of the indazole derivative include 5-aminoindazole, 6-aminoindazole, 1-benzyl-3-hydroxy-1H-indazole, 5-bromoindazole, 6-hydroxyindazole, 3-carboxyindazole and 5-nitroindazole.
Specific examples of triazole and derivatives thereof, and thiadiazole and derivatives thereof are as described above.
Among these, 5-amino-1H-tetrazole, 5-carboxybenzotriazole, 5-aminoindazole, and 5-amino-1, 2, 3-thiadiazole are particularly preferable from the viewpoint of rust prevention and adhesion.
When the highly reactive photopolymerization initiator as in the present invention is used, the photosensitive resin composition is cured and shrunk by exposure or heat treatment, and stress is generated between the cured film and the substrate, so that there is a problem that the adhesion between the cured film and the substrate is deteriorated. However, by using the component (C) shown in the present embodiment in combination with the component (D) which is preferable from the viewpoint of rust prevention and adhesion, sensitivity, rust prevention, bendability, resolution, storage stability, and adhesion can be expressed at a practically satisfactory level in a well-balanced manner.
In the present embodiment, 1 kind of the rust inhibitor described above may be used alone, or 2 or more kinds may be used in combination.
From the viewpoint of rust prevention and developability, the content of the rust inhibitor in the photosensitive resin composition is preferably 0.05 to 10 mass%, more preferably 0.1 to 5 mass%, and even more preferably 0.2 to 3 mass%, based on the mass of the photosensitive resin composition.
< E) silane coupling agent >
In the present embodiment, the photosensitive resin composition preferably contains a silane coupling agent from the viewpoint of adhesion to a substrate, rust prevention, and developability. Examples of the silane coupling agent include 3-glycidoxypropylmethyldimethoxy (or ethoxy) silane (KBM-402, KBE-402, product name, manufactured by shin-Etsu chemical Co., Ltd.), 3-glycidoxypropyltrimethoxy (or ethoxy) silane (KBM-403, KBE-403, product name, manufactured by shin-Etsu chemical Co., Ltd.), 3-methacryloxypropylmethyldimethoxy (or ethoxy) silane (KBM-502, KBE-502, product name, manufactured by shin-Etsu chemical Co., Ltd.), 3-methacryloxypropyltrimethoxy (or ethoxy) silane (KBM-503, KBE-503, product name, manufactured by shin-Etsu chemical Co., Ltd.), and 3-aminopropyltrimethoxy (or ethoxy) silane (KBM-903, manufactured by shin chemical Co., Ltd.), KBE-903, product name), tris (trimethoxysilylpropyl) isocyanurate (KBM-9659, product name, manufactured by shin-Etsu chemical Co., Ltd.), 3-mercaptopropylmethyldimethoxysilane (KBM-802, product name, manufactured by shin-Etsu chemical Co., Ltd.), 3-mercaptopropyltrimethoxysilane (KBM-803, product name, manufactured by shin-Etsu chemical Co., Ltd.), 2- [3- (triethoxysilyl) propyl ] succinic anhydride, 3-trimethoxysilylpropyl succinic anhydride (X-12-967C, manufactured by shin-Etsu chemical Co., Ltd.), and the like.
The content of the silane coupling agent in the photosensitive resin composition is preferably 0.1 to 5% by mass, more preferably 0.5 to 3% by mass, based on the mass of the photosensitive resin composition, from the viewpoint of adhesion to a substrate, rust prevention, and developability.
< amine Compound >
In the present embodiment, in order to further improve the effect of the (D) rust inhibitor, the photosensitive resin composition preferably contains an amine compound. Examples of the amine compound include ammonia, ethylenediamine, triethylenetetramine, monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, triisopropanolamine, diethylenetriamine, diethylamine, dibutylamine, hexahydroaniline, tetraethylenepentamine, pentaethylenehexamine, allylamine, 2-aminopropanol, 3-aminopropanol, 4-aminobutanol, 4-methylaminobutanol, ethylaminoethylamine, 2-ethylhexylamine, di-2-ethylhexylamine, tris (2-ethylhexyl) amine, oleylamine, dodecylamine, dicyclohexylamine, octylamine, octadecylamine, and hexylamine. These amine compounds may be used alone in 1 kind, or in combination of 2 or more kinds. Among these amine compounds, dibutylamine is particularly preferable.
The content of the amine compound in the photosensitive resin composition is preferably 0.05 to 3 mass%, more preferably 0.1 to 2 mass%, based on the mass of the photosensitive resin composition, from the viewpoint of rust prevention.
< other ingredients >
In the present embodiment, the photosensitive resin composition may contain a polymerization inhibitor such as an aluminum salt to which 3 moles of nitrosophenylhydroxylamine is added, a leveling agent, a plasticizer, a filler, an antifoaming agent, a flame retardant, and the like, in addition to the components (a) to (F), and these may be used alone or in combination of 2 or more.
< photosensitive resin layer >
The photosensitive resin layer of the present embodiment preferably has a thickness of 15 μm or less, and the absorbance of the photosensitive resin layer at a wavelength of 365nm is 0.01 to 0.05 per 1 μm of the thickness of the photosensitive resin layer. Since the flexibility is deteriorated when the film thickness of the photosensitive resin layer is too thick, the thickness of the photosensitive resin layer is preferably 15 μm or less, and is preferably 3 μm or more from the viewpoint of following the unevenness of the wiring and the viewpoint of ensuring the rust-proof property. When the absorbance of the photosensitive resin layer is high, the surface curing is promoted, the rust-proofing property is improved as described above, the curing of the bottom portion is not excessively progressed, and the bendability can be maintained, so that the absorbance of the photosensitive resin layer is preferably 0.01 or more, while when the absorbance of the photosensitive layer is excessively high, the curing of the bottom portion becomes excessively weak, and the adhesion to the substrate is deteriorated, and therefore, it is preferably 0.05 or less.
< details of the photosensitive resin laminate >
The photosensitive resin laminate comprises: a photosensitive resin layer formed from the photosensitive resin composition, and a support film. Specifically, a layer formed of the photosensitive resin composition is laminated on a support film. The photosensitive resin laminate may have a protective layer on the surface of the photosensitive resin layer opposite to the support film side, if necessary.
The support film used in this embodiment is desirably a transparent material that transmits light emitted from the exposure light source. Examples of such a support film include a polyethylene terephthalate film, a polyvinyl alcohol film, a polyvinyl chloride film, a vinyl chloride copolymer film, a polyvinylidene chloride film, a vinylidene chloride copolymer film, a polymethyl methacrylate copolymer film, a polystyrene film, a polyacrylonitrile film, a styrene copolymer film, a polyamide film, a film made of cellulose or a derivative thereof, and the like. These films may also be stretched films as required. The haze of the support film is preferably 5 or less. The smaller the thickness of the support film, the better the resolution and the economical efficiency, but the thickness is preferably 10 μm to 30 μm in order to maintain the strength.
Regarding the adhesion force to the photosensitive resin layer, the adhesion force of the protective layer is sufficiently smaller than the adhesion force of the support film, and the protective layer can be easily peeled off. As the protective layer, for example, a polyethylene film, a polypropylene film, or the like can be preferably used. Further, as the protective layer, a film excellent in releasability as shown in jp 59-202457 a may be used. The thickness of the protective layer is preferably 10 to 100 μm, more preferably 10 to 50 μm.
The method for producing a photosensitive resin laminate comprises: the method for producing a photosensitive resin film includes a step of applying a coating liquid to a support (for example, a support film) and drying the coating liquid, and a step of laminating a protective layer on the photosensitive resin layer as necessary. The coating liquid can be obtained by uniformly dissolving the photosensitive resin composition described above in a solvent.
Examples of the solvent for dissolving the photosensitive resin composition include ketones such as Methyl Ethyl Ketone (MEK); alcohols typified by methanol, ethanol, and isopropanol. The solvent is preferably added to the photosensitive resin composition so that the solution viscosity of the photosensitive resin composition applied to the support becomes 10 to 800 mPas at 25 ℃. Examples of the coating method include a blade coating method, a meyer bar coating method, a roll coating method, a screen coating method, a spin coating method, an inkjet coating method, a spray coating method, a dip coating method, a gravure coating method, a curtain coating method, and a die coating method. The drying conditions of the coating liquid are not particularly limited, and the drying temperature is preferably 50 to 130 ℃ and the drying time is preferably 30 seconds to 30 minutes.
In the present embodiment, the photosensitive resin laminate is preferably used for forming a protective film for the conductor portion, and in this case, the conductor portion is more preferably a copper electrode, an alloy electrode of copper and nickel, or a transparent electrode. More specifically, the photosensitive resin laminate can be used as a protective film for lead-out wiring in the edge region of a touch panel (touch sensor or pressure sensor) or a protective film for copper electrodes in the sensing region.
[ resin Pattern and cured film Pattern and method for producing the same ]
When the resin pattern is formed using the photosensitive resin laminate, the resin pattern can be formed by a method for manufacturing a resin pattern including the steps of: a laminating step of laminating the photosensitive resin laminate on a substrate; an exposure step of exposing the laminated photosensitive resin laminate; and a developing step of developing the exposed photosensitive resin laminate. Further, in order to use the resin pattern as a protective film for the conductor portion, the method for producing the resin pattern preferably includes the steps of: and a step of subjecting the resin pattern to post-exposure treatment and/or heating treatment after the developing step to form a cured film pattern.
An example of a specific method is shown below. As the substrate, a substrate in which copper wiring is formed on a flexible copper clad laminate; a touch panel substrate or a touch sensor substrate (e.g., a pressure sensor) in which a transparent electrode (e.g., ITO, Ag nanowire substrate, etc.) or a metal electrode (e.g., Cu, Al, Ag, Ni, Mo, and an alloy of at least 2 of these, etc.) is formed on a glass substrate or a transparent resin substrate. The flexible copper-clad laminate, the substrate for forming a touch panel electrode, or the substrate for forming a touch sensor electrode is a substrate in which a copper layer, a transparent electrode, or a metal layer serving as a raw material of a metal electrode is formed on a flexible film. Examples of the film include films formed from film materials such as polyimide, polyester (PET, PEN), and cycloolefin polymer (COP). The thickness of the film is preferably 10 to 100. mu.m. As the copper, an alloy containing copper as a main component may be used in addition to pure copper. Here, "main component" means that at least 50 mass% of the alloy is copper. Examples of the alloy metal include alloys of copper and nickel, palladium, silver, titanium, molybdenum, and the like. The thickness of the copper layer is preferably 50nm to 2 μm. The thickness of the copper layer is more preferably 100nm or more from the viewpoint of uniformity of the copper layer.
By performing the step of laminating the photosensitive resin laminate on the substrate as described above, a photosensitive resin layer is formed on the copper layer of the substrate. When the photosensitive resin laminate has a protective layer, it is preferable that the photosensitive resin laminate is heat-pressed against the surface of the substrate by a laminator after the protective layer is peeled off and laminated. In this case, the photosensitive resin laminate may be laminated on only one surface of the substrate, or may be laminated on both surfaces. The heating temperature is generally about 40 ℃ to 160 ℃. The heat-pressure bonding may be performed using a two-stage laminator provided with two rollers, or may be performed by repeatedly passing the photosensitive resin laminate and the substrate through the rollers a plurality of times. Further, when the vacuum laminator is used, the protective film has good conformability to irregularities caused by wiring on the substrate, and the defect that air is mixed between the photosensitive resin laminate and the substrate can be prevented.
Next, an exposure process is performed using an exposure machine. If necessary, the support film is peeled off from the photosensitive resin laminate, and the photosensitive resin layer is exposed to active light through a photomask. The exposure amount is determined by the illuminance of the light source and the exposure time. The exposure amount may be measured using a light meter. Examples of the exposure machine include a scattered light exposure machine using an ultra-high pressure mercury lamp as a light source, a parallel light exposure machine in which parallelism is adjusted, and a proximity exposure machine in which a pitch is provided between a mask and a workpiece. Further, as the exposure machine, a projection type exposure machine in which the size ratio of the mask to the image is 1:1, a reduction projection exposure machine called ステッパー (registered trademark) with high illuminance, or an exposure machine using a concave lens called ミラープロジェクションアライナ (registered trademark) may be cited.
In the exposure step, a direct writing exposure method may be used. Direct writing exposure is a method of directly writing and exposing on a substrate without using a photomask. As the light source, for example, a solid laser, a semiconductor laser, or an ultra-high pressure mercury lamp having a wavelength of 350nm to 410nm can be used. The drawing pattern is controlled by a computer. The exposure amount at this time is determined according to the illuminance of the light source and the moving speed of the substrate.
Next, a developing process is performed using a developing device. After exposure, when the support film is present on the photosensitive resin layer, the support film is removed as necessary, and then the unexposed portions are developed and removed with a developer containing an alkali aqueous solution, thereby obtaining a resin pattern. As the aqueous alkali solution, Na is preferably used2CO3Or K2CO3Aqueous solution (alkaline aqueous solution). The alkali aqueous solution is appropriately selected depending on the characteristics of the photosensitive resin layer, but is usually about 0.2 to 2 mass% in concentration and about 20 to 40 ℃ in Na2CO3An aqueous solution. The aqueous alkali solution may contain a surfactant, a defoaming agent, a small amount of an organic solvent for promoting development, and the like. In consideration of the influence on the substrate, an aqueous amine base such as a tetramethylammonium hydroxide (TMAH) aqueous solution may be used. The concentration of the alkali compound in the aqueous solution can be appropriately selected according to the developing speed. Na of 1 mass% and 30 to 35 ℃ is particularly preferable from the viewpoint of reducing odor, excellent handleability, and easy management and post-treatment2CO3An aqueous solution. Examples of the developing method include known methods such as alkali water spraying, showering, shaking dipping, brushing, and scraping.
After the development, the alkali in the aqueous alkali solution remaining on the resin pattern may be subjected to an acid treatment (neutralization treatment) by a known method such as spraying, swing dipping, brushing, or scraping using an organic acid, an inorganic acid, or an aqueous acid solution thereof. Further, after the acid treatment (neutralization treatment), a water washing step may be performed.
A resin pattern can be obtained through the above steps, and a post-exposure step and/or a heating step can be further performed. By performing the post-exposure step and/or the heating step, the rust prevention property is further improved. The exposure amount in the post-exposure treatment is preferably 200mJ/cm2～1000mJ/cm2In the heating step, the treatment is preferably performed at 40 to 200 ℃, and the heating time is preferably 60 minutes or less from the viewpoint of the production process. As a method of heat treatment, a heating furnace of an appropriate method such as hot air, infrared ray, far infrared ray and the like can be used, and as an atmosphere of heat treatment, N can be mentioned2Under atmosphere or N2/O2Under an atmosphere.
According to the present embodiment, a photosensitive resin composition and a photosensitive resin laminate which are excellent in a balance among rust resistance, flexibility, resolution, and sensitivity and suitable for protecting a conductor portion such as a wiring or an electrode can be provided. Such a photosensitive resin laminate is suitable as a protective film for, for example, a touch panel, a wiring for a touch sensor or a pressure sensor, an electrode, or the like.
Touch panel display device, device having touch sensor or pressure sensor
By forming the cured film of the photosensitive resin laminate according to the present embodiment on a substrate for a touch panel, a touch panel display device having the cured film of the photosensitive resin laminate and a touch sensor and/or a pressure sensor can be provided.
Examples of the substrate for a touch panel include substrates generally used for a touch panel, a touch sensor, and a pressure sensor, such as a glass plate, a plastic film, and a ceramic plate. The substrate may be provided with electrodes or metal wirings for a touch panel of ITO, Cu, Al, Ag, Ni, Mo, an alloy containing at least 2 of these, or the like, which is an object of forming a protective film, and an insulating layer may be provided between the substrate and the electrodes.
The substrate for a touch panel having the electrode for a touch panel can be obtained, for example, by the following steps. After a metal film is formed on a substrate for a touch panel such as a polyester film or a COP film in the order of ITO and Cu by a sputtering method, a photosensitive film for etching is attached to the metal film to form a desired resist pattern, unnecessary Cu is removed by an etching solution such as an iron chloride aqueous solution, and the resist pattern is further peeled off and removed.
The method for forming a cured film as a protective film on a substrate for a touch panel preferably comprises the following steps in this order: a first step of laminating the photosensitive resin laminate of the present embodiment on a substrate for a touch panel; a second step of curing a specific portion of the protective film by irradiation with active light; a 3 rd step of removing a specific portion of the protective film (a portion of the protective film not irradiated with the active light) to form a cured product of the patterned protective film; and a 4 th step of exposing and/or heat-treating the patterned protective film.
By producing the substrate for a touch panel having the cured film pattern of the photosensitive resin laminate as described above, a touch panel display device having the cured film of the photosensitive resin laminate or a device having the cured film of the photosensitive resin laminate and a touch sensor and/or a pressure sensor can be suitably provided.
Examples
The present invention will be specifically described based on the following examples, but the present invention is not limited thereto.
First, a method for measuring the absorption coefficient of an initiator is shown. Next, the methods for producing the evaluation films of examples 1 to 38 and comparative examples 1 to 6 will be described, and the evaluation methods and evaluation results of the obtained films will be shown.
1. Method for measuring absorption coefficient of initiator
100mg of each initiator described in Table 1 below was weighed by a precision balance and dissolved in 100mL of ethanol. After the initiator was completely dissolved, 10mL of the solution was collected and diluted 10-fold with ethanol using a 100mL measuring flask. The diluted solution was similarly diluted 10-fold again to obtain a 1mg/100mL solution. The 1mg/100mL solution was put into a quartz cuvette having an optical path length of 1cm of the sample and placed on the measurement side, and the quartz cuvette into which ethanol was put was placed on the reference side, and the absorbance was calculated from the measurement value by a spectrophotometer (U-3010) manufactured by Hitachi ハイテクノロジーズ K.K. The results are shown in Table 1.
2. Production of film for evaluation
The evaluation films in examples and comparative examples were produced as follows.
< production of photosensitive resin laminate >
A photosensitive resin composition liquid preparation was obtained by sufficiently stirring and mixing a photosensitive resin composition having the composition shown in tables 2 to 6 below (wherein the number of each component represents the amount of solid content (parts by mass)) and a solvent. A photosensitive resin composition preparation was uniformly applied to the surface of a 16 μm-thick polyethylene terephthalate film (R310-16B, manufactured by Mitsubishi resin corporation) as a support film by means of a blade coater, and dried in a 95 ℃ dryer for 3 minutes to form a uniform photosensitive resin layer on the support film. The film thicknesses of the support film and the sample having the uniform photosensitive resin layer formed thereon were measured using a table thickness gauge (RC-1W-200/1000) manufactured by Minkoku corporation, and the thickness of the photosensitive resin layer was calculated by subtracting the film thickness of the support film from the film thickness of the sample having the uniform photosensitive resin layer formed thereon, and as a result, the thickness of the photosensitive resin layer was 10 μm. Subsequently, a 33 μm-thick polyethylene film (GF-858, manufactured by タマポリ K) was attached as a protective film to the surface of the photosensitive resin layer to obtain a photosensitive resin laminate. The names of the material components in the photosensitive resin composition blend liquids shown in tables 2 to 6 by short are shown in table 7.
3. Absorbance measurement of photosensitive resin layer
The polyethylene film of the obtained photosensitive resin laminate was peeled off using a spectrophotometer (U-3010) manufactured by Hitachi ハイテクノロジーズ K.K., and the resultant was placed on the measurement side in a state where the support and the photosensitive resin layer were laminated, and the absorbance (365nm) of the photosensitive resin laminate was measured with the support film placed on the reference side. The measured values were divided by the film thickness, and the absorbance per 1 μm of the film thickness was shown in tables 2 to 4.
4. Sensitivity and resolution evaluation
< method for preparing sample >
While the protective film of the photosensitive resin laminate was peeled off, the resultant was laminated on the copper surface of a substrate, on which a resin, ITO and sputtered copper were sequentially laminated, at a roll temperature of 100 ℃ by means of a hot roll laminator (manufactured by Kasei ラミネーター Co., Ltd., VA-400 III). The air pressure was set to 0.4MPa and the lamination speed was set to 1.0 m/min. After leaving the film for 15 minutes, a PET mask and a Schwark 21-stage exposure scale (a stage exposure scale in which the optical density of 0.00 is the 1 st stage and the optical density of each 1 stage is increased by 0.15) were placed side by side on a support film, and the PET mask and the stage exposure scale were exposed to an optimum exposure amount for each composition by a parallel light exposure machine (HMW-801, manufactured by Kabushiki Kaisha オーク). As the PET mask, a mask having a pattern in which an unexposed portion exhibits a circular hole was used. After leaving the mixture for at least 15 minutes, the support film of the photosensitive resin laminate was peeled off, and 1% by mass Na was sprayed at 35 ℃ for 60 seconds with a developing spray pressure of 0.07MPa by a full cone nozzle using a developing device manufactured by Fuji Press Ltd2CO3The unexposed portion of the photosensitive resin layer is dissolved and removed by developing with an aqueous solution. At this time, the water washing step was performed at the same time as the developing step with a water washing spray pressure of 0.07MPa through a flat nozzle, and the washed sample was dried by air blowing to form a pattern for evaluation. The optimum exposure amount is: through the above processing, when exposure is performed by means of a schleph 21-level exposure scale, the level of residual film reaches 8-9 levels of exposure.
< evaluation method >
Sensitivity of
The optimum exposure dose obtained by the sample preparation method is classified as follows, and is summarized in tables 2 to 4. The protective film is preferably a C-class or higher protective film.
A: the optimum exposure amount is 30mJ or less
B: the optimum exposure amount is more than 30mJ and 60mJ or less
C: the optimum exposure amount is more than 60mJ and less than 90mJ
D: the optimal exposure is more than 90mJ
Resolution of
The sample preparation method described above was performed to rank the resolution as described below using the minimum round hole mask diameter, on which the round hole pattern was normally formed, as a value of the resolution, and the results are summarized in tables 2 to 4. The protective film is preferably a B-class or higher protective film.
A: the resolution value is more than 70 μm and 80 μm or less
B: the resolution exceeds 80 μm and is 100 μm or less
C: resolution values in excess of 100 μm
5. Evaluation of bending resistance
< method for preparing sample >
The photosensitive resin laminate was cut into 2cm × 20cm, and exposed from the support film side with exposure amounts of the respective compositions by a scattered light exposure machine (HMW-201 KB, manufactured by オーク Co., Ltd.). After leaving the mixture for 15 minutes, the protective film was peeled off from the photosensitive resin laminate, and the development, washing with water, and drying steps were performed by the same method as the method for producing the sensitivity/resolution evaluation sample. Thereafter, the photosensitive layer was exposed to a scattered light exposure machine at a rate of 350mJ/cm2The exposure was carried out at the exposure dose of (1), and then, the substrate was treated in a hot air circulation oven at 150 ℃ for 30 minutes. The prepared samples were subjected to humidity control at 23 ℃ and 50% RH for 1 day, and then tested
< evaluation method >
As shown in fig. 1, the photosensitive resin layer of the sample (1) thus produced was bent outward at 90 ℃ for 1 to 2 seconds with a cylindrical mandrel (2) of a fixed specific diameter Φ as a fulcrum, and the same operation was repeated a specific number of times with this operation set to 1. Thereafter, with respect to the sample (1), the presence or absence of peeling and cracking of the photosensitive resin layer was observed with a microscope, and the classification was performed as follows. The results are shown in tables 2 to 4. The protective film is preferably a C-class or higher protective film.
A: bending 10 times with 0.5mm phi core rod without cracks and peeling
B: bending with 0.5mm phi core rod for 1 time without crack and peeling
C: bending 10 times with a 1mm phi core rod without cracks and peeling
D: bending 10 times with 2mm phi core rod without cracks and peeling
6. Evaluation of rust inhibitive Property
< preparation of test base >
As described in example 2 of japanese patent No. 4515123, a photosensitive resin laminate was produced, and the photosensitive resin laminate was laminated on a copper surface of a flexible substrate having a size of 5cm × 10cm, on which resin, ITO, and sputtered copper were sequentially laminated, by a hot roll laminator while peeling off the protective film. At this time, the roller temperature was set to 100 ℃, the air pressure was set to 0.4MPa, and the lamination speed was set to 1.5 m/min. After leaving the mixture for 15 minutes, a PET mask was placed on the support film, and the support film was exposed to light at 120mJ/cm with a parallel light exposure machine from the PET mask side2And (6) carrying out exposure. The PET mask used a pattern with a line width/pitch of 80 μm/80 μm. After leaving the mixture for at least 15 minutes, the support film was peeled off from the photosensitive resin laminate, and 1% by mass of Na at 30 ℃ was sprayed at a developing spray pressure of 0.15MPa using a full cone nozzle at a developing spray pressure of 0.15MPa for a period of 2 times the minimum developing time using a developing apparatus manufactured by Fuji Press2CO3And dissolving and removing the unexposed part of the photosensitive resin layer by using an aqueous solution. Here, the minimum development time means: a minimum time required until the unexposed portion of the photosensitive resin composition layer is completely dissolved and removed. At this time, the water washing step was performed at the same time as the developing step with a water washing spray pressure of 0.15MPa through a flat nozzle, and the washed sample was dried by air blowing to form a resist pattern on the copper surface.
Next, the substrate on which the resist pattern was formed was etched by a dipping method in an aqueous solution having a hydrochloric acid concentration of 2 mass% and ferrous chloride of 2 mass% at a liquid temperature of 30 ℃ for 1.5 times the minimum etching time. Thereafter, water washing and air drying treatment were performed. Here, the minimum etching time means: the minimum time required for the copper foil on the substrate to be completely dissolved and removed under the above conditions.
After the etching, the substrate was immersed in a 3 mass% NaOH aqueous solution at a liquid temperature of 50 ℃, and the resist layer was removed by an immersion method, followed by water washing and air drying. Thus, a test substrate was obtained in which ITO was laminated on a resin, and a copper wiring pattern was further formed on the ITO layer. To describe the copper wiring pattern in more detail, the line width: the pitch was 1:1 to form 10 copper wires having a length of 8cm and a width of 80 μm.
< method for preparing sample >
The surface of the substrate having the copper wiring formed thereon, which was produced by the above-described method, on which the copper wiring was present was laminated by using a hot roll laminator (manufactured by Kagaku ラミネーター Co., Ltd., VA-400III) while peeling the protective films of the photosensitive resin laminates of examples 1 to 38 and comparative examples 1 to 3. At this time, the roller temperature was set to 100 ℃, the air pressure was set to 0.4MPa, and the lamination speed was set to 1.0 m/min. After leaving for 15 minutes, the resist was exposed to the optimum exposure amount for each composition from the support film side of the resist over the entire surface by a scattered light exposure machine. After leaving the mixture for 15 minutes, the support film was peeled from the photosensitive resin laminate, and 1% by mass Na was added at 35 ℃ under a developing spray pressure of 0.07MPa using a developing device manufactured by Fuji Kogyo Co., Ltd, using a full cone nozzle2CO3The aqueous solution was sprayed for 60 seconds to develop the photosensitive resin layer, and the unexposed portions of the photosensitive resin layer were dissolved and removed. At this time, the water washing step was performed at the same time as the developing step with a water washing spray pressure of 0.07MPa by a flat nozzle, and the washed sample was dried by air blowing. Thereafter, the photosensitive layer was exposed to a scattered light exposure machine at a rate of 350mJ/cm2The sample was exposed to light at the exposure level of (1), and then treated in a hot air circulation oven at 150 ℃ for 30 minutes to prepare a sample for evaluation.
< evaluation method >
Acidic artificial sweat described in JIS L0848 was dropped on the copper wire of the prepared evaluation sample, and then stored in a constant temperature and humidity oven (アドバンテック, manufactured by toyoyo co., ltd., THN050FA) at 85 ℃ and 85% RH. After a predetermined time had elapsed, the sample was taken out of the oven, and the surface of the protective film and the opposite surface of the protective film were observed with a microscope to confirm the presence or absence of discoloration or corrosion of the copper wiring, and the copper wiring was classified as follows. The results are shown in tables 2 to 4. The protective film is preferably a D-class or higher protective film.
A: the color change or corrosion occurs after more than 144 hours under the environment of 85 ℃ and 85% RH
B: discoloration or corrosion occurs in an atmosphere of 85 ℃ and 85% RH for 120 hours or more and less than 144 hours
C: discoloration or corrosion occurs in an atmosphere of 85 ℃ and 85% RH for 96 hours or more and less than 120 hours
D: discoloration or corrosion occurs in an atmosphere of 85 ℃ and 85% RH for 72 hours or more and less than 96 hours
E: discoloration or corrosion occurs in an environment of 85 ℃ and 85% RH for less than 72 hours
7. Evaluation of storage stability
< method for preparing sample >
For examples 29 to 32 and comparative example 4, 2 photosensitive resin laminates of 20cm × 30cm were prepared, 1 of the laminates was stored in a constant temperature and humidity oven (LH 21-11M, manufactured by ナガノサイエンス K.) at 50 ℃ and 60% RH for 3 days, and the other was stored at room temperature for 3 days to obtain two samples. Then, these photosensitive resin laminates were laminated on the copper surface of a substrate on which a resin, ITO and sputtered copper were sequentially laminated, using a hot roll laminator (manufactured by ラミネーター, VA-400III) while peeling the protective film of the photosensitive resin laminate. At this time, the roller temperature was set to 100 ℃, the air pressure was set to 0.4MPa, and the lamination speed was set to 1.0 m/min. After leaving the film for 15 minutes, the film was exposed from the support film side of the protective film through a Schmuth 21 stage exposure scale by a scattered light exposure machine. At this time, both samples were exposed together with the optimum exposure amount of the photosensitive resin laminate stored at room temperature for 3 days. After leaving the mixture for 15 minutes, the support film was peeled from the photosensitive resin laminate, and 1% by mass Na was added at 35 ℃ under a developing spray pressure of 0.07MPa using a developing device manufactured by Fuji Kogyo Co., Ltd, using a full cone nozzle2CO3The aqueous solution was sprayed for 60 seconds to develop the photosensitive resin layer, and the unexposed portions of the photosensitive resin layer were dissolved and removed. At this time, the water washing step was carried out at the same time as the developing step with a water washing spray pressure of 0.07MPa by a flat nozzle, and passedThe water washed sample was dried by air blowing.
< evaluation method >
The residual film numbers of the schwarfare 21-level exposure scale of each sample obtained by the above sample preparation method were read, and the difference between the residual film numbers of the samples stored at room temperature for 3 days and the samples stored at 50 ℃ and 60% RH was classified as follows, and the results are shown in table 5. In the case of class A, the practical performance does not change even if the sample is stored at room temperature for a long period of time, and there is no problem. In the case of class B, if the storage is not performed for a long period of time, the sensitivity changes, which causes a practical problem. In the case of using a photosensitive resin laminate industrially, the photosensitive resin laminate can be stably used even in the B-stage when it is stored in a refrigerated state, but the a-stage is more preferable from the viewpoint of management cost and energy.
A: the difference of the residual film grade is below 3 grades
B: the difference of the residual film grade is more than 3 grades
8. Length of circular hole pattern lower hem
< evaluation method >
As the PET mask, a circular hole pattern was obtained by the sample production method described in "4. evaluation of sensitivity and resolution" using a circular hole mask having a diameter of 100 μm and having an unexposed portion formed into a circular hole. The circular hole pattern was enlarged to 5000-fold with a scanning electron microscope (S-3400N, manufactured by Hitachi ハイテクノロジーズ K.K.), and the bottom of the circular hole pattern was observed. The observation results were ranked as follows. The number of stages is shown in Table 5. The length of the skirt is measured as the distance along the surface of the base plate from the side wall surface of the circular hole to the end of the skirt. The a-stage or B-stage is preferable as the protective film.
A: the length of the circular hole is less than 2.0 μm
B: the length of the circular hole is more than 2.0 μm and less than 3.0 μm
C: the length of the circular hole is more than 3.0 mu m
9. Evaluation of adhesion
< method for preparing sample >
Samples were produced in the same manner as in < sample production method > of "6. evaluation of rust resistance", except that the substrate was changed to a substrate in which resin, ITO, and sputtered copper were laminated in this order, and the protective film of the photosensitive resin laminate obtained in examples 33 to 38 and comparative examples 5 and 6 was peeled off and laminated on the copper surface.
< evaluation method >
Using the prepared sample, a cross cutting test was performed in the following manner in accordance with a method based on JIS K-5600-5-6 for an evaluation process not particularly mentioned. The sample was scribed with 10 scratches in parallel with a guide cutter blade at 1mm intervals, and 10 scratches were scribed perpendicularly thereto so as to form a grid pattern. After an adhesive tape (セロテープ (registered trademark) manufactured by ニチバン co., ltd., product name) having a width of 15mm was pressure-bonded to the lattice-shaped scratched portion, the adhesive tape was peeled off at an angle of 60 ° with respect to the pressure-bonded surface for 0.5 to 1 second. The surface of the sample from which the adhesive tape was peeled was observed with an optical microscope and classified as follows. The results are shown in Table 6. The a-stage or B-stage is preferable as the protective film.
A: the area of the protective film peeled from the copper surface of the substrate was less than 10%.
B: the area of the protective film peeled from the copper surface of the base material is 10% or more and less than 20%.
C: the area of the protective film peeled from the copper surface of the base material is 20% or more.
10. Evaluation results
As shown in tables 2 to 6, it is understood that the initiators and rust inhibitors described in the present embodiment are used in examples 1 to 38, and the rust inhibitors, corrosion inhibitors, bendability, sensitivity and resolution required for the protective film are excellent in the evaluation results of examples 1 to 38 and comparative examples 1 to 6. On the other hand, in comparative examples 1 to 3 which did not contain the initiator or the rust inhibitor according to the present embodiment, the results were that any of the rust-preventive property, the bendability, the sensitivity, and the resolution was poor, comparative example 4 showed the result of the difference in the skirt length of the circular hole pattern, and comparative examples 5 and 6 showed the result of the poor adhesion.
It will be clear that, if described in more detail: in comparison with example 17, the photosensitive resin composition of comparative example 1 did not contain an oxime initiator having an absorption coefficient at 365nm in ethanol of 17 mL/(mg. cm) to 60 mL/(mg. cm), and thus comparative example 1 was inferior in all of the performances of rust prevention, flexibility, sensitivity and resolution. Furthermore, it can be seen that: comparative example 2 is inferior in rust prevention, bendability, and sensitivity for the same reason as in example 13. Further, it is clear that: in comparison with example 21, the photosensitive resin composition of comparative example 3 does not contain a rust inhibitor, and therefore is inferior in terms of rust prevention.
From a comparison of example 2 with example 3, it can be seen that: the photosensitive resin composition contains an amine compound, thereby improving rust resistance. Then, from a comparison of example 6 with example 7, it can be seen that: the photosensitive resin composition has improved rust resistance by adding a silane coupling agent. In addition, by comparing example 17 with example 18, it can be seen that: rust prevention and bendability are improved by using an alkali-soluble resin having an aromatic group in a side chain. On the other hand, from a comparison of example 1 with example 4, it can be seen that: by containing the component (D) having 3 or less N and/or S in the same heterocycle in the photosensitive resin composition, the rust-proofing property is improved. Further, when example 22, example 23 and example 24 were compared, it was found that: among the (D) components having 3 or less N and/or S in the same heterocycle, benzotriazole and its derivatives are preferable from the viewpoint of rust prevention. Further, when example 17 is compared with example 19, it is found that: among the benzotriazole and its derivatives and imidazole and its derivatives listed above as preferred rust inhibitors, a photosensitive resin composition containing 5-carboxybenzotriazole as one particularly preferred example is more excellent in terms of rust inhibition. It is to be noted that, from a comparison between example 20 and example 21: the photosensitive resin layer can have more excellent rust prevention properties by adjusting the absorbance at 365nm to 0.01 to 0.05 per 1 μm of the film thickness.
Further, when example 29 is compared with example 30, it is found that: by containing the component (C) represented by the formula (4) in the photosensitive resin composition, the balance of the performance of the rust prevention property and the bending resistance is improved, and further the storage stability is improved. In addition, when comparative example 4 was compared with example 32, it was confirmed that: by adding the component (D) to the photosensitive resin composition, the sag of the circular hole pattern is reduced. Furthermore, when example 32 is compared with examples 30 and 31, it can be confirmed that: by using benzotriazole or a derivative thereof listed above as the component (D) which is preferable from the viewpoint of developability, the developability is improved and the run-down of the circular hole pattern is made smaller. Further, when comparative examples 5 and 6 are compared with examples 33 to 38, it is understood that: by adding the component (D) to the photosensitive resin composition, the adhesion is improved. Furthermore, from the comparison of example 36 with examples 33 to 35 or the comparison of example 38 with example 37, it can be confirmed that: when tetrazole and its derivative, triazole and its derivative, indazole and its derivative, and thiadiazole and its derivative are added to the photosensitive resin composition as the component (D), the adhesion is further improved.
[ Table 1]
Figure BDA0001190434340000371
[ Table 2]
Figure BDA0001190434340000381
[ Table 3]
Figure BDA0001190434340000391
[ Table 4]
Figure BDA0001190434340000401
[ Table 5]
TABLE 5
Figure BDA0001190434340000411
[ Table 6]
TABLE 6
Figure BDA0001190434340000421
[ Table 7]
TABLE 7
Figure BDA0001190434340000431

Claims (21)

1. A photosensitive resin composition for forming a protective film of a conductor part, comprising the following components:
(A) an alkali-soluble resin;
(B) a compound having an ethylenically unsaturated double bond;
(C) a photopolymerization initiator; and
(D) the rust inhibitor, not including the case consisting of only 1-hydroxybenzotriazole,
and an oxime compound having an absorption coefficient at 365nm in an ethanol solution of 17 mL/(mg. cm) to 60 mL/(mg. cm) is contained as component (C),
the photosensitive resin composition for forming a protective film of a conductor part contains, as the component (D), a compound having a heterocyclic ring composed of a carbon (C) atom and a nitrogen (N) atom and/or a sulfur (S) atom, and having, in the same heterocyclic ring, 3 or less N atoms, 3 or less S atoms, or 3 or less total number of N atoms and S atoms,
the content of the component (C) in the photosensitive resin composition for forming the protective film of the conductor part is 0.05-5 mass%, and the content of the component (D) in the photosensitive resin composition for forming the protective film of the conductor part is 0.05-10 mass%.
2. The photosensitive resin composition according to claim 1, wherein the photosensitive resin composition for forming a protective film of the conductor part contains at least 1 compound selected from the group consisting of benzotriazole, benzotriazole derivatives, imidazole and imidazole derivatives as the component (D).
3. The photosensitive resin composition according to claim 2, wherein the photosensitive resin composition for forming a protective film of the conductor part contains benzotriazole or a benzotriazole derivative as the component (D).
4. The photosensitive resin composition according to claim 1, wherein the photosensitive resin composition for forming a protective film of the conductor part contains at least 1 compound selected from the group consisting of triazole, triazole derivatives, tetrazole derivatives, thiadiazole derivatives, indazole, and indazole derivatives as the component (D).
5. The photosensitive resin composition according to claim 4, wherein the photosensitive resin composition for forming a protective film of the conductor part contains triazole or a triazole derivative as the component (D).
6. The photosensitive resin composition according to claim 4, wherein the photosensitive resin composition for forming a protective film of the conductor part contains tetrazole or a tetrazole derivative as the component (D).
7. The photosensitive resin composition according to claim 4, wherein the photosensitive resin composition for forming a protective film of the conductor part contains thiadiazole or a thiadiazole derivative as the component (D).
8. The photosensitive resin composition according to claim 4, wherein the photosensitive resin composition for forming a protective film of a conductor part contains indazole or an indazole derivative as the component (D).
9. The photosensitive resin composition according to claim 1, wherein the photosensitive resin composition for forming a protective film of the conductor part comprises a compound represented by the following formula (4) as a component (C),
formula (4)
Figure FDA0002403082880000021
In the formula (4), X4And X5Each independently represents a monovalent organic group, at least one of which has a structure represented by the following formula (5), and Y4Represents H or a 1-valent organic group,
formula (5)
Figure FDA0002403082880000022
10. The photosensitive resin composition according to claim 9, wherein the photosensitive resin composition for forming a protective film of the conductor part comprises a compound represented by the following formula (6) as a component (C),
formula (6)
Figure FDA0002403082880000031
In the formula (6), Y5Is H, -CH3An aliphatic hydrocarbon group having 2 or more carbon atoms, or an alicyclic hydrocarbon group having 3 or more carbon atoms and optionally substituted with a hetero atom or/and a halogen atom; n is an integer of 0 or 1; y is5Is H or-CH3When n is 0; y is5When the alkyl group is an aliphatic hydrocarbon group having 2 or more carbon atoms or an alicyclic hydrocarbon group having 3 or more carbon atoms and optionally having a heteroatom or/and a halogen atom, n is 1; and Y is6Represents H or a 1-valent organic group.
11. The photosensitive resin composition according to claim 1, wherein the photosensitive resin composition for forming a protective film of a conductor part comprises a compound represented by the following formula (1) and/or a compound represented by the following formula (2) as a component (C),
Figure FDA0002403082880000032
in the formula (1), X1Represents a 1-valent group containing a heterocyclic ring optionally having a substituent; y is1Represents a substituent selected from the group consisting of an alkyl group having 1 to 8 carbon atoms which optionally forms a branched structure or a ring structure, and a phenyl group which optionally has a substituent; and Z is1Represents a 1-valent organic group, and a compound represented by the formula,
Figure FDA0002403082880000033
in the formula (2), X2And X3Represent the same or different electron withdrawing groups; y is2And Y3Identical or different, Y2And Y3Represents a substituent selected from the group consisting of an alkyl group having 1 to 10 carbon atoms which optionally forms a branched structure or a ring structure, and a phenyl group which optionally has a substituent; and Z is2Represents a 2-valent group selected from the group consisting of an alkylene group having 1 to 16 carbon atoms and an optionally substituted phenylene group.
12. The photosensitive resin composition according to claim 11, wherein the photosensitive resin composition for forming a protective film of the conductor part comprises X in the formula (1)1A compound having a 1-valent group represented by the following formula (3) as the component (C),
Figure FDA0002403082880000041
in formula (3), A represents an oxygen (O) atom or an S atom.
13. The photosensitive resin composition according to claim 1, wherein the photosensitive resin composition for forming a protective film of the conductor part comprises an alkali-soluble resin having an aromatic group in a side chain as the component (a).
14. The photosensitive resin composition according to claim 1, wherein the photosensitive resin composition for forming a protective film of the conductor part comprises (E) a silane coupling agent.
15. The photosensitive resin composition according to claim 1, wherein the photosensitive resin composition for forming a protective film of the conductor part comprises (F) an amine compound.
16. A photosensitive resin laminate comprising: a support film, and a photosensitive resin layer formed on the support film and comprising the photosensitive resin composition for a protective film of a conductor part according to any one of claims 1 to 15.
17. A photosensitive resin laminate according to claim 16, wherein the thickness of the photosensitive resin layer is 15 μm or less, and the absorbance of the photosensitive resin layer at a wavelength of 365nm is 0.01 to 0.05 per 1 μm of the thickness.
18. A method for producing a pattern, comprising the step of forming a pattern by laminating the photosensitive resin laminate according to claim 16 or 17 on a substrate, exposing the laminate to light, and developing the exposed laminate.
19. A cured film pattern manufacturing method, comprising:
a step of forming a pattern by laminating the photosensitive resin laminate according to claim 16 or 17 on a substrate, and exposing and developing the laminate; and
and a step of subjecting the pattern to post-exposure treatment and/or heat treatment to cure the pattern.
20. A cured film produced by the cured film pattern production method according to claim 19.
21. A touch panel display device, a device having a touch sensor, or a device having a pressure sensor,
the apparatus includes the cured film produced by the cured film pattern production method according to claim 19.
CN201611208215.8A 2015-12-25 2016-12-23 Photosensitive resin composition, photosensitive resin laminate, method for producing resin pattern and cured film pattern, and display device Active CN106918995B (en)

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