JP7162448B2 - Photosensitive resin composition, transfer film using photosensitive resin composition, method for producing resin pattern, and method for producing cured film pattern - Google Patents

Description

TECHNICAL FIELD The present invention relates to a photosensitive resin composition, a transfer film, a method for producing a resin pattern using the transfer film, and a method for producing a cured film pattern. More specifically, the present invention relates to the formation of flattening films, protective films, and interlayer insulating films of electronic components such as liquid crystal display devices, organic EL display devices, touch panel display devices, integrated circuit devices, solid-state imaging devices, and semiconductor devices, or The present invention relates to a photosensitive resin composition suitable for rigid printed wiring boards, solder resists for flexible printed wiring boards, or interlayer insulating films, a transfer film, and a method for producing a resin pattern using the same.

2. Description of the Related Art In recent years, as electronic devices have become more sophisticated, diversified, and reduced in size and weight, the number of devices equipped with a transparent touch panel (touch sensor) on the entire surface of a display element such as liquid crystal has increased. Characters, symbols, patterns, and the like displayed on a display element are visually recognized and selected through a transparent touch panel, and each function of the device is switched by operating the transparent touch panel. Touch panels are used not only in large electronic devices such as personal computers and televisions, but also in small electronic devices such as car navigation systems, mobile phones, electronic dictionaries, and display devices such as OA/FA equipment. An electrode made of material is provided. As transparent conductive electrode materials, ITO (Indium-Tin-Oxide), indium oxide and tin oxide are known. These materials have high visible light transmittance and are therefore used as electrode materials for substrates for liquid crystal display elements and the like. is mainly used as

Existing touch panel methods include resistive film method, optical method, pressure method, capacitance method, electromagnetic wave induction method, image recognition method, vibration detection method, ultrasonic method, etc. Various methods have been put into practical use. ing. In recent years, the use of capacitive touch panels has been most advanced. In a capacitive touch panel, when a fingertip, which is a conductor, contacts the touch input surface, capacitive coupling occurs between the fingertip and the conductive film to form a capacitor. Therefore, the capacitive touch panel detects the coordinates of the contact position by capturing the change in electric charge at the contact position of the fingertip. In particular, projected capacitive touch panels are capable of multi-point detection of fingertips, and have excellent operability that allows complicated instructions to be given. It is being used more and more as an input device on the display screen of equipment having such a device. Generally, in a projected capacitive touch panel, in order to express two-dimensional coordinates by the X axis and the Y axis, a plurality of X electrodes and a plurality of Y electrodes orthogonal to the plurality of X electrodes have a two-layer structure. and ITO is used as the electrode material.

Since the frame area of the touch panel is an area where the touch position cannot be detected, narrowing the area of the frame area is an important factor for improving the product value. A metal wiring is required in the frame area to transmit a touch position detection signal, and the width of the metal wiring must be narrowed in order to narrow the frame area. Since the conductivity of ITO is not high enough, copper or alloys are generally used for metal wiring.

However, in the touch panel as described above, corrosive components such as moisture and salt may enter the inside from the sensing area when the touch panel is touched by a fingertip. If corrosive components enter the interior of the touch panel, the metal wiring will corrode, increasing the electrical resistance between the electrodes and the drive circuit, or breaking the wire. is required. In general, the lower the moisture permeability of the protective film, the higher the antirust effect of the metal wiring.

In addition, since the metal wiring for transmitting the detection signal is connected to other members at the terminal portion, it is necessary to ensure continuity, and the protective film must be removed from the terminal portion. Therefore, the protective film is required to have good developability and to have good removal properties in various patterns such as circular holes. As a developer, a dilute alkaline aqueous solution such as an aqueous sodium carbonate solution is most often used, and development at a low temperature of less than 30° C. is desired in order to maintain long-term stability of developer concentration.

Furthermore, in the touch panel manufacturing process, a load may be applied to the touch panel itself. In particular, when a protective film is provided on a flexible display substrate, the bending of the substrate increases the load on the protective film, and cracks and peeling of the protective film are likely to occur. As an example of the manufacturing process for forming a protective film on a touch panel, there is a method in which a photosensitive film is laminated on a base material, exposed, developed, post-exposed and heat-treated in this order. After going through the heat treatment process, the adhesion of the protective film is improved, but the adhesion and film strength of the film after development and post-exposure are weak, and it cannot withstand the load in the manufacturing process described above. Film cracking and delamination from the substrate are often problems. Therefore, there is a demand for a protective film that suppresses corrosion of metal wiring and has adhesiveness and film strength such that the post-exposure film after development can withstand the bending and impact of the substrate during the manufacturing process.

Patent Documents 1 to 3 are listed as protective films for touch panels.
Patent Literature 1 discloses a photosensitive resin composition as a protective film for a touch panel and evaluates moisture permeability, but does not describe adhesion, film strength, and developability.
Patent Document 2 discloses a photosensitive resin composition using a photopolymerizable compound containing butylene oxide in the molecule as a protective film for a touch panel. However, no mention is made of the adhesion and strength of the film after exposure (after development), and the level of rust prevention required in recent years is not satisfied.
Patent Document 3 describes a photosensitive resin composition using an epoxy acrylate acid-modified product having a ring structure in the main chain. However, there is no description about moisture permeability, adhesion, and strength.

JP 2016-157451 A WO2016/047691 JP 2009-251286 A

As described above, the techniques described in Patent Documents 1 to 3 still have room for improvement. Therefore, the problem to be solved by the present invention is to improve the developability, the moisture permeability as a cured film, the adhesion of the exposed film after development and the film strength to the conductor substrate, and the protection of the conductor part such as the electrode. It is to provide a photosensitive resin composition, a transfer film, and a method for producing the same suitable for .

｛式中、Ｗ_Ａ－１、・・・Ｗ_Ａ－ｎは、前記重合体Ａ－１、・・・Ａ－ｎの重量平均分子量をそれぞれ表し、Ｘ_Ａ－１、・・・Ｘ_Ａ－ｎは、前記重合体Ａ－１、・・・Ａ－ｎの感光性樹脂組成物中の質量％をそれぞれ表す。｝で算出される前記（Ａ）成分の重量平均分子量が６，０００～２０，０００であり、
前記（Ｂ－ii）成分を前記感光性樹脂組成物の固形分全質量に対して３質量%以上含有し、かつ、
支持体上に前記感光性樹脂組成物にて３０μｍ厚みの感光性樹脂層を積層した転写フィルムを形成し、該転写フィルムを、６ｍｍφの開口部を有する基板上にラミネートした後に全面露光して露光膜を形成した後、該支持体を剥がし、前記開口部の中心に対応する部分を、１．５ｍｍφの円柱で速度１００ｍｍ／ｍｉｎで突き刺し試験を行った際の最大点荷重が３５ｇｆ以上であることを特徴とする感光性樹脂組成物。
［２］
前記（Ｂ－ｉ)成分が、下記式（２）：

｛式中、Ｙ_１、Ｙ_２はそれぞれ独立に（メタ）アクリロイル基を表し、ｎは２～３０の整数を示す。｝で表される化合物を含む、［１］に記載の感光性樹脂組成物。
［３］
前記（Ｂ－ii)成分として、１分子中に芳香環を複数有する化合物を少なくとも１種含む、［１］または［２］に記載の感光性樹脂組成物。
［４］
前記（Ａ）成分として、（Ａ－ii）酸性基を有し、エチレン性不飽和基を有さないアルカリ可溶性重合体を含む、［１］～［３］のいずれかに記載の感光性樹脂組成物。
［５］
前記（Ｂ－ｉ）成分を、前記感光性樹脂組成物の固形分全質量に対して３質量%～１５質量％含有する、［１］～［４］のいずれかに記載の感光性樹脂組成物。
［６］
前記（Ａ－ｉ）成分として、（Ａ－iii）重量平均分子量が６，０００以上であり、酸価が６０～１２０ｍｇＫＯＨ／ｇのエチレン性不飽和基及び酸性基を有し、主鎖に環構造を含む重合体を、前記（Ａ）成分の固形分全質量に対して９０質量％以上含有する、［５］に記載の感光性樹脂組成物。
［７］
前記（Ａ）成分として、（Ａ－iv）重量平均分子量１０，０００～３６，０００であり、酸価１３０～１５０ｍｇＫＯＨ／ｇの酸性基を有し、エチレン性不飽和基を有さないアルカリ可溶性重合体を含有する、［５］または［６］に記載の感光性樹脂組成物。
［８］
（Ｄ）１分子中に少なくとも２つのメルカプト基を有するチオール化合物をさらに含む、［１］～［７］のいずれかに記載の感光性樹脂組成物。
［９］
前記（Ｃ）成分がオキシム化合物である、［１］～［８］のいずれかに記載の感光性樹脂組成物。
［１０］
支持フィルムと、該支持フィルム上に設けられた［１］～［９］のいずれかに記載の感光性樹脂組成物から成る感光性樹脂層と、を備える転写フィルム。
［１１］
導体用保護膜に使用される、［１０］に記載の転写フィルム。
［１２］
基材上に、［１１］に記載の転写フィルムをラミネートし、露光し、そして現像することによりパターンを作製する、パターン製造方法。
［１３］
［１２］に記載の方法で得られた上記パターンを後露光処理、及び／又は加熱処理して得られた 硬化膜パターン。
［１４］
［１３］に記載の硬化膜パターンを有するタッチパネル表示装置又はタッチセンサを有する装置。 The present inventors have conducted intensive studies to solve the above problems, and found that an alkali-soluble polymer having a specific structure and weight-average molecular weight and a photopolymerizable compound having a specific structure and a defined content. The inventors have found that the above problems can be solved by forming a combined photosensitive resin composition.
That is, the present invention is as follows.
[1]
Ingredients for:
(A) an alkali-soluble polymer having an acidic group,
(B) a photopolymerizable compound, and (C) a photopolymerizable initiator, a photosensitive resin composition,
As the component (A), (Ai) a polymer having an ethylenically unsaturated group and an acidic group and containing a ring structure in the main chain,
As the component (B), (Bi) a compound having at least two ethylenically unsaturated groups and containing butylene oxide in its structure as a repeating unit (excluding compounds corresponding to the component (A)). , and (B-ii) a compound having one ethylenically unsaturated group,
The component (A) comprises at least one polymer A-1, . including the following formula (1):

{Wherein, W _A-1 , . . . , W _A-n represent the weight average molecular weights of the polymers A- ₁ , _{. n} represents the mass % of each of the polymers A-1, . . . An in the photosensitive resin composition. } is 6,000 to 20,000, and the weight average molecular weight of the component (A) calculated by
Containing the component (B-ii) in an amount of 3% by mass or more relative to the total mass of the solid content of the photosensitive resin composition, and
A transfer film is formed by laminating a photosensitive resin layer having a thickness of 30 μm with the above photosensitive resin composition on a support, and the transfer film is laminated on a substrate having an opening of 6 mmφ, and then the entire surface is exposed to light. After the film is formed, the support is peeled off, and the portion corresponding to the center of the opening is subjected to a piercing test with a cylinder of 1.5 mmφ at a speed of 100 mm/min, and the maximum point load is 35 gf or more. A photosensitive resin composition characterized by:
[2]
The (Bi) component has the following formula (2):

{In the formula, Y ₁ and Y ₂ each independently represent a (meth)acryloyl group, and n represents an integer of 2-30. } containing the compound represented by [1].
[3]
The photosensitive resin composition according to [1] or [2], which contains at least one compound having a plurality of aromatic rings in one molecule as the component (B-ii).
[4]
The photosensitive resin according to any one of [1] to [3], comprising (A-ii) an alkali-soluble polymer having an acidic group and no ethylenically unsaturated group as the component (A). Composition.
[5]
The photosensitive resin composition according to any one of [1] to [4], wherein the component (Bi) is contained in an amount of 3% by mass to 15% by mass with respect to the total solid content of the photosensitive resin composition. thing.
[6]
As the component (Ai), (A-iii) has a weight average molecular weight of 6,000 or more, an acid value of 60 to 120 mgKOH/g, an ethylenically unsaturated group and an acidic group, and a ring in the main chain. The photosensitive resin composition according to [5], wherein the polymer containing the structure is contained in an amount of 90% by mass or more based on the total solid content of the component (A).
[7]
As the component (A), (A-iv) an alkali-soluble having a weight average molecular weight of 10,000 to 36,000, an acid value of 130 to 150 mgKOH/g and an acidic group having no ethylenically unsaturated group The photosensitive resin composition according to [5] or [6], containing a polymer.
[8]
(D) The photosensitive resin composition according to any one of [1] to [7], further comprising a thiol compound having at least two mercapto groups in one molecule.
[9]
The photosensitive resin composition according to any one of [1] to [8], wherein the component (C) is an oxime compound.
[10]
A transfer film comprising a support film and a photosensitive resin layer comprising the photosensitive resin composition according to any one of [1] to [9] provided on the support film.
[11]
The transfer film according to [10], which is used as a protective film for conductors.
[12]
A method for producing a pattern, comprising laminating the transfer film of [11] on a substrate, exposing to light, and developing to form a pattern.
[13]
A cured film pattern obtained by post-exposure treatment and/or heat treatment of the pattern obtained by the method according to [12].
[14]
A touch panel display device having the cured film pattern according to [13] or a device having a touch sensor.

According to the present invention, it is possible to provide a photosensitive resin composition and a transfer film which are excellent in developability, moisture permeability as a cured film, adhesion between an exposed film and a conductor substrate after development, and film strength. .

It is a figure which shows the mask pattern used in the Example. FIG. 4 is a diagram showing a copper-clad laminate having openings used in Examples.

EMBODIMENT OF THE INVENTION Hereinafter, the form (it abbreviates as "embodiment" hereafter) for implementing this invention is demonstrated in detail. It should be noted that the present invention is not limited to the following embodiments, and can be modified in various ways within the scope of the gist of the present invention.
<(A) Alkali-soluble polymer having an acidic group>
The alkali-soluble polymer according to the present embodiment is not particularly limited as long as it is a polymer having an acidic group, and the acidic group is preferably a carboxyl group.

(Ai) A polymer having an ethylenically unsaturated group and an acidic group and containing a ring structure in the main chain (Ai) according to the present embodiment is one or more ethylenically unsaturated groups and one Although there are no particular limitations as long as it is a polymer having the above acidic groups and a ring structure in its main chain, for example, an epoxy (meth)acrylate acid-modified product can be preferably used. Here, (meth)acrylate means acrylate and/or methacrylate, and the same applies hereinafter including (meth)acryl.

Examples of ring structures in the main chain include cresol skeleton, phenol skeleton, biphenyl skeleton, naphthalene skeleton, fluorene skeleton, bisphenol A skeleton, bisphenol F skeleton, tricyclodecane skeleton, trisphenolmethane skeleton, tetrakisphenolethane skeleton, and the like. mentioned.

Commercial products of epoxy (meth)acrylate acid-modified products containing a cresol skeleton include CCR-1171H, CCR-1307H, CCR-1309H (manufactured by Nippon Kayaku Co., Ltd.), PR-300 (Showa Denko Co., Ltd.) made) and the like.
Commercial products of epoxy (meth)acrylate modified products containing a phenol skeleton include PCR-1222H, PCR-1173H, PCR-1221H and PCR-1220H (manufactured by Nippon Kayaku Co., Ltd.).
Commercially available epoxy (meth)acrylate acid-modified products containing a biphenyl skeleton include ZCR-1569H, ZCR-1761H, ZCR-1797H and ZCR-1798H (manufactured by Nippon Kayaku Co., Ltd.).

Commercially available epoxy (meth)acrylate acid-modified products containing a naphthalene skeleton include ZCR-1809H, ZCR-1835H and ZCR-1834H (manufactured by Nippon Kayaku Co., Ltd.).
Commercially available epoxy (meth)acrylate acid-modified products containing a fluorenyl skeleton include FCA-954, FCA-293, FCA-506 (manufactured by Nagase ChemteX Corporation) or TR-B201, TR-B202 (Changzhou Strong Electronic Materials company) and the like.
Commercially available epoxy (meth)acrylate acid-modified products containing a bisphenol A skeleton include ZAR-1494H and ZAR-2001H (manufactured by Nippon Kayaku Co., Ltd.).
Examples of commercially available epoxy (meth)acrylate acid-modified products containing a bisphenol F skeleton include ZFR-1491H (manufactured by Nippon Kayaku Co., Ltd.).

Examples of commercial products of acid-modified epoxy (meth)acrylates containing a tricyclodecane skeleton include ZXR-1807H, ZXR-1816H and ZXR-1810H (manufactured by Nippon Kayaku Co., Ltd.).
Commercially available epoxy (meth)acrylate acid-modified products containing a trisphenolmethane skeleton include TCR-1348H, TCR-1323H, TCR-1347H, and TCR-1338H (manufactured by Nippon Kayaku Co., Ltd.). .
Examples of commercially available epoxy (meth)acrylate acid-modified products containing a tetrakisphenolethane skeleton include ZGR-1678H and ZGR-1844H (manufactured by Nippon Kayaku Co., Ltd.).

(Ai) The acid value (mgKOH/g) of the polymer having an ethylenically unsaturated group and an acidic group and containing a ring structure in the main chain is preferably 50-200. The acid value is preferably 200 or less from the viewpoint of reducing the moisture permeability of the cured film of the photosensitive resin composition and improving the rust resistance of the conductor, and 50 or more from the viewpoint of improving the developability of the photosensitive resin composition layer. and more preferably 60 to 120 from the viewpoint of the balance between both performances.
The acid value is measured by potentiometric titration using 0.1 mol/L potassium hydroxide using a Hiranuma automatic titrator (COM-555) manufactured by Hiranuma Sangyo Co., Ltd.

(Ai) The polymer having an ethylenically unsaturated group and an acidic group and containing a ring structure in its main chain preferably has a weight average molecular weight of 1,000 or more and 9,500 or less. The weight-average molecular weight of (Ai) is 1,000 from the viewpoint of the properties of the unexposed film such as tackiness, edge-fuse properties, and cut-chip properties when used as a transfer film, and from the viewpoint of the strength of the exposed film after development. The above is preferable, from the viewpoint of compatibility with other polymerizable compounds such as the developability of the photosensitive resin composition and (A-ii) an alkali-soluble polymer having an acidic group and not having an ethylenically unsaturated group. It is preferably 9,500 or less, more preferably 6,000 or more and 8,000 or less. Here, the tackiness indicates the tackiness when the photosensitive resin composition is used as a transfer film. Problems such as peeling off in an unintended process of the body occur. The edge fuse property is a phenomenon in which a photosensitive resin composition layer protrudes from the end face of the roll when wound into a roll as a transfer film. The cut-chip property is a phenomenon in which chips fly when an unexposed film is cut with a cutter. If the scattered chips adhere to the upper surface of the transfer film or the like, they will be transferred to the mask in the subsequent exposure process or the like, causing defects.

The weight-average molecular weight is measured using gel permeation chromatography (GPC) manufactured by JASCO Corporation under the following conditions. The obtained weight average molecular weight becomes a polystyrene conversion value.
Pump: Gulliver, PU-1580 type Column: Showa Denko Co., Ltd. Shodex (registered trademark) (KF-807, KF-806M, KF-806M, KF-802.5) 4 in series,
Mobile bed solvent: tetrahydrofuran Calibration curve: Calibration curve defined using a polystyrene standard sample {using a calibration curve based on a polystyrene standard sample (Shodex STANDARD SM-105 manufactured by Showa Denko Co., Ltd.)}

(A-ii) Alkali-soluble polymer having an acidic group and no ethylenically unsaturated group (A-ii) according to the present embodiment does not contain an ethylenically unsaturated group and has one or more acidic groups There is no particular limitation as long as it is a polymer having a A carboxyl group-containing polyimide, a carboxyl group-containing urethane resin, and the like are included. An acrylic copolymer is preferable from the viewpoint of compatibility with the photopolymerizable compound (B) described below and transparency.

・Acrylic copolymer The acrylic copolymer contained in component (A-ii) is obtained by polymerizing at least one monomer containing an acidic group in the molecule, and other acidic groups described later. Those obtained by copolymerizing with at least one monomer having no are preferred.
Examples of monomers containing acidic groups include (meth)acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, maleic anhydride, and maleic acid esters.

Examples of monomers having no acidic group include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl ( meth)acrylate, tert-butyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, (meth)acrylonitrile, acetic acid vinyl alcohol esters such as vinyl; (meth)acrylic acid aromatic esters such as benzyl (meth)acrylate; styrene and its polymerizable derivatives;

Among these copolymers, from the viewpoint of reducing moisture permeability and improving the rust resistance of conductors, structural units derived from (meth)acrylic acid and (meth)acrylic acid aromatic esters or styrene and derivatives thereof A copolymer containing a structural unit is more preferred.
By copolymerizing the unit having an aromatic group, the hydrophobicity of the acrylic copolymer is increased, and the antirust property is improved. In addition, it is believed that the presence of an aromatic group in the acrylic copolymer increases the film density of the cured photosensitive resin composition, thereby improving the rust prevention of the conductor. In terms of achieving both developability and moisture permeability reduction, the acrylic copolymer contains 7.7% by mass or more and 30% by mass or less of a structure derived from (meth)acrylic acid, and 30% by mass of a structure derived from styrene or a derivative thereof. It is more preferable to contain at least 80% by mass or less.

• Polyimide Precursor The polyimide precursor contained in component (A-ii) does not mean only polyamic acid, but also includes partially imidized polyamic acid.

A polyimide precursor can be obtained, for example, by mixing and reacting a tetracarboxylic dianhydride and a diamine in an organic solvent at a molar ratio of 0.8:1 to 1.2:1. The tetracarboxylic dianhydride to be used is not limited, and conventionally known tetracarboxylic dianhydrides can be used. As the tetracarboxylic dianhydride, an aromatic tetracarboxylic acid, an aliphatic tetracarboxylic dianhydride, or the like can be applied. Moreover, the diamine to be used is not limited, and conventionally known diamines can be used.

Tetracarboxylic dianhydrides include biphenyl-3,3′,4,4′-tetracarboxylic dianhydride, benzophenone-3,3′,4,4′-tetracarboxylic dianhydride, oxydiphthalic dianhydride, anhydride, diphenylsulfone-3,3',4,4'-tetracarboxylic dianhydride, ethylene glycol bis (trimellitic monoester anhydride), p-phenylene bis (trimellitic monoester anhydride) ), p-biphenylene bis (trimellitic monoester anhydride), m-phenylene bis (trimellitic monoester anhydride), o-phenylene bis (trimellitic monoester anhydride), pentanediol bis (trimellitic monoester anhydride), decanediol bis (trimellitic monoester anhydride), pyromellitic anhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, 4,4'- (2,2-hexafluoroisopropylidene)diphthalic dianhydride, meta-terphenyl-3,3′,4,4′-tetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic acid dianhydride, bicyclo[2,2,2]oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, cyclobutane-1,2,3,4-tetracarboxylic dianhydride, 1-carboxymethyl-2,3,5-cyclopentatricarboxylic acid-2,6: 3,5-dianhydride, 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3, 4-tetrahydronaphthalene-1,2-dicarboxylic anhydride, and 5-(2,5-dioxotetrahydrofuryl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, etc. . The tetracarboxylic dianhydrides mentioned above may be used alone, or two or more of them may be mixed and used.

Diamines include 1,3-bis(4-aminophenoxy)alkane, 1,4-bis(4-aminophenoxy)alkane, 1,5-bis(4-aminophenoxy)alkane, 1,4-diaminobenzene, 1,3-diaminobenzene, 2,4-diaminotoluene, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 3,3'-dimethyl-4,4'- diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 3,7-diamino-dimethyldibenzothiophene-5, 5-dioxide, 4,4′-diaminobenzophenone, 3,3′-diaminobenzophenone, 4,4′-bis(4-aminophenyl)sulfide, 4,4′-diaminobenzanilide, 1,3-bis(4 -aminophenoxy)-2,2-dimethylpropane, 1,2-bis[2-(4-aminophenoxy)ethoxy]ethane, 9,9-bis(4-aminophenyl)fluorene, 5-amino-1-( 4-aminomethyl)-1,3,3-trimethylindane, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-amino phenoxy)benzene, 4,4'-bis(4-aminophenoxy)biphenyl, 4,4'-bis(3-aminophenoxy)biphenyl, 2,2-bis(4-aminophenoxyphenyl)propane, trimethylene-bis( 4-aminobenzoate), 4-aminophenyl-4-aminobenzoate, 2-methyl-4-aminophenyl-4-aminobenzoate, bis[4-(4-aminophenoxy)phenyl]sulfone, bis[4- (3-aminophenoxy)phenyl]sulfone, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane, 3, 3'-dicarboxy-4,4'-diaminodiphenylmethane, 3,5-diaminobenzoic acid, 3,3'-dihydroxy-4,4'-diaminobiphenyl, and 1,3-bis(4-aminophenoxybenzene ) and the like. For the purpose of imparting appropriate flexibility and folding resistance to the polyimide precursor, a diamine having a siloxane skeleton and/or a diamine having a polyalkylene oxide skeleton may be used in combination.

The main chain end of the polyimide precursor is not particularly limited as long as it has a structure that does not affect the performance, and may be a terminal structure derived from the acid dianhydride or diamine used in producing the polyimide precursor. , other acid anhydrides, or a structure in which the ends are blocked with an amine compound or the like.

A polyimide precursor having a polyimide structure and a polyamic acid structure as repeating units, respectively, is synthesized by reacting an acid dianhydride and a diamine in non-equimolar amounts to synthesize a polyimide portion in the first step (step 1), followed by 2 It can be produced by the step (step 2) of synthesizing the polyamic acid portion of the stage. As a method for producing a polyimide precursor, step 1 may not necessarily be included. Each step will be described below.

(Step 1)
A process for synthesizing the polyimide portion in the first stage will be described. The step of synthesizing the polyimide portion in the first step is not particularly limited, and known methods can be applied. More specifically, the polyimide portion can be synthesized by the following method. First, a diamine is dissolved and/or dispersed in a polymerization solvent, and dianhydride powder is added thereto. Then, a solvent that is azeotropic with water is added, and a mechanical stirrer is used to heat and stir for 0.5 to 96 hours, more preferably 0.5 to 30 hours, while azeotropically removing by-produced water.

The polyimide portion can be synthesized with or without a known imidization catalyst. Examples of imidization catalysts include, but are not limited to, acid anhydrides such as acetic anhydride, γ-valerolactone, γ-butyrolactone, γ-tetronic acid, γ-phthalide, γ-coumarin, and γ-phthalidic acid. and tertiary amines such as pyridine, quinoline, N-methylmorpholine, and triethylamine. Moreover, you may use 1 type, or 2 or more types of these mixtures as needed. Among these, a mixed system of γ-valerolactone and pyridine and no catalyst are particularly preferable from the viewpoint of high reactivity and reduction of influence on the subsequent reaction.

The reaction solvent used in synthesizing the polyimide moiety includes dimethyl ether, diethyl ether, methyl ethyl ether, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, and triethylene glycol dimethyl ether. Ether compounds with 9 or less; Ketone compounds with 2 to 6 carbon atoms such as acetone and methyl ethyl ketone; Normal pentane, cyclopentane, normal hexane, cyclohexane, methylcyclohexane, and 5 or more carbon atoms such as decalin Saturated hydrocarbon compounds having 10 or less carbon atoms; benzene, toluene, xylene, mesitylene, and aromatic hydrocarbon compounds having 6 to 10 carbon atoms such as tetralin; methyl acetate, ethyl acetate, γ-butyrolactone, and , ester compounds having 3 to 12 carbon atoms such as methyl benzoate; chloroform, methylene chloride, and halogen-containing compounds having 1 to 10 carbon atoms such as 1,2-dichloroethane; acetonitrile, N , N-dimethylformamide, N,N-dimethylacetamide, and nitrogen-containing compounds having 2 to 10 carbon atoms such as N-methyl-2-pyrrolidone; and sulfur-containing compounds such as dimethylsulfoxide. These may be used singly or as a mixed solvent of two or more as needed. Particularly preferred solvents include ether compounds having 2 to 9 carbon atoms, ester compounds having 3 to 12 carbon atoms, aromatic hydrocarbon compounds having 6 to 10 carbon atoms, and 2 carbon atoms. Nitrogen-containing compounds having 10 or less carbon atoms are exemplified. These can be arbitrarily selected in consideration of industrial productivity, influence on subsequent reactions, and the like.

In synthesizing the polyimide portion, the reaction temperature is preferably 100° C. or higher and 250° C. or lower.

(Step 2)
Next, the process of synthesizing the polyamic acid moiety in the second step will be described. Synthesis of the polyamic acid moiety in the second stage can be carried out by using the polyimide moiety obtained in step 1 as a starting material, adding a diamine and/or an acid dianhydride, and polymerizing it. The polymerization temperature for synthesizing the polyamic acid moiety in the second step is preferably 0° C. or higher and 80° C. or lower. The time required for the reaction varies depending on the purpose or reaction conditions, but is usually in the range of 30 minutes to 30 hours.

When performing step 2 without performing step 1, first, diamine is dissolved and/or dispersed in a polymerization solvent, and acid dianhydride powder is added thereto. The polymerization solvent is the same as those exemplified in step 1. The polymerization temperature is preferably 0°C or higher and 80°C or lower. The time required for the reaction is usually 30 minutes to 30 hours.

Carboxyl group-containing polyimide A carboxyl group-containing polyimide is synthesized by mixing and reacting a tetracarboxylic dianhydride and a diamine in an organic solvent at a molar ratio of 0.8:1 to 1.2:1. It is characterized by containing a carboxyl group in the skeleton even after the conversion, but the polyamic acid structure may partially remain.

A carboxyl group-containing polyimide is usually synthesized using a carboxyl group-containing diamine. From the viewpoint of solubility in organic solvents or availability, 3,5-diaminobenzoic acid, 3,3'-dicarboxy-4,4'-diaminodiphenylmethane and the like can be used as the carboxyl group-containing diamine. can. These diamines may be used alone or in combination of two or more.

Examples of the tetracarboxylic dianhydride, the diamine used in combination with the carboxyl group-containing diamine, the solvent used for synthesis, and the imidization catalyst are the same as those described above for the polyimide precursor.

Carboxyl group-containing polyurethane The carboxyl group-containing polyurethane according to the present embodiment is prepared by dissolving a diisocyanate compound, a carboxyl group-containing diol compound, and other diol compounds in an aprotic solvent with a known active catalyst according to their reactivity. It is synthesized by adding and heating. The molar ratio of the diisocyanate and the diol compound to be used is preferably 0.8:1 to 1.2:1, and if the isocyanate group remains at the end of the polymer, it can be treated with alcohols or amines to remove the is synthesized in a form in which no isocyanate group remains in the

Diisocyanate compounds include 2,4-tolylene diisocyanate, dimers of 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, p-xylylene diisocyanate, m-xylylene diisocyanate, 4,4′- Aromatic diisocyanate compounds such as diphenylmethane diisocyanate, 1,5-naphthylene diisocyanate, 3,3'-dimethylbiphenyl-4,4'-diisocyanate, etc.: hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate, dimer acid diisocyanate, etc. Aliphatic diisocyanate compounds such as; group diisocyanate compounds; diisocyanate compounds which are reaction products of diols and diisocyanates, such as adducts of 1 mol of 1,3-butylene glycol and 2 mol of tolylene diisocyanate.

Carboxyl group-containing diols include 3,5-dihydroxybenzoic acid, 2,2-bis(hydroxymethyl)propionic acid, 2,2-bis(2-hydroxyethyl)propionic acid, 2,2-bis(3-hydroxy propyl)propionic acid, bis(hydroxymethyl)acetic acid, bis(4-hydroxydiphenyl)acetic acid, 4,4-bis(4-hydroxydiphenyl)pentanoic acid, tartaric acid, N,N-dihydroxyethylglycine, N,N-bis (2-Hydroxyethyl)-3-carboxy-propionamide and the like.

Other diol compounds used in combination with the carboxyl group-containing diol compound include high molecular weight diols such as polytetramethylene diol, polybutadiene diol, hydrogenated polybutadiene diol, polycarbonate diol, polyester diol, and polycaprolactone diol; , 2-propylene glycol, 1,3-propylene glycol, 1,3-butylene glycol, 2,3-butylene glycol, 1,4-butanediol, 2,2′-dimethyl-1,3-propanediol, diethylene glycol, triethylene glycol, 1,5-pentamethylene glycol, dipropylene glycol, neopentyl glycol, 1,6-hexamethylene glycol, cyclohexane-1,4-diol, cyclohexane-1,4-diol, cyclohexane-1,4- dimethanol, 2-butene-1,4-diol, 2,2,4-trimethyl-1,3-pentanediol, xylylene glycol, 1,4-bis-β-hydroxyethoxycyclohexane, tridiclodecane dimethanol, Hydrogenated bisphenol A, hydrogenated bisphenol F, bisphenol A, bisphenol S, hydroquinone dihydroxyethyl ether, p-xylylene glycol, dihydroxyethyl sulfone, bis(2-hydroxyethyl)-2,4-tolylene dicarbamate, 2,4-tolylene-bis(2-hydroxyethylcarbamide), bis(2-hydroxyethyl)-m-xylylene dicarbamate, bis(2-hydroxyethyl) isophthalate, 1,4-bis(β-hydroxyethoxy) Low molecular weight diols such as benzene and bis(β-hydroxyethyl) terephthalate are included.

The acid value (mgKOH/g) of (A-ii) is preferably 60-200. The acid value is preferably 200 or less from the viewpoint of reducing moisture permeability and improving the rust resistance of the conductor, and is 60 or more from the viewpoint of improving the developability, and from the viewpoint of the balance between the rust resistance and low-temperature developability of the conductor. Therefore, it is more preferably 80 to 180, and still more preferably 90 to 160. In addition, the weight average molecular weight of (A) the alkali-soluble polymer having an acidic group is 11,000 to 50, from the viewpoint of coatability, transfer film tackiness, film strength after exposure (after development), and developability. 000 is preferred. The weight-average molecular weight of the alkali-soluble polymer having an acidic group is determined from the viewpoint of the properties of the unexposed film such as tack, edge fuse, and cut-tip properties when used as a transfer film, and the strength of the film after exposure (after development). 11,000 or more from the viewpoint of developability and (Ai) compatibility with a polymer having an ethylenically unsaturated group and an acidic group and containing a ring structure in the main chain is 50,000 or less. is preferred. More preferably, it is 15,000 or more and 30,000 or less. By improving the compatibility, it becomes easier to exhibit strength, developability, and moisture permeability performance.

In addition, (A) an alkali-soluble polymer having an acidic group, which does not correspond to (Ai) or (A-ii) described above, can also be used if necessary. A polymer having one or more ethylenically unsaturated groups and one or more acidic groups and having no ring structure in the main chain can also be used. By adding glycidyl methacrylate to an acrylic copolymer that does not have a ring structure in the main chain, which is obtained by copolymerizing a monomer having a group and a monomer that does not contain an acidic group, an ethylenic group is added to the side chain. A saturated group can be introduced, and a polymer having one or more ethylenically unsaturated groups and one or more acidic groups as described above and having no ring structure in the main chain can be obtained.

｛式中、Ｗ_Ａ－１、・・・Ｗ_Ａ－ｎは、（Ａ）成分に該当する各重合体Ａ－１、・・・Ａ－ｎの重量平均分子量を表し、Ｘ_Ａ－１、・・・Ｘ_Ａ－ｎは（Ａ）成分に該当する各重合体Ａ－１、・・・Ａ－ｎの感光性樹脂組成物中の質量％を表す。｝で算出した重量平均分子量が６，０００～２０，０００である。転写フィルムとした際のタック性、エッジフューズ性、カットチップ性等の未露光膜の性状の観点、現像後の露光膜の強度及び密着性の観点から６，０００以上であり、現像性の観点から２０，０００以下である。より好ましくは、１０，０００以上１５，０００以上である。 On the other hand, the alkali-soluble polymer (A) having an acidic group described above is at least one type of polymer A-1, . . . An ( n represents an integer of 1 or more.) and the following formula (1):

{Wherein, W _{A- 1 ,} . . . . X An represents mass % of each polymer _A -1, . . . An corresponding to component (A) in the photosensitive resin composition. } is 6,000 to 20,000. It is 6,000 or more from the viewpoint of the properties of the unexposed film such as tackiness, edge fuse properties, and cut chip properties when it is made into a transfer film, and from the viewpoint of the strength and adhesion of the exposed film after development, and from the viewpoint of developability. to 20,000 or less. More preferably, it is 10,000 or more and 15,000 or more.

<(B) Photopolymerizable compound>
The (B) photopolymerizable compound according to the present embodiment is a compound having polymerizability due to having an ethylenically unsaturated group in its structure.
(Bi) a compound having at least two ethylenically unsaturated groups and containing butylene oxide in its structure as a repeating unit (excluding compounds corresponding to (A));
(Bi) according to the present embodiment is not particularly limited as long as it is a compound having two or more ethylenically unsaturated groups and containing butylene oxide as a repeating unit in one molecule. When the polymer has an acidic group, it is designated as component (A), and when it further has a ring structure in the main chain of the polymer, it is designated as component (Ai).

(Bi) is a compound having two ethylenically unsaturated groups in one molecule, for example, a compound having (meth)acryloyl groups at both ends of a polybutylene oxide chain, or a polybutylene oxide chain and a polyethylene oxide chain. or/and a compound having (meth)acryloyl groups at both ends of an alkylene oxide chain randomly or block-bonded with a polypropylene oxide chain, or bisphenol A, bisphenol F, or tricyclodecane modified with polybutylene oxide, and Examples thereof include compounds having (meth)acryloyl groups at both ends. In addition, a urethane compound which is a reaction product of a diisocyanate compound, polybutylene glycol, and a compound having a hydroxyl group and a (meth)acrylic group in one molecule can be used.

Further, the component (Bi) having more than two ethylenically unsaturated groups in one molecule has 3 mol or more of a group capable of adding an alkylene oxide group in the molecule as a central skeleton, It is obtained by converting an alcohol obtained by adding a butylene oxide group to a (meth)acrylate. Examples of compounds that can serve as the central skeleton include glycerin, trimethylolpropane, pentaerythritol, diglycerin, ditrimethylolpropane, dipentaerythritol, and isocyanurate rings. By having the (Bi) component and incorporating a butylene oxide chain into the crosslinked structure, the film strength after exposure is increased.

｛式中、Ｙ_１、Ｙ_２はそれぞれ独立に（メタ）アクリロイル基を表し、ｎは２～３０の整数を示す。｝で表される化合物が、透湿度、基材との密着性及び現像後の露光膜の強度の観点で好ましい。ｎが大きいほど膜強度と密着性は向上するが、透湿度が悪化し、それらのバランスの観点から、より好ましくは、ｎは８以上２８以下である。 On the other hand, as the (Bi) component, the following formula (2):

{In the formula, Y ₁ and Y ₂ each independently represent a (meth)acryloyl group, and n represents an integer of 2-30. } is preferable from the viewpoint of moisture permeability, adhesion to the substrate, and strength of the exposed film after development. As n increases, film strength and adhesion improve, but moisture permeability deteriorates.

Commercially available products of formula (2) include FA-PTG9M (manufactured by Hitachi Chemical Co., Ltd., a dimethacrylate to which an average of 9 moles of butylene oxide units are added), FA-PTG28M (manufactured by Hitachi Chemical Co., Ltd., a butylene oxide unit of dimethacrylate with an average addition of 28 mol), A-PTMG-65 (manufactured by Shin-Nakamura Chemical Co., Ltd., a diacrylate with an average addition of 9 mol of butylene oxide units), and the like.

The amount of component (Bi) to be added is preferably 3% by mass to 15% by mass based on the total mass of the solid content of the photosensitive resin composition. From the viewpoint of exposure film strength after development, it is preferably 3% by mass or more, and from the viewpoints of moisture permeability and developability, it is preferably 15% by mass or less.

(B-ii) Compound having one ethylenically unsaturated group In the present embodiment, the component (B-ii), which is a compound having 11 ethylenically unsaturated groups in one molecule, is added to the photosensitive resin composition. It contains 3% or more based on the total solid content. By adding component (B-ii), curing shrinkage of the film after exposure can be reduced, and adhesion to the substrate is improved. 3% or more is preferable from the viewpoint of adhesion, and 15% or less is preferable from the point of maintaining an appropriate crosslink density and not deteriorating moisture permeability. More preferably, it is 4% or more and 10% or less.

As the component (B-ii), a compound obtained by adding (meth)acrylic acid to one end of a polyalkylene oxide, adding (meth)acrylic acid to one end and converting the other end to an alkyl ether or allyl ether and the like. Examples include isostearyl acrylate, lauryl acrylate, 2-phenoxyethyl acrylate, ethoxylated nonylphenyl acrylate, isobornyl acrylate, 4-nonylphenylheptaethylene glycol dipropylene glycol acrylate, and the like. A compound having a plurality of aromatic rings therein is preferred. It is believed that the inclusion of a plurality of aromatic rings increases the hydrophobicity and Tg of the composition, thereby improving the moisture permeability. A structure containing a plurality of condensed benzene rings, such as naphthalene or anthracene, in one molecule is also counted as containing a plurality of aromatic rings. Examples of compounds having multiple aromatic rings in one molecule include m-phenoxybenzyl acrylate (POB-A manufactured by Kyoeisha Chemical Co., Ltd., product name), o-phenylphenoxyethyl acrylate (OPP-1 manufactured by Nippon Kayaku Co., Ltd. product name), 4-methacryloyloxybenzophenone, 1-naphthyl acrylate, and the like.

Photopolymerizable compounds other than (Bi) and (B-ii) described above can also be used as necessary. For example, (Bi) mentioned a photopolymerizable compound having a butylene oxide chain, but not butylene oxide but a compound having (meth)acryloyl groups at both ends of a polyalkylene oxide chain, glycerin, trimethylol Propane, pentaerythritol, diglycerin, ditrimethylolpropane, dipentaerythritol, compounds obtained by converting alcohols obtained by adding a polyalkylene oxide group to an isocyanurate ring, etc., into (meth)acrylates, and A compound directly reacted with (meth)acrylic acid without being modified with an alkylene oxide group can also be used.

<(C) Photopolymerization initiator>
The (C) photopolymerization initiator according to the present embodiment is a compound capable of generating radicals by actinic rays and polymerizing an ethylenically unsaturated group-containing compound or the like. (C) Photopolymerization initiators include, for example, benzophenone, N,N,N',N'-tetramethyl-4,4'-diaminobenzophenone (Mihira-ketone), N,N,N',N'- Tetraethyl-4,4'-diaminobenzophenone, 4-methoxy-4'-dimethylaminobenzophenone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1,2-methyl-1-[ Aromatic ketones such as 4-(methylthio)phenyl]-2-morpholino-propanone-1, acrylated benzophenone, 4-benzoyl-4′-methyldiphenyl sulfide; benzoins such as benzoin methyl ether, benzoin ethyl ether, benzoin phenyl ether ether compounds;
Benzoin compounds such as benzoin, methylbenzoin, ethylbenzoin; 1,2-octanedione, 1-[4-(phenylthio)-, 2-(O-benzoyloxime)], ethanone, 1-[9-ethyl-6- (2-methylbenzoyl)-9H-carbazol-3-yl]-,1-(O-acetyloxime), 1-[4-(phenylthio)phenyl]-3-cyclopentylpropane-1,2-dione-2- (o-benzoyloxime), 1,2-propanedione, 3-cyclohexyl-1-[9-ethyl-6-(2-furanylcarbonyl)-9H-carbazol-3-yl]-, 2-(O- benzyl derivatives such as benzyldimethylketal; acridine derivatives such as 9-phenylacridine and 1,7-bis(9,9′-acridinyl)heptane; N-phenyl such as N-phenylglycine glycine derivatives; coumarin compounds; oxazole compounds; and phosphine oxide compounds such as 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide. A photoinitiator can also be used individually or in mixture of 2 or more types.

Among these, oxime ester compounds are preferable, and compounds having a high molar absorption coefficient at 365 nm are more preferable, from the viewpoints of improving the rust resistance of the conductor, reducing the moisture permeability of the cured film, and improving the chemical resistance. By using an oxime initiator having a high absorption coefficient at a wavelength of 365 nm, a highly sensitive protective film can be obtained by i-line exposure. It is presumed that this provides a high surface curability, suppresses the entry of sodium ions in the developing process, and as a result provides a highly rust-proof conductor.

A specific oxime ester compound is 1,2-octanedione, 1-[(4-phenylthio)phenyl-,2-(O-benzoyloxime)] (manufactured by BASF Japan Ltd., Irgacure Oxe01, product name). , Ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime) (manufactured by BASF Japan Ltd., Irgacure Oxe02), 1 -[4-(Phenylthio)phenyl]-3-cyclopentylpropane-1,2-dione-2-(O-benzoyloxime) (TR-PBG-305 manufactured by Changzhou Power Electronics New Materials Co., Ltd., product name), and 1, 2-propanedione, 3-cyclohexyl-1-[9-ethyl-6-(2-furanylcarbonyl)-9H-carbazol-3-yl]-, 2-(O-acetyloxime) (Changzhou Power Electronics New Materials company TR-PBG-326, product name), (7-nitro-9,9-dipropyl-9H-fluoren-2-yl) (orthotolyl) methanone O-acetyloxime (DFI-020 manufactured by Daito Chemix Co., Ltd.), 1,8-octanedione, 1,8-bis[9-(2-ethylhexyl)-6-nitro-9H-carbazol-3-yl]-, 1,8-bis(O-acetyloxime), 3-cyclohexyl -1-(6-(2-(benzoyloxyimino)octanoyl)-9-ethyl-9H-carbazol-3-yl)-propane-1,2-dione-2-(O-benzoyloxime) (Changzhou strong electron TR-PBG-371 manufactured by New Materials Co., Ltd., product name), 3-cyclohexyl-1-(6-(2-(benzoyloxyimino)hexanoyl)-9-ethyl-9H-carbazol-3-yl)-propane-1 , 2-dione-2-(O-benzoyloxime) (TR-PBG-391 manufactured by Changzhou Yuan Electronics New Materials Co., Ltd., product name).

(C) The content of the photopolymerization initiator in the photosensitive resin composition is 0.1% by mass to 10% by mass based on the total solid content of the photosensitive resin composition, and sensitivity and resolution From the viewpoint of properties, it is more preferably 0.3% by mass to 5% by mass. If the content of the photopolymerization initiator is in the range of 0.1% by mass to 10% by mass, the photosensitivity is sufficient, and the absorption on the surface of the composition increases when irradiating actinic rays. It is possible to suppress problems such as insufficient photocuring of the inside and a decrease in visible light transmittance.

<(D) A thiol compound having at least two mercapto groups in one molecule>
The photosensitive resin composition preferably further contains (D) a thiol compound having at least two mercapto groups in one molecule from the viewpoint of expressing higher film strength and adhesion.
Examples of such compounds include 1,10-decanedithiol, 1,4-bis(mercaptoacetoxy)butane, tetraethylene glycol bis(3-mercaptopropionate), trimethylolpropane trismercaptopropionate, tri Methylolethane trismercaptopropionate, tris-[(3-mercaptopropionyloxy)-ethyl]-isocyanurate, pentaerythritol tetrakis(3-mercaptopropionate), dipentaerythritol hexakis(3-mercaptopropionate) A primary thiol compound having a mercapto group bonded to the fatty chain such as 1,4-(3-mercaptobutyryloxy)butane, 1,3,5-tris(3-mercaptobutyryloxyethyl)-1,3 ,5-triazine-2,4,6-(1H,3H,5H)-trione, trimethylolpropane tris(3-mercaptobutyrate), trimethylolethane tris(3-mercaptobutyrate), pentaerythritol tetrakis(3 -Mercaptobutyrate), a secondary thiol compound in which a mercapto group is bound to a fatty chain; 6-(dibutylamino)-1,3,5-triazine-2,4-dithiol, 6-anilino-1,3, Compounds in which a mercapto group is bound to a heterocyclic ring such as 5-triazine-2,4-dithiol and 1,3,4-thiadiazole-2,5-dithiol; 1,2-benzenedithiol, 1,3-benzenedithiol, Compounds having a mercapto group bonded to an aromatic ring such as 1,4-benzenedithiol, toluene-3,4-dithiol, 4,4'-biphenyldithiol, and 1,5-naphthalene dithiol can be mentioned. (D) The thiol compound which is a component is used individually by 1 type or in combination of 2 or more types. Addition of a thiol compound increases the strength of the film after exposure (after development) and improves adhesion. From the viewpoint of film strength and adhesiveness, one having a mercapto group bonded to the fatty chain is preferred. Furthermore, from the viewpoint of odor and storage stability, secondary thiols are preferred, and commercially available products include Karenz MT PE1, NR1, and BD1 (manufactured by Showa Denko KK).

<(E) Thermal cross-linking agent>
It is preferable to further add (E) a thermal cross-linking agent to the photosensitive resin composition from the viewpoint of exhibiting higher rust prevention performance. (E) The thermal cross-linking agent includes (A) an alkali-soluble polymer having an acidic group, (B) a photopolymerizable compound having an unreacted ethylenically unsaturated double bond, and (E) added at the same time. It means a compound that causes an addition reaction or a condensation polymerization reaction with a thermal cross-linking agent. The temperature at which the addition reaction or condensation polymerization reaction occurs is preferably 100°C to 150°C. The addition reaction or condensation reaction occurs during heat treatment after pattern formation by development.

Specific thermal cross-linking agents include, but are not limited to, blocked isocyanate compounds, diol compounds, epoxy compounds, and thermal cross-linking agents described after paragraph [0054] of WO 2016/047691.

A blocked isocyanate compound is a compound obtained by reacting an isocyanate compound having two or more isocyanate groups in the molecule with a blocking agent.

Examples of isocyanate compounds include 1,6-hexanediisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, xylylene diisocyanate, and 4,4'-dicyclohexylmethane diisocyanate. , 4,4′-hydroxy diisocyanate, isophorone diisocyanate, 1,5-naphthalene diisocyanate, 4,4-diphenyl diisocyanate, 1,3-bis(isocyanatomethyl)cyclohexane, 1,4-phenylene diisocyanate, 2,6-phenylene Diisocyanates, 1,3,6-hexamethylene triisocyanate, and hexamethylene diisocyanate.

Examples of blocking agents include alcohols, phenols, ε-caprolactam, oximes, active methylenes, mercaptans, amines, imides, acid amides, imidazoles, ureas, carbamates, imines, and sulfites.

Specific examples of the blocked isocyanate compound include hexamethylene diisocyanate-based blocked isocyanate (for example, Asahi Kasei Co., Ltd. Duranate SBN-70D, SBB-70P, SBF-70E, TPA-B80E, 17B-60P, MF-B60B, E402- B80B, MF-K60B, and WM44-L70G, Mitsui Chemicals Takenate B-882N, Baxenden 7960, 7961, 7982, 7991, and 7992, etc.), tolylene diisocyanate-based blocked isocyanate (e.g., Mitsui Chemicals ( Co., Ltd. Takenate B-830, etc.), 4,4′-diphenylmethane diisocyanate-based blocked isocyanate (e.g., Mitsui Chemicals Co., Ltd. Takenate B-815N, Taiei Sangyo Co., Ltd. Bronate PMD-OA01, and PMD-MA01 etc.), 1,3-bis(isocyanatomethyl)cyclohexane-based blocked isocyanate (e.g., Mitsui Chemicals Takenate B-846N, Tosoh Corporation Coronate BI-301, 2507, and 2554, etc.), isophorone diisocyanate blocked isocyanates (eg 7950, 7951 and 7990 manufactured by Baxenden); These blocked isocyanate compounds may be used alone or in combination of two or more.

A diol compound refers to a compound containing two hydroxyl groups per molecular chain. Examples of skeletons include those containing hydrocarbon groups such as aliphatic, aromatic, and alicyclic groups.
Specific examples of diol compounds include polytetramethylene diol (e.g., Mitsubishi Chemical Corporation P4TMG650, PTMG850, PTMG1000, PTMG1300, PTMG1500, PTMG1800, PTMG2000, and PTMG3000), polybutadiene diol (e.g., Nippon Soda Co., Ltd.) G-1000, G-2000, and G-3000 manufactured by Nippon Soda Co., Ltd.), hydrogenated polybutadiene diol (eg, GI-1000, GI-2000, and GO-3000 manufactured by Nippon Soda Co., Ltd.), polycarbonate diol (eg, Asahi Kasei Duranol T5651, Duranol T5652, Duranol T4671, Duranol G4672, Duranol G3452, and Duranol G3450J manufactured by Kuraray Co., Ltd., and Kuraray Polyol C-590, Kuraray Polyol C-1090, Kuraray Polyol C-2090, and Kuraray Polyol manufactured by Kuraray Co., Ltd. C-3090, etc.), polycaprolactone diols (e.g., PLAXEL 205PL, PLAXEL 210, PLAXEL 220, PLAXEL 220PL, etc. manufactured by Daicel Corporation), polyester diols (eg, Kuraray Polyol P-530 manufactured by Kuraray Co., Ltd., Kuraray Polyol P-2030, and Kuraray Polyol P-2050, and HS2N-220S manufactured by Toyokuni Oil Co., Ltd.), bisphenols (eg, bisphenol A manufactured by Mitsubishi Chemical Co., Ltd.), and hydrogenated bisphenols (eg, New Japan Rikkainol HB manufactured by Rika Co., Ltd., etc.). These diol compounds may be used alone or in combination of two or more.

(E) The thermal cross-linking agent is preferably a blocked isocyanate compound from the viewpoint of the storage stability of the transfer film and the reduction of the moisture permeability of the cured film. is more preferred.

(E) The content of the thermal cross-linking agent in the photosensitive resin composition is 0.2% by mass to 40% by mass based on the total solid content of the photosensitive resin composition, and developability and low water permeability From the viewpoint of , it is more preferably 1% by mass to 30% by mass, and even more preferably 2% by mass to 20% by mass.

Since the blocked isocyanate compound reacts with the hydroxyl group of the alkali-soluble polymer (A) or the diol compound used in combination in the heat treatment after pattern formation by development, the moisture permeability of the cured film is lowered, and the substrate, electrode, etc. Good rust resistance for protection. Furthermore, cross-linking between the (A) alkali-soluble polymers via a polyfunctional blocked isocyanate compound increases the cross-linking density of the cured film and reduces the diffusivity of water, thereby lowering the moisture permeability of the cured film. It is thought that the corrosion resistance of the conductor is improved. In addition, since the isocyanate group of the blocked isocyanate is blocked with a blocking agent, the reaction with the (A) alkali-soluble resin or diol compound at room temperature is suppressed, and the stability of the photosensitive resin composition and the transfer film is improved. be kept.

Since the diol compound has a hydrophilic hydroxyl group, the developability is improved. Further, in the heat treatment after pattern formation by development, the hydroxyl group of the diol compound reacts with the blocked isocyanate compound, so that excellent rust prevention of the conductor is maintained. The diol compound preferably has a molecular weight of 300 to 3,000, more preferably 500 to 2,000, from the viewpoint of developability. On the other hand, if unreacted hydroxyl groups remain after thermosetting, the moisture permeability of the cured film deteriorates, which may be a factor in impairing the rust prevention performance of the conductor. Accordingly, the diol compound is preferably added so that the hydroxyl value of the photosensitive resin composition is 20 mgKOH/g or less, more preferably 15 mgKOH/g or less. When the hydroxyl value of the photosensitive resin composition is 20 or less, the moisture permeability of the cured product of the photosensitive resin composition can be lowered, thereby improving the rust prevention of the conductor.

<(F) Rosin ester compound>
It is preferable to further add (F) a rosin ester compound to the photosensitive resin composition from the viewpoint of exhibiting lower water permeability. The (F) rosin ester compound according to the present embodiment includes rosin acid, which is a tricyclic diterpenoid having 20 carbon atoms and is a non-volatile component of rosin, a dimer of rosin acid, a hydrogenated product of rosin acid, and A compound having an ester bond obtained by reacting a compound selected from the group consisting of disproportions of rosin acid (hereinafter collectively referred to as "rosin acid derivatives") with any one of a hydroxyl compound, a phenol compound and a glycidyl compound, It is a compound having an ester bond obtained by glycidylating a rosin acid derivative and reacting it with either a carboxyl compound or a phenol compound.

(F) Specific examples of the rosin ester compound include products of Arakawa Chemical Co., Ltd. such as Estergum series, Pine Crystal series, Super Ester series, Pencel series, Beamset 101, etc., Harima Kasei Co., Ltd. ) company's products include the Harrier Star series, the Neotor series, and the Haritak series.

(F) The rosin ester compound has an alicyclic structure and an ester structure, and is a compound that becomes highly hydrophobic. Since the compound and (C) have good compatibility with the photopolymerization initiator, the developability as a composition is not hindered, and therefore, the developability of the transfer film, the moisture permeability of the cured film, and the rust prevention of the conductor Excellent balance of each performance.

From the viewpoint of conductor rust prevention, the acid value of (F) the rosin ester compound is more preferably 20 mgKOH/g or less. For example, Pine Crystal KE-100, Estergum 105, Superester A-115, Superester A-125, Pencel A, Pencel C, Pencel D-125, Pencel D-135, Pencel D-160, Beamset 101, Harrier Star S, Neotor 125HK, Harytac F105, Harytac FK125, Harytac PCJ and the like.

Furthermore, from the viewpoint of reducing the moisture permeability of the cured film, the softening point of (F) the rosin ester compound is more preferably 100° C. or higher. Super Ester A-115, Super Ester A-125, Pencel A, Pencel C, Pencel D-125, Pencel D-135, Pencel D-160, Neotol 125HK, etc., and have a softening point of 110°C or higher. Specific compounds that are particularly preferred and meet these conditions include Superester A-115, Superester A-125, Pencel A, Pencel C, Pencel D-125, Pencel D-135, Pencel D-160, and Neotol. 125HK is mentioned. (F) The rosin ester compound can be used alone or in combination of two or more.

(F) The content of the rosin ester compound in the photosensitive resin composition is 1% by mass to 20% by mass with respect to the total solid mass of the photosensitive resin composition, and from the viewpoint of moisture permeability and developability, It is more preferably 5% by mass to 20% by mass, and more preferably 5% by mass to 15% by mass from the viewpoint of adhesion to the substrate. When the content of the rosin ester compound (F) is within the range of 1% by mass to 20% by mass, the low-temperature developability of the transfer film and the moisture permeability of the cured film are well balanced.

<(G) Antirust agent>
The antirust agent according to the present embodiment refers to a compound having an antirust effect, such as a substance that forms a film on a metal surface to prevent metal corrosion or rust.

From the viewpoint of compatibility and sensitivity with the photosensitive resin composition according to the present embodiment, the rust inhibitor is preferably a heterocyclic compound containing N, S, O, etc. Examples include tetrazole and its derivatives, triazole and derivatives thereof, imidazole and its derivatives, indazole and its derivatives, pyrazole and its derivatives, imidazoline and its derivatives, oxazole and its derivatives, isoxazole and its derivatives, oxadiazole and its derivatives, thiazole and its derivatives, isothiazole and its derivatives, thiadiazole and its derivatives, thiophene and its derivatives, and the like. The derivatives described here include compounds in which a substituent is introduced into the base structure. For example, tetrazole derivatives include compounds in which a substituent is introduced into tetrazole. The substituent is not particularly limited, but for example, a hydrocarbon group (saturated or unsaturated, linear or branched, may contain a cyclic structure in the structure), a hydroxyl group, or a carbonyl group. , a carboxyl group, an amino group, an amide group, a nitro group, a cyano group, a mercapto group, and a substituent group containing one or more heteroatom-containing functional groups such as halogen (fluorine, chlorine, bromine, iodine, etc.) groups.

Furthermore, from the viewpoint of rust prevention, the heterocyclic compound has 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, Compounds having 3 or less S atoms or 3 or less total N and S atoms are preferred. More preferred heterocyclic compounds are triazole and its derivatives, imidazole and its derivatives, imidazoline and its derivatives, thiazole and its derivatives, isothiazole and its derivatives, thiadiazole and its derivatives, thiophene and its derivatives and the like. Benzotriazole and its derivatives, and imidazole and its derivatives are more preferable as the compound from the viewpoint of rust prevention and developability.

having a heterocyclic ring composed of C and N and/or S, and in the same heterocyclic ring, the number of N atoms is 3 or less, the number of S atoms is 3 or less, or the N atom and S Specific examples of compounds having a total number of atoms of 3 or less are shown below:
triazoles, such as 1,2,3-triazole, 1,2,4-triazole;
triazole derivatives such as 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, etc.;

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-aminobenzimidazole, 5-amino-2-mercaptobenzimidazole, etc.;
imidazolines; imidazoline derivatives such as 2-undecylimidazoline, 2-propyl-2-imidazoline, 2-phenylimidazoline and the like;
thiazole; thiazole derivatives such as 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;
Thiadiazoles, such as 1,2,3-thiadiazole, 1,2,5-thiadiazole, 1,3,4-thiadiazole, etc.;
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 etc.; 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 preferred from the viewpoint of conductor rust prevention and developability.
On the other hand, tetrazole and its derivatives, triazole and its derivatives, indazole and its derivatives, and thiadiazole and its derivatives are preferable as the (G) component from the viewpoint of the rust prevention of the conductor and the adhesion of the cured film to the substrate.

A specific example of tetrazole is 1H-tetrazole. Specific examples of tetrazole derivatives 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, 5-phenyl-1H-tetrazole and the like.

Specific examples of indazole include 1H-indazole. Indazole derivatives include 5-aminoindazole, 6-aminoindazole, 1-benzyl-3-hydroxy-1H-indazole, 5-bromoindazole, 6-bromoindazole, 6-hydroxyindazole, 3-carboxyindazole and 5-nitro Indazole etc. are mentioned.

Specific examples of triazoles and derivatives thereof and thiadiazoles and derivatives thereof have already been described above.
Among them, 5-amino-1H-tetrazole, 5-carboxybenzotriazole, 5-aminoindazole and 5-amino-1,2, 3-thiadiazole is particularly preferred.
In this embodiment, one of the rust inhibitors described above may be used alone, or two or more may be used in combination.

The content of the rust preventive agent in the photosensitive resin composition is preferably 0.05 based on the total solid mass of the photosensitive resin composition, from the viewpoint of the rust preventive property of the conductor or the low-temperature developability of the transfer film. % to 10% by mass, more preferably 0.1% to 5% by mass, and even more preferably 0.2% to 3% by mass.

<Other ingredients>
In the present embodiment, in addition to components (A) to (G), other components (H) include a polymerization inhibitor such as an aluminum salt to which 3 mol of nitrosophenylhydroxylamine is added, an antioxidant, and an adhesion aid. , a leveling agent, a filler, an antifoaming agent, a flame retardant, and the like can also be contained in the photosensitive resin composition, and these can be used alone or in combination of two or more.

<Puncture Strength>
For the photosensitive resin composition of the present invention, a transfer film having a photosensitive layer with a thickness of 30 μm was prepared, and an exposed film was formed on a substrate having an opening of 6 mmφ with the film, and then a piercing test was performed using a Tensilon. The maximum point load is 35 gf or more.
Specifically, a photosensitive resin composition is coated on a support to form a transfer film in which a photosensitive resin layer having a thickness of 30 μm is laminated, and the transfer film is placed on a substrate having an opening of 6 mmφ. After lamination, the entire surface is exposed to form an exposed film, then the support is peeled off, and the portion corresponding to the center of the opening is cut using a Tensilon equipped with a cylindrical jig of 1.5 mmφ at a speed of 100 mm/. The maximum point load is 35 gf or more when a puncture test is performed at min.
A more specific method for measuring the maximum point load by the piercing test will be described in detail in Examples described later.

The photosensitive resin composition has a maximum point load of 35 gf or more during a puncture test, and exhibits good adhesion to substrates.
When applying a protective film to a flexible substrate, flexible substrates are often produced in a roll-to-roll process. Delamination from the substrate occurs. On the other hand, in the cross-cut test of the examples described later, the cured film is cut in a grid pattern with a cutter blade, and then the tape is peeled off to evaluate the adhesion. At the time of exposure, the protective film cracked and peeled off from the base material, but this did not occur with the protective film having a maximum point load of 35 gf or more during the puncture test, and the adhesion and the maximum point load (exposed film The inventors thought that there was a correlation between the strength of Therefore, in order to eliminate the cracks and peeling of the protective film in the roll to roll described above, if the protective film has a strong strength with a maximum point load of 35 gf or more during the puncture test, these defects will be improved. they think.

On the other hand, the photosensitive resin composition of the present invention uses (Ai) an alkali-soluble polymer having an ethylenically unsaturated group and an acidic group and a ring structure in the main chain or a compound having a rigid structure. With this, a high Tg and a high cross-linking density can be obtained and a low moisture permeability can be obtained, but the strength tends to be insufficient and the material tends to be brittle, resulting in poor adhesion. As long as the maximum point load during the puncture test is 35 gf or more, there are no restrictions on the method of increasing the strength, but (Bi) addition of a photopolymerizable compound containing butylene oxide in the structure, By setting the calculated weight average molecular weight of the component (A) to 6,000 or more, the maximum point load can be 35 gf or more. When the (Bi) component has the formula (2), the strength of the exposed film can be easily expressed. By incorporating the butylene oxide chain into the crosslinked structure, the flexibility of the crosslinked body is increased and the strength is improved. It is thought that the portion that is the starting point of the exposure film is reduced and the strength of the exposed film is increased.

Furthermore, although not limited to the following, from the viewpoint that the compatibility of the polymer is good and the film strength is easily obtained, the following condition 1 and / or condition 2 is satisfied for the component (A), and the following condition is satisfied for the component (B) Satisfying 3 is more preferable in order to obtain the strength of the exposed film.
Condition 1: As component (Ai), (A-iii) having a weight average molecular weight of 6,000 or more and an acid value of 60 to 120 mgKOH/g having an ethylenically unsaturated group and an acidic group and a ring on the main chain The polymer containing the structure is contained in an amount of 90% by mass or more based on the total solid mass of the component (A).
Condition 2: (Ai) and (A-iv) as components (A): acidic groups with a weight average molecular weight of 10,000 to 36,000 (more preferably 25,000 or less) and an acid value of 130 to 150 mgKOH/g and contains an alkali-soluble polymer having no ethylenically unsaturated groups.
Condition 3: Component (Bi) is contained in an amount of 3% to 15% by mass based on the total solid content of the photosensitive resin composition.

<Transfer film>
The photosensitive resin layer according to the present embodiment has a thickness of 15 μm or less, and the absorbance of the photosensitive resin layer at a wavelength of 365 nm is 0.01 to 0.05 per 1 μm of the thickness of the photosensitive resin layer. is preferred. If the film thickness of the photosensitive resin layer is too thick, the flexibility deteriorates. Therefore, the thickness of the photosensitive resin layer is preferably 15 μm or less. 3 μm or more is preferable.

The transfer film includes a photosensitive resin layer made of a photosensitive resin composition and a support film. Specifically, a layer made of the photosensitive resin composition described above is laminated on the support film. If necessary, the transfer film may have a protective film on the surface of the photosensitive resin layer opposite to the support film side.

As the support film used in this embodiment, a transparent film that transmits the light emitted from the exposure light source is desirable. Examples of such support films include polyethylene terephthalate film, polyvinyl alcohol film, polyvinyl chloride film, vinyl chloride copolymer film, polyvinylidene chloride film, vinylidene chloride copolymer film, and polymethyl methacrylate copolymer film. , polystyrene films, polyacrylonitrile films, styrene copolymer films, polyamide films, films made of cellulose and derivatives thereof, and the like. These films can also be used in a stretched form, if desired. The haze of the support film is preferably 5 or less. The thickness of the support film is preferably 10 μm to 30 μm in order to maintain strength, although a smaller thickness is advantageous in terms of resolution and economy.

An important characteristic of the protective film used for the transfer film is that the adhesive strength of the protective film to the photosensitive resin layer is sufficiently smaller than that of the support film, so that the protective film can be easily peeled off. As the protective layer, for example, a polyethylene film, a polypropylene film, or the like can be preferably used.

A method for producing a transfer film includes a step of applying a coating liquid onto a support (for example, a support film) and drying it, and further includes a step of laminating a protective film on the photosensitive resin layer, if 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 such as methanol, ethanol, and isopropanol.
The solvent is preferably added to the photosensitive resin composition so that the viscosity of the solution of the photosensitive resin composition to be coated on the support is 10 mPa·s to 800 mPa·s at 25°C.

Examples of coating methods include doctor blade coating, Meyer bar coating, roll coating, screen coating, spinner coating, inkjet coating, spray coating, dip coating, gravure coating, curtain coating, and die coating. coating method and the like. The drying conditions for the coating liquid are not particularly limited, but the drying temperature is preferably 50° C. to 130° C., and the drying time is preferably 30 seconds to 30 minutes.

In this embodiment, the transfer film is preferably used to form a protective film for the conductor. An alloy electrode with copper or a transparent electrode is more preferable. More specifically, the transfer film can be used as a protective film for lead wires in the frame area of a touch panel (touch sensor or force sensor) and as a protective film for copper or alloy electrodes in the sensing area. It can also be used as an electrode protective film for a strain sensor that senses changes in resistance value with a strain gauge, a wiring protective film for AI-related electronic equipment, and a protective film for display elements.

[Resin pattern, cured film pattern and method for producing them]
Formation of a resin pattern using a transfer film includes the following steps:
A lamination step of laminating the transfer film described above onto a substrate;
an exposure step of exposing the laminated photosensitive resin laminate; and a developing step of developing the exposed transfer film;
It can be performed by a method for manufacturing a resin pattern including Furthermore, in order to use the resin pattern as a protective film for the conductor part, the resin pattern manufacturing method includes a step of subjecting the resin pattern to post-exposure treatment and/or heat treatment after the development step to form a cured film pattern. is preferred.

An example of a specific method is shown below. As the base material, a base material in which copper wiring is formed on a copper-clad laminate, a glass base material, a transparent resin base material and a transparent electrode (e.g., ITO, Ag nanowire base material, etc.), or a metal electrode (e.g., Cu , Al, Ag, Ni, Mo, and alloys of at least two of these) can be used. A flexible copper-clad laminate, a base material for forming a touch panel electrode, or a base material for forming a touch sensor electrode includes a copper layer, a copper-nickel alloy layer, a transparent electrode, or a metal used as a raw material for a metal electrode on a flexible film. It is a base material on which a layer is formed.

Examples of the film include films made of film raw materials such as polyimide, polyester (PET, PEN), and cycloolefin polymer (COP). The thickness of the film is preferably 10 μm to 100 μm.

A photosensitive resin layer is formed on the copper layer of the substrate by performing the step of laminating the transfer film onto the substrate as described above. When the transfer film has a protective layer, preferably after peeling off the protective layer, the transfer film is heat-pressed onto the surface of the substrate with a laminator to laminate. In this case, the transfer film may be laminated only on one side of the base material surface, or may be laminated on both sides. The heating temperature is generally about 40°C to 160°C. The thermocompression bonding may be performed using a two-stage laminator equipped with two rolls, or may be performed by repeatedly passing the transfer film and the substrate through the rolls multiple times. . Also, when a vacuum roll laminator is used, the protective film can follow well the unevenness caused by the wiring on the base material, and the defect of air entering between the transfer film and the base material can be prevented. On the other hand, when a vacuum roll laminator is used, the concentration of oxygen that inhibits radical polymerization is extremely low, so that the photopolymerization initiator is cleaved and the dark reaction easily proceeds. Therefore, the temperature of the rolls is preferably 40°C to 100°C, more preferably 40°C to 80°C.

Next, an exposure process is performed using an exposure machine. If necessary, the support film is peeled off from the transfer film, and the photosensitive resin layer is exposed to actinic light through a photomask. The amount of exposure is determined by the illuminance of the light source and the exposure time. Exposure may be measured using a photometer. 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 with adjusted parallelism, a proximity exposure machine with a gap between the mask and the workpiece, and the like. Further, as the exposure machine, a projection type exposure machine with a mask to image size ratio of 1:1, a reduction projection exposure machine called a high-illuminance stepper (registered trademark), or a concave mirror called a mirror projection aligner (registered trademark) can be used. The exposure machine used can be mentioned.

Also, in the exposure process, a direct drawing exposure method may be used. Direct drawing exposure is a method of directly drawing and exposing a substrate without using a photomask. As the light source, for example, a solid-state laser with a wavelength of 350 nm to 410 nm, a semiconductor laser, or an ultra-high pressure mercury lamp is used. The drawing pattern is controlled by a computer. The exposure amount in this case is determined by 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, if there is a support film on the photosensitive resin layer, the support film is removed if necessary, and then the unexposed area is removed by development using an alkaline aqueous developer to obtain a resin pattern. As the alkaline aqueous solution, it is preferable to use an aqueous solution of Na ₂ CO ₃ or K ₂ CO ₃ (aqueous alkaline solution). The alkaline aqueous solution is appropriately selected according to the properties of the photosensitive resin layer, but is generally a Na ₂ CO ₃ aqueous solution with a concentration of about 0.2% by mass to 2% by mass and a temperature of about 20°C to 40°C. When the temperature of the developer is high, moisture tends to volatilize under a negative pressure environment such as exhaust air as a countermeasure against odor, and the developer tends to concentrate over time, which tends to impair stable productivity. Therefore, the developer temperature is preferably less than 30°C. Further, the alkaline aqueous solution may contain a surfactant, an antifoaming agent, a small amount of an organic solvent for promoting development, and the like. Considering the influence on the substrate, an amine-based alkaline aqueous solution such as a tetramethylammonium hydroxide (TMAH) aqueous solution can also be used. The concentration of the alkali compound in the aqueous solution can be appropriately selected according to the development speed. A 1% by weight aqueous solution of Na ₂ CO ₃ at 25° C. to 30° C. is particularly preferred from the viewpoints of less odor of the developer, excellent handleability, and simple management and post-treatment. Examples of the developing method include known methods such as alkaline water spray, shower, rocking immersion, brushing and scraping.

After development, the base of the alkaline aqueous solution remaining in the resin pattern is acid-treated (neutralized) by a known method such as spraying, swinging immersion, brushing, scraping, etc. using an organic acid, an inorganic acid, or an aqueous acid solution thereof. )can do. Furthermore, a step of washing with water can also be performed after the acid treatment (neutralization treatment).

Although a resin pattern can be obtained through each of the above steps, a post-exposure step and/or a heating step may be further performed. By performing the post-exposure step and/or the heating step, the rust prevention is further improved. The exposure amount in the post-exposure treatment is preferably 200 mJ/cm ² to 1,000 mJ/cm ² , and the heating step is preferably performed at 40° C. to 200° C. From the viewpoint of the manufacturing process, the heat treatment time is adjusted. is preferably 60 minutes or less. As the method of heat treatment, a heating furnace of an appropriate method such as hot air, infrared rays, or far infrared rays can be used, and the atmosphere of heat treatment includes an N ₂ atmosphere or an N ₂ /O ₂ atmosphere. .

According to this embodiment, the adhesion of the transfer film to the conductor substrate, the developability, the strength of the exposed film, and the moisture permeability of the cured film are all good, and are suitable for protecting conductor parts such as wiring and electrodes. A photosensitive resin composition and a transfer film can be provided. Such a transfer film is suitable as, for example, a touch panel, a touch sensor, a force sensor, a strain sensor, or a protective film for wires and electrodes used in AI-related electronic devices, or as a solder resist for printed wiring boards.

[Touch Panel Display Device, Device Having Touch Sensor or Force Sensor]
By forming the cured film of the transfer film according to the present embodiment on the substrate for touch panel, the touch panel display device having the cured film of the transfer film, and the cured film of the transfer film and the touch sensor and / or the force sensor are provided. Equipment can be provided.
Touch panel substrates generally include substrates used for touch panels, touch sensors, or force sensors, such as glass plates, plastic plates, plastic films, ceramic plates, and the like. Touch panel electrodes or metal wirings such as ITO, Cu, Al, Ag, Ni, Mo, and alloys containing at least two of these, which are targets for forming a protective film, are provided on the substrate. An insulating layer may be provided between the electrodes.

A touch panel substrate having a touch panel electrode can be obtained, for example, by the following procedure. After forming a metal film by sputtering an alloy of copper and nickel on a touch panel substrate such as polyester or COP film, a photosensitive film for etching is attached on the metal film to form a desired resist pattern, Unnecessary alloys are removed with an etchant such as an aqueous iron chloride solution, and the resist pattern is stripped and removed.

A method for forming a cured film as a protective film on a touch panel substrate includes a first step of laminating the transfer film according to the present embodiment onto the touch panel substrate, and irradiating a predetermined portion of the protective film with actinic rays. A second step of curing, a third step of removing a portion other than a predetermined portion of the protective film (a portion of the protective film not irradiated with actinic rays) to form a cured product of the patterned protective film, and a patterned protection A fourth step of exposing and/or heat-treating the film is preferably included in this order.

By producing a touch panel substrate having a cured film pattern of a transfer film as described above, a touch panel display device having a cured film of a transfer film, or having a cured film of a transfer film and a touch sensor and/or a force sensor. A device can be conveniently provided.

EXAMPLES The present invention will be specifically described below based on examples, but the present invention is not limited to these.

1. Component (A) As (Ai) the alkali-soluble polymer having an ethylenically unsaturated group and an acidic group and containing a ring structure in the main chain, the following commercially available solution was used.

A-1 ZCR-1797H (acid-modified epoxy acrylate having a biphenyl skeleton; manufactured by Nippon Kayaku Co., Ltd.)
A-2 ZCR-1569H (acid-modified epoxy acrylate having a biphenyl skeleton; manufactured by Nippon Kayaku Co., Ltd.)
A-3 ZXR-1807H (acid-modified epoxy acrylate having a tricyclodecane skeleton; manufactured by Nippon Kayaku Co., Ltd.)
A-4 ZXR-1810H (acid-modified epoxy acrylate having a tricyclodecane skeleton; manufactured by Nippon Kayaku Co., Ltd.)
A-5 FCA-954 (acid-modified epoxy acrylate having a fluorenyl skeleton, manufactured by Nagase ChemteX Corporation)

Table 1 shows the weight average molecular weight and acid value of the alkali-soluble polymer having an ethylenically unsaturated group and an acidic group and containing a ring structure in the main chain. The weight-average molecular weight and acid value were measured by the method described in detail in <(A) Alkali-soluble polymer having acidic group> above.

Next, (A-ii) production of an alkali-soluble polymer having an acidic group and no ethylenically unsaturated group will be described.
<Production of (A-6)>
A flask equipped with a stirrer, a reflux condenser, an inert gas inlet and a thermometer was charged with 100% by mass of methyl ethyl ketone and heated to 75° C. under a nitrogen gas atmosphere. Methacrylic acid (MAA) 20% by mass, methyl methacrylate (MMA) 25% by mass, styrene (St) 55% by mass, and an azo polymerization initiator (manufactured by Wako Pure Chemical Industries, Ltd., V-601) were added for 2 hours. Dropped evenly. After the dropwise addition, the reaction system was stirred at 75° C. for 10 hours, and after completion of the reaction, the resulting resin solution was diluted with methyl ethyl ketone to give a solid content acid value of 130 mgKOH/g and a weight average molecular weight of about 13,000. An alkali-soluble polymer solution (solid content: 50% by mass) (A-6) was obtained.

<Production of (A-7)>
In the same manner as the above alkali-soluble polymer solution (A-6), using 20% by mass of MAA, 25% by mass of MMA, and 55% by mass of St, the solid content acid value is 130 mgKOH / g and the weight average molecular weight is about 35,000. An alkali-soluble polymer solution (solid content: 50% by mass) (A-7) was obtained.

<Production of (A-8)>
In the same manner as for the alkali-soluble polymer solution (A-6), using 22.5% by mass of MAA, 12.5% by mass of MMA, 60% by mass of St, and 5% by mass of butyl acrylate (BA), solid content acid value was 147 mgKOH/g and the weight average molecular weight was about 22,500 (solid content: 54% by mass) (A-8).

<Production of (A-9)>
In the same manner as the above alkali-soluble polymer solution (A-6), using 29% by mass of MAA, 19% by mass of MMA, and 52% by mass of St, the solid content acid value is 189 mgKOH / g and the weight average molecular weight is about 50,000. An alkali-soluble polymer solution (solid content: 38% by mass) (A-7) was obtained.

Table 2 shows the copolymer composition, weight-average molecular weight and acid value of the obtained alkali-soluble polymer having an acidic group and not having an ethylenically unsaturated group. The weight-average molecular weight and acid value of the alkali-soluble polymer were measured by the method described in detail in <(A) Alkali-soluble polymer having an acidic group> above.

2. Production of Transfer Film for Evaluation The transfer film for evaluation in Examples and Comparative Examples was produced as follows.
<Production of transfer film>
Each component was weighed into a 250 ml plastic bottle according to the composition shown in Tables 4 to 6 below (however, the number of each component indicates the amount (mass part) as a solid content), and the solid content concentration was 53. Methyl ethyl ketone was added so as to make the mass %, and dissolved and mixed using a stirrer for 5 hours to obtain a photosensitive resin composition. Thereafter, the photosensitive resin composition was passed through a 3 μm filter to prepare photosensitive resin composition preparations (Examples 1 to 23 and Comparative Examples 1 to 11).

The photosensitive resin composition preparation solution is evenly coated on the surface of a 16 μm thick polyethylene terephthalate film (manufactured by Toray Industries, Inc., FB40) as a support using a blade coater, and dried to uniformly coat the surface of the support. A photosensitive resin layer was formed. The thickness of the photosensitive resin layer was 8 μm and 30 μm, and the drying conditions were 7 minutes in a 95° C. dryer for 8 μm and 9 minutes in a 95° C. dryer for 30 μm. Then, a 33 μm-thick polyethylene film (GF-858, manufactured by Tamapoly Co., Ltd.) was laminated as a protective film on the surface of the photosensitive resin layer to obtain a transfer film for evaluation.
Tables 4 to 6 show the following evaluation results. The abbreviations in Tables 4 to 6 and the names of the components in the photosensitive resin composition mixture are shown in Table 3.

3. Developability <Sample preparation method>
A sample for evaluation of developability was prepared as follows.
A hot roll laminator (Taisei Laminator Co., Ltd.) was placed on the alloy surface (size: 5 cm × 10 cm) of the substrate on which the copper-nickel alloy was sputtered on the resin while peeling off the protective film of the transfer film with a thickness of 8 μm for the photosensitive resin layer. ) manufactured by VA-400III) at a roll temperature of 80°C. The air pressure was set at 0.2 MPa and the lamination speed was set at 2 m/min. (However, for compositions that were not transferred under the condition of 80 ° C., the roll temperature was raised to 100 ° C. and laminated.) After standing for 15 minutes, a PET mask and a Stufer 21 step tablet (optical density 0) were placed on the support film. 0.00 as the first step, and the optical density increases by 0.15 for each step) are placed side by side. ) Exposure was performed by HMW-801 manufactured by Oak Manufacturing Co., Ltd.). A PET mask having a pattern as shown in FIG. 1 was used. In FIG. 1, the shaded portions represent the light-blocking portions, and the white portions represent the light-transmitting portions. Also, arrows and numerical values in the drawing represent dimensions, not actual mask patterns.

Then, after standing still for 15 minutes or more, the support was peeled off, and using a developing device manufactured by Fuji Kiko Co., Ltd., development was performed with a full cone type nozzle at a spray pressure of 0.12 MPa and 1 mass% Na at 28 ° C. to 30 ° C. ₂ CO ₃ aqueous solution was sprayed for 45 seconds for development, and the unexposed portions of the photosensitive resin layer were dissolved and removed. After the development process, it was dried by an air blow and then washed with water. The water washing process was carried out at the same time as the development process using a flat type nozzle with a washing spray pressure of 0.12 MPa. The sample was dried by an air blow to prepare a sample for evaluation of developability. The optimum exposure amount is defined as an exposure amount that leaves 7 to 8 steps of a remaining film when exposed through a 21-step Stufer step tablet.

<Evaluation method>
The substrate surface state of the portion of the protective film-attached substrate from which the photosensitive layer was removed was observed under a microscope and judged as follows.
A: No development residue on the substrate alloy under development conditions of 28°C.
B: Under the development condition of 28°C, there is a development residue on the alloy of the substrate, but under the development condition of 30°C, there is no development residue on the alloy of the substrate.
C: Development residue is generated even under development conditions of 30°C.
In the developability evaluation, it is considered that up to B rank is a practically good result as a conductor protective film.

4. Moisture Permeability Test <Sample preparation method>
While peeling off the protective film of the transfer film having a photosensitive resin layer with a thickness of 30 μm, No. 4 filter paper (manufactured by Advantech) was laminated using a hot roll laminator (manufactured by Taisei Laminator Co., Ltd., VA-400III). The roll temperature was set at 60° C., the air pressure was set at 0.2 MPa, and the lamination speed was set at 1.0 m/min. (However, for compositions that were not transferred under the condition of 60 ° C., the roll temperature was raised to 100 ° C. and laminated.) , HMW-201KB) at an exposure amount of 350 mJ/cm ² . After standing still for 30 minutes, the support film was peeled off and treated in a hot air circulating oven at 150° C. for 30 minutes to prepare a sample.

<Evaluation method>
The moisture permeability was measured according to the cup method of JIS Z0208 under the conditions of temperature 65° C. and humidity 90%.
A: Moisture permeability of 200 g/(m ² ·day) or more and less than 265 g/(m ² ·day) B: Moisture permeability of 265 g/(m ² ·day) or more and less than 330 g/(m ² ·day) C: Moisture permeability 330 g/(m ² ·day) or more, less than 400 g/(m ² ·day) D: Moisture permeability 400 g/(m ² ·day) or more In the moisture permeability test, up to C rank It is considered that this is a practically good result as a protective film for a conductor.

5. Adhesion evaluation (cross-cut test)
<Sample preparation method>
While peeling off the protective film of the transfer film with a thickness of 8 μm of the photosensitive resin layer, a hot roll laminator (Taisei Laminator Co., Ltd.) was placed on the alloy surface (size: 4 cm × 4 cm) of the substrate on which the copper-nickel alloy was sputtered on the resin. and VA-400III). The roll temperature was 80° C., the air pressure was 0.2 MPa, and the lamination speed was 2 m/min. (However, for compositions that were not transferred under the condition of 80°C, the roll temperature was raised to 100°C for lamination.) After standing for 15 minutes, <3. The entire surface was exposed to the optimum exposure amount for each composition evaluated in the item Developability>.

Then, after standing still for 15 minutes or more, the support was peeled off, and using a developing device manufactured by Fuji Kiko Co., Ltd., a development spray pressure of 0.12 MPa was used with a full cone type nozzle, and 1 mass% Na ₂ CO ₃ was applied at 30°C. An aqueous solution was sprayed for 45 seconds for development, and the unexposed portions of the photosensitive resin layer were dissolved and removed. After the development process, it was dried by an air blow and then washed with water. The water washing process was carried out at the same time as the development process using a flat type nozzle with a washing spray pressure of 0.12 MPa. The sample was dried by an air blow.
The developed sample was exposed from the side of the photosensitive resin layer with a scattered light exposure device at an exposure amount of 300 mJ/cm ² to prepare a sample for adhesion evaluation.

<Evaluation method>
A 100-square cross-cut test was performed on the sample after the above treatment with reference to JIS K5400. Using a cutter knife, cut a 1 mm × 1 mm square grid on the side where the protective film is laminated, and apply a 15 mm wide adhesive tape (Nichiban Co., Ltd. Sellotape (registered trademark), (product name) was strongly pressed, and the edge of the tape was gently peeled off at an angle of approximately 0°.
A: Peeling is less than 5% in the total area.
B: 5 to 15% of the total area is peeled off.
C: Peeling of 15% or more of the total area In the cross-cut test, up to B rank is considered to be a practically good result as a conductor protective film.

6. Maximum point load measurement (puncture test)
<Sample preparation method>
One side of a 1.6 mm thick copper-clad laminate having an opening of 6 mmφ shown in FIG. The surface was laminated using a hot roll laminator (VA-400III, manufactured by Taisei Laminator Co., Ltd.). The roll temperature was 80° C., the air pressure was 0.2 MPa, and the lamination speed was 2 m/min. (However, for compositions that were not transferred under the condition of 80°C, the roll temperature was raised to 100°C for lamination.) After standing for 15 minutes, <3. The entire surface was exposed to the optimum exposure amount for each composition evaluated in the item Developability>.

Next, after leaving it for 30 minutes or more, the support was peeled off, and the center of the 6 mmφ opening was pierced with a cylinder of 1.5 mmφ at a speed of 100 mm/min from the surface where the support was peeled off. 500) measured the maximum point load. Measurements were taken at 10 points, and the average value of the top 5 points was taken as the maximum point load in the puncture test.
A thickness of 35 gf or more is considered to be a practically favorable result for a conductor protective film.

From the results shown in Tables 4 to 6, Examples 1 to 22 satisfy the requirements specified in the present invention, and are excellent in developability, moisture permeability of the cured film, and adhesion of the exposed film to the substrate. It is shown that there are On the other hand, in Comparative Examples 1 to 11, since any of the requirements specified in the present invention is not satisfied, any of the developability, the moisture permeability of the cured film, and the adhesion of the exposed film to the substrate is inferior. It is shown.

Compared with Example 1, Comparative Example 1 has a composition that does not contain the (Bi) component, but the maximum point load in the puncture test is less than 35 gf, and the moisture permeability is good, but the adhesion performance is poor. It is out of the allowable range and the performance balance is poor. Furthermore, looking at Comparative Example 2, although the component (Bi) is included, it does not satisfy the maximum point load of 35 gf, which also results in poor adhesion. In Comparative Example 3, the component (Bi) of Example 18 was replaced with dimethacrylate of polyalkylene glycol to which propylene oxide and ethylene oxide were added. Although it is good, the moisture permeability is deteriorated and the performance balance is poor.

Subsequently, in Comparative Example 4, the (B-ii) component of Example 2 was replaced with another polymerizable compound, and the (B-ii) component was not included, but the maximum point load was 35 gf or more, but the adhesion was poor. . This is because the (B-ii) component is not included, so the cross-linking after exposure becomes too dense and curing shrinkage occurs, stress is generated between the substrate and the adhesion strength is reduced, and the strength of the exposed film is reduced. The inventors believe that some resulted in poor adhesion. Compared with Example 2, Comparative Example 5 also has a composition in which part of the component (B-ii) is replaced with another polymerizable compound, but the component (B-ii) is 3% of the total solid content of the composition. Since it does not meet the requirement of including the above, for the same reason as in Comparative Example 4, it is considered that the result is poor adhesion.

On the other hand, Comparative Example 8 is a composition in which the (Ai) component is divided into the (A-ii) component and the (Ai) component is not included in the composition of Example 11, but (A- Since the weight average molecular weight and maximum point load of component i) and component (A) are not satisfied, all of developability, moisture permeability and adhesion are inferior. In addition, Comparative Example 7 satisfies the weight average molecular weight of component (A) as compared with Comparative Example 8, but does not satisfy the requirements of component (Ai) and the maximum point load, so developability, moisture permeability and adhesion All are unacceptable performance. Furthermore, Comparative Example 6 satisfies the requirements except that it does not contain the component (Ai), but it does not satisfy all the requirements, so it is inferior in developability and moisture permeability. These results show that the component (Ai) has the effect of improving moisture permeability and developability. In addition, Comparative Example 9 contains the same component (Ai) as in Example 1, but the weight average molecular weight of the component (A) is 2500, which is below the specified value, so the maximum point load is low and the adhesion is poor. result. Comparative example 10 is also the same. Comparative Example 11 has a larger weight-average molecular weight than Comparative Example 9 and Example 1, but the weight-average molecular weight exceeds the predetermined weight-average molecular weight, resulting in poor developability. These results show that adjusting the weight-average molecular weight of the component (A) is useful for achieving well-balanced film strength, adhesion and developability.

Moreover, Examples are compared. Examples 1 to 3 differ in the amount of the (Bi) component, but it can be seen that the maximum point load increases and the adhesion improves as the content of the (Bi) component increases. . On the other hand, it can be seen that increasing the amount of the component (Bi) tends to worsen the moisture permeability. In addition, when looking at Example 4, although the component (Bi) is contained only 3.2% in the total solid content of the composition, the maximum point load exceeds 35 gf, the adhesion is good, and even if it is added in a small amount It turns out that there is an effect. On the other hand, Example 20 has a composition in which the amount of component (Bi) is further reduced and the amount added is less than 3%, but the moisture permeability is inferior to that of Example 5 and the content of component (Bi) is 3. Since it is not in the range of ~15%, it can be seen that it is difficult to balance the performance. Since Example 2 contains the (Bi) component and its structure satisfies the formula (2), it is transparent compared to Example 5 using the (Bi) component that is not the formula (2). Humidity performance is improved. Subsequently, Examples 6 and 8 contain the component (B-ii) and furthermore the structure uses a compound having multiple aromatic rings in one molecule, so there is only one aromatic ring in one molecule. Compared to Example 7 in which only the component (B-ii) was used, the moisture permeability was improved.

Subsequently, Examples 9 and 10 were obtained by adding (D) a thiol compound having at least two mercapto groups in one molecule to Example 1, but the maximum point load was large, compared with Example 1. However, the adhesion is improved, and it can be seen that the component (D) is useful for improving the adhesion.

In Example 13, the (Ai) component of Example 12 was divided into the (A-ii) component, and the composition containing the (A-ii) component was used. Developability, moisture permeability and adhesion are well balanced. The use of component (A-ii) makes it easier to balance performance.

Examples 14 to 18 have almost the same composition except for the (Ai) component, and are compositions using the (Ai) component with various structures, but all the predetermined conditions are satisfied. It satisfies developability, moisture permeability and adhesion.

Example 22 compared with Example 2 and used a photopolymerization initiator that was not an oxime compound as the component (C), but Example 2 was superior in terms of moisture permeability, and the oxime initiator was It can be seen that it is effective in improving the moisture permeability.

Although the embodiment of the present invention has been described above, the present invention is not limited to this, and can be modified as appropriate without departing from the gist of the invention.

By using the photosensitive resin composition and the transfer film according to the present invention, it is suitable for protecting conductors such as wiring and electrodes, and has excellent rust resistance, developability and adhesion. Alternatively, it can be widely used as a protective film for wires, electrodes, etc. for force sensor applications and printed wiring board solder resist applications.

Claims (14)

Ingredients for:
(A) an alkali-soluble polymer having an acidic group,
(B) a photopolymerizable compound, and (C) a photopolymerizable initiator, a photosensitive resin composition,
As the component (A), (Ai) a polymer having an ethylenically unsaturated group and an acidic group and containing a ring structure in the main chain,
As the component (B), (Bi) a compound having at least two ethylenically unsaturated groups and containing butylene oxide in its structure as a repeating unit (excluding compounds corresponding to the component (A)). , and (B-ii) a compound having one ethylenically unsaturated group,
The component (A) comprises at least one polymer A-1, . including the following formula (1):

{Wherein, W _A-1 , . . . , W _A-n represent the weight average molecular weights of the polymers A- ₁ , _{. n} represents the mass % of each of the polymers A-1, . . . An in the photosensitive resin composition. } is 6,000 to 17,462 , and the weight average molecular weight of the component (A) calculated by
Containing the component (B-ii) in an amount of 3% by mass or more relative to the total mass of the solid content of the photosensitive resin composition, and
A transfer film is formed by laminating a photosensitive resin layer having a thickness of 30 μm with the above photosensitive resin composition on a support, and the transfer film is laminated on a substrate having an opening of 6 mmφ, and then the entire surface is exposed to light. After the film is formed, the support is peeled off, and the portion corresponding to the center of the opening is subjected to a piercing test with a cylinder of 1.5 mmφ at a speed of 100 mm/min, and the maximum point load is 35 gf or more. A photosensitive resin composition characterized by: The (Bi) component has the following formula (2):

{In the formula, Y ₁ and Y ₂ each independently represent a (meth)acryloyl group, and n represents an integer of 2-30. } The photosensitive resin composition of Claim 1 containing the compound represented by. 3. The photosensitive resin composition according to claim 1, wherein the component (B-ii) comprises at least one compound having multiple aromatic rings in one molecule. The photosensitive resin according to any one of claims 1 to 3, comprising (A-ii) an alkali-soluble polymer having an acidic group and no ethylenically unsaturated group as the component (A). Composition. The photosensitive resin composition according to any one of claims 1 to 4, wherein the component (Bi) is contained in an amount of 3% by mass to 15% by mass with respect to the total solid content of the photosensitive resin composition. thing. As the component (Ai), (A-iii) has a weight average molecular weight of 6,000 or more, an acid value of 60 to 120 mgKOH/g, an ethylenically unsaturated group and an acidic group, and a ring in the main chain. 6. The photosensitive resin composition according to claim 5, wherein the polymer containing the structure is contained in an amount of 90% by mass or more based on the total solid mass of component (A). As the component (A), (A-iv) an alkali-soluble having a weight average molecular weight of 10,000 to 36,000, an acid value of 130 to 150 mgKOH/g and an acidic group having no ethylenically unsaturated group 7. The photosensitive resin composition according to claim 5 or 6, containing a polymer. 8. The photosensitive resin composition according to any one of claims 1 to 7, further comprising (D) a thiol compound having at least two mercapto groups in one molecule. The photosensitive resin composition according to any one of claims 1 to 8, wherein the component (C) is an oxime compound. A transfer film comprising a support film and a photosensitive resin layer comprising the photosensitive resin composition according to any one of claims 1 to 9 provided on the support film. 11. The transfer film according to claim 10, which is used as a protective film for conductors. A method for producing a pattern, comprising laminating the transfer film according to claim 11 on a substrate, exposing and developing to form a pattern. A cured film pattern obtained by subjecting the pattern obtained by the method according to claim 12 to post-exposure treatment and/or heat treatment. A touch panel display device having the cured film pattern according to claim 13 or a device having a touch sensor.

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