JP7149173B2 - Photosensitive resin composition, and transfer film, resin pattern, and cured film pattern using the photosensitive resin composition - Google Patents

Description

TECHNICAL FIELD The present invention relates to a photosensitive resin composition, and a transfer film, resin pattern and cured film pattern using the photosensitive resin composition. The present invention also relates to a touch panel display device having a cured film pattern or a device having a touch sensor.

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, it is desirable that the portions of the terminal portions from which the protective film has been removed be free from discoloration and corrosion from the viewpoint of maintaining appearance and good electrical continuity. If the performance of the protective film is insufficient, the components of the protective film may seep out from the edge of the protective film and contaminate the terminals around the protective film. is desired.

In Patent Documents 1 and 2, a composition containing a polymer having an ethylenically unsaturated group and an acidic group and having a ring structure in the main chain is used as a solder resist. Some compositions using a tetrazole compound are also disclosed, but there is no mention of moisture permeability, discoloration of the protective film-removed portion, and developability, and it is believed that these performances are not satisfied.
Patent Document 3 discloses a protective film for a touch panel using a tetrazole compound, and describes the moisture permeability and the rust prevention of the part covered with the cured film, but the developability and the protective film from the edge No mention is made of the discoloration of the Also, the moisture permeability described is not satisfactory for the level required in recent years.

Japanese Patent No. 5051460 Japanese Patent No. 4830051 JP 2016-157451 A

As described above, the techniques described in Patent Documents 1 to 3 still have room for improvement. Therefore, one of the problems to be solved by the present invention is to provide a transfer film excellent in developability, and a cured film pattern having low moisture permeability and reduced discoloration of the substrate from the end of the protective film. It is to provide a photosensitive resin composition capable of

｛式中、Ｒは１価の有機基を表す。｝で表される化合物を含む、感光性樹脂組成物。
［２］
上記（Ａ）成分は、すくなくとも上記（Ａ－ｉ）成分に対応する重合体を含む１種又は２種以上の重合体Ａ－１、・・・Ａ－ｎ（ｎは１以上の整数を表す。）を含み、下記式（２）：

｛式中、Ｗ_Ａ－１、・・・Ｗ_Ａ－ｎは、上記重合体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、上記重合体Ａ－１、・・・Ａ－ｎの上記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、上記（Ａ）成分の重量平均分子量が６，０００～２０，０００である、項目１に記載の感光性樹脂組成物。
［３］
上記（Ｄ）成分は、（Ｄ－ｉｉ）２５℃における水への溶解度が３０ｇ／Ｌ未満であり、かつ上記式（１）で表される化合物を含む、項目１又は２に記載の感光性樹脂組成物。
［４］
（Ｆ）熱架橋剤を更に含む、項目１～３のいずれか一項に記載の感光性樹脂組成物。
［５］
上記（Ｃ）成分がオキシム化合物である、項目１～４のいずれか一項に記載の感光性樹脂組成物。
［６］
支持体と、前記支持体上に設けられた、項目１～５のいずれか一項に記載の感光性樹脂組成物から形成される感光性樹脂層とを備える、転写フィルム。
［７］
導体用保護膜に使用される、項目６に記載の転写フィルム。
［８］
項目６又は７に記載の転写フィルムの露光現像物から形成される、樹脂パターン。
［９］
項目８に記載の樹脂パターンの硬化物から形成される、硬化膜パターン。
［１０］
項目９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 made intensive studies to solve the above problems, and have found that an alkali-soluble polymer having a specific structure and a tetrazole compound having a specific structure and a specific water solubility are included. We have found that the above problems can be solved by a photosensitive resin composition. Examples of embodiments of the invention are listed below.
[1]
A photosensitive resin composition comprising the following components:
(A) an alkali-soluble polymer,
(B) a photopolymerizable compound,
(C) a photopolymerization initiator, and (D) a tetrazole compound,
The above component (A) contains (Ai) a polymer having an ethylenically unsaturated group and an acidic group and containing a ring structure in the main chain,
The above component (D) has a solubility in water of 55 g/L or less at 25°C, and the following formula (1):

{In the formula, R represents a monovalent organic group. } containing the compound represented by the photosensitive resin composition.
[2]
The above component (A) includes at least one or two or more polymers A-1, . ), including the following formula (2):

{Wherein, W _A -1, ... W _A -n represent the weight average molecular weights of the polymers A-1, ... An, respectively, and X _A -1, ... X _A - n represents the mass % of the polymers A-1, . . . An in the photosensitive resin composition. }, the photosensitive resin composition according to item 1, wherein the weight average molecular weight of component (A) is 6,000 to 20,000.
[3]
Item 1 or 2, wherein the component (D) has a solubility in water of (D-ii) 25 ° C. of less than 30 g / L and contains a compound represented by the above formula (1). Resin composition.
[4]
(F) The photosensitive resin composition according to any one of Items 1 to 3, further comprising a thermal cross-linking agent.
[5]
5. The photosensitive resin composition according to any one of items 1 to 4, wherein the component (C) is an oxime compound.
[6]
A transfer film comprising a support and a photosensitive resin layer formed from the photosensitive resin composition according to any one of items 1 to 5 provided on the support.
[7]
7. The transfer film according to item 6, which is used as a protective film for conductors.
[8]
A resin pattern formed from an exposed and developed product of the transfer film according to item 6 or 7.
[9]
A cured film pattern formed from a cured product of the resin pattern according to Item 8.
[10]
A device comprising a touch panel display device or a touch sensor having the cured film pattern according to item 9.

According to the present invention, there is provided a photosensitive resin composition capable of providing a transfer film excellent in developability and a cured film pattern having low moisture permeability and reduced substrate discoloration from the edge of the protective film. can do. Less discoloration from the protective film edge of the cured film pattern leads to higher reliability of the cured film pattern. The photosensitive resin composition of the present invention can preferably be used to protect conductors such as electrodes.

It is a figure which shows the mask pattern used in the Example. It is a figure which shows the mask pattern used in the Example.

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 various modifications can be made within the scope of the gist of the present invention.

<(A) Alkali-soluble polymer>
The (A) alkali-soluble polymer according to the present embodiment includes (Ai) an alkali-soluble polymer having an ethylenically unsaturated group and an acidic group and containing a ring structure in the main chain. A carboxyl group is preferred as the acidic group. Further, in the photosensitive resin composition according to the present embodiment, the component (A) further contains (A-ii) an alkali-soluble polymer having an acidic group and no ethylenically unsaturated group. This is preferable from the viewpoint of suppressing discoloration of the base material from the edge of the protective film.

(Ai) A polymer having an ethylenically unsaturated group and an acidic group and containing a ring structure in the main chain In the present embodiment, (Ai) is one or more ethylenically unsaturated groups and one or more There is no particular limitation as long as it is a polymer having an acidic group of and having a ring structure in its main chain. As (Ai), for example, an epoxy (meth)acrylate acid-modified product is preferable. Here, (meth)acrylate means acrylate and/or methacrylate, and (meth)acryl means acrylic and/or methacrylic. The same applies to "(meta)" hereinafter.

Examples of ring structures contained 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, resorcinol skeleton and the like.

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 determined from the viewpoint of the properties of the unexposed film such as tackiness, edge fuse properties, and cut chip properties when it is used as a transfer film, and from the viewpoint of suppressing discoloration of the substrate from the edges of the cured film. It is preferably 1,000 or more, and from the viewpoint of the developability of the transfer film and compatibility with other polymerizable compounds such as (A-ii) polymers, preferably 9,500 or less, more preferably 6,000 or more. 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.)}

The alkali-soluble polymer, particularly the component (Ai), preferably has a large molecular weight within a range that does not deteriorate the developability, from the viewpoint of substrate discoloration at the edge of the protective film. The reason for this is presumed by the present inventors as follows.
The evaluation of the reliability of the protective film, that is, the evaluation of discoloration from the edge of the protective film, is mainly carried out by an accelerated test under a high-temperature and high-humidity environment. When a conductor base material with a protective film patterned on it is subjected to a reliability evaluation, discoloration occurs on the base material as if something has seeped out from the edge of the protective film formed by patterning (lower part of the wall surface). It may cause a defect or poor continuity.
When the photosensitive resin composition is exposed to light, the alkali-soluble polymer with a small molecular weight migrates slightly at the boundary between the exposed and unexposed areas, and the boundary between the exposed and unexposed areas becomes ambiguous. It is presumed that the edge of the is likely to swell. As a result, during reliability evaluation, the components of the protective film tend to be eluted from the ends of the protective film, and discoloration of the substrate around the protective film is likely to occur. On the other hand, an alkali-soluble polymer with a large molecular weight is less likely to migrate at the boundary between the exposed area and the unexposed area during exposure, suppresses swelling at the edge of the exposed film, and prevents discoloration of the substrate at the edge of the protective film. It is thought that it can be reduced more.

(A-ii) a polymer having an acidic group and no ethylenically unsaturated groups In this embodiment, (A-ii) 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 Examples of (A-ii) include acrylic copolymers such as (meth)acrylic acid, (meth)acrylic ester, (meth)acrylonitrile, and (meth)acrylamide, polyimide precursors, carboxyl group-containing polyimides, carboxyl and group-containing urethanes. (A-ii) is preferably an acrylic copolymer in terms of compatibility with the photopolymerizable compound (B) described below and transparency.

Acrylic copolymer The acrylic copolymer contained in component (A-ii) is preferably obtained by polymerizing at least one monomer containing an acidic group in the molecule. More preferably, it is obtained by copolymerizing at least one monomer containing an acidic group and at least one other monomer having no acidic group, which will be described later.
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 aromatic (meth)acrylic acid esters or styrene and derivatives thereof A copolymer containing a structural unit that
By copolymerizing the unit having an aromatic group, the hydrophobicity of the acrylic copolymer is increased, and the moisture permeability and rust resistance are 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 moisture permeability and the rust prevention of the conductor. In terms of achieving both developability, moisture permeability reduction, and rust prevention, as an acrylic copolymer, the structure derived from (meth)acrylic acid is 7.7% by mass or more and 30% by mass or less, and the structure derived from styrene or a derivative thereof. 30% by mass or more and 80% by mass or less is more preferable.

Polyimide Precursor The polyimide precursor contained in the component (A-ii) means not only polyamic acid that is not imidized, but also polyamic acid that is partially imidized.

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 stage (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.

Process 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.

Process 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 The carboxyl group-containing polyimide contained in (A-ii) can be synthesized, for example, by reacting tetracarboxylic dianhydride and diamine in an organic solvent. The molar ratio of tetracarboxylic dianhydride to diamine may be, for example, 0.8:1 to 1.2:1. The carboxyl group-containing polyimide may contain carboxyl groups in its skeleton even after being imidized, and may partially have a polyamic acid structure.

A carboxyl group-containing polyimide can be 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 include the examples described above in the item (A-ii) "polyimide precursor". It is the same.

The carboxyl group-containing polyurethane contained in the carboxyl group-containing polyurethane (A-ii) is, for example, a diisocyanate compound, a carboxyl group-containing diol compound, and other diol compounds in an aprotic solvent, and known to have an activity corresponding to each reactivity. can be synthesized by adding a suitable catalyst and heating. The molar ratio of the diisocyanate compound and the diol compound used is preferably 0.8:1 to 1.2:1. When isocyanate groups remain at polymer terminals, treatment with alcohols, amines, or the like can be used to finally synthesize the polymer in a form in which no isocyanate groups remain.

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 even more preferably 90 to 170. Also, the weight average molecular weight of (A-ii) is preferably 11,000 to 50,000. The weight average molecular weight of (A-ii) is 11, 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 suppressing discoloration of the substrate from the edges of the cured film. 000 or more, and preferably 50,000 or less from the viewpoint of developability and compatibility with the (Ai) polymer. More preferably, it is 15,000 or more and 35,000 or less. By improving the compatibility, it becomes easier to express the performance of developability and moisture permeability.

The photosensitive resin composition of the present embodiment can also contain (A) an alkali-soluble polymer that does not correspond to (Ai) or (A-ii) described above, if necessary. For example, the photosensitive resin composition may contain an alkali-soluble polymer having one or more ethylenically unsaturated groups and one or more acidic groups and having no ring structure in its main chain. For example, a ring structure in the main chain obtained by copolymerizing a monomer having a carboxyl group and a monomer not containing an acidic group as described in (A-ii) "acrylic copolymer" Ethylenically unsaturated groups can be introduced into side chains by adding glycidyl methacrylate to an acrylic copolymer having no As a result, an alkali-soluble polymer having one or more ethylenically unsaturated groups and one or more acidic groups 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。｝で算出される重量平均分子量が、６，０００～２０，０００であることが好ましい。転写フィルムのタック性、エッジフューズ性及びカットチップ性等の未露光膜の性状の観点、並びに硬化膜端部からの基材の変色を抑制する観点から、（Ａ）アルカリ可溶性重合体の重量平均分子量は、６，０００以上であり、現像性の観点から、好ましくは２０，０００以下であり、より好ましくは１０，０００以上１５，０００以下である。 (A) weight-average molecular weight of the alkali-soluble polymer, the above-mentioned (A) alkali-soluble polymer is one or more polymers A-1 containing at least a polymer corresponding to the component (Ai); ... including An (n represents an integer of 1 or more), and the following formula (2):

{Wherein, W _{A- 1 ,} . . . . X An represents mass % of each polymer _A -1, . . . An corresponding to component (A) in the photosensitive resin composition. } is preferably 6,000 to 20,000. From the viewpoint of the properties of the unexposed film such as the tackiness of the transfer film, the edge fuse property and the cut chip property, and from the viewpoint of suppressing the discoloration of the substrate from the edge of the cured film, the weight average of (A) the alkali-soluble polymer The molecular weight is 6,000 or more, preferably 20,000 or less, more preferably 10,000 or more and 15,000 or less, from the viewpoint of developability.

<(B) Photopolymerizable compound>
In the present embodiment, the photopolymerizable compound (B) means a compound having polymerizability due to having an ethylenically unsaturated group in its structure.
Component (B) is not particularly limited as long as it is a compound containing one or more ethylenically unsaturated groups in one molecule. However, a polymer that further has one or more acidic groups and contains a ring structure in its main chain may also correspond to component (Ai) at the same time, and such a polymer is (A) regarded as an ingredient.

As the component (B), for example, 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.

As the component (B), a compound having (meth)acryloyl groups at both ends of a polyalkylene oxide chain, or a (meth) A compound having an acryloyl group, a compound having a (meth)acryloyl group at both ends by modifying bisphenol A with an alkylene oxide, and the like are also included.

Component (B) also includes a urethane compound which is a reaction product of a diisocyanate compound and a compound having a hydroxyl group and a (meth)acrylic group in one molecule.

As component (B), a compound having three or more (meth)acryloyl groups in one molecule can also be used. Such a compound has 3 mol or more of a group to which an alkylene oxide group can be added in the molecule as a central skeleton, to which an alkyleneoxy group such as an ethylene oxide group, a propylene oxide group, or a butylene oxide group is added. It is obtained by making the obtained alcohol into (meth)acrylate. Examples of compounds that can serve as the central skeleton include glycerin, trimethylolpropane, pentaerythritol, ditrimethylolpropane, dipentaerythritol, and isocyanurate rings. From the viewpoint of rust prevention, the component (B) preferably contains a compound having three or more (meth)acryloyl groups in one molecule, such as dipentaerythritol hexa(meth)acrylate, trimethylolpropane tri( More preferably, it contains meth)acrylates or ditrimethylolpropane tri(meth)acrylates.

From the viewpoint of moisture permeability, rust prevention, and substrate discoloration from the edge of the cured film, the photosensitive resin composition of the present embodiment has three or more ethylenically unsaturated double bonds per molecule (B). It is preferable to contain a component, and from the viewpoint of improving the reaction rate of the entire photosensitive resin composition and reducing the moisture permeability of the cured film, it has one ethylenically unsaturated double bond per molecule (B) It preferably contains further ingredients.
The content of the component (B) in the photosensitive resin composition is, from the viewpoint of resolution, adhesion, moisture permeability and rust prevention, based on the total solid content of the photosensitive resin composition, 20% by mass to It is preferably 60% by mass, more preferably 30% to 50% by mass.

<(C) Photopolymerization initiator>
In the present embodiment, the photopolymerization initiator (C) 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; benzoin methyl ether, benzoin ethyl ether, benzoin phenyl ether, etc. benzoin 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 -Oxime ester compounds such as (O-acetyloxime); benzyl derivatives such as benzyl dimethyl ketal; acridine derivatives such as 9-phenylacridine and 1,7-bis(9,9'-acridinyl)heptane; N-phenylglycine and the like 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 preferably 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.

｛式中、Ｒは１価の有機基を表す。｝で表される化合物であり、２５℃における水への溶解度が５５ｇ/Ｌ以下であれば特に制限は無い。式（１）の構造を有し、水への溶解度が５５ｇ/Ｌ以下であることで、硬化膜端部からの基材変色が抑制される。 <(D) Tetrazole compound>
In this embodiment, (D) the tetrazole compound has the following formula (1):

{In the formula, R represents a monovalent organic group. }, and there is no particular limitation as long as the solubility in water at 25° C. is 55 g/L or less. By having the structure of formula (1) and having a solubility in water of 55 g/L or less, discoloration of the base material from the edges of the cured film is suppressed.

Component (D) may have a structure represented by the above formula (1), and (D-i) may have a solubility in water of 30 g/L or more and 55 g/L or less, and (D- ii) may have a solubility in water of less than 30 g/L; From the viewpoint of suppressing discoloration of the base material from the edge of the cured film, (D-ii) the solubility in water is preferably less than 30 g/L. For the method of measuring solubility in water, see "2. Water solubility of components (D) and (E)" in Examples.

(Di) Examples of the tetrazole compound having a solubility in water of 30 g/L or more and 55 g/L or less include 5-amino-1H-tetrazole. (D) From the viewpoint of increasing the hydrophobicity of the tetrazole compound and improving the effect of suppressing discoloration of the substrate from the edges of the cured film, R in formula (1) is a monovalent organic group containing an aromatic ring. is preferred. Examples of the monovalent organic group containing an aromatic ring include, but are not limited to, a phenyl group, a halogenated phenyl group, a benzyl group, a halogenated benzyl group, a benzylthio group, and the like. may have. Examples of halogenated phenyl groups include bromophenyl groups and chlorophenyl groups, and examples of halogenated benzyl groups include bromobenzyl groups and chlorobenzyl groups. (D-ii) Examples of tetrazole compounds having a water solubility of less than 30 g/L include 5-phenyl-1H-tetrazole, 5-benzyl-1H-tetrazole, 5-(benzylthio)-1H-tetrazole, 5 -(2-bromophenyl)-1H-tetrazole, 5-(2-chlorophenyl)-1H-tetrazole and the like.

When a protective film is laminated on a conductor substrate, the mobility of the component (D) increases, making it easier for the component (D) to be unevenly distributed at the interface of the conductor. From this point of view, the molecular weight of the component (D) is preferably 300 or less, more preferably 200 or less.

(D) The content of the tetrazole compound in the photosensitive resin composition is preferably 0.05% by mass to 10% by mass based on the total solid content of the photosensitive resin composition. It is more preferably 0.2% by mass or more from the viewpoint of suppressing discoloration of the base material, and more preferably 5% by mass or less from the viewpoint of developability.

The reason why the photosensitive resin composition of the present embodiment contains (D) a tetrazole compound can suppress discoloration from the edge of the protective film is presumed as follows. ing.
The evaluation of the reliability of the protective film, that is, the evaluation of discoloration from the edge of the protective film, is mainly carried out by an accelerated test under a high-temperature and high-humidity environment. When a conductor base material with a protective film patterned on it is subjected to a reliability evaluation, discoloration occurs on the base material as if something has seeped out from the edge of the protective film formed by patterning (lower part of the wall surface). It may cause a defect or poor continuity.
This is because the hardening of the lower part of the wall surface of the protective film is insufficient, and as the protective film absorbs moisture and swells, the components of the protective film tend to elute, and the base material appears to have leaked out from the edge of the protective film. It is presumed that discoloration occurs on the top.
When the photosensitive resin composition contains (D) a tetrazole compound, the component (D) is unevenly distributed at the interface of the conductor base material, which makes the lower part of the protective film hydrophobic, making it difficult to absorb moisture, thereby eluting the protective film component. can be suppressed, and defects due to discoloration of the substrate from the end of the protective film can be reduced.

<(E) heterocyclic compound>
The photosensitive resin composition of the present embodiment may contain an antirust agent and/or adhesion aid (E) heterocyclic compound from the viewpoint of exhibiting higher antirust performance and/or adhesion. However, the (E) heterocyclic compound excludes those corresponding to the (D) component. A rust preventive is a compound having a rust preventive effect, and is, for example, a substance that forms a film on a metal surface to prevent corrosion or rust of the metal.

As component (E), from the viewpoint of compatibility and sensitivity with the photosensitive resin composition according to the present embodiment, heterocyclic compounds containing N, S, O, etc. are preferable. 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.

(E) Examples of tetrazole compounds and derivatives thereof include 1H-tetrazole, 5-methyl-1H-tetrazole, 1H-tetrazole-5-acetic acid, 1-methyl-5-ethyl-1H-tetrazole, 1-methyl -5-mercapto-1H-tetrazole, 1-phenyl-5-mercapto-1H-tetrazole, 1-(dimethylaminoethyl)-5-mercapto-1H-tetrazole and the like.

Examples of triazole compounds and derivatives thereof as component (E) include 1,2,3-triazole, 1,2,4-triazole, 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-chlorobenzo triazole, 5-nitrobenzotriazole and the like.

Examples of (E) component imidazole compounds and derivatives thereof include imidazole, 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. mentioned.

Examples of imidazoline compounds and derivatives thereof include 2-undecylimidazoline, 2-propyl-2-imidazoline, 2-phenylimidazoline and the like. Thiazole compounds and derivatives thereof include 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 and the like.

Examples of isothiazoles, thiadiazoles, thiophenes and derivatives thereof include 3-chloro-1,2-benzisothiazole, 1,2,3-thiadiazole, 1,2,5-thiadiazole, 1,3,4-thiadiazole , 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, 2-thiophenecarboxylic acid, 3-amino-2-thiophenecarboxylic acid Examples include methyl acid, 3-methylbenzothiophene, and the like.

Further examples of indazoles and derivatives thereof include 1H-indazole, 5-aminoindazole, 6-aminoindazole, 1-benzyl-3-hydroxy-1H-indazole, 5-bromoindazole, 6-bromoindazole, 6-hydroxy Indazole, 3-carboxyindazole, 5-nitroindazole and the like.

Among component (E), 5-carboxybenzotriazole, 5-aminoindazole and 5-amino-1,2,3-thiadiazole are preferred from the viewpoint of conductor rust prevention, adhesion and developability. In this embodiment, one type of component (E) may be used alone, or two or more types may be used in combination.

The content of the component (E) in the photosensitive resin composition is preferably 0.00, based on the total solid mass of the photosensitive resin composition, from the viewpoint of the rust resistance of the conductor or the low-temperature developability of the transfer film. 05 mass % to 10 mass %, more preferably 0.1 mass % to 5 mass %, still more preferably 0.2 mass % to 3 mass %.

<(F) Thermal cross-linking agent>
The photosensitive resin composition preferably further contains a thermal cross-linking agent from the viewpoint of higher antirust performance and suppression of discoloration of the base material from the edges of the cured film. The thermal cross-linking agent is, by heat, (A) an alkali-soluble polymer, (B) a photopolymerizable compound having an unreacted ethylenically unsaturated double bond, and a thermal cross-linking agent added at the same time, addition reaction, or condensation polymerization. It means a compound that causes a reaction. 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, 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.

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, and more preferably used in combination with a diol compound described later from the viewpoint of the developability of the transfer film.

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 from the viewpoint of developability and low water permeability. , more preferably 1% by mass to 30% by mass, and even more preferably 2% by mass to 25% 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. At the same time, since swelling of the cured film is suppressed by increasing the cross-linking density, discoloration of the base material from the edge of the protective film can also be suppressed. 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.

<(G) Other additives>
Diol compound The photosensitive resin composition preferably further contains a diol compound in order to improve the developability of the transfer film and reduce the curing shrinkage of the cured film pattern, and improve the flexibility, low moisture permeability and rust prevention of the cured film pattern. From the viewpoint of above, it is more preferable to contain a blocked isocyanate and a diol compound. 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.

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.

Rosin Ester Compound The photosensitive resin composition preferably further contains a rosin ester compound from the viewpoint of further reducing the water permeability of the cured film pattern. The rosin ester compound according to the present embodiment includes rosin acid, which is a tricyclic diterpenoid having 20 carbon atoms, which is a non-volatile component of pine resin, a dimer of rosin acid, a hydrogenated product of rosin acid, and an imbalance of rosin acid. A compound having an ester bond or a rosin acid derivative is obtained by reacting a compound selected from the group consisting of homogenates (hereinafter collectively referred to as "rosin acid derivative") with any of a hydroxyl compound, a phenol compound and a glycidyl compound. It is a compound having an ester bond by glycidylating and reacting with either a carboxyl compound or a phenol compound.

Specific examples of rosin ester compounds include products of Arakawa Chemical Co., Ltd. such as Ester Gum series, Pine Crystal series, Super Ester series, Pencel series, Beamset 101, etc., and products of Harima Kasei Co., Ltd. Products include the Harrier Star series, the Neotor series, and the Haritak series.

A rosin ester compound is a compound that has an alicyclic structure and an ester structure, thereby increasing hydrophobicity. Since the rosin ester compound has good compatibility with (A) the alkali-soluble polymer, (B) the photopolymerizable compound, and (C) the photopolymerization initiator in the photosensitive resin composition, it does not inhibit developability. Therefore, the transfer film developability, the moisture permeability of the cured film, and the rust resistance of the conductor are well balanced.

From the viewpoint of conductor rust prevention, the rosin ester compound (F) preferably has an acid value of 20 mgKOH/g or less. Kasei Co., Ltd. products include, for example, Pine Crystal KE-100, Ester Gum 105, Super Ester A-115, Super Ester A-125, Pencel A, Pencel C, Pencel D-125, Pencel D-135, Pencel D-160, Beamset 101, Harrier 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, it is more preferable that the softening point of the rosin ester compound is 100° C. or higher. A-125, Pensel A, Pensel C, Pensel D-125, Pensel D-135, Pensel D-160, Neotol 125HK and the like. It is particularly preferable that the rosin ester compound has a softening point of 110° C. or higher. D-135, Pencel D-160, Neotol 125HK. (F) The rosin ester compound can be used alone or in combination of two or more.

The content of the rosin ester compound in the photosensitive resin composition is 1% by mass to 20% by mass relative to the total solid mass of the photosensitive resin composition, and from the viewpoint of moisture permeability and developability, 5% by mass. It is more preferably up to 20% by mass, and further preferably 5% by mass to 15% by mass from the viewpoint of adhesion to the substrate. When the content of the rosin ester compound 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.

The photosensitive resin composition also contains a polymerization inhibitor such as an aluminum salt to which 3 mol of nitrosophenylhydroxylamine is added, an antioxidant, an adhesion aid, a leveling agent, a filler, an antifoaming agent, a flame retardant, and the like. These can be used alone or in combination of two or more.

<Transfer film>
The transfer film of the present embodiment includes a support and a photosensitive resin layer formed from the photosensitive resin composition of the present embodiment provided on the support. 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 0.07 per 1 μm of the thickness of the photosensitive resin layer. is preferred. If the thickness of the photosensitive resin layer is too thick, the developability and flexibility deteriorate, so the thickness of the photosensitive resin layer is preferably 15 μm or less, from the viewpoint of following the unevenness of the wiring and ensuring rust prevention. From the point of view, 3 μm or more is preferable.

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

The support used in this embodiment is desirably a transparent one that transmits light emitted from the exposure light source. The support may for example be in the form of a support film. 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 layer used for the transfer film is that the adhesive strength to the photosensitive resin layer is much smaller than that of the support and that the protective layer can be easily peeled off. The protective layer may be in the form of a protective film, and for example, polyethylene film, polypropylene film, etc. can be preferably used.

A method for producing a transfer film includes a step of applying a coating liquid onto a support (e.g., support film) and drying it, and if necessary, forming a protective layer (e.g., protective film) on the photosensitive resin layer. Including the step of laminating. 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 conductors, in which case the conductors are copper electrodes, nickel, palladium, silver, titanium, molybdenum, etc. and copper. It is more preferable that the electrode is an alloy electrode with or a transparent electrode. 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>
The resin pattern of this embodiment is formed from the exposed and developed product of the transfer film of this embodiment. Formation of a resin pattern using the transfer film of the present embodiment includes the following steps:
A lamination step of laminating the transfer film of the present embodiment on 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, it is preferable to form a cured film pattern in order to use the resin pattern as a protective film for the conductor portion. The cured film pattern of this embodiment is formed from the cured resin pattern of this embodiment. The method for forming a cured film pattern of the present embodiment preferably further includes a step of subjecting the resin pattern to post-exposure treatment and/or heat treatment after the developing step to form a cured film pattern.

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. . Further, 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 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 on the photosensitive resin layer, the support 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 the photosensitive resin composition of the present embodiment, it is possible to provide a transfer film excellent in developability, and a cured film pattern having low moisture permeability and reduced substrate discoloration from the end of the protective film. Less substrate discoloration from the overcoat edge leads to higher reliability of the cured film pattern. Such a transfer film using the photosensitive resin composition of the present embodiment is suitable for protecting conductor parts such as wiring and electrodes, and is preferably, for example, a touch panel, a touch sensor, a force sensor, a strain sensor or an AI It can be used as a protective film for wiring, electrodes, etc. for use in related electronic devices, or as a solder resist for printed wiring boards.

<Touch panel display device, device having touch sensor or force sensor>
A touch panel display device or a device having a touch sensor of the present embodiment has the cured film pattern of the present embodiment. By forming the cured film pattern of the transfer film according to the present embodiment on the substrate for touch panel, a touch panel display device having the cured film pattern of the transfer film, and the cured film of the transfer film, the touch sensor and/or the force sensor are formed. can provide a device with
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.

The method of forming a cured film as a protective film on a touch panel substrate includes the first step of laminating the transfer film according to the present embodiment onto the touch panel substrate, and curing a predetermined portion of the protective film by irradiation with actinic rays. a third step of forming a cured product of the patterned protective film by removing portions other than a predetermined portion of the protective film (a portion of the protective film not irradiated with actinic rays), and a patterned protective 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 pattern of a transfer film, or a cured film of a transfer film and a touch sensor and/or a force sensor can be formed. can provide a device with

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: ZCR-6001H (acid-modified epoxy acrylate having a triphenylmethane skeleton, manufactured by Nippon Kayaku Co., Ltd.)
A-4: ZCR-8001H (acid-modified epoxy acrylate having a resorcinol 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 weights and acid values of (A-1) to (A-5) above. The weight average molecular weight and acid value were measured by the methods described in the section <(A) Alkali-soluble polymer> above.

Next, (A-ii) preparation 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 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-7).

<Production of (A-8)>
In the same manner as the above alkali-soluble polymer solution (A-6), using 25% by mass of MAA, 20% by mass of MMA, and 55% by mass of St, the solid content acid value is 163 mgKOH / g and the weight average molecular weight is about 31,000. An alkali-soluble polymer solution (solid content: 50% by mass) (A-8) was obtained.

Table 2 shows the copolymer composition, weight average molecular weight and acid value of (A-6) to (A-8) thus obtained. The weight average molecular weight and acid value of the alkali-soluble polymer were measured by the methods described in detail in <(A) Alkali-soluble polymer> above.

2. Water solubility of component (D) and component (E) A method for measuring the solubility of component (D) and component (E) in water will be described.
0.7 g of component (D) or (E) and 4 mL of deionized water were placed in a 5 mL vial, sealed, and stirred for 24 hours with a variable mix rotor (manufactured by AS ONE Corporation, VMR-5). At this time, the rotation speed was set to 80 rpm, and stirring was performed at room temperature (25° C.).
After 24 hours, the sample was subjected to suction filtration using filter paper for funnel (manufactured by Kiriyama Seisakusho, filter paper for Kiriyama funnel 60 mmφ, No. 5B) to collect undissolved matter. At this time, the weight of the filter paper to be used was weighed in advance. The collected undissolved matter was stored and dried together with the filter paper in a vacuum dryer at 50°C for 15 hours. After drying, each filter paper is weighed, and the amount of undissolved matter is calculated by subtracting the weight of the previously weighed filter paper, and the dissolved amount is calculated from the difference from the initial input amount of 0.7 g. It was taken as the solubility in water of the component and (E) component. The results are summarized in Table 3.

3. 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 and 5 below (however, the number of each component indicates the amount (parts by mass) as a solid content), and the solid content concentration was 53 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 14 and Comparative Examples 1 to 7).

The photosensitive resin composition preparation is evenly applied to the surface of a 16 μm thick polyethylene terephthalate film (manufactured by Mitsubishi Chemical Corporation, R310-16B) as a support film using a blade coater, and dried to form a support film. A uniform photosensitive resin layer was formed thereon. The thickness of the photosensitive resin layer was set to 8 μm and 40 μm, and the drying conditions were set to 4 minutes in a dryer at 95° C. for 8 μm and 9 minutes in a dryer at 95° C. for 40 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.
The obtained transfer film for evaluation was evaluated by the following methods. Evaluation results are shown in Tables 4 and 5. Table 6 shows the names and the like of the material components in the photosensitive resin composition formulations shown in Tables 4 and 5.

4. Developability <Sample preparation method>
A sample for evaluation of developability was prepared as follows. In this evaluation, an alloy substrate (manufactured by Toho Kaken Co., Ltd.) in which a copper-nickel alloy (composition ratio 50:50) was deposited on a polyethylene terephthalate film to a thickness of 0.1 μm was used as a base material. ing.
A hot roll laminator (VA-400III, manufactured by Taisei Laminator Co., Ltd.) was applied onto the alloy surface (size: 5 cm × 10 cm) of the copper-nickel alloy substrate while peeling off the protective film of the transfer film having a thickness of 8 μm. was used to laminate 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 at 80°C, the roll temperature was raised to 100°C for lamination. After standing still for 15 minutes, a PET mask and a Stouffer 21-step tablet (a step tablet with an optical density of 0.00 as the first step and an optical density that increases by 0.15 for each step) were placed on the support film. They were placed side by side and exposed with a parallel light exposure machine (HMW-801, manufactured by ORC Manufacturing Co., Ltd.) from the PET mask and step tablet side at the optimum exposure amount for each composition. A PET mask having a pattern as schematically 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, the arrows and numerical values in the drawing schematically represent the dimensions, not the actual mask patterns.

Then, after standing still for 15 minutes or more, the support film 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 55 seconds for development, and the unexposed portions of the photosensitive resin layer were dissolved and removed. After the development process, the film was dried by an air blow and then washed with water. The water washing process was carried out using a flat type nozzle at a washing spray pressure of 0.12 MPa for the same period as the developing process, and the washed 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 8 to 9 steps of a remaining film when exposed through a Stufer 21-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, A and B ranks are considered to be practically good results as protective films for conductors. The evaluation results are summarized in Tables 4 and 5.

5. 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 40 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 at 60°C, the roll temperature was raised to 100°C for lamination. After standing still for 15 minutes, the entire surface was exposed from the support film side of the protective film with an exposure dose of 350 mJ/cm ² using a scattered light exposure machine (HMW-201KB, manufactured by Oak Manufacturing Co., Ltd.). 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./humidity 90% and judged as follows.
A Moisture permeability 150 g/(m ² ·day) or more and less than 200 g/(m ² ·day) B Moisture permeability 200 g/(m ² ·day) or more and less than 250 g/(m ² ·day) C: Moisture permeability of 250 g/(m ² ·day) or more and less than 300 g/(m ² ·day) D: Moisture permeability of 300 g/(m ² ·day) or more In the moisture permeability test, ranks A to C is considered to be a practically good result as a protective film for conductors. The evaluation results are summarized in Tables 4 and 5.

6. Evaluation of discoloration at the edge of the protective film (reliability evaluation)
<Sample preparation method>
Samples for evaluation of discoloration at the edge of the protective film are described in <4. Using the same alloy substrate as used in Developability>, it was produced as follows.
A hot roll laminator (VA-400III, manufactured by Taisei Laminator Co., Ltd.) was placed on the alloy surface (size: 5 cm × 5 cm) of the copper-nickel alloy substrate while peeling off the protective film of the transfer film having a thickness of 8 μm. was used to laminate 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 for lamination. After standing still for 15 minutes, a PET mask was placed on the support film, and <4. Developability> was exposed using a parallel light exposure machine (HMW-801, manufactured by OAK Mfg. Co., Ltd.) at the same exposure amount as the exposure amount irradiated in Developability>. As the PET mask, one having a line:space=1:1 pattern as schematically shown in FIG. 2 was used. In FIG. 2, the shaded portions represent light shielding portions, and the white portions represent light transmitting portions. Also, the arrows and numerical values in the drawing schematically represent the dimensions, not the actual mask patterns.

Then, after standing still for 15 minutes or longer, the support film was peeled off, and the developer was developed with a full-cone type nozzle using a developing device manufactured by Fuji Kiko Co., Ltd. with a spray pressure of 0.12 MPa and 1 mass% Na ₂ CO ₃ at 28°C. An aqueous solution was sprayed for 55 seconds for development, and the unexposed portions of the photosensitive resin layer were dissolved and removed. After the developing process, the film was dried by an air blow and then washed with water. The washing process was carried out using a flat type nozzle at a washing spray pressure of 0.12 MPa for the same period as the developing process, and the washed sample was dried by air blowing.

Subsequently, the washed and dried sample was entirely exposed at an exposure dose of 300 mJ/cm ² using a scattered light exposure machine (HMW-201KB, manufactured by Oak Manufacturing Co., Ltd.). After standing still for 30 minutes, it was treated in a hot air circulating oven at 150° C. for 30 minutes to prepare a sample.

<Evaluation method>
The heat-treated samples were stored for 200 hours in a constant temperature and humidity oven (manufactured by Espec Co., Ltd., SH-641) at 85° C. and 85% RH, and the samples were observed with an optical microscope at a magnification of 500. At that time, the edge of the patterned cured film was observed to determine whether or not there was discoloration of the substrate around the cured film as follows.
A: Discoloration is less than 5 μm from the edge of the protective film.
B . . . Discoloration is 5 μm or more and less than 10 μm from the edge of the protective film.
C: Discoloration is 10 μm or more and less than 20 μm from the edge of the protective film.
D: Discoloration is 20 μm or more from the edge of the protective film.
In the evaluation of discoloration at the edge of the protective film, the A to C ranks are considered to be reliable as protective films for conductors. The evaluation results are summarized in Tables 4 and 5.

From the results shown in Tables 4 and 5, it is shown that Examples 1 to 14 are excellent in developability, moisture permeability and reliability of the cured film by satisfying the requirements defined in the present invention. On the other hand, Comparative Examples 1 to 7 do not satisfy any of the requirements defined in the present invention, and are inferior in any of developability, water vapor permeability and reliability of the cured film.

Compared with Examples 1 to 3, Comparative Examples 1 to 5 do not contain the component (D), so the cured films are inferior in reliability and are not suitable as protective films for conductors. Although Comparative Examples 1 to 4 contain a heterocyclic compound (E), E-1 and E-2 in Comparative Examples 1 and 2 satisfy the structure of formula (1), but have a solubility in water of 55 g. /L, and as a result, the effect of improving reliability cannot be obtained. Further, although E-3 and E-4 in Comparative Examples 3 and 4 have low solubility in water, they do not have a structure that satisfies the formula (1), so that the effect of improving reliability cannot be obtained. In addition, Comparative Examples 6 and 7 are inferior to Example 3 in developability and moisture permeability because they do not contain (Ai). Due to poor developability, reliability evaluation has not been carried out.

Next, the examples will be compared. Since Examples 2 and 3 contain the component (D-ii) having a solubility in water of less than 30 g/L, the examples containing only the component (D-i) having a solubility in water of 30 g/L or more Compared to 1, the reliability is better. In addition, Example 4 is the same as Example 3 except for the (A) component, but uses a higher molecular weight polymer as the (A-ii) component, and the average molecular weight of the (A) component is greater than 20,000, the developability is inferior to that of Example 3. On the other hand, Example 6 is the same as Example 5 except for the (A) component, but the (Ai) component is large, and the average molecular weight of the (A) component is less than 6,000. The properties are inferior to those of Example 5. Furthermore, Example 7 has a composition in which part of the (A-ii) component of Example 3 is replaced with the (Ai) component and the amount of the (Ai) component is increased, and although the moisture permeability is improved, the reliability It can be seen that the sexuality has deteriorated slightly. The improvement in moisture permeability by component (Ai) has a trade-off relationship with reliability, but when combined with the effect of improving reliability by component (D), a composition with a good performance balance can be obtained.
In addition, although Example 9 has a composition excluding the thermal cross-linking agent from Example 8, the moisture permeability and reliability are inferior to those of Example 8, and the thermal cross-linking agent has the effect of improving moisture permeability and reliability. I know there is. In addition, Example 11 has a composition in which the (C) component of Example 10 is changed to a non-oxime initiator, but the moisture permeability is inferior to that of Example 10, and the oxime initiator improves moisture permeability. It turns out that there is an effect.

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

The transfer film formed from the photosensitive resin composition according to the present invention has excellent developability, and the cured film pattern obtained by curing the transfer film has low moisture permeability and is resistant to discoloration of the substrate from the end of the protective film. Fewer. Therefore, the cured film pattern of the present invention is highly reliable as a protective film for conductors such as wiring and electrodes. For example, the cured film pattern of the present invention can be applied to liquid crystal display devices, organic EL display devices, touch panels, touch sensors, force sensors, integrated circuit devices, solid-state imaging devices, semiconductor devices, and other electronic components. It can be widely used for forming an interlayer insulating film, or as a protective film for wires, electrodes, etc. for solder resist applications of rigid printed wiring boards and flexible printed wiring boards.

Claims (10)

A photosensitive resin composition comprising the following components:
(A) an alkali-soluble polymer,
(B) a photopolymerizable compound,
(C) a photopolymerization initiator, and (D) a tetrazole compound,
The component (A) includes (Ai) a polymer having an ethylenically unsaturated group and an acidic group and containing a ring structure in the main chain,
The component (D) has a solubility in water of 55 g/L or less at 25°C, and the following formula (1):

{In the formula, R represents a monovalent organic group. } containing the compound represented by the photosensitive resin composition. The component (A) includes at least one or two or more polymers A-1, . ), including the following formula (2):

{wherein W _A -1, ... W _A -n represent the weight average molecular weights of the polymers A-1, ... An, respectively, and X _A -1, ... X _A - n represents mass % of the polymers A-1, . . . An in the photosensitive resin composition. }, the photosensitive resin composition according to claim 1, wherein the weight average molecular weight of component (A) is 6,000 to 20,000. 3. The photosensitive material according to claim 1, wherein the component (D) comprises (D-ii) a compound having a solubility in water at 25° C. of less than 30 g/L and represented by the formula (1). elastic resin composition. 4. The photosensitive resin composition according to any one of claims 1 to 3, further comprising (F) a thermal cross-linking agent. The photosensitive resin composition according to any one of claims 1 to 4, wherein the component (C) is an oxime compound. A transfer film comprising a support and a photosensitive resin layer formed from the photosensitive resin composition according to any one of claims 1 to 5 provided on the support. 7. The transfer film according to claim 6, which is used as a protective film for conductors. A resin pattern formed from the exposed and developed product of the transfer film according to claim 6 or 7. A cured film pattern formed from the cured resin pattern according to claim 8 . A device comprising a touch panel display device or a touch sensor having the cured film pattern according to claim 9 .

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