JP2019207321A - Photosensitive resin composition, transfer film using photosensitive resin composition, production method of resin pattern, and production method of cured film pattern - Google Patents

Abstract

To provide a photosensitive resin composition that exhibits good developability, moisture permeability as a cured film, adhesiveness of an exposed film to a conductor substrate after development, and film strength and that is suitable for protecting a conductor part such as an electrode, a transfer film and a production method of the film.SOLUTION: The photosensitive resin composition comprises (A) an alkali-soluble polymer having an acidic group, (B) a photopolymerizable compound, and (C) a photopolymerization initiator. The composition contains: as the (A) component, (A-i) a polymer having an ethylenically unsaturated group and an acidic group and including a cyclic structure in the main chain; and as the (B) component, (B-i) a compound having at least two ethylenically unsaturated groups and including butylene oxide as a repeating unit in the structure (excluding a compound belonging to (A-i)) and (B-ii) a compound having one ethylenically unsaturated group. The (A) component has a weight average molecular weight of 6,000 to 20,000; and the composition contains the (B-ii) component by 3 mass% or more based on the whole solid content mass of the photosensitive resin composition.SELECTED DRAWING: None

Description

  The present invention relates to a photosensitive resin composition, a transfer film, a resin pattern manufacturing method using the transfer film, and a cured film pattern manufacturing method. More specifically, the present invention relates to a liquid crystal display device, an organic EL display device, a touch panel display device, an integrated circuit element, a solid-state imaging device, a planarization film of an electronic component such as a semiconductor element, formation of a protective film and an interlayer insulating film, or The present invention relates to a photosensitive resin composition suitable for a rigid printed wiring board, a solder resist of a flexible printed wiring board, or an interlayer insulating film, a transfer film, and a resin pattern manufacturing method using the same.

  In recent years, as electronic devices have been improved in performance, 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 a liquid crystal has increased. Increasingly, it is possible to visually recognize and select characters, symbols, patterns, and the like displayed on a display element through a transparent touch panel, and to switch each function of the device by operating the transparent touch panel. Touch panels are used not only for large electronic devices such as personal computers and televisions, but also for small electronic devices such as car navigation systems, mobile phones, and electronic dictionaries, and display devices such as OA / FA devices. An electrode made of a material is provided. As the transparent conductive electrode material, ITO (Indium-Tin-Oxide), indium oxide, and tin oxide are known, and these materials have high visible light transmittance, so that they are electrode materials such as substrates for liquid crystal display elements. It 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. 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, thereby forming a capacitor. For this reason, the capacitive touch panel detects the coordinates of the contact position by capturing a change in charge at the contact position of the fingertip. In particular, the projected capacitive touch panel can detect multiple points on the fingertip, and thus has a good operability that allows complicated instructions to be given. Therefore, a small display such as a mobile phone or a portable music player can be used. The use as an input device on a display surface in a device having the device is advancing. In general, in a projected capacitive touch panel, a plurality of X electrodes and a plurality of Y electrodes orthogonal to the plurality of X electrodes have a two-layer structure in order to express two-dimensional coordinates by the X axis and the Y axis. ITO is used as the electrode material.

  Since the frame area of the touch panel is an area in which the touch position cannot be detected, reducing the area of the frame area is an important factor for improving the product value. In the frame area, metal wiring is required to transmit a touch position detection signal, but in order to reduce the frame area, it is necessary to reduce the width of the metal wiring. Since the conductivity of ITO is not sufficiently high, copper or an alloy is generally used for metal wiring.

  However, in the touch panel as described above, corrosive components such as moisture and salt may intrude into the inside from the sensing region when touching the fingertip. If a corrosive component enters the inside of the touch panel, the metal wiring will corrode, which may increase the electrical resistance between the electrode and the drive circuit, or cause a disconnection. To prevent these, a protective film with an antirust effect on the metal wiring is required. Generally, there exists a tendency for the rust prevention effect of metal wiring to increase, so that the moisture permeability of a protective film is low.

  In addition, since the metal wiring for transmitting the detection signal is connected to another member at the terminal portion, it is necessary to ensure conduction, and the protective film should be removed from the terminal portion. For this reason, the protective film is required to have good developability, and it is required to have good detachability in various patterns such as circular holes. As the 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 the long-term stability of the developer concentration.

  Furthermore, in the touch panel manufacturing process, a load may be applied to the touch panel itself. In particular, when the protective film is provided on the flexible display substrate, the load on the protective film increases as the substrate is curved, and cracks and peeling of the protective film easily occur. As an example of a production process for forming a protective film on a touch panel, there is a method in which a photosensitive film is laminated on a substrate in the order of lamination, exposure, development, post-exposure, and heat treatment. After the heat treatment process, the adhesion of the protective film also improves, but the film after development and post-exposure has poor adhesion and film strength and cannot withstand the load in the manufacturing process described above, thus protecting after development. Film cracks and delamination from the substrate are often problematic. Therefore, there is a demand for a protective film that suppresses corrosion of the metal wiring and has an adhesion and film strength that allows the post-exposure film after development to withstand bending and impact of the substrate during the manufacturing process.

Patent documents 1-3 are mentioned as a protective film about a touch panel.
Patent Document 1 discloses a photosensitive resin composition as a protective film for a touch panel and has been evaluated for moisture permeability, but there is no description about adhesion, film strength, and developability.
Patent Document 2 discloses a photosensitive resin composition using a photopolymerizable compound containing butylene oxide in the molecule as a protective film for a touch panel, but rust prevention and adhesion of the protective film after heat treatment are disclosed. However, the adhesion and strength of the film after exposure (after development) are not mentioned, and the anti-rust property is not satisfied with the recent required level.
Patent Document 3 discloses a solder resist that prevents corrosion of a conductor layer of a printed wiring board and maintains electrical insulation between conductor layers for a photosensitive resin composition using a modified epoxy acrylate acid having a ring structure in the main chain. However, there is no description about moisture permeability, adhesion, and strength.

JP 2006-157451 A International Publication No. 2016/047691 JP 2009-251286 A

  As described above, the technologies described in Patent Documents 1 to 3 still have room for improvement. Therefore, the problems to be solved by the present invention are: developability, moisture permeability as a cured film, adhesion of a post-exposure film after development with a conductor base material and film strength, and protection of conductor parts such as electrodes. A photosensitive resin composition, a transfer film, and a method for producing the same.

As a result of intensive studies to solve the above problems, the inventors of the present invention obtained an alkali-soluble polymer having a specific structure and a weight average molecular weight, and a photopolymerizable compound having a specific structure and having a specified content. It discovered that the said subject could be solved by setting it as the photosensitive resin composition combined.
That is, the present invention is as follows.
[1]
The following ingredients:
(A) an alkali-soluble polymer having an acidic group,
(B) a photopolymerizable compound, and (C) a photopolymerizable initiator, a photosensitive resin composition,
As the component (A), (Ai) a polymer having an ethylenically unsaturated group and an acidic group and having a ring structure in the main chain,
As the component (B), (Bi) a compound having at least two ethylenically unsaturated groups and including butylene oxide in the structure as a repeating unit (however, a compound corresponding to the component (A) is excluded) And (B-ii) a compound having one ethylenically unsaturated group,
The component (A) is at least one polymer A-1,..., An (where n represents an integer of 1 or more) including at least a polymer corresponding to the component (Ai). Including the following formula (1):
{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% in the photosensitive resin composition of said polymer A-1, ... An. }, The weight average molecular weight of the component (A) calculated in 6,000 to 20,000,
The component (B-ii) is contained in an amount of 3% by mass or more based on the total solid content of the photosensitive resin composition, and
A transfer film in which a photosensitive resin layer having a thickness of 30 μm is laminated with the photosensitive resin composition on a support is formed, and the transfer film is laminated on a substrate having an opening of 6 mmφ, and then exposed to the whole surface. After the film is formed, the support is peeled off, and the maximum point load is 35 gf or more when the portion corresponding to the center of the opening is pierced at a speed of 100 mm / min with a 1.5 mmφ cylinder. A photosensitive resin composition characterized by the above.
[2]
The component (Bi) is represented by the following formula (2):
{Wherein Y ₁ and Y ₂ each independently represents a (meth) acryloyl group, and n represents an integer of 2 to 30. } The photosensitive resin composition as described in [1] containing the compound represented by these.
[3]
The photosensitive resin composition according to [1] or [2], which contains at least one compound having a plurality of aromatic rings in one molecule as the component (B-ii).
[4]
The photosensitive resin according to any one of [1] to [3], comprising (A-ii) an alkali-soluble polymer having an acidic group and no ethylenically unsaturated group as the component (A). Composition.
[5]
The photosensitive resin composition according to any one of [1] to [4], wherein the component (Bi) is contained in an amount of 3% by mass to 15% by mass with respect to the total solid content of the photosensitive resin composition. Stuff.
[6]
As the component (Ai), (A-iii) has a weight average molecular weight of 6,000 or more, an acid value of 60 to 120 mgKOH / g, an ethylenically unsaturated group and an acidic group, and a ring in the main chain. The photosensitive resin composition as described in [5] which contains the polymer containing a structure 90 mass% or more with respect to the solid content total mass of the said (A) component.
[7]
As the component (A), (A-iv) a weight-average molecular weight of 10,000 to 36,000, an acid group having an acid group of 130 to 150 mgKOH / g, and an alkali-soluble compound having no ethylenically unsaturated group The photosensitive resin composition as described in [5] or [6] containing a polymer.
[8]
(D) The photosensitive resin composition according to any one of [1] to [7], further comprising a thiol compound having at least two mercapto groups in one molecule.
[9]
The photosensitive resin composition in any one of [1]-[8] whose said (C) component is an oxime compound.
[10]
A transfer film provided with a support film and the photosensitive resin layer which consists of the photosensitive resin composition in any one of [1]-[9] provided on this support film.
[11]
The transfer film according to [10], which is used for a protective film for a conductor.
[12]
A pattern production method, wherein a pattern is produced by laminating, exposing and developing the transfer film according to [11] on a substrate.
[13]
A cured film pattern obtained by post-exposure treatment and / or heat treatment of the pattern obtained by the method according to [12].
[14]
A device having a touch panel display device or a touch sensor having the cured film pattern according to [13].

  According to the present invention, it is possible to provide a photosensitive resin composition and a transfer film that have good developability, moisture permeability as a cured film, adhesion between an exposed film after development and a conductive substrate, and film strength. .

It is a figure which shows the mask pattern used in the Example. It is a figure which shows the copper clad laminated board which has an opening part used in the Example.

Hereinafter, modes for carrying out the present invention (hereinafter abbreviated as “embodiments”) will be described in detail. In addition, this invention is not limited to the following embodiment, It can implement by changing variously within the range of the summary.
<(A) Alkali-soluble polymer having acidic group>
The alkali-soluble polymer according to the present embodiment is not particularly limited as long as it is a polymer having an acidic group, and the acidic group is preferably a carboxyl group.

(Ai) Polymer having an ethylenically unsaturated group and an acidic group and containing a ring structure in the main chain (Ai) according to the present embodiment is one or more ethylenically unsaturated groups and one polymer The polymer is not particularly limited as long as it is a polymer having the above acidic group and having a ring structure in the main chain. For example, an epoxy (meth) acrylate acid-modified product can be suitably used. Here, (meth) acrylate refers to acrylate and / or methacrylate, and the same applies hereinafter including (meth) acryl.

  Examples of the ring structure that enters the main chain include a cresol skeleton, a phenol skeleton, a biphenyl skeleton, a naphthalene skeleton, a fluorene skeleton, a bisphenol A skeleton, a bisphenol F skeleton, a tricyclodecane skeleton, a trisphenol methane skeleton, and a tetrakisphenol ethane skeleton. Can be mentioned.

Commercially available modified epoxy (meth) acrylate acids containing a cresol skeleton include CCR-1171H, CCR-1307H, CCR-1309H (manufactured by Nippon Kayaku Co., Ltd.), PR-300 (Showa Denko Co., Ltd.) Manufactured) and the like.
Examples of commercially available modified epoxy (meth) acrylate acids containing a phenol skeleton include PCR-1222H, PCR-1173H, PCR-1221H, PCR-1220H (manufactured by Nippon Kayaku Co., Ltd.), and the like.
ZCR-1569H, ZCR-1761H, ZCR-1797H, ZCR-1798H (made by Nippon Kayaku Co., Ltd.) etc. are mentioned as a commercial item of the epoxy (meth) acrylate acid modification containing a biphenyl skeleton.

ZCR-1809H, ZCR-1835H, ZCR-1834H (made by Nippon Kayaku Co., Ltd.) etc. are mentioned as a commercial item of the epoxy (meth) acrylate acid modified material containing a naphthalene skeleton.
Commercially available epoxy (meth) acrylate modified products containing a fluorenyl skeleton include FCA-954, FCA-293, FCA-506 (manufactured by Nagase ChemteX) or TR-B201, TR-B202 (Changzhou Powerful Electronic Materials). Etc.).
ZAR-1494H, ZAR-2001H (made by Nippon Kayaku Co., Ltd.) etc. are mentioned as a commercial item of the epoxy (meth) acrylate acid modification containing a bisphenol A frame | skeleton.
ZFR-1491H (made by Nippon Kayaku Co., Ltd.) etc. are mentioned as a commercial item of the epoxy (meth) acrylate acid modified substance containing a bisphenol F frame | skeleton.

ZXR-1807H, ZXR-1816H, ZXR-1810H (made by Nippon Kayaku Co., Ltd.) etc. are mentioned as a commercial item of the epoxy (meth) acrylate modified product containing a tricyclodecane skeleton.
Examples of commercially available modified epoxy (meth) acrylate acids containing a trisphenolmethane skeleton include TCR-1348H, TCR-1323H, TCR-1347H, TCR-1338H (manufactured by Nippon Kayaku Co., Ltd.), and the like. .
ZGR-1678H, ZGR-1844H (made by Nippon Kayaku Co., Ltd.) etc. are mentioned as a commercial item of the epoxy (meth) acrylate acid modified substance containing a tetrakisphenol ethane frame | skeleton.

(Ai) The acid value (mgKOH / g) of a polymer having an ethylenically unsaturated group and an acidic group and containing a ring structure in the main chain is preferably 50 to 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 prevention property of the conductor, and is 50 or more from the viewpoint of improving the developability of the photosensitive resin composition layer. It is more preferable that it is 60-120 from a viewpoint of balance of both performance.
The acid value is measured by a potentiometric titration method using a Hiranuma automatic titrator (COM-555) manufactured by Hiranuma Sangyo Co., Ltd. and using 0.1 mol / L potassium hydroxide.

  (Ai) The weight average molecular weight of the polymer having an ethylenically unsaturated group and an acidic group and containing a ring structure in the main chain is preferably 1,000 or more and 9,500 or less. The weight average molecular weight of (A-i) is 1,000 from the viewpoint of the properties of the unexposed film such as tackiness, edge fuse, and cut chip properties when used as a transfer film, and from the viewpoint of the strength of the exposed film after development. From the viewpoints of compatibility with other polymerizable compounds, such as developability of the photosensitive resin composition and (A-ii) an alkali-soluble polymer having an acidic group and no ethylenically unsaturated group. It is preferably 9,500 or less, more preferably 6,000 or more and 8,000 or less. Here, the tackiness indicates the adhesiveness when the photosensitive resin composition is used as a transfer film. If the tackiness is too large, the cover film or the support will not be peeled properly, and if it is too weak, the cover film cannot be pasted. Problems such as peeling of the body in unintended processes occur. The edge fuse property is a phenomenon in which the photosensitive resin composition layer protrudes from the end surface of the roll when the transfer film is wound into a roll. The cut chip property is a phenomenon in which a chip flies 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, it is transferred to a mask in the subsequent exposure process or the like, causing a defect.

The measurement of a weight average molecular weight is performed using the gel permeation chromatography (GPC) by JASCO Corporation set to the following conditions. The obtained weight average molecular weight is a polystyrene equivalent value.
Pump: Gulliver, PU-1580 type Column: Shodex (trademark) manufactured by Showa Denko K.K. (KF-807, KF-806M, KF-806M, KF-802.5) 4 in series,
Moving bed solvent: Tetrahydrofuran Calibration curve: Calibration curve defined using polystyrene standard sample {Use of calibration curve based on polystyrene standard sample (Shodex STANDARD SM-105 manufactured by Showa Denko KK)}

(A-ii) Alkali-soluble polymer having an acidic group and not having an ethylenically unsaturated group (A-ii) according to the present embodiment is free of an ethylenically unsaturated group and has at least one acidic group Is not particularly limited, for example, (meth) acrylic acid, (meth) acrylic acid ester, (meth) acrylonitrile, (meth) acrylamide and other acrylic copolymers, polyimide precursor, Examples thereof include a carboxyl group-containing polyimide and a carboxyl group-containing urethane resin. An acrylic copolymer is preferable from the viewpoint of compatibility with the photopolymerizable compound (B) described later and transparency.

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

  Examples of the monomer 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 Examples include vinyl alcohol esters such as vinyl; (meth) acrylic acid aromatic esters such as benzyl (meth) acrylate; styrene and polymerizable derivatives thereof.

Among these copolymers, structural units derived from (meth) acrylic acid and (meth) acrylic acid aromatic ester or styrene and derivatives thereof from the viewpoint of reducing moisture permeability and improving the rust prevention property of the conductor. A copolymer containing a structural unit is more preferable.
By copolymerizing the unit having an aromatic group, the hydrophobicity of the acrylic copolymer is increased, and the rust prevention property is improved. Moreover, it is thought that the film density after hardening of the photosensitive resin composition becomes high, and the rust prevention property of a conductor improves because an acrylic copolymer has an aromatic group. As an acrylic copolymer in which both developability and moisture permeability reduction can be achieved, the structure derived from (meth) acrylic acid is 7.7% by mass to 30% by mass, and the structure derived from styrene or a derivative thereof is 30% by mass. More preferably, the content is 80% by mass or less.

-Polyimide precursor The polyimide precursor contained in the component (A-ii) does not mean only polyamic acid, but also includes a part of the polyamic acid imidized.

  The polyimide precursor can be obtained, for example, by mixing and reacting tetracarboxylic dianhydride and diamine in an organic solvent at a molar ratio of 0.8: 1 to 1.2: 1. There is no restriction | limiting in the tetracarboxylic dianhydride to be used, A conventionally well-known tetracarboxylic dianhydride can be used. As tetracarboxylic dianhydride, aromatic tetracarboxylic acid, aliphatic tetracarboxylic dianhydride, etc. can be applied. Moreover, there is no restriction | limiting in the diamine to be used, A conventionally well-known diamine can be used.

  Examples of the tetracarboxylic dianhydride include biphenyl-3,3 ′, 4,4′-tetracarboxylic dianhydride, benzophenone-3,3 ′, 4,4′-tetracarboxylic dianhydride, oxydiphthalic acid Anhydride, diphenylsulfone-3,3 ′, 4,4′-tetracarboxylic dianhydride, ethylene glycol bis (trimellitic acid monoester acid anhydride), p-phenylenebis (trimellitic acid monoester acid anhydride) ), P-biphenylenebis (trimellitic acid monoester acid anhydride), m-phenylenebis (tomellitic acid monoester acid anhydride), o-phenylenebis (trimellitic acid monoester acid anhydride), pentanediol bis (Trimellitic acid monoester acid anhydride), decanediol bis (trimellitic acid monoester acid anhydride), pyro anhydride Littic acid, 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 dianhydride, bicyclo [2,2,2] oct-7-ene-2,3,5,6-tetra Carboxylic 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, and the like. The tetracarboxylic dianhydrides described above may be used alone or in combination of two or more.

  Examples of the diamine 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, , 3-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) 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- Minobenzoate, 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, Examples include 3,5-diaminobenzoic acid, 3,3′-dihydroxy-4,4′-diaminobiphenyl, 1,3-bis (4-aminophenoxybenzene), and the like. Further, 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 terminal of the polyimide precursor is not particularly limited as long as it does not affect the performance, and may be an acid dianhydride or a terminal structure derived from a diamine used for producing the polyimide precursor. The terminal may be sealed with other acid anhydrides or amine compounds.

  A polyimide precursor having a polyimide structure and a polyamic acid structure as repeating units, respectively, is a step of reacting acid dianhydride and diamine in a non-equal molar amount to synthesize a first-stage polyimide portion (step 1), followed by 2 It can be produced by a step of synthesizing the polyamic acid portion at the stage (step 2). As a method for producing a polyimide precursor, step 1 is not necessarily included. Hereinafter, each process will be described.

(Process 1)
The process of synthesizing the first stage polyimide portion will be described. The step of synthesizing the first-stage polyimide portion is not particularly limited, and a known method can be applied. More specifically, the polyimide portion can be synthesized by the following method. First, diamine is dissolved and / or dispersed in a polymerization solvent, and acid dianhydride powder is added thereto. Then, a solvent azeotroped with water is added, and the mixture is heated and stirred for 0.5 hours to 96 hours, more preferably 0.5 hours to 30 hours while removing by-product water azeotropically using a mechanical stirrer.

  The polyimide part can be synthesized by adding a known imidization catalyst or without a catalyst. The imidation catalyst is not particularly limited, but may be an acid anhydride such as acetic anhydride, γ-valerolactone, γ-butyrolactone, γ-tetronic acid, γ-phthalide, γ-coumarin, and γ-phthalide acid. Lactone compounds, 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 non-catalyst are particularly preferable from the viewpoint of high reactivity and reducing the influence on the next reaction.

  The reaction solvent used in the synthesis of the polyimide part includes 2 or more carbon atoms such as dimethyl ether, diethyl ether, methyl ethyl ether, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, and triethylene glycol dimethyl ether. 9 or less ether compounds; Cone compounds having 2 to 6 carbon atoms such as acetone and methyl ethyl ketone; 5 or more carbon atoms such as normal pentane, cyclopentane, normal hexane, cyclohexane, methylcyclohexane, and decalin Saturated hydrocarbon compounds having 10 or less carbon atoms; aromatic hydrocarbon compounds having 6 to 10 carbon atoms such as benzene, toluene, xylene, mesitylene, and tetralin An ester compound having 3 to 12 carbon atoms such as methyl acetate, ethyl acetate, γ-butyrolactone, and methyl benzoate; 1 or more carbon atoms such as chloroform, methylene chloride, and 1,2-dichloroethane; A halogen-containing compound having 10 or less carbon atoms; a nitrogen-containing compound having 2 to 10 carbon atoms such as acetonitrile, N, N-dimethylformamide, N, N-dimethylacetamide, and N-methyl-2-pyrrolidone; And sulfur-containing compounds such as dimethyl sulfoxide. These may be used alone or as a mixed solvent of two or more as required. Particularly preferable 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. Examples thereof include nitrogen-containing compounds having 10 or less carbon atoms. These can be arbitrarily selected in consideration of industrial productivity and influence on the next reaction.

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

(Process 2)
Next, the process for synthesizing the second stage polyamic acid moiety will be described. The synthesis of the polyamic acid moiety at the second stage can be carried out by using the polyimide moiety obtained in Step 1 as a starting material and adding diamine and / or acid dianhydride for polymerization. The polymerization temperature in the synthesis of the second stage polyamic acid moiety 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 that 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 from 30 minutes to 30 hours.

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

  The carboxyl group-containing polyimide is usually synthesized using a carboxyl group-containing diamine. From the viewpoint of solubility in organic solvents or availability, 3,5-diaminobenzoic acid, 3,3′-dicarboxy-4,4′-diaminodiphenylmethane, or the like may be used as the carboxyl group-containing diamine. it 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 the synthesis, and the imidization catalyst are the same as those described above for the polyimide precursor.

-Carboxyl group-containing polyurethane The carboxyl group-containing polyurethane according to the present embodiment is a diisocyanate compound, a carboxyl group-containing diol compound, and other diol compounds in an aprotic solvent, which are known active catalysts according to their respective reactivities. It is synthesized by adding and heating. The molar ratio of the diisocyanate and diol compound to be used is preferably 0.8: 1 to 1.2: 1. When an isocyanate group remains at the end of the polymer, the molar ratio of the diisocyanate and diol compound can be determined by treating with an alcohol or an amine. Is synthesized in a form in which no isocyanate group remains.

  As the diisocyanate compound, 2,4-tolylene diisocyanate, dimer 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: hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate, dimer acid diisocyanate, etc. An aliphatic diisocyanate compound such as: isophorone diisocyanate, 4,4′-methylenebis (cyclohexyl isocyanate), methylcyclohexane-2,4- (or 2, A reaction product of a diol and a diisocyanate such as an adduct of 1 mol of 1,3-butylene glycol and 2 mol of tolylene diisocyanate; an alicyclic diisocyanate compound such as diisocyanate and 1,3- (isocyanatomethyl) cyclohexane; A certain diisocyanate compound etc. are mentioned.

  Examples of carboxyl group-containing diols include 3,5-dihydroxybenzoic acid, 2,2-bis (hydroxymethyl) propionic acid, 2,2-bis (2-hydroxyethyl) propionic acid, and 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 a 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; or ethylene glycol, 1 , 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-dioe , 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-tolylenedicarbamate, 2,4-tolylene-bis (2-hydroxyethylcarbamide), bis (2-hydroxyethyl) -m-xylylenedicarbamate, bis (2-hydroxyethyl) ) Isophthalate, 1,4-bi And low molecular weight diols such as bis (β-hydroxyethoxy) benzene and bis (β-hydroxyethyl) terephthalate.

  The acid value (mgKOH / g) of (A-ii) is preferably 60 to 200. The acid value is preferably 200 or less from the viewpoint of reducing moisture permeability and improving the rust prevention property of the conductor, and is 60 or more from the viewpoint of improving developability, and from the viewpoint of the balance between the rust prevention property and low temperature developability of the conductor Therefore, it is more preferable that it is 80-180, and it is still more preferable that it is 90-160. The weight average molecular weight of the (A) alkali-soluble polymer having an acidic group is 11,000 to 50, from the viewpoints of coatability, transfer film tackiness, post-exposure (after development) film strength, and developability. 000 is preferred. The weight average molecular weight of the alkali-soluble polymer having an acidic group is determined from the viewpoint of the properties of the unexposed film such as tackiness, edge fuse property, cut chip property and the like after the exposure (after development). 11,000 or more from the viewpoint, and 50,000 or less from the viewpoint of developability and compatibility with a polymer having an ethylenically unsaturated group and an acidic group and having a cyclic structure in the main chain. It is preferable. More preferably, it is 15,000 or more and 30,000 or less. By improving the compatibility, the strength, developability, and moisture permeability are easily developed.

  Moreover, the alkali-soluble polymer which has the (A) acidic group which does not correspond to (Ai) and (A-ii) mentioned above can also be used as needed. Polymers having one or more ethylenically unsaturated groups and one or more acidic groups and having no ring structure in the main chain can also be used. For example, the carboxyl described in the description of the acrylic copolymer By adding glycidyl methacrylate to an acrylic copolymer that does not have a ring structure in the main chain, a monomer having a group and an acid group-free monomer are copolymerized. A saturated group can be introduced, and a polymer having one or more ethylenically unsaturated groups and one or more acidic groups as described above and having no ring structure in the main chain can be obtained.

On the other hand, the above-mentioned alkali-soluble polymer having an acidic group (A) is at least one polymer A-1, including a polymer corresponding to the component (Ai),. n represents an integer of 1 or more), and the following formula (1):
{Wherein W _A-1 , ... W _A-n represents the weight average molecular weight of each polymer A-1, ... An corresponding to the component (A), X _A-1 , ... X _A-n represents the mass% in the photosensitive resin composition of each polymer A-1, ... An corresponding to the component (A). } Is a weight average molecular weight calculated in 6,000 to 20,000. From the viewpoint of the properties of the unexposed film, such as tackiness, edge fuse, and cut chip properties when used as a transfer film, from the viewpoint of the strength and adhesion of the exposed film after development, it is 6,000 or more, and from the viewpoint of developability To 20,000 or less. More preferably, it is 10,000 or more and 15,000 or more.

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

  As (Bi), as a compound having two ethylenically unsaturated groups in one molecule, for example, a compound having (meth) acryloyl groups at both ends of a polybutylene oxide chain, or a polybutylene oxide chain and a polyethylene oxide chain Or / and a compound having a (meth) acryloyl group at both ends of an alkylene oxide chain bonded to a polypropylene oxide chain in a random or block manner, or bisphenol A, bisphenol F, tricyclodecane modified with polybutylene oxide, and Examples thereof include compounds having (meth) acryloyl groups at both ends. In addition, the urethane compound etc. which are the reaction products of a diisocyanate compound, polybutylene glycol, and the compound which has a hydroxyl group and a (meth) acryl group in 1 molecule are mentioned.

  Furthermore, as the component (Bi) having more than two ethylenically unsaturated groups in one molecule, it has 3 moles or more of a group that can add an alkylene oxide group in the molecule as a central skeleton. It is obtained by converting an alcohol obtained by adding a butylene oxide group to a group to (meth) acrylate. Examples of the compound that can be a central skeleton include glycerin, trimethylolpropane, pentaerythritol, diglycerin, ditrimethylolpropane, dipentaerythritol, and isocyanurate rings. (Bi) It has a component, and the film | membrane intensity | strength after exposure goes up by incorporating a butylene oxide chain in a crosslinked structure.

On the other hand, as the component (Bi), the following formula (2):
{Wherein Y ₁ and Y ₂ each independently represents a (meth) acryloyl group, and n represents an integer of 2 to 30. } Is preferable from the viewpoints of moisture permeability, adhesion to a substrate, and strength of an exposed film after development. The film strength and adhesion improve as n increases, but the water vapor transmission rate deteriorates. From the viewpoint of the balance, n is more preferably 8 or more and 28 or less.

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

  Moreover, as addition amount of (Bi) component, 3 mass%-15 mass% are preferable with respect to the solid content total mass of the photosensitive resin composition. 3 mass% or more is preferable from the viewpoint of the exposure film strength after development, and 15 mass% or less is preferable from the viewpoint of moisture permeability and developability.

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

  As the component (B-ii), a compound in which (meth) acrylic acid is added to one end of polyalkylene oxide, (meth) acrylic acid is added to one end, and the other end is alkyl ether or allyl etherified. And the like. For example, isostearyl acrylate, lauryl acrylate, 2-phenoxyethyl acrylate, ethoxylated nonylphenyl acrylate, isobornyl acrylate, 4-nonylphenylheptaethylene glycol dipropylene glycol acrylate, etc., and one molecule from the viewpoint of moisture permeability A compound having a plurality of aromatic rings therein is preferred. It is considered that moisture permeability is improved by including a plurality of aromatic rings because the hydrophobicity and Tg of the composition are increased. A case where a plurality of benzene rings are condensed, for example, a structure such as naphthalene or anthracene in one molecule is counted as including a plurality of aromatic rings. As a compound having a plurality of aromatic rings in one molecule, m-phenoxybenzyl acrylate (POB-A, product name) manufactured by Kyoeisha Chemical Co., Ltd., o-phenylphenoxyethyl acrylate (OPP-1 manufactured by Nippon Kayaku Co., Ltd.) Product name), 4-methacryloyloxybenzophenone, 1-naphthyl acrylate and the like.

  Moreover, the photopolymerizable compound which does not correspond to (Bi) and (B-ii) mentioned above can also be used as needed. For example, in (Bi), a photopolymerizable compound having a butylene oxide chain was mentioned, but a compound having (meth) acryloyl groups at both ends of other polyalkylene oxide chains instead of butylene oxide, glycerin, trimethylol Propane, pentaerythritol, diglycerin, ditrimethylolpropane, dipentaerythritol, compounds obtained by adding polyalkylene oxide groups to isocyanurate rings, etc. and converting them to (meth) acrylates, A compound obtained by directly reacting (meth) acrylic acid without modification with an alkylene oxide group can also be used.

<(C) Photopolymerizable initiator>
The (C) photopolymerizable initiator according to the present embodiment is a compound capable of generating a radical by active light and polymerizing an ethylenically unsaturated group-containing compound. (C) As the photopolymerization initiator, for example, benzophenone, N, N, N ′, N′-tetramethyl-4,4′-diaminobenzophenone (Michler-ketone), N, N, N ′, N′— Tetraethyl-4,4′-diaminobenzophenone, 4-methoxy-4′-dimethylaminobenzophenone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, 2-methyl-1- [ Aromatic ketones such as 4- (methylthio) phenyl] -2-morpholino-propanone-1, acrylated benzophenone, 4-benzoyl-4′-methyldiphenyl sulfide; benzoins such as benzoin methyl ether, benzoin ethyl ether, benzoin phenyl ether Ether compounds;
Benzoin compounds such as benzoin, methylbenzoin, ethylbenzoin; 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)], ethanone, 1- [9-ethyl-6- (2-Methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime), 1- [4- (phenylthio) phenyl] -3-cyclopentylpropane-1,2-dione-2- (O-benzoyloxime), 1,2-propanedione, 3-cyclohexyl-1- [9-ethyl-6- (2-furanylcarbonyl) -9H-carbazol-3-yl]-, 2- (O- Oxime ester compounds such as acetyl oxime; benzyl derivatives such as benzyl dimethyl ketal; 9-phenylacridine, 1,7-bis (9,9′- Acridinyl) acridine derivatives such as heptane; N-phenylglycine derivatives such as N-phenylglycine; coumarin compounds; oxazole compounds; 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, an oxime ester compound is preferable and a compound having a high molar extinction coefficient of 365 nm is more preferable from the viewpoint of improving the rust prevention property 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. Thereby, high surface curability is obtained, it is speculated that the penetration of sodium ions in the development process can be suppressed, and as a result, high rust prevention properties of the conductor can be obtained.

  As specific oxime ester compounds, 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, product name, Changzhou Power Electronics New Materials Co., Ltd.), and 1, 2-propanedione, 3-cyclohexyl-1- [9-ethyl-6- (2-furanylcarbonyl) -9H-carbazole- 3-yl]-, 2- (O-acetyloxime) (TR-PBG-326, product name, Changzhou Power Electronics New Materials Co., Ltd.), (7-nitro-9,9-dipropyl-9H-fluoren-2-yl ) (Orthotolyl) methanone O-acetyloxime (DFI-020 manufactured by Daitokemix Co., Ltd.), 1,8-octanedione, 1,8-bis [9- (2-ethylhexyl) -6-nitro-9H-carbazole-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) (TR-PBG-371, product name, Changzhou Power Electronics New Materials Co., Ltd.), 3-cyclohexyl-1- (6- 2- (Benzoyloxyimino) hexanoyl) -9-ethyl-9H-carbazol-3-yl) -propane-1,2-dione-2- (O-benzoyloxime) (TR-PBG manufactured by Changzhou Power Electronics New Materials Co., Ltd.) -391, product name).

  (C) The content of the photopolymerization initiator in the photosensitive resin composition is 0.1% by mass to 10% by mass based on the total mass of the solid content of the photosensitive resin composition, and sensitivity and resolution. From a viewpoint of property, it is more preferable that it is 0.3 mass%-5 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 actinic rays are irradiated. Problems such as insufficient internal photocuring and a decrease in visible light transmittance can be suppressed.

<(D) Thiol compound having at least two mercapto groups in one molecule>
It is preferable to further blend (D) a thiol compound having at least two mercapto groups in one molecule from the viewpoint of expressing higher film strength and adhesion to the photosensitive resin composition.
Examples of such compounds include 1,10-decanedithiol, 1,4-bis (mercaptoacetoxy) butane, tetraethylene glycol bis (3-mercaptopropionate), trimethylolpropane trismercaptopropionate, tri Methylolethane trismercaptopropionate, tris-[(3-mercaptopropionyloxy) -ethyl] -isocyanurate, pentaerythritol tetrakis (3-mercaptopropionate), dipentaerythritol hexakis (3-mercaptopropionate) A primary thiol compound having a mercapto group bonded to a fatty chain such as 1,4- (3-mercaptobutyryloxy) butane, 1,3,5-tris (3-mercaptobutyryloxyethyl) -1,3 , 5-Triazine 2,4,6- (1H, 3H, 5H) -trione, trimethylolpropane tris (3-mercaptobutyrate), trimethylolethane tris (3-mercaptobutyrate), pentaerythritol tetrakis (3-mercaptobutyrate) Secondary thiol compound having a mercapto group bonded to a fatty chain such as 6- (dibutylamino) -1,3,5-triazine-2,4-dithiol, 6-anilino-1,3,5-triazine-2 , 4-dithiol, 1,3,4-thiadiazole-2,5-dithiol or the like, a compound having a mercapto group bonded to a heterocyclic ring; 1,2-benzenedithiol, 1,3-benzenedithiol, 1,4-benzene Such as dithiol, toluene-3,4-dithiol, 4,4′-biphenyldithiol, 1,5-naphthalenedithiol, etc. Compound mercapto group is bonded to the incense ring. (D) The thiol compound which is a component is used individually by 1 type or in combination of 2 or more types. By adding a thiol compound, the strength of the film after exposure (after development) is increased, and the adhesion is improved. From the viewpoint of film strength and adhesion, those having a mercapto group bonded to the fatty chain are preferred. Furthermore, secondary thiol is preferable from the viewpoint of odor and storage stability, and commercially available products include Karenz MT PE1, NR1, BD1 (manufactured by Showa Denko KK) and the like.

<(E) Thermal crosslinking agent>
It is preferable to further blend (E) a thermal crosslinking agent in the photosensitive resin composition from the viewpoint of developing higher rust prevention performance. (E) A thermal crosslinking agent is (A) an alkali-soluble polymer having an acidic group, (B) a photopolymerizable compound having an unreacted ethylenically unsaturated double bond, and (E) It means a compound that causes an addition reaction or a condensation polymerization reaction with a thermal crosslinking agent. As temperature which raise | generates an addition reaction or a condensation polymerization reaction, 100 to 150 degreeC is preferable. The addition reaction or condensation reaction occurs during heat treatment after pattern formation by development.

  Specific examples of the thermal cross-linking agent include, but are not limited to, a blocked isocyanate compound, a diol compound, an epoxy compound, and a thermal cross-linking agent described in paragraph [0054] and thereafter of International Publication No. 2016/047691.

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

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

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

  Specific examples of the block isocyanate compound include hexamethylene diisocyanate block isocyanate (for example, Duranate SBN-70D, SBB-70P, SBF-70E, TPA-B80E, 17B-60P, MF-B60B, E402- manufactured by Asahi Kasei Corporation). B80B, MF-K60B, and WM44-L70G, Takenate B-882N manufactured by Mitsui Chemicals, Inc., 7960, 7961, 7982, 7991, and 7992 manufactured by Baxenden), tolylene diisocyanate type block isocyanate (for example, Mitsui Chemicals ( Takenate B-830, etc.), 4,4′-diphenylmethane diisocyanate block isocyanate (for example, Takenate B-815N manufactured by Mitsui Chemicals, Inc., Bronate PMD- manufactured by Taiho Sangyo Co., Ltd.) A01, PMD-MA01, etc.), 1,3-bis (isocyanatemethyl) cyclohexane block isocyanate (for example, Takenate B-846N manufactured by Mitsui Chemicals, Inc., Coronate BI-301, 2507, and 2554 manufactured by Tosoh Corporation). Etc.) and isophorone diisocyanate block isocyanate (for example, 7950, 7951 and 7990 manufactured by Baxenden). These blocked isocyanate compounds may be used alone or in combination of two or more.

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

  (E) The thermal crosslinking agent is preferably a blocked isocyanate compound from the viewpoint of storage stability of the transfer film and reduced moisture permeability of the cured film, and is further used in combination with a diol compound from the viewpoint of developability of the photosensitive resin composition layer. Is more preferable.

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

  Since the blocked isocyanate compound reacts with the hydroxyl group of the (A) alkali-soluble polymer 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. The rust prevention property for protecting becomes good. Furthermore, the crosslinking density of the cured film is increased by crosslinking between the alkali-soluble polymers (A) via the polyfunctional blocked isocyanate compound, and the moisture permeability of the cured film is lowered because the water diffusibility is reduced. It is thought that the rust prevention property of the conductor is improved. Moreover, since the isocyanate group is sealed with the blocking agent in the blocked isocyanate, 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. Kept.

  Since the diol compound has a hydrophilic hydroxyl group, the developability is good. In addition, 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 resistance of the conductor is maintained. The molecular weight of the diol compound is preferably from 300 to 3,000, more preferably from 500 to 2,000, from the viewpoint of developability. On the other hand, if unreacted hydroxyl groups remain after thermal curing, the moisture permeability of the cured film is deteriorated, which may be a factor that impairs the rust prevention performance of the conductor. Therefore, the diol compound is preferably added so that the hydroxyl value of the photosensitive resin composition is 20 mgKOH / g or less, and more preferably 15 mgKOH / g or less. Since the moisture permeability of the hardened | cured material of the photosensitive resin composition can be reduced because the hydroxyl value of the photosensitive resin composition is 20 or less, the rust prevention property of a conductor improves.

<(F) Rosin ester compound>
In the photosensitive resin composition, it is preferable to further blend (F) a rosin ester compound from the viewpoint of expressing lower water permeability. The (F) rosin ester compound according to the present embodiment is a rosin acid that is a non-volatile component of rosin, a rosin acid that is a tricyclic diterpenoid having 20 carbon atoms, a dimer of rosin acid, a hydrogenated product of rosin acid, and A compound having an ester bond by reacting a compound selected from the group consisting of disproportionates of rosin acid (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 a rosin acid derivative and reacting either a carboxyl compound or a phenol compound.

  (F) Specific examples of rosin ester compounds include, for example, Arakawa Chemical Co., Ltd. products such as Ester Gum Series, Pine Crystal Series, Super Ester Series, Pencel Series, Beam Set 101, etc. ) The company's products include the Harrier Star Series, Neotor Series, and Harituck Series.

  (F) The rosin ester compound has a cycloaliphatic structure and an ester structure, so that the hydrophobicity is increased, but (A) an alkali-soluble polymer and (B) photopolymerizable in the photosensitive resin composition. Since the compatibility with the compound and (C) the photopolymerizable initiator is good, the developability as a composition is not hindered. Therefore, the developability of the transfer film, the moisture permeability of the cured film, and the rust preventive property of the conductor Excellent performance balance.

  From the viewpoint of the rust prevention property of the conductor, the acid value of the (F) rosin ester compound is more preferably 20 mgKOH / g or less. In the above-mentioned products of Arakawa Chemical Co., Ltd. and Harima Kasei Co., Ltd., 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, Beam Set 101, Harrier Star S, Neotol 125HK, Haritac F105, Haritac FK125, Haritac PCJ, and the like.

  Further, from the viewpoint of reducing moisture permeability of the cured film, the rosin ester compound (F) preferably has a softening point of 100 ° C. or higher. Specific examples of compounds satisfying these conditions include, for example, ester gum 105, Superester A-115, Superester A-125, Pencel A, Pencel C, Pencel D-125, Pencel D-135, Pencel D-160, Neotol 125HK, etc. may be mentioned, and the softening point may be 110 ° C. or higher. Particularly preferred examples of the specific compounds that satisfy these conditions include Superester A-115, Superester A-125, Pencel A, Pencel C, Pencel D-125, Pencel D-135, Pencel D-160, and Neotol. 125HK is mentioned. (F) The rosin ester compound may be used alone or in combination of two or more.

  (F) Content in the photosensitive resin composition of a rosin ester compound is 1 mass%-20 mass% with respect to the total solid content mass of the photosensitive resin composition, From a viewpoint of moisture permeability and developability, It is more preferably 5% by mass to 20% by mass, and further preferably 5% by mass to 15% by mass from the viewpoint of adhesion to the substrate. (F) When the content of the rosin ester compound is in the range of 1% by mass to 20% by mass, the performance balance between the low-temperature developability of the transfer film and the moisture permeability of the cured film is good.

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

  As the rust preventive agent, from the viewpoint of compatibility with the photosensitive resin composition according to the present embodiment and sensitivity, heterocyclic compounds containing N, S, O and the like are preferable. For example, tetrazole and its derivatives, triazole and Derivatives thereof, imidazole and derivatives thereof, indazole and derivatives thereof, pyrazole and derivatives thereof, imidazoline and derivatives thereof, oxazole and derivatives thereof, isoxazole and derivatives thereof, oxadiazole and derivatives thereof, thiazole and derivatives thereof, isothiazole and derivatives thereof Derivatives, thiadiazole and derivatives thereof, thiophene and derivatives thereof, and the like. The derivatives described here include compounds in which a substituent is introduced into the base structure. For example, if it is a tetrazole derivative, the compound which introduce | transduced the substituent into tetrazole is contained. The substituent is not particularly limited. For example, the substituent may be a hydrocarbon group (saturated or unsaturated, may be linear or branched, and may include a cyclic structure in its structure), or a hydroxyl group or a carbonyl group. And a substituent containing one or more functional groups having a hetero atom such as a carboxyl group, an amino group, an amide group, a nitro group, a cyano group, a mercapto group, and a halogen (fluorine, chlorine, bromine, iodine, etc.) group.

  Furthermore, from the viewpoint of rust prevention, the heterocyclic compound has a heterocyclic ring composed of C and N and / or S, and the number of N atoms is 3 or less in the same heterocyclic ring, A compound having 3 or less S atoms or a total number of N and S atoms of 3 or less is preferred. More preferred heterocyclic compounds are triazole and its derivatives, imidazole and its derivatives, imidazoline and its derivatives, thiazole and its derivatives, isothiazole and its derivatives, thiadiazole and its derivatives, thiophene and its derivatives, and the like. From the viewpoint of rust prevention and developability, the compound is more preferably benzotriazole and its derivatives, and imidazole and its derivatives.

It has a heterocyclic ring composed of C and N and / or S, and in the same heterocyclic ring, the number of N atoms is 3 or less, the number of S atoms is 3 or less, or the N atom and S Specific examples of compounds having a total number of atoms of 3 or less are shown below:
Triazoles such as 1,2,3-triazole, 1,2,4-triazole, etc .;
Triazole derivatives such as 3-mercaptotriazole, 3-amino-5-mercaptotriazole, benzotriazole, 1H-benzotriazole-1-acetonitrile, 1- [N, N-bis (2-ethylhexyl) aminomethyl] benzotriazole, 1- (2-di-n-butylaminomethyl) -5-carboxybenzotriazole, 1- (2-di-n-butylaminomethyl) -6-carboxybenzotriazole, 1H-benzotriazole-1-methanol, 5 -Methyl-1H-benzotriazole, 5-carboxybenzotriazole, 1-hydroxybenzotriazole, 5-chlorobenzotriazole, 5-nitrobenzotriazole and the like;

Imidazole; Imidazole derivatives such as undecyl imidazole, 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 .;
An imidazoline; an imidazoline derivative such as 2-undecylimidazoline, 2-propyl-2-imidazoline, 2-phenylimidazoline;
Thiazole; thiazole derivatives such as 2-amino-4-methylthiazole, 5- (2-hydroxyethyl) -4-methylthiazole, benzothiazole, 2-mercaptobenzothiazole, 2-aminobenzothiazole, 2-amino-6 -Methylbenzothiazole, (2-benzothiazolylthio) acetic acid, 3- (2-benzothiazolylthio) propionic acid and the like;

Isothiazole; isothiazole derivatives such as 3-chloro-1,2-benzisothiazole and the like;
Thiadiazole, such as 1,2,3-thiadiazole, 1,2,5-thiadiazole, 1,3,4-thiadiazole, etc .;
Thiadiazole derivatives such as 4-amino-2,1,3-benzothiadiazole, 2-amino-5-mercapto-1,3,4-thiadiazole, 2-amino-5-methyl-1,3,4-thiadiazole, 2-amino-1,3,4-thiadiazole, 5-amino-1,2,3-thiadiazole, 2-mercapto-5-methyl-1,3,4-thiadiazole, etc .; thiophene; thiophene derivatives such as 2- Thiophenecarboxylic acid, methyl 3-amino-2-thiophenecarboxylate, 3-methylbenzothiophene and the like.

Among the rust inhibitors, benzotriazole, 5-carboxybenzotriazole, 1-hydroxybenzotriazole, and 5-chlorobenzotriazole are particularly preferable from the viewpoints of rust prevention and developability of the conductor.
On the other hand, as the component (G), tetrazole and its derivatives, triazole and its derivatives, indazole and its derivatives, and thiadiazole and its derivatives are preferable from the viewpoint of the rust prevention property of the conductor and the adhesion between the cured film and the base material.

  Specific examples of tetrazole include 1H-tetrazole. Specific examples of the tetrazole derivatives include 5-amino-1H-tetrazole, 5-methyl-1H-tetrazole, 1-methyl-5-ethyl-1H-tetrazole, 1-methyl-5-mercapto-1H-tetrazole, 1- Examples include phenyl-5-mercapto-1H-tetrazole, 1- (dimethylaminoethyl) -5-mercapto-1H-tetrazole, and 5-phenyl-1H-tetrazole.

  A specific example of indazole is 1H-indazole. Examples of indazole derivatives include 5-aminoindazole, 6-aminoindazole, 1-benzyl-3-hydroxy-1H-indazole, 5-bromoindazole, 6-bromoindazole, 6-hydroxyindazole, 3-carboxyindazole, and 5-nitro. And indazole.

Specific examples of triazole and its derivatives and thiadiazole and its derivatives are as already described above.
Among them, 5-amino-1H-tetrazole, 5-carboxybenzotriazole, 5-aminoindazole and 5-amino-1,2, from the viewpoint of the rust prevention property of the conductor and the adhesion to the base material of the cured film 3-thiadiazole is particularly preferred.
In this Embodiment, 1 type of the antirust agent demonstrated above may be used independently, and 2 or more types may be used together.

  The content of the rust inhibitor in the photosensitive resin composition is preferably 0.05 on the basis of the total solid content of the photosensitive resin composition from the viewpoint of rust prevention of the conductor or low temperature developability of the transfer film. The mass% is 10% by mass, more preferably 0.1% by mass to 5% by mass, and still more preferably 0.2% by mass to 3% by mass.

<Other ingredients>
In the present embodiment, in addition to components (A) to (G), as other component (H), a polymerization inhibitor such as an aluminum salt to which 3 moles of nitrosophenylhydroxylamine have been added, an antioxidant, and an adhesion assistant Leveling agents, fillers, antifoaming agents, flame retardants, and the like can also be contained in the photosensitive resin composition, and these can be used alone or in combination of two or more.

<Puncture strength>
In the photosensitive resin composition of the present invention, a transfer film having a photosensitive layer thickness of 30 μm is prepared, an exposure film is formed on a substrate having an opening of 6 mmφ with the film, and then a piercing test is performed with Tensilon. The maximum point load is 35 gf or more.
Specifically, a photosensitive resin composition is applied on a support to form a transfer film in which a photosensitive resin layer having a thickness of 30 μm is laminated, and the transfer film is formed on a substrate having an opening of 6 mmφ. After laminating, after exposing the entire surface to form an exposure film, the support is peeled off, and a portion corresponding to the center of the opening is formed at a speed of 100 mm / sec using a tensilon equipped with a 1.5 mmφ cylindrical jig. The maximum point load when performing a piercing test at min is 35 gf or more.
The more specific measuring method of the maximum point load by the piercing test will be described in detail in Examples described later.

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

  On the other hand, the photosensitive resin composition of the present invention uses (Ai) an alkali-soluble polymer having an ethylenically unsaturated group and an acidic group and a ring structure in the main chain, or a compound having a rigid structure. However, although high Tg and high crosslink density are obtained and low moisture permeability is obtained, there is a tendency that the strength is insufficient and the adhesiveness is deteriorated. If the maximum point load at the time of the piercing test is 35 gf or more, there is no limitation on the method for increasing the strength, but (Bi) addition of a photopolymerizable compound containing butylene oxide in the structure or the formula (1) By setting the calculated weight average molecular weight of the component (A) to 6,000 or more, the maximum point load can be set to 35 gf or more. When the component (Bi) is represented by the formula (2), the strength of the exposed film is more easily expressed. By incorporating a butylene oxide chain into the crosslinked structure, the flexibility of the crosslinked body is improved and the strength is improved, and by increasing the weight average molecular weight, there is a relative increase in cracks and cracks compared to the case of using a smaller one. It is considered that the starting point of the thickness decreases and the strength of the exposure film increases.

Further, although not limited to the following, from the viewpoint of good compatibility of the polymer and easy film strength, the following conditions 1 and / or 2 are satisfied for the component (A), and the following conditions are satisfied for the component (B): 3 is more preferable for obtaining the strength of the exposed film.
Condition 1: (A-iii) Component (A-iii) has a weight average molecular weight of 6,000 or more, an acid value of 60 to 120 mgKOH / g, an ethylenically unsaturated group, an acidic group, and a ring in the main chain. 90 mass% or more of the polymer containing a structure is contained with respect to the solid content total mass of (A) component.
Condition 2: (A) as component (A-i) and (A-iv) an acid group having a weight average molecular weight of 10,000 to 36,000 (more preferably 25,000 or less) and an acid value of 130 to 150 mgKOH / g And an alkali-soluble polymer having no ethylenically unsaturated group.
Condition 3: (Bi) component is contained in an amount of 3% by mass to 15% by mass with respect to the total solid content of the photosensitive resin composition.

<Transfer film>
The photosensitive resin layer according to the present embodiment has a thickness of 15 μm or less, and the absorbance at a wavelength of 365 nm of the photosensitive resin layer is 0.01 to 0.05 per 1 μm of the thickness of the photosensitive resin layer. It is preferable. Since the flexibility deteriorates if the film thickness of the photosensitive resin layer is too thick, the thickness of the photosensitive resin layer is preferably 15 μm or less, from the viewpoint of following the unevenness of the wiring, and from the viewpoint of ensuring rust prevention. 3 μm or more is preferable.

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

  The support film used in this embodiment is preferably a transparent film that transmits light emitted from the exposure light source. 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 film, polyacrylonitrile film, styrene copolymer film, polyamide film, film made of cellulose and derivatives thereof, and the like. These films can be stretched if necessary. The haze of the support film is preferably 5 or less. The smaller the thickness of the support film, the more advantageous in terms of resolution and economy, but it is preferably 10 μm to 30 μm in order to maintain the strength.

  An important characteristic of the protective film used for the transfer film is that the protective film is sufficiently smaller in adhesion to the photosensitive resin layer than the support film and can be easily peeled off. As a protective layer, a polyethylene film, a polypropylene film, etc. can be used preferably, for example.

  The method for producing a transfer film includes a step of applying a coating solution on a support (for example, a support film) and drying, and further includes a step of laminating a protective film on the photosensitive resin layer as necessary. The coating liquid can be obtained by uniformly dissolving the photosensitive resin composition described above in a solvent.

Examples of the solvent that dissolves the photosensitive resin composition include ketones typified by methyl ethyl ketone (MEK); alcohols typified by methanol, ethanol, or isopropanol.
The solvent is preferably added to the photosensitive resin composition so that the viscosity of the solution of the photosensitive resin composition applied on the support is 10 mPa · s to 800 mPa · s at 25 ° C.

  Application methods include, for example, doctor blade coating method, Meyer bar coating method, roll coating method, screen coating method, spinner coating method, inkjet coating method, spray coating method, dip coating method, gravure coating method, curtain coating method, die coating Examples thereof include a coating method. Although there is no restriction | limiting in particular in the drying conditions of a coating liquid, It is preferable that drying temperature is 50 to 130 degreeC, and it is preferable that drying time is 30 second-30 minutes.

  In the present embodiment, the transfer film is preferably used to form a protective film for the conductor portion. In this case, the conductor portion is made of a copper electrode, nickel, palladium, silver, titanium, molybdenum, and the like. An alloy electrode with copper or a transparent electrode is more preferable. More specifically, the transfer film can be used as a protective film for lead-out wiring in the frame area of the 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 of a strain sensor that performs sensing by changing a resistance value with a strain gauge, a wiring protective film of an AI-related electronic device, or a protective film of a display element.

[Resin pattern, cured film pattern and method for producing them]
Formation of the resin pattern using the transfer film includes the following steps:
A laminating step of laminating the transfer film described above on a substrate;
An exposure step for exposing the laminated photosensitive resin laminate; and a development step for developing the exposed transfer film;
It can carry out by the manufacturing method of the resin pattern containing this. Furthermore, in order to use the resin pattern as a protective film for the conductor part, a process for forming a cured film pattern by subjecting the resin pattern to post-exposure treatment and / or heat treatment after the development step is included as a method for producing the resin pattern. Is preferred.

  Hereinafter, an example of a specific method will be shown. 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 with a transparent electrode (for example, ITO, Ag nanowire base material, etc.), or a metal electrode (for example, Cu , Al, Ag, Ni, Mo, and at least two kinds of alloys thereof, or the like can be used. A touch panel substrate or a touch sensor substrate (for example, a force sensor) can be used. A flexible copper-clad laminate, a touch panel electrode forming substrate, or a touch sensor electrode forming substrate is formed on a flexible film, a copper layer, a copper-nickel alloy layer or a transparent electrode, or a metal used as a raw material for a metal electrode. It is a base material in which a layer is formed.

  As said film, the film which consists of film raw materials, such as a polyimide, polyester (PET, PEN), a cycloolefin polymer (COP), is mentioned, for example. 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 a process of laminating a transfer film on the substrate as described above. When the transfer film has a protective layer, the protective layer is preferably peeled off, and then the transfer film is heat-pressed and laminated on the substrate surface with a laminator. In this case, the transfer film may be laminated only on one side of the substrate 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 provided with two rolls, or may be performed by repeatedly passing the transfer film and the substrate through the roll a plurality of times. . In addition, when a vacuum roll laminator is used, the followability of the protective film to the unevenness due to wiring or the like on the substrate is good, and the disadvantage that air is mixed between the transfer film and the substrate can be prevented. On the other hand, when a vacuum roll laminator is used, since the oxygen concentration that suppresses radical polymerization is extremely low, the photopolymerization initiator is cleaved and the dark reaction easily proceeds. Therefore, the roll temperature is preferably 40 ° C to 100 ° C, and more preferably 40 ° C to 80 ° C.

  Next, an exposure process is performed using an exposure machine. If necessary, the support film is peeled off from the transfer film, and the photosensitive resin layer is exposed with active light through a photomask. The exposure amount is determined by the light source illuminance and the exposure time. The exposure amount may be measured using a light meter. Examples of the exposure machine include a scattered light exposure machine using an ultra-high pressure mercury lamp as a light source, a parallel light exposure machine with adjusted parallelism, and a proximity exposure machine that provides a gap between a mask and a workpiece. Further, as an 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 illumination stepper (registered trademark), or a concave mirror called a mirror projection aligner (registered trademark) is used. The used exposure machine can be mentioned.

  In the exposure process, a direct drawing exposure method may be used. Direct drawing exposure is a method in which exposure is performed by drawing directly on a substrate without using a photomask. As the light source, for example, a solid laser having a wavelength of 350 nm to 410 nm, a semiconductor laser, or an ultrahigh pressure mercury lamp is used. The drawing pattern is controlled by a computer. The exposure amount in this case is determined by the light source illuminance and the moving speed of the substrate.

Next, a developing process is performed using a developing device. After exposure, when there is a support film on the photosensitive resin layer, the support film is removed if necessary, and then the unexposed portion is developed and removed using an aqueous alkaline developer to obtain a resin pattern. As the alkaline aqueous solution, an aqueous solution (alkaline aqueous solution) of Na ₂ CO ₃ or K ₂ CO ₃ is preferably used. The alkaline aqueous solution is appropriately selected according to the characteristics of the photosensitive resin layer, but a Na ₂ CO ₃ aqueous solution having a concentration of about 0.2% by mass to 2% by mass and about 20 ° C. to 40 ° C. is generally used. When the temperature of the developer is high, moisture tends to volatilize in a negative pressure environment such as exhaust as an odor countermeasure, and the developer tends to be concentrated over time, and stable productivity tends to be impaired. Therefore, the developer temperature is preferably less than 30 ° C. Further, a surface active agent, an antifoaming agent, a small amount of an organic solvent for promoting development, and the like may be mixed in the alkaline aqueous solution. In consideration of the influence on the substrate, an amine-based alkaline aqueous solution such as a tetramethylammonium hydroxide (TMAH) aqueous solution can also be used. Depending on the developing speed, the concentration of the alkali compound in the aqueous solution can be appropriately selected. From the viewpoints that the odor of the developer is small, the handling property is excellent, and the management and post-treatment are simple, an aqueous solution of Na ₂ CO _{3 of} 1% by mass and 25 ° C. to 30 ° C. is particularly preferable. Examples of the developing method include known methods such as alkaline water spraying, showering, rocking immersion, brushing, and scraping.

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

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 property is further improved. The exposure amount in the post exposure treatment ^is preferably ^{200mJ / cm 2 ~1,000mJ / cm 2} , it is preferable to carry out the treatment at 40 ° C. to 200 DEG ° C. The heating step, from the viewpoint of the manufacturing process, heat treatment time Is preferably 60 minutes or less. As a heat treatment method, a heating furnace of an appropriate method such as hot air, infrared rays, far infrared rays, or the like can be used. As an atmosphere of the heat treatment, an N ₂ atmosphere or an N ₂ / O ₂ atmosphere can be given. .

  According to the present embodiment, the adhesion of the transfer film to the conductor base material, the developability, the strength of the exposed film, and the moisture permeability of the cured film are all good, and suitable for the protection of conductor parts such as wiring and electrodes. Photosensitive resin composition and transfer film can be provided. Such a transfer film is suitable, for example, as a touch resist, a touch sensor, a force sensor, a strain sensor, a wiring for use in AI-related electronic equipment, a protective film such as an electrode, or a solder resist for a printed wiring board.

[Device with touch panel display, touch sensor or force sensor]
By forming the cured film of the transfer film according to the present embodiment on the touch panel substrate, the touch panel display device having the cured film of the transfer film, and the cured film of the transfer film and the touch sensor and / or the force sensor are included. An apparatus can be provided.
Generally as a base material for touch panels, the base material used for a touch panel, a touch sensor, or a force sensor, for example, a glass plate, a plastic plate, a plastic film, a ceramic plate etc., is mentioned. On this base material, electrodes for touch panel such as ITO, Cu, Al, Ag, Ni, Mo and an alloy containing at least two of them, or metal wiring, which is a target for forming a protective film, are provided. An insulating layer may be provided between the electrodes.

  The base material for touch panels which has the electrode for touch panels can be obtained with the following procedures, for example. After forming a metal film by sputtering a copper and nickel alloy on a touch panel substrate such as polyester or COP film, an etching photosensitive film is pasted on the metal film to form a desired resist pattern, Unnecessary alloys are removed with an etching solution such as an aqueous iron chloride solution, and the resist pattern is peeled off and removed.

  The method for forming a cured film as a protective film on a touch panel substrate is a first step of laminating the transfer film according to the present embodiment on the touch panel substrate, and a predetermined portion of the protective film is irradiated with actinic rays. A second step of curing, a third step of forming a cured product of the patterned protective film by removing a portion other than the predetermined portion of the protective film (a portion of the protective film not irradiated with active light), and a patterned protection It is preferable to include the 4th process which exposes and / or heat-processes a film | membrane in this order.

  By producing a touch panel substrate having a cured film pattern of a transfer film as described above, a touch panel display device having a cured film of the transfer film, or a cured film of the transfer film and a touch sensor and / or a force sensor is provided. An apparatus can be suitably provided.

  Hereinafter, the present invention will be specifically described based on examples, but the present invention is not limited thereto.

1. About (A) component (AI) The following solution marketed was used as an alkali-soluble polymer which has an ethylenically unsaturated group and an acidic group, and contains a ring structure in the principal chain.

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

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

Next, preparation of an alkali-soluble polymer having (A-ii) 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. in 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 (Wako Pure Chemical Industries, Ltd., V-601) take 2 hours. It was dripped uniformly. After the dropwise addition, the reaction system was continuously stirred at 75 ° C. for 10 hours. After completion of the reaction, the obtained resin solution was diluted with methyl ethyl ketone, the solid content acid value was 130 mgKOH / g, and the weight average molecular weight was about 13,000. An alkali-soluble polymer solution (solid content 50% by mass) (A-6) was obtained.

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

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

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

  Table 2 shows the copolymer composition, weight average molecular weight and acid value of the obtained alkali-soluble polymer having acidic groups and no ethylenically unsaturated groups. In addition, the measurement of the weight average molecular weight of an alkali-soluble polymer and an acid value was performed by the method described in detail of said <(A) alkali-soluble polymer which has an acidic group>.

2. Preparation of Evaluation Transfer Film Evaluation transfer films in Examples and Comparative Examples were prepared as follows.
<Production of transfer film>
Each component was weighed into a 250 ml plastic bottle according to the composition shown in the following Tables 4 to 6 (however, the number of each component indicates the blending amount (part by mass) as the solid content), and the solid content concentration was 53 Methyl ethyl ketone was added so that it might become the mass%, and it melt | dissolved and mixed over 5 hours using the stirrer, and obtained the photosensitive resin composition. Thereafter, the photosensitive resin composition was passed through a 3 μm filter to prepare photosensitive resin composition preparation solutions (Examples 1 to 23 and Comparative Examples 1 to 11).

The photosensitive resin composition preparation liquid is uniformly applied to the surface of a 16 μm-thick polyethylene terephthalate film (FB40, manufactured by Toray Industries, Inc.) as a support using a blade coater, and dried to be uniform on the support. A photosensitive resin layer was formed. The thickness of the photosensitive resin layer was 8 μm and 30 μm, and the drying conditions were 8 μm for 7 minutes in a 95 ° C. dryer and 30 μm for 9 minutes in a 95 ° C. dryer. Next, a transfer film for evaluation was obtained by bonding a 33 μm-thick polyethylene film (manufactured by Tamapoly Co., Ltd., GF-858) as a protective film on the surface of the photosensitive resin layer.
The following evaluation results are shown in Tables 4 to 6. In addition, Table 3 shows the names of the material components in the photosensitive resin composition preparation liquid represented by abbreviations in Tables 4 to 6.

3. Developability <Sample preparation method>
A sample for evaluation of developability was prepared as follows.
A hot roll laminator (Taisei Laminator Co., Ltd.) was formed on the alloy surface (size: 5 cm × 10 cm) of the substrate on which the copper nickel alloy was sputtered on the resin while peeling off the protective film of the transfer film having a photosensitive resin layer thickness of 8 μm. VA-400III) and a roll temperature of 80 ° C. for lamination. The air pressure was set to 0.2 MPa, and the laminating speed was set to 2 m / min. (However, regarding the composition that does not transfer under the condition of 80 ° C., the roll temperature was increased to 100 ° C. and laminated.) After standing for 15 minutes, a PET mask and a stuber 21-step tablet (optical density 0) were placed on the support film. Step tablet with optical density increased by 0.15 for each stage is placed side by side, and the optimal exposure dose of each composition from the side of the PET mask and step tablet is determined by a parallel light exposure machine ) Exposed by Oak Seisakusho, HMW-801). A PET mask having a pattern as shown in FIG. 1 was used. In FIG. 1, a shaded portion represents a light shielding portion, and a white portion represents a portion that transmits light. In addition, the arrows and numerical values in the figure represent dimensions, not actual mask patterns.

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

<Evaluation method>
The base material surface state of the part where the photosensitive layer of the produced protective film-coated substrate was removed was observed with a microscope, and determined as follows.
A: No development residue on the base alloy under development conditions of 28 ° C.
B: Under development conditions of 28 ° C., there is a development residue on the base alloy, but under development conditions of 30 ° C., there is no development residue on the base alloy.
C: Development residue is generated even under development conditions of 30 ° C.
In the evaluation of developability, it is considered that the results up to rank B are practically good results as a conductor protective film.

4). Moisture permeability test <sample preparation method>
While peeling off the protective film of the transfer film having a thickness of the photosensitive resin layer of 30 μm, Lamination was performed on 4 filter papers (manufactured by Advantech) using a hot roll laminator (manufactured by Taisei Laminator Co., Ltd., VA-400III). The roll temperature was set to 60 ° C., the air pressure was set to 0.2 MPa, and the laminating speed was set to 1.0 m / min. (However, the composition which is not transferred under the condition of 60 ° C. was laminated by raising the roll temperature to 100 ° C.) After standing for 15 minutes, from the support film side of the protective film, a scattered light exposure machine (manufactured by Oak Manufacturing Co., Ltd.). , HMW-201KB) was exposed at an exposure amount of 350 mJ / cm ² . After leaving 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 measurement of moisture permeability was performed according to the cup method of JIS Z0208, and the moisture permeability conditions were a temperature of 65 ° C./a humidity of 90%.
A: Moisture permeability of 200 g / (m ² · day) or more, less than 265 g / (m ² · day) B: Moisture permeability of 265 g / (m ² · day) or more, less than 330 g / (m ² · day) C: Moisture permeability: 330 g / (m ² · day) or more, less than 400 g / (m ² · day) D: Moisture permeability: 400 g / (m ² · day) or more In the moisture permeability test, up to rank C This is considered to be a good result in practical use as a conductor protective film.

5. Adhesion evaluation (cross cut test)
<Sample preparation method>
A hot roll laminator (Taisei Laminator Co., Ltd.) is formed on the alloy surface (size: 4 cm × 4 cm) of the substrate on which the copper-nickel alloy is sputtered on the resin while peeling the protective film of the transfer film having a photosensitive resin layer thickness of 8 μm. And VA-400III). The roll temperature was 80 ° C., the air pressure was 0.2 MPa, and the laminating speed was 2 m / min. (However, regarding the composition that does not transfer under the condition of 80 ° C., the roll temperature was increased to 100 ° C. and laminated.) After standing for 15 minutes, it was <3. The optimum exposure amount of each composition evaluated in the item of developability> was exposed on the entire surface.

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

<Evaluation method>
The sample after the above treatment was subjected to a 100-mass cross-cut test with reference to JIS standard K5400. Using a cutter knife on the surface on which the protective film is laminated, a 1 mm × 1 mm square cut is made, and a 15 mm wide adhesive tape (cello tape (registered trademark) manufactured by Nichiban Co., Ltd.) The product name) was strongly pressure-bonded and the end of the tape was gently peeled off at an angle of approximately 0 °, and then the state of the grid was observed with an optical microscope and determined as follows.
A: Peeling is less than 5% in the entire area.
B: There is peeling of 5 to 15% in the entire area.
C: 15% or more peeled over the entire area In the cross-cut test, it is considered that up to rank B is practically a good result as a conductor protective film.

6). Maximum point load measurement (piercing test)
<Sample preparation method>
One of the 1.6 mm thick copper-clad laminates having 6 mmφ openings shown in FIG. 2 preheated in an oven at 60 ° C. for 10 minutes while peeling off the protective film of the transfer film having a thickness of 30 μm. The surface was laminated using a hot roll laminator (VA-400III, manufactured by Taisei Laminator Co., Ltd.). The roll temperature was 80 ° C., the air pressure was 0.2 MPa, and the laminating speed was 2 m / min. (However, regarding the composition that does not transfer under the condition of 80 ° C., the roll temperature was increased to 100 ° C. and laminated.) After standing for 15 minutes, it was <3. The optimum exposure amount of each composition evaluated in the item of developability> was exposed on the entire surface.

Next, after leaving for 30 minutes or more, the support is peeled off, and the center of the 6 mmφ opening is stabbed at a speed of 100 mm / min from the surface from which the support is peeled off, and Tensilon (Orientec RTM- 500), the maximum point load was measured. Ten points were measured, and the average value of the top five points was pierced and used as the maximum point load of the test.
35 gf or more is considered to be a good result as a protective film for conductors in practice.

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

  Although the comparative example 1 is a composition which does not contain (Bi) component compared with Example 1, the maximum point load in a piercing test is less than 35 gf, and a water vapor transmission rate is favorable, but adhesiveness performance is Out of tolerance and poor performance balance. Furthermore, when the comparative example 2 is seen, since (Bi) component is included, since the prescription | regulation of the maximum point load 35gf is not satisfy | filled, this is also a result with inferior adhesiveness. Comparative Example 3 was obtained by replacing the component (Bi) of Example 18 with dialkyl methacrylate of polyalkylene glycol to which propylene oxide and ethylene oxide were added. The maximum point load was 35 gf or more, and the adhesion was Although it is good, the moisture permeability is deteriorated and the performance balance is poor.

  Subsequently, in Comparative Example 4, the component (B-ii) of Example 2 was transferred to another polymerizable compound and the component (B-ii) was not included, but the maximum point load was 35 gf or more, but the adhesion was poor. . This is because the (B-ii) component is not included, and crosslinking after exposure becomes too dense and curing shrinkage occurs, stress is generated between the substrate and the adhesive strength is lowered, and the strength of the exposed film is The inventors consider that the adhesion of some things was poor. Compared with Example 2, the comparative example 5 is a composition in which a part of the component (B-ii) is transferred to another polymerizable compound, but the component (B-ii) is 3% in the total solid content of the composition. Since it does not satisfy the rule of including the above, it is considered that the adhesion is poor for the same reason as in Comparative Example 4.

  On the other hand, Comparative Example 8 is a composition in which the component (Ai) is assigned to the component (A-ii) and the component (Ai) is not included in the composition of Example 11, but (A- Since the components (i) and (A) do not satisfy the requirements of the weight average molecular weight and maximum point load, all of developability, moisture permeability and adhesion are inferior. Moreover, although the comparative example 7 satisfy | fills the weight average molecular weight of (A) component with respect to the comparative example 8, it does not satisfy | fill the prescription | regulation of (Ai) component and the maximum point load, but also developability, moisture permeability, and adhesiveness All are out of tolerance performance. Further, Comparative Example 6 satisfies the specifications except that it does not contain the component (A-i), but developability and moisture permeability are inferior because all the specifications are not satisfied. From these results, it can be seen that the component (Ai) has an effect of improving moisture permeability and developability. Moreover, although the comparative example 9 contains the (Ai) component similarly to Example 1, although the weight average molecular weight of (A) component is less than 2500 and a prescription | regulation, a maximum point load is low and adhesiveness is inferior. It is the result. The same applies to Comparative Example 10. Comparative Example 11 has a weight average molecular weight larger than that of Comparative Example 9 and Example 1, but exceeds the predetermined weight average molecular weight, resulting in poor developability. From these, it can be seen that adjusting the weight average molecular weight of the component (A) is useful for expressing the strength, adhesion and developability of the film in a well-balanced manner.

  Also, the examples are compared. Although Examples 1-3 are the amount difference of (Bi) component, it turns out that the maximum point load increases and adhesiveness is improving because content of (Bi) component increases. . On the other hand, it can be seen that the moisture permeability tends to deteriorate by increasing the amount of the component (Bi). Moreover, when Example 4 is seen, although (Bi) component contains only 3.2% in the total solid of a composition, a maximum point load exceeds 35 gf, adhesiveness is also favorable, and even if it adds a little It turns out that there is an effect. On the other hand, Example 20 is a composition in which the component (Bi) was further reduced and the amount added was less than 3%, but the moisture permeability was inferior to that of Example 5 (Bi) and the component content was 3. It can be seen that it is difficult to balance performance because it is not in the range of ~ 15%. Since Example 2 includes the component (Bi) and further has a structure satisfying the formula (2), the second example is more transparent than the example 5 using the component (Bi) that is not the formula (2). Humidity performance is improved. Subsequently, Examples 6 and 8 include a component (B-ii), and the structure thereof uses a compound having a plurality of aromatic rings in one molecule, and therefore has only one aromatic ring in one molecule. The moisture permeability is improved as compared with Example 7 in which only the non- (B-ii) component is used.

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

  In Example 13, the component (A-i) in Example 12 was assigned to the component (A-ii) to obtain the component-containing composition (A-ii). The balance between developability, moisture permeability, and adhesion is improved. Using the component (A-ii) makes it easy to balance the performance.

  Examples 14 to 18 are compositions using almost the same composition except for the (A-i) component, and using the (A-i) component of various structures, but all satisfy the predetermined conditions. It satisfies the developability, moisture permeability, and adhesion.

  In Example 22, compared with Example 2, a photopolymerizable initiator that is not an oxime compound was used as the component (C). However, Example 2 was superior in terms of moisture permeability, and the oxime initiator was It can be seen that there is an effect in improving moisture permeability.

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

  By using the photosensitive resin composition and transfer film according to the present invention, the rust prevention property, developability, and adhesion are all good, and it is suitable for protection of conductor parts such as wiring and electrodes. Alternatively, it can be widely used as a protective film for wiring, electrodes, etc. for use as a force sensor and as a solder resist for printed wiring boards.

Claims (14)

The following ingredients:
(A) an alkali-soluble polymer having an acidic group,
(B) a photopolymerizable compound, and (C) a photopolymerizable initiator, a photosensitive resin composition,
As the component (A), (Ai) a polymer having an ethylenically unsaturated group and an acidic group and having a ring structure in the main chain,
As the component (B), (Bi) a compound having at least two ethylenically unsaturated groups and including butylene oxide in the structure as a repeating unit (however, a compound corresponding to the component (A) is excluded) And (B-ii) a compound having one ethylenically unsaturated group,
The component (A) is at least one polymer A-1,..., An (where n represents an integer of 1 or more) including at least a polymer corresponding to the component (Ai). Including the following formula (1):
{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% in the photosensitive resin composition of said polymer A-1, ... An. }, The weight average molecular weight of the component (A) calculated in 6,000 to 20,000,
The component (B-ii) is contained in an amount of 3% by mass or more based on the total solid content of the photosensitive resin composition, and
A transfer film in which a photosensitive resin layer having a thickness of 30 μm is laminated with the photosensitive resin composition on a support is formed, and the transfer film is laminated on a substrate having an opening of 6 mmφ, and then exposed to the whole surface. After the film is formed, the support is peeled off, and the maximum point load is 35 gf or more when the portion corresponding to the center of the opening is pierced at a speed of 100 mm / min with a 1.5 mmφ cylinder. A photosensitive resin composition characterized by the above. The component (Bi) is represented by the following formula (2):
{Wherein Y ₁ and Y ₂ each independently represents a (meth) acryloyl group, and n represents an integer of 2 to 30. } The photosensitive resin composition of Claim 1 containing the compound represented by these.   The photosensitive resin composition of Claim 1 or 2 containing at least 1 type of compound which has two or more aromatic rings in 1 molecule as said (B-ii) component.   The photosensitive resin of any one of Claims 1-3 containing the alkali-soluble polymer which has an acidic group and does not have an ethylenically unsaturated group as said (A) component. Composition.   The photosensitive resin composition of any one of Claims 1-4 which contains the said (Bi) component 3 mass%-15 mass% with respect to the solid content total mass of the said photosensitive resin composition. Stuff.   As the component (Ai), (A-iii) has a weight average molecular weight of 6,000 or more, an acid value of 60 to 120 mgKOH / g, an ethylenically unsaturated group and an acidic group, and a ring in the main chain. The photosensitive resin composition of Claim 5 which contains the polymer containing a structure 90 mass% or more with respect to solid content total mass of the said (A) component.   As the component (A), (A-iv) a weight-average molecular weight of 10,000 to 36,000, an acid group having an acid group of 130 to 150 mgKOH / g, and an alkali-soluble compound having no ethylenically unsaturated group The photosensitive resin composition of Claim 5 or 6 containing a polymer.   (D) The photosensitive resin composition of any one of Claims 1-7 which further contains the thiol compound which has at least 2 mercapto group in 1 molecule.   The photosensitive resin composition of any one of Claims 1-8 whose said (C) component is an oxime compound.   A transfer film provided with a support film and the photosensitive resin layer which consists of the photosensitive resin composition of any one of Claims 1-9 provided on this support film.   The transfer film of Claim 10 used for the protective film for conductors.   A pattern production method, wherein a pattern is produced by laminating, exposing and developing the transfer film according to claim 11 on a substrate.   A cured film pattern obtained by post-exposure treatment and / or heat treatment of the pattern obtained by the method according to claim 12.   A device having a touch panel display device or a touch sensor having the cured film pattern according to claim 13.