TW201940342A - Transfer film, resin pattern forming method using transfer film, and cured film pattern forming method - Google Patents

Abstract

The present invention provides: a photosensitive resin composition that is suitable for protection of a conductor part such as an electrode and that allows a transfer film to have satisfactory tack property, developability at low temperature, lamination property at low temperature, moisture permeability when in the form of a cured film, and adhesion to a conductor base material; a transfer film; and a production method therefor. The transfer film for forming a protective film for a conductor part comprises a support film and a photosensitive resin composition layer. The photosensitive resin composition layer includes (A) an alkali-soluble resin (excluding acid-modified epoxy (meth)acrylate compounds), (B) a compound containing a carboxyl group and an ethylenically unsaturated group, (C) a photopolymerizable compound, and (D) a photopolymerizable initiator. The alkali-soluble resin (A) has a weight-average molecular weight of 11,000-29,000 and an acid value not less than 100 mgKOH/g. The compound (B) has a weight-average molecular weight of 1,000-9,500, an acid value not less than 60 mgKOH/g, and a refractive index not less than 1.570. The ratio of the mass of the resin (A) to the mass of the compound (B) is 0.18-6.0.

Description

Transfer film, method for producing resin pattern using transfer film, and method for producing cured film pattern

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

In recent years, with the progress of high performance, diversification, and miniaturization of electronic devices, 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 begun to increase. Visual recognition and selection of characters, symbols, patterns, etc. displayed on the display element through the transparent touch panel, and the increase in the number of cases where the functions of the machine are switched by the operation of the transparent touch panel. Touch panels are not only used for large electronic devices such as computers and televisions, but also for small electronic devices such as car navigation, mobile phones, electronic dictionaries, and display devices such as OA / FA (Office Automation / Factory automation). An electrode including a transparent conductive electrode material is disposed in the touch panel. As transparent conductive electrode materials, ITO (Indium-Tin-Oxide, Indium Tin Oxide), indium oxide, and tin oxide are known. These materials have high visible light transmittance, and are therefore mainly used as electrodes for substrates for liquid crystal display elements and the like. material.

Existing touch panel methods include resistive film methods, optical methods, pressure methods, electrostatic capacitance methods, electromagnetic wave induction methods, image recognition methods, vibration detection methods, and ultrasonic methods. Various methods have been put into practical use. . In recent years, the use of electrostatic capacitive touch panels has progressed the most. In an electrostatic capacitance type touch panel, if a fingertip as a conductor contacts the touch input surface, electrostatic capacitance coupling occurs between the fingertip and the conductive film to form a capacitor. Therefore, the touch panel of the electrostatic capacitance method detects the coordinates of the contact position by capturing the charge change at the contact position of the fingertips. In particular, the projection type capacitive touch panel can perform multi-point detection with fingertips, so it has good operability for complex instructions. Therefore, it is used as a device with a small display device such as a mobile phone and a portable music player. The use of input devices on the display surface continues to evolve. Generally, in a projection type capacitive touch panel, in order to show the two-dimensional coordinates of the X-axis and the Y-axis, a plurality of X electrodes and a plurality of Y electrodes orthogonal to the X electrodes form a two-layer structure, and are used. ITO is used as an electrode material.

The border area of the touch panel is an area where the touch position cannot be detected. Therefore, narrowing the area of the border area is an important element for increasing the value of the product. In the frame area, in order to transmit the detection signal of the touch position, metal wiring is required, and in order to narrow the frame area, the width of the metal wiring needs to be narrowed. The conductivity of ITO is not high enough, so copper is usually used for metal wiring.

However, in the touch panel as described above, when touched by a fingertip, corrosive components such as moisture and salt may invade from the sensing area. If a corrosive component invades the inside of the touch panel, the metal wiring is corroded, and there is a risk that the resistance between the electrode and the driving circuit is increased or disconnected. To prevent such a situation, a protective film with an anti-rust effect is required on the metal wiring. Generally, the lower the moisture permeability of the protective film, the higher the rust-preventive effect of the metal wiring.

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

On the other hand, it is not limited to the above-mentioned touch panel field. In recent years, from the viewpoint of high-speed productivity and high productivity, the demand for manufacturing various substrates or devices by a roll-to-roll method has increased. To cope with this demand, it is desirable that the photosensitive resin composition for forming a protective film is provided not only as a liquid resist but also as a transfer film property.

In the step of laminating the transfer film to the substrate in a roll-to-roll manner, a vacuum roll laminator is usually used. However, after the transfer film is attached, the photosensitive resin composition layer is applied to the temperature due to the heat of the roller, and is placed under a condition that the free radical polymerization inhibited oxygen does not exist in the environment for a long time. The polymerization initiator was cleaved and the dark reaction proceeded, which became the cause of the significant decrease in developability. Therefore, the roller temperature of the vacuum roller lamination is required to be a low temperature, specifically, less than 100 ° C.

In addition, recently, there has been a large demand for increasing the substrates of flexible displays. As a protective film for protecting a wiring board surface or a pattern circuit provided on the substrate, in addition to the above protective film, a photosensitive solder resist, Various film-like photosensitive materials such as a photosensitive dry film resist.

In Patent Document 1, a composition combining two epoxy acrylate acid modified products is used as a photosensitive coverlay film, but there is no description about low-temperature developability, low-temperature lamination property, or moisture permeability.
In Patent Documents 2 and 3, a composition containing an acrylic copolymer having a weight average molecular weight of 30,000 or more or a carboxyl group-containing polyurethane having a weight average molecular weight of 10,000 and an epoxy acrylate acid modified product is used. As a photosensitive dry film solder resist. There is no record of low-temperature developability, low-temperature lamination, or adhesion to a substrate in any of the documents, and it is estimated that not all of these properties are satisfied.
In Patent Document 4, a composition containing an acrylic copolymer having a weight average molecular weight of 12,000 and a cresol novolac-based epoxy acrylate acid modified product is used as a photosensitive dry film solder resist, but there is no description about low-temperature development. Description of properties, low-temperature lamination, or adhesion to the substrate. In addition, the solder resist described in Patent Document 4 is capable of imparting a certain level of moisture resistance. However, recently, the level of required moisture resistance has been further increased, and it cannot be satisfied.
[Prior technical literature]
[Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2013-228723
[Patent Document 2] Japanese Patent Laid-Open No. 2009-251286
[Patent Document 3] Japanese Patent Laid-Open No. 2012-215804
[Patent Document 4] Japanese Patent Laid-Open No. 2006-243564

[Problems to be solved by the invention]

As described above, the technologies described in Patent Documents 1 to 4 still have room for improvement. Therefore, the problem to be solved by the present invention is to provide a transfer film having good adhesion, low-temperature developability, low-temperature lamination, and moisture permeability as a cured film, and good adhesion to a conductive substrate, and is suitable for electrodes and the like. A conductive resin-protected photosensitive resin composition, a transfer film, and a method for producing the same.
[Technical means to solve the problem]

The above problems are solved by the following technical means.
[1]
A transfer film for forming a conductor portion protective film, characterized in that the transfer film includes a support film and a photosensitive resin composition layer, and the photosensitive resin composition layer contains the following components:
(A) alkali-soluble resin (except for acid-modified epoxy (meth) acrylate compounds);
(B) a compound containing a carboxyl group and an ethylenically unsaturated group;
(C) a photopolymerizable compound; and
(D) a photopolymerizable initiator;
The weight average molecular weight of the (A) alkali-soluble resin is 11,000 to 29,000, and the acid value is 100 mgKOH / g or more.
The weight average molecular weight of the compound (B) containing a carboxyl group and an ethylenically unsaturated group is 1,000 or more and 9,500 or less, the acid value is 60 mgKOH / g or more, and the refractive index is 1.570 or more, and the (A) alkali-soluble resin relative to The mass ratio (A) / (B) of the compound (B) containing a carboxyl group and an ethylenically unsaturated group is 0.18 to 6.0.
[2]
The transfer film of item 1, wherein the acid value of the (A) alkali-soluble resin is less than 200 mgKOH / g.
[3]
For example, the transfer film of item 1 or 2, wherein the (B) compound containing a carboxyl group and an ethylenically unsaturated group has an acid value of 200 mgKOH / g or less and a refractive index of 1.650 or less.
[4]
The transfer film according to any one of items 1 to 3, wherein the hydroxyl value of the photosensitive resin composition layer is 15.0 mgKOH / g or less.
[5]
The transfer film according to item 4, wherein the hydroxyl value of the photosensitive resin composition layer is 0.01 mgKOH / g or more.
[6]
The transfer film according to any one of items 1 to 5, wherein the refractive index of the photosensitive resin composition layer is 1.550 or more.
[7]
The transfer film according to item 6, wherein the refractive index of the photosensitive resin composition layer is 1.630 or less.
[8]
The transfer film according to any one of items 1 to 7, wherein the (A) alkali-soluble resin contains a structure derived from (meth) acrylic acid of 12% by mass to 30% by mass, and 30% by mass to 80% by mass The following structures are derived from styrene or its derivatives.
[9]
The transfer film according to any one of items 1 to 8, wherein the compound (B) containing a carboxyl group and an ethylenically unsaturated group is an acid-modified epoxy (meth) acrylate compound.
[10]
The transfer film according to any one of items 1 to 9, which is used for any of a protective film for a touch panel or a protective film for a force sensor.
[11]
A transfer film for forming a conductor portion protective film, comprising a support film and a photosensitive resin composition layer, and the photosensitive resin composition layer satisfies the following (I) and (II):
(I) In a differential molecular weight distribution curve obtained from a GPC dissolution curve obtained by measuring a component dissolved in tetrahydrofuran by gel permeation chromatography (GPC),
(i) The ratio R _{20k / 5k} of the dw / d (logM) value of the molecular weight M = 20,000 to the molecular weight M = 5000 is in the range of 0.20 to 1.50, and
(ii) In the above-mentioned differential molecular weight distribution curve, when the area of a region with a molecular weight M ≧ 2000 is set to 100%, the ratio S of the area of a region with a molecular weight M ≧ 50,000 is S _{≧ 50k} is 1.0 to 9.0%; and
(II) Components that are soluble in tetrahydrofuran and insoluble in a mixed solvent of tetrahydrofuran / cyclohexane (mass ratio = 1/2) at 23 ° C
(i) the acid value A2 is above 95 mgKOH / g, and
(ii) The refractive index n2 is 1.560 or more.
[12]
If the transfer film for forming a conductive protective film of item 11 further satisfies the following (III):
(III) Components that are soluble in tetrahydrofuran and insoluble in a mixed solvent of tetrahydrofuran / cyclohexane (mass ratio = 1 / 1.3) at 23 ° C
(i) the acid value A1 is 100 mgKOH / g or more, and
(ii) The refractive index n1 is 0.005 or more smaller than the above-mentioned n2.
[13]
For example, the transfer film for conductor protective film formation of item 12, wherein the above-mentioned acid value A1 is 200 mgKOH / g or less.
[14]
The transfer film according to any one of items 11 to 13, wherein the component in the region of the molecular weight M ≧ 50,000 in the differential molecular weight distribution curve described above contains an aromatic ring.
[15]
The transfer film according to any one of items 11 to 14, which is used for any of a protective film for a touch panel or a protective film for a force sensor.
[16]
A transfer film for forming a conductive protective film, comprising a support film and a photosensitive resin composition layer, and the photosensitive resin composition layer satisfies the following (II) and (III):
(II) Components that are soluble in tetrahydrofuran and insoluble in a mixed solvent of tetrahydrofuran / cyclohexane (mass ratio = 1/2) at 23 ° C
(i) the acid value A2 is above 95 mgKOH / g, and
(ii) the refractive index n2 is 1.560 or more;
(III) Components that are soluble in tetrahydrofuran and insoluble in a mixed solvent of tetrahydrofuran / cyclohexane (mass ratio = 1 / 1.3) at 23 ° C
(i) the acid value A1 is 100 mgKOH / g or more, and
(ii) The refractive index n1 is 0.005 or more smaller than the above-mentioned n2.
[17]
For example, the transfer film for forming a conductor protective film according to item 16, wherein the above-mentioned acid value A1 is 200 mgKOH / g or less.
[18]
The transfer film of item 16 or 17 is used for any of a protective film for a touch panel or a protective film for a force sensor.
[19]
A transfer film for forming a conductor portion protective film, characterized in that the transfer film includes a support film and a photosensitive resin composition layer, and the photosensitive resin composition layer contains the following components:
(A) alkali-soluble resin (except for acid-modified epoxy (meth) acrylate compounds);
(B) a compound containing a carboxyl group and an ethylenically unsaturated group;
(C) a photopolymerizable compound; and
(D) a photopolymerizable initiator; and (A) the weight-average molecular weight of the alkali-soluble resin is 11,000 or more and 29,000 or less, and the acid value is 100 mgKOH / g or more,
The compound (B) containing a carboxyl group and an ethylenically unsaturated group has a weight average molecular weight of 1,000 or more and 9,500 or less, an acid value of 60 mgKOH / g or more, and includes at least the following general formulae (1) to (3):
[Chemical 1]

(In the formula, R _l is an alkyl group or a halogen atom, l is an integer of 0 to 4; when l is 2 or more, the substituents may be the same or different from each other)
[Chemical 2]

(In the formula, R _m is an alkyl group or a halogen atom, and m is an integer of 0 to 3; when m is 2 or more, the substituents may be the same as or different from each other)
[Chemical 3]

(In the formula, R _n is an alkyl group or a halogen atom, and n is an integer of 0 to 4; when n is 2 or more, the substituents may be the same as or different from each other)
The structure described in any one, and the mass ratio (A) / (B) of the (A) alkali-soluble resin to the (B) compound containing a carboxyl group and an ethylenically unsaturated group is 0.18 to 6.0.
[20]
The transfer film of item 19, wherein the acid value of the (A) alkali-soluble resin is less than 200 mgKOH / g.
[twenty one]
The transfer film of item 19 or 20, wherein the acid value of the compound (B) containing a carboxyl group and an ethylenically unsaturated group is 200 mgKOH / g or less.
[twenty two]
The transfer film according to item 19, wherein the hydroxyl value of the photosensitive resin composition layer is 15.0 mgKOH / g or less.
[twenty three]
The transfer film according to item 22, wherein the hydroxyl value of the photosensitive resin composition layer is 0.01 mgKOH / g or more.
[twenty four]
The transfer film according to any one of items 19 to 23, wherein the refractive index of the photosensitive resin composition layer is 1.550 or more.
[25]
The transfer film according to item 24, wherein the refractive index of the photosensitive resin composition layer is 1.630 or less.
[26]
The transfer film according to any one of items 19 to 25, wherein the (A) alkali-soluble resin contains a structure derived from (meth) acrylic acid of 12% by mass or more and 30% by mass or less, and 30% by mass or more and 80% by mass The following structures are derived from styrene or its derivatives.
[27]
The transfer film according to any one of items 19 to 26, wherein the compound (B) containing a carboxyl group and an ethylenically unsaturated group is an acid-modified epoxy (meth) acrylate compound.
[28]
The transfer film according to any one of items 19 to 27, which is used for any of a protective film for a touch panel or a protective film for a force sensor.
[29]
A pattern manufacturing method characterized in that a pattern is produced by laminating a transfer film according to any one of items 1 to 28 on a substrate, exposing and developing.
[30]
A method for manufacturing a hardened film pattern, characterized in that a pattern obtained by the pattern manufacturing method as in item 29 is subjected to a post-exposure treatment and / or a heat treatment.
[31]
A method for manufacturing a touch panel display device or a device with a touch sensor, which is characterized in that a hardened film pattern obtained by a hardened film pattern manufacturing method such as item 30 is used.
[Effect of the invention]

According to the present invention, it is possible to provide a photosensitive resin composition and a transfer film having a good transferability, low-temperature developability, low-temperature lamination property, moisture permeability as a cured film, and good adhesion to a conductive substrate. membrane.

Hereinafter, the form for implementing this invention (it abbreviates as "embodiment form" hereafter) is demonstrated in detail. The present invention is not limited to the following embodiments, and can be implemented with various changes within the scope of the gist thereof.

＜ (A) Alkali soluble resin ＞
The (A) alkali-soluble resin in this embodiment is not limited as long as it is a polymer containing a carboxyl group but not containing an acid-modified epoxy (meth) acrylate compound, and examples thereof include (meth) acrylic acid, ( (Meth) acrylic acid esters, (meth) acrylonitrile, (meth) acrylamide, acrylic copolymers (A1), polyimide precursors (A2), carboxyl-containing polyimides (A3) , Carboxyl group-containing urethane resin (A4) and the like.

(A) The acid value (mgKOH / g) of the alkali-soluble resin is 100 or more, and preferably 100 to 200. The acid value is preferably 200 or less from the viewpoint of reducing the moisture permeability and improving the rust prevention property of the conductor, 100 or more from the viewpoint of improving the low temperature developability, and the rust prevention property and low temperature developability of the conductor From the viewpoint of balance, it is more preferably 110 to 180, and still more preferably 120 to 160.

The measurement of the acid value was carried out using a Hiranuma automatic titration device (COM-555) manufactured by Hiranuma Sangyo Co., Ltd., and a potentiometric titration method using 0.1 mol / L potassium hydroxide.
(A) The alkali-soluble resin may have an ethylenically unsaturated group at the end of the main chain and / or the side chain.

The weight average molecular weight of the (A) alkali-soluble resin is 11,000 or more and 29,000 or less in terms of coatability, coating film strength, tackiness and developability of a transfer film. As the weight-average molecular weight of the alkali-soluble resin, the viewpoints of the properties of the unexposed film such as the properties of the developed aggregate, the tackiness when used as a transfer film, the edge melting properties, and the cut chip properties, etc. The printed film is formed on a substrate with a conductor on the substrate and cured, and the adhesion to the substrate is 11,000 or more, and the low-temperature developability is 29,000 or less. Here, the term “edge meltability” refers to a phenomenon in which the photosensitive resin composition layer overflows from the end surface of the roll when the transfer film is wound in a roll shape. The so-called chipping property refers to a phenomenon in which fragments are scattered when an unexposed film is cut by a cutter. If the scattered debris adheres to the upper surface of the transfer film or the like, it is transferred to a mask in a subsequent exposure step or the like and becomes a cause of defective products. (A) The weight-average molecular weight of the alkali-soluble resin is more preferably 13,000 or more and 27,000 or less, and even more preferably 15,000 or more and 26,000 or less. The measurement of the weight-average molecular weight in this embodiment is performed using a gel permeation chromatography (GPC) manufactured by JASCO Corporation. The obtained weight average molecular weight becomes a polystyrene conversion value.
Pump: Gulliver, PU-1580 Column: Shodex (registered trademark) (KF-807, KF-806M, KF-806M, KF-802.5) manufactured by Showa Denko Co., Ltd. 4 detectors in series: RI
Column temperature: 40 ℃
Flow rate: 1.0 mL / min
Injection volume: 0.02 mL
Moving bed solvent: Tetrahydrofuran calibration curve: Calibration curve specified using polystyrene standard sample {using calibration curve based on polystyrene standard sample (Shodex STANDARD SM-105 manufactured by Showa Denko Corporation)}

(A) The hydroxyl value (mgKOH / g) of the alkali-soluble resin is preferably 40 or less, and more preferably 30 or less. When the hydroxyl value is 40 or less, the moisture permeability of the cured product after exposure and thermal curing of the photosensitive resin composition can be reduced, so that the rust prevention property of the conductor is improved.

(A) The hydroxyl value of an alkali-soluble resin can be measured as follows.
First, a solution of the alkali-soluble resin (A) as a measurement object of the hydroxyl value was put on an aluminum pan, and heated at a temperature of 10 ° C higher than the boiling point of the solvent in the solution for 4 hours to completely remove the solvent. 1 g of the solid content of the (A) alkali-soluble resin thus obtained was accurately weighed, 10 mL of a 10% by mass acetic anhydride-pyridine solution was added thereto, and they were uniformly dissolved, and heated at 100 ° C. for 1 hour. After heating, 10 mL of water and 10 mL of pyridine were added and heated at 100 ° C for 10 minutes. Thereafter, using an automatic titrator ("COM-555" manufactured by Hiranuma Sangyo Co., Ltd.), the above-mentioned hydroxyl value was measured by performing neutralization titration with a 0.1 mol / L potassium hydroxide in ethanol solution.
The hydroxyl value can be calculated by the following formula.
Hydroxyl value = (A－B) × f × 28.05 / sample (g) + acid value
{Where A is the amount of 0.1 mol / L potassium hydroxide ethanol solution (mL) used in the blank test, B is the amount of 0.1 mol / L potassium hydroxide ethanol solution (mL) used in the titration, f Representation factor}

(A1) Acrylic copolymer The (A1) acrylic copolymer according to this embodiment means, for example, (meth) acrylic acid, (meth) acrylate, (meth) acrylonitrile, (meth) acrylamide, and styrene And its derivatives.

As an example of the copolymer, in addition to the constituent units described above, other monomers that can be copolymerized with these constituent units may be contained as constituent units. Examples of other monomers include hydroxyalkyl (meth) acrylate, fumaric acid, cinnamic acid, butenoic acid, itaconic acid, maleic anhydride, and tetrahydrofurfuryl (meth) acrylate Ester, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, glycidyl (meth) acrylate, benzyl (meth) acrylate, (meth) acrylate 2, 2,2-trifluoroethyl, 2,2,3,3-tetrafluoropropyl (meth) acrylate, styrene and its derivatives. Examples of the styrene derivative include 4-methylstyrene, 4-hydroxystyrene, 4-methoxystyrene, 4-chlorostyrene, 4- (chloromethyl) styrene, and 4-vinyl. benzoic acid.
Among these copolymers, from the viewpoint of reducing the moisture permeability and improving the rust resistance of the conductor, it is more preferable that the copolymer contains a structural unit derived from (meth) acrylic acid and an aromatic ester derived from (meth) acrylic acid or benzene. Copolymer of ethylene and its constituent units.

By copolymerizing a unit having an aromatic group, the hydrophobicity of the acrylic copolymer is increased, and the rust resistance is improved. In addition, it is considered that by making the acrylic copolymer have an aromatic group, the film density of the photosensitive resin composition after curing is increased, and the rust prevention property of the conductor is improved. Considering both low-temperature developability and reduction in moisture permeability, the (A1) acrylic copolymer is more preferably a structure derived from (meth) acrylic acid containing 12% by mass or more and 30% by mass or less, and 30% by mass. 80% by mass or more of a structure derived from styrene or a derivative thereof.
(A1) The acrylic copolymer is prepared by combining the above-mentioned monomers in a specific weight ratio and radical polymerization. As the photopolymerization initiator at this time, an azo-based polymerization initiator is preferably used. Examples of commercially available azo-based initiators include V-601 (manufactured by FUJIFILM Wako Pure Chemical Co., Ltd.) and the like.

(A2) Polyimide precursor The so-called (A2) polyimide precursor of this embodiment does not only refer to polyamidic acid, but also includes a part of polyamidic acid that has been imidized with amidine.

The polyfluorene imide precursor can be obtained, for example, by mixing and reacting a tetracarboxylic dianhydride with a diamine at a molar ratio of 0.8: 1 to 1.2: 1 in an organic solvent. The tetracarboxylic dianhydride to be used is not limited, and a tetracarboxylic dianhydride previously known can be used. As the tetracarboxylic dianhydride, an aromatic tetracarboxylic acid, an aliphatic tetracarboxylic dianhydride, or the like can be applied. In addition, the diamine used is not limited, and a conventionally 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 dianhydride, diphenylphosphonium-3,3 ', 4,4'-tetracarboxylic dianhydride, ethylene glycol bis (trimellitic acid monoester anhydride), p-phenylene bis ( Trimellitic acid monoester anhydride), p-phenylene bis (trimellitic acid monoester anhydride), m-phenylene bis (trimellitic acid monoester anhydride), o-phenylene bis (trimellitic acid) Monoester anhydride), pentanediol bis (trimellitic acid monoester anhydride), decanediol bis (trimellitic acid monoester anhydride), pyromellitic dianhydride, bis (3,4-dicarboxyphenyl) ) Ether dianhydride, 4,4 '-(2,2-hexafluoroisopropylidene) diphthalic dianhydride, m-triphenyl-3,3', 4,4'-tetracarboxylic dianhydride 1,2,4,5-cyclohexanetetracarboxylic dianhydride, bicyclo [2,2,2] oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, cyclobutane- 1,2,3,4-tetracarboxylic dianhydride, 1-carboxymethyl-2,3,5-cyclopentanetricarboxylic 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-dioxotetrahydrofuranyl) -3-methyl -3-cyclohexene-1,2-dicarboxylic anhydride and the like. These tetracarboxylic dianhydrides 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, and 1,5-bis (4-aminophenylbenzene) (Oxy) alkane, 1,4-diaminobenzene, 1,3-diaminobenzene, 2,4-diaminotoluene, 4,4'-diaminodiphenylmethane, 4,4'-di Amino diphenyl ether, 3,4'-diamino diphenyl ether, 3,3'-dimethyl-4,4'-diamino biphenyl, 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'-Diaminobenzidine aniline, 1,3-bis (4-aminophenoxy) -2,2-dimethylpropane, 1,2-bis [2- (4-aminobenzene (Oxy) ethoxy] ethane, 9,9-bis (4-aminophenyl) fluorene, 5-amino-1- (4-aminomethyl) -1,3,3-trimethyl Indane, 1,4-bis (4-aminophenoxy) benzene, 1,3-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-aminophenoxy) Phenyl) propane, trimethylene-bis (4-aminobenzyl) (Ester), 4-aminobenzoate 4-aminophenyl ester, 4-aminobenzoate 2-methyl-4-aminophenyl ester, bis [4- (4-aminophenoxy) phenyl] Hydrazone, bis [4- (3-aminophenoxy) phenyl] fluorene, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 1-amino-3 -Aminomethyl-3,5,5-trimethylcyclohexane, 3,3'-dicarboxy-4,4'-diaminodiphenylmethane, 3,5-diaminobenzoic acid, 3 , 3'-dihydroxy-4,4'-diaminobiphenyl, and 1,3-bis (4-aminophenoxybenzene). In addition, in order to impart appropriate flexibility and folding resistance to the polyimide precursor, a diamine having a siloxane skeleton and / or a diamine having a polyalkylene oxide skeleton may be used in combination.

The main chain end of the polyimide precursor is not particularly limited as long as it has a structure that does not affect performance, and may be a structure derived from an acid dianhydride or a diamine end used in the production of the polyimide precursor. It is also possible to have a structure in which the terminal is blocked by other acid anhydrides or amine compounds.

Polyimide precursors each having a polyimide structure and a polyamidic acid structure as repeating units can be synthesized in the first stage by reacting an acid dianhydride with a diamine in an unequal molar amount. Step of imine part (step 1); followed by step 2 of step 2 for synthesizing a polyamic acid part (step 2). It is not necessary to include Step 1 as a method for producing a polyimide precursor. Each step will be described below.

(step 1)
The procedure for synthesizing the polyfluorene portion of the first stage will be described. The step of synthesizing the polyfluorene imine part in the first stage is not particularly limited, and a known method can be applied. More specifically, a polyfluoreneimine moiety can be synthesized by the following method. First, a diamine is dissolved and / or dispersed in a polymerization solvent, and an acid dianhydride powder is added thereto. In addition, a solvent azeotropic with water is added, and a mechanical stirrer is used to azeotropically remove water as a by-product, and heat and stir for 0.5 to 96 hours, more preferably 0.5 to 30 hours.

The polyfluorene imine moiety can be synthesized by adding a known fluorene imidization catalyst or can be synthesized without a catalyst. There is no particular limitation on the sulfonium imidization catalyst, and examples thereof include acid anhydrides such as acetic anhydride, such as γ-valerolactone, γ-butyrolactone, γ-tetronic acid, γ-phthalolactone, γ-fragrant Beans and lactone compounds of γ-phthalolactone, and tertiary amines such as pyridine, quinoline, N-methylline and triethylamine. Moreover, if necessary, a mixture of one or two or more of these may be used. Among these, a mixed system of γ-valerolactone and pyridine and catalyst-free are particularly preferable from the viewpoints of high and low reactivity and reduced influence on subsequent reactions.

Examples of the reaction solvent used in the synthesis of the polyimide moiety include dimethyl ether, diethyl ether, methyl ethyl ether, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, and diethylene glycol diethylene glycol. Methyl ether and triethylene glycol dimethyl ether ether compounds having a carbon number of 2 or more and a carbon number of 9 or less; such as acetone and methyl ethyl ketone compounds having a carbon number of 2 or more and a carbon number of 6 or less; such as n-pentane , Cyclopentane, n-hexane, cyclohexane, methylcyclohexane, and decalin saturated hydrocarbon compounds having a carbon number of 5 or more and a carbon number of 10 or less; such as benzene, toluene, xylene, mesitylene, and tetralin Aromatic hydrocarbon compounds having 6 to 10 carbon atoms in hydronaphthalene; such as methyl acetate, ethyl acetate, γ-butyrolactone, and methyl benzoate ester compounds having 3 to 12 carbon atoms; Such as chloroform, dichloromethane, and 1,2-dichloroethane halogen compounds containing 1 to 10 carbon atoms; such as acetonitrile, N, N-dimethylformamide, N, N-dimethyl N-methylamidine and N-methyl-2-pyrrolidone are nitrogen-containing compounds having a carbon number of 2 or more and a carbon number of 10 or less; such as a sulfur-containing compound of dimethylsulfinium. These can be used singly or as a mixed solvent of two or more kinds as needed. Examples of particularly preferred solvents include ether compounds having 2 to 9 carbon atoms, ester compounds having 3 to 12 carbon atoms, aromatic hydrocarbon compounds having 6 to 10 carbon atoms, and carbon numbers. 2 or more nitrogen-containing compounds having a carbon number of 10 or less. These can be arbitrarily selected in consideration of industrial productivity and influence on subsequent reactions.

In the synthesis of the polyfluorene imine moiety, the reaction temperature is preferably 100 ° C to 250 ° C.

(Step 2)
Next, the procedure for synthesizing a polyamic acid moiety in the second stage will be described. The synthesis of the polyamidic acid part in the second stage can be carried out by using the polyamidoimide part obtained in step 1 as a starting material and polymerizing by adding diamine and / or acid dianhydride. The polymerization temperature during the synthesis of the polyamic acid moiety in the second stage 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, and is usually in the range of 30 minutes to 30 hours.

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

(A3) Carboxyl-containing polyfluorene imide Carboxyl-containing polyfluorene imide is synthesized by mixing and reacting a tetracarboxylic dianhydride with a diamine in an organic solvent at a molar ratio of 0.8: 1 to 1.2: 1, It is characterized in that the fluorene also contains a carboxyl group in the skeleton, but may partially retain the polyfluorene acid structure.

Carboxyl-containing polyfluorene imine is generally synthesized using a carboxyl-containing diamine. From the viewpoint of solubility or availability of organic solvents, as the carboxylic group-containing diamine, 3,5-diaminobenzoic acid, 3,3'-dicarboxy-4,4'-di Amino diphenylmethane and the like. These diamines can be used alone or in combination of two or more.

Examples of tetracarboxylic dianhydrides, diamines used in combination with carboxyl-containing diamines, solvents used in synthesis, and fluorinated imidization catalysts are described in (A2) Polyfluorene imine precursors above. The example is the same.

(A4) Carboxyl-containing polyurethane The carboxyl-containing polyurethane of this embodiment is synthesized by: diisocyanate compound, carboxyl-containing diol compound, and other diol compounds In a protic solvent, a known catalyst which responds to the activity of each reactivity is added and heated. The molar ratio of the diisocyanate and the diol compound used is preferably 0.8: 1 to 1.2: 1. When isocyanate groups remain at the polymer end, they are treated with alcohols or amines, etc. Synthesis without isocyanate groups.

Examples of the diisocyanate compound include 2,4-toluene diisocyanate, dimer of 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, p-xylylene diisocyanate, and m-xylylene. Aromatic diisocyanate compounds such as diisocyanate, 4,4'-diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, 3,3'-dimethylbiphenyl-4,4'-diisocyanate: such as six Methylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate, dimer acid diisocyanate and other aliphatic diisocyanate compounds; such as isophorone diisocyanate, 4,4'-methylene Alicyclic diisocyanate compounds such as bis (cyclohexyl isocyanate), methylcyclohexane-2,4- (or 2,6) diisocyanate, 1,3- (isocyanate methyl) cyclohexane; such as 1, Diisocyanate compounds, etc., which are adducts of 3-butanediol 1 mole and toluene diisocyanate 2 mole, are reactants of diol and diisocyanate.

Examples of the carboxyl group-containing diol include 3,5-dihydroxybenzoic acid, 2,2-bis (hydroxymethyl) propionic acid, 2,2-bis (2-hydroxyethyl) propionic acid, and 2,2 -Bis (3-hydroxypropyl) propionic acid, bis (hydroxymethyl) acetic acid, bis (4-hydroxyphenyl) acetic acid, 4,4-bis (4-hydroxyphenyl) valeric acid, tartaric acid, N, N -Dihydroxyethylglycine, N, N-bis (2-hydroxyethyl) -3-carboxy-propanamide and the like.

Examples of other diol compounds used in combination with a carboxyl group-containing diol compound include polytetramethylene glycol, polybutadiene glycol, hydrogenated polybutadiene glycol, polycarbonate diol, and polyester. High molecular weight diols such as diols and polycaprolactone diols; or ethylene glycol, 1,2-propylene glycol, 1,3-propanediol, 1,3-butanediol, 2,3-butanediol, 1, 4-butanediol, 2,2'-dimethyl-1,3-propanediol, diethylene glycol, triethylene glycol, 1,5-pentanediol, dipropylene glycol, neopentyl glycol, 1,6 -Hexanediol, cyclohexane-1,4-diol, cyclohexane-1,4-diol, cyclohexane-1,4-dimethanol, 2-butene-1,4-diol, 2,2,4-trimethyl-1,3-pentanediol, benzenedimethanol, 1,4-bis-β-hydroxyethoxycyclohexane, tricyclodecanedimethanol, hydrogenated bisphenol A, Hydrogenated bisphenol F, bisphenol A, bisphenol S, hydroquinone dihydroxyether, p-xylylene glycol, dihydroxyethylamidine, 2,4-toluenediaminocarboxylic acid bis (2-hydroxyethyl) ester , 2,4-methylphenyl-bis (2-hydroxyethylurea), bis (2-hydroxyethyl) m-xylylenediaminoformate, bis (2-hydroxyethyl) isophthalate ) Ester, 1,4-bis (β-hydroxyethoxy) benzene, Bis (hydroxyethyl [beta]) a low molecular weight glycol ester and the like.

(B) Compound containing a carboxyl group and an ethylenically unsaturated group (B) Compound containing a carboxyl group and an ethylenic unsaturated group in this embodiment, as long as it has one or more carboxyl groups and one or more ethylenically unsaturated groups in the molecule There is no limitation on the base compound. For example, (B1) an epoxy (meth) acrylate acid modified product can be preferably used.

(B) The acid value (mgKOH / g) of the compound containing a carboxyl group and an ethylenically unsaturated group is 60 or more, and preferably 60 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 resistance of the conductor, and from the viewpoint of improving the low-temperature developability of the photosensitive resin composition layer. It is 60 or more, and from the viewpoint of the balance of the two properties, it is more preferably 70 to 170, and even more preferably 80 to 150. The measurement of the acid value is performed by the same method as described above with respect to the (A) alkali-soluble resin.

(B) The weight average molecular weight of the compound containing a carboxyl group and an ethylenically unsaturated group is in terms of compatibility with (A) an alkali-soluble resin, viscosity when used as a transfer film, and low-temperature developability. In other words, it is 1,000 to 9,500. The weight average molecular weight of the compound containing a carboxyl group and an ethylenically unsaturated group is 1,000 or more from the viewpoint of the properties of an unexposed film such as viscosity, edge melting, and chipping when used as a transfer film, and in terms of sensitivity From the viewpoint of low-temperature developability and low-temperature lamination properties of the resin composition layer, it is 9,500 or less, and preferably 2,000 or more and 8,000 or less.

(B) The hydroxyl value (mgKOH / g) of the compound containing a carboxyl group and an ethylenically unsaturated group is preferably 30 or less, and more preferably 20 or less. When the hydroxyl value is 30 or less, the moisture permeability of the cured product of the photosensitive resin composition can be reduced, and the rust prevention property of the conductor is improved. The measurement of the hydroxyl value was performed by the same method as described above with respect to the (A) alkali-soluble resin.

(B) The compound containing a carboxyl group and an ethylenically unsaturated group in this embodiment is characterized in that 1) the refractive index is 1.570 or more and / or 2) it contains at least the following general formulae (1) to (3) Any of the skeletons. By satisfying the above 1) and / or 2), the moisture permeability of the hardened material obtained from the photosensitive resin composition of this embodiment can be reduced, and the rust prevention property of the conductor can be improved. From the viewpoint of moisture permeability, the refractive index of the component (B) is preferably 1.570 or more, and from the viewpoint of low-temperature developability of the photosensitive resin composition layer, 1.650 or less is preferable.
[Chemical 4]

(In the formula, R _l is an alkyl group or a halogen atom, l is an integer of 0 to 4; when l is 2 or more, the substituents may be the same or different from each other)
[Chemical 5]

(In the formula, R _m is an alkyl group or a halogen atom, and m is an integer of 0 to 3; when m is 2 or more, the substituents may be the same as or different from each other)
[Chemical 6]

(In the formula, R _n is an alkyl group or a halogen atom, and n is an integer of 0 to 4; when n is 2 or more, the substituents may be the same as or different from each other)

The refractive index of the component (B) in this embodiment can be measured by the following method.
First, prepare (B) a compound containing a carboxyl group and an ethylenically unsaturated group and dissolve it in an organic solvent having a boiling point of 200 ° C. or lower at 1 atmosphere (for example, soluble in ethanol, acetone, methyl ethyl ketone, and 1-methoxy group). -2-propanol, propylene glycol-1-monomethyl ether-2-acetate, etc.). At this time, it prepared so that solid content concentration might become 30-70 mass%. The obtained solution was coated on a commercially available polyethylene terephthalate (PET) film (thickness: 16 μm) with a bar coater, and dried in a hot air oven at 100 ° C. for 10 minutes to obtain a solution containing (B ) A layered body having a layer of a compound containing a carboxyl group and an ethylenically unsaturated group having a thickness of 5 μm. The refractive index measurement was performed using a Prism Coupler Model 2010 / M (laser wavelength: 532 nm) manufactured by Metricon Corporation in a state where a layer containing a compound containing a carboxyl group and an ethylenically unsaturated group was in contact with europium.

(B1) Epoxy (meth) acrylate acid modified product The so-called (B1) epoxy (meth) acrylate acid modified system of this embodiment is defined as a compound that satisfies the following two conditions, and is also referred to as an acid Modified epoxy (meth) acrylate compound.
i) It can be synthesized from a compound containing two or more epoxy groups in the molecule as a starting material.
ii) One or more carboxyl groups and one or more (meth) acrylfluorenyl groups in the molecule.

<A compound containing two or more epoxy groups in the molecule>
In order to adjust the refractive index of the (B1) epoxy (meth) acrylic acid modified product to 1.570 or more, a compound containing two or more epoxy groups in the molecule is preferable from the viewpoint of availability. In order to contain an epoxy compound or the like having at least any one of the general formulae (1) to (3) in the skeleton, among commercially available products, as the one containing the general formula (1), NC-3000 series (Japanese Chemicals) (Manufactured by the company), BPAE (manufactured by Nippon Steel Chemical Co., Ltd.), and those containing the general formula (2) include HP-4700, 4770, 5000, 6000 (manufactured by DIC), NC-7000, 7300 (Nippon Kayaku) (Manufactured by the company), ESN-175 (manufactured by Nippon Steel Chemical Co., Ltd.), and those containing the general formula (3) include epoxy compounds such as OGSOL PG-100 and OGSOL EG-200 (Osaka Gas Chemicals).

The following describes two methods for synthesizing (B1) epoxy (meth) acrylic acid modified products using a compound containing two or more epoxy groups as a starting material, but (B1) of this embodiment The chemical structure and production method of the epoxy (meth) acrylate acid modified product are not limited thereto.

＜ Synthesis method (1) ＞
As a first reaction, a carboxyl group of a monocarboxylic acid having a (meth) acrylfluorenyl group is reacted with an epoxy group of a compound containing two or more epoxy groups in a molecule. The monocarboxylic acid having a (meth) acrylfluorenyl group is, for example, acrylic acid or methacrylic acid. For this reaction, known reaction conditions can be applied. By the reaction, the epoxy group is cleaved to generate a hydroxyl group.

The second reaction is a reaction between a hydroxyl group of a compound produced in the first reaction and a dicarboxylic anhydride. As the dicarboxylic anhydride, either a saturated dicarboxylic anhydride or an unsaturated dicarboxylic anhydride can be used. Examples of such dicarboxylic anhydrides include succinic anhydride, maleic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, and methyltetrahydrophthalic acid. Acid anhydride, methylhexahydrophthalic anhydride, inner methylenetetrahydrophthalic anhydride, methylbutenyltetrahydrophthalic anhydride, and the like. Among these, succinic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, and methyltetrahydrophthalic anhydride are particularly preferred. These dicarboxylic anhydrides may be used singly or in combination of two or more.
Regarding the second reaction between the hydroxyl group and the acid anhydride group, known reaction conditions can also be used. By the reaction, the acid anhydride group is cleaved to generate an ester group and a carboxyl group.

The reaction is carried out in such a proportion that the acid anhydride group of the dicarboxylic dianhydride in the second reaction is usually 60 to 100 mol parts, preferably 75 mol parts, relative to 100 mol parts of the hydroxyl group generated in the first reaction. Ears above 100 moles.
In addition, the epoxy (meth) acrylate acid modified product synthesized through the first and second reactions may be further combined with one having one epoxy group and one or more radically polymerizable unsaturated groups in the molecule. The compound reacts to increase the content of ethylenically unsaturated groups (third reaction). Examples of the compound having one epoxy group and one or more radically polymerizable unsaturated groups in the molecule include glycidyl acrylate, glycidyl methacrylate, and allyl glycidyl ether.

＜ Synthesis method (2) ＞
As a first reaction, the carboxyl group of a monocarboxylic acid having a (meth) acrylfluorenyl group is reacted with the epoxy group of a compound containing two or more epoxy groups in the same manner as in the above-mentioned synthesis method (1). . The monocarboxylic acid having a (meth) acrylfluorenyl group is, for example, acrylic acid or methacrylic acid. For this reaction, known reaction conditions can be applied. Through the reaction, the epoxy group is cleaved to generate a hydroxyl group.

The second reaction is a reaction between the hydroxyl group of the compound produced in the first reaction and tetracarboxylic anhydride. Examples of the tetracarboxylic anhydride include biphenyl-3,3 ', 4,4'-tetracarboxylic dianhydride, benzophenone-3,3', 4,4'-tetracarboxylic dianhydride, and oxydicarboxylic acid. Phthalic dianhydride, diphenylphosphonium-3,3 ', 4,4'-tetracarboxylic dianhydride, ethylene glycol bis (trimellitic acid monoester anhydride), p-phenylene bis (trimylene Tricarboxylic acid monoester anhydride), p-phenylene bis (trimellitic acid monoester anhydride), m-phenylene bis (trimellitic acid monoester anhydride), o-phenylene bis (trimellitic acid monoester) Anhydride), pentanediol bis (trimellitic acid monoester anhydride), decanediol bis (trimellitic acid monoester anhydride), pyromellitic dianhydride, bis (3,4-dicarboxyphenyl) ether Dianhydride, 4,4 '-(2,2-hexafluoroisopropylidene) diphthalic dianhydride, m-triphenyl-3,3', 4,4'-tetracarboxylic dianhydride, 1 , 2,4,5-cyclohexanetetracarboxylic dianhydride, bicyclo [2,2,2] oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, cyclobutane-1, 2,3,4-tetracarboxylic dianhydride, 1-carboxymethyl-2,3,5-cyclopentanetricarboxylic acid-2,6: 3,5-dianhydride, 4- (2,5-di Pendant oxytetrahydrofuran-3-yl) -1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride, and 5- (2,5-di pendant oxytetrahydrofuranyl) -3-methyl-3 -Cyclohexene-1,2-dicarboxylic anhydride and the like. These tetracarboxylic dianhydrides may be used alone or in combination of two or more.

The third reaction is a reaction between a residual hydroxyl group of a compound produced in the second reaction and a dicarboxylic anhydride. As the dicarboxylic anhydride, either a saturated dicarboxylic anhydride or an unsaturated dicarboxylic anhydride can be used. Examples of such dicarboxylic anhydrides include succinic anhydride, maleic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, and methyltetrahydrophthalic acid. Acid anhydride, methylhexahydrophthalic anhydride, inner methylenetetrahydrophthalic anhydride, methylbutenyltetrahydrophthalic anhydride, and the like. Among these, succinic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, and methyltetrahydrophthalic anhydride are particularly preferred. These dicarboxylic anhydrides may be used singly or in combination of two or more.
In the third reaction between the hydroxyl group and the dicarboxylic anhydride group, known reaction conditions can be used. Through the reaction, the anhydride group is cleaved to generate an ester group and a carboxyl group, and an epoxy (meth) acrylate acid modified product can be obtained.

The reaction is performed such that the total amount of the acid anhydride groups of the tetracarboxylic dianhydride in the second reaction and the dicarboxylic anhydride in the third reaction is usually 100 moles of the hydroxyl group generated in the first reaction. 60 to 100 moles, preferably 75 to 100 moles. The second reaction and the third reaction may be performed simultaneously. As a specific synthesis method, a method described in Japanese Patent Laid-Open No. 06-001938 can be used.

In addition, the epoxy (meth) acrylate acid modified product synthesized through the first to third reactions may be further combined with one having one epoxy group and one or more radically polymerizable unsaturated groups in the molecule. The compound reacts to increase the content of ethylenically unsaturated groups (4th reaction). Examples of the compound having one epoxy group and one or more radically polymerizable unsaturated groups in the molecule include glycidyl acrylate, glycidyl methacrylate, and allyl glycidyl ether.

The epoxy (meth) acrylic acid modified product of this embodiment can be obtained by the synthesis method (1), the synthesis method (2), etc., but a commercial item can also be used. Examples of commercially available products containing an epoxy (meth) acrylate acid modified product of the general formula (1) include ZCR-1569H, ZCR-1601H, ZCR-1797H, and ZCR-1798H (manufactured by Nippon Kayaku Co., Ltd.) Examples of commercially available products containing an epoxy (meth) acrylate acid modified product of the general formula (3) include FCA-954, FCA-293, FCA-506 (manufactured by Nagase chemteX) or TR- B201, TR-B202 (made by Changzhou Qiangli Electronic Materials Co., Ltd.), etc.

Mass ratio of (A) alkali-soluble resin to (B) compounds containing carboxyl and ethylenically unsaturated groups in this embodiment A / B ((A) mass of alkali-soluble resins ÷ (B) containing carboxyl and ethylenic unsaturated The mass of the base compound is 0.18 to 6.0. When A / B is 0.18 or more, the adhesiveness of a transfer film becomes favorable, and the adhesiveness with a conductor base material improves. When A / B is 6.0 or less, low-temperature lamination property and moisture permeability of a cured film are reduced. Surprisingly, with regard to low-temperature developability, deterioration occurs in both cases where A / B is less than 0.18 and when it exceeds 6.0. From the viewpoint of the balance of various performances, the more preferable range of A / B is 0.40 to 1.0.

<(C) Photopolymerizable compound>
The photopolymerizable compound of the present embodiment is a compound having an ethylenically unsaturated double bond, and for example, a compound having a polymerizability because it has an ethylenically unsaturated group in its structure. The compound having an ethylenically unsaturated double bond is preferably a compound containing (c1) having three or more polymerizable groups in the molecule, and / or more preferably one containing (c2) having one polymerizable group in the molecule. Compound. The compound having an ethylenically unsaturated double bond may be used in combination with a compound other than the above.

When the component (C) contains (c1) a compound having three or more polymerizable groups in the molecule, the cross-linking density of the protective film is increased, and moisture and the like are difficult to pass through, which can reduce the moisture permeability of the cured film. (C1) A compound having three or more polymerizable groups in the molecule can be obtained by having, as a central skeleton, a group having 3 mol or more of an alkylene oxide group in the molecule to make the ring An alkylene oxide group such as oxyethylene group, propylene oxide group, or butylene oxide is added to this group to obtain an alcohol, and the alcohol is converted into a (meth) acrylate. Further, the central skeleton may not be modified with an alkylene oxide group, and (meth) acrylic acid may be directly reacted with the central skeleton. Examples of compounds that can serve as a central skeleton include glycerol, trimethylolpropane, pentaerythritol, diglycerol, bis-trimethylolpropane, dipentaerythritol, and an isocyanurate ring. From the viewpoint of reducing the moisture permeability of the cured film, it is more preferable to contain dipentaerythritol hexa (meth) acrylate, pentaerythritol tetra (meth) acrylate, trimethylolpropane tri (meth) acrylate or di- Trimethylolpropane tri (meth) acrylate. The photosensitive resin composition further preferably contains a compound having a molecular weight of 430 or less as (c1) a compound having three or more polymerizable groups in the molecule. When the molecular weight of the (c1) component is 430 or less, the low-temperature developability of the photosensitive resin composition layer is improved. Examples of compounds having a molecular weight of 430 or less include compounds having a central skeleton such as glycerol, trimethylolpropane, pentaerythritol, and the like. From the viewpoint of considering both the low-temperature developability of the photosensitive resin composition layer and the decrease in moisture permeability of the cured film, the (C) component preferably contains pentaerythritol tetra (meth) acrylate or trimethylolpropane tri (methyl) )Acrylate.

By not containing the compound (c1) or containing (c2) a compound having one polymerizable group in the molecule in addition to the compound (c1), it can be seen that (C) the overall reaction rate of the compound having an ethylenically unsaturated double bond The improvement is expected to reduce the moisture permeability of the cured film. In addition, the low-temperature developability of the photosensitive resin composition layer may sometimes be improved. Examples of the compound (c2) having one polymerizable group in the molecule include a compound obtained by adding (meth) acrylic acid to one end of a polyalkylene oxide, adding (meth) acrylic acid to one end, and Compounds such as alkyl ether or allyl etherification at the other end. Examples include: m-phenoxy benzyl acrylate, o-phenylphenoxy ethyl acrylate, 4-methacryloxy benzophenone, EO (Ethylene Oxide, ethylene oxide) modified p-isopropyl Phenylphenol acrylate, nonylphenoxyethyl acrylate, 4-nonylphenyl heptaethylene glycol dipropylene glycol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, phenoxyhexaethylene glycol Acrylate, 4-n-octylphenoxy pentapropylene glycol acrylate, 1,6-hexanediol (meth) acrylate. From the viewpoint of the rust prevention property of the conductor and the moisture permeability of the cured film, it is more preferable to contain m-phenoxy benzyl acrylate, o-phenylphenoxyethyl acrylate, and 4-methacryloxydiphenyl Methyl ketone, EO modified p-cumylphenol acrylate, nonylphenoxyethyl acrylate.

Moreover, as another compound (c3) which has an ethylenically unsaturated double bond (C), For example, the compound which has a (meth) acryl fluorenyl group in the both ends of a polyalkylene oxide chain, or a polyepoxide Compounds having a (meth) acrylfluorenyl group at both ends of an oxirane chain or a polypropylene oxide chain randomly or block-bonded, a bisphenol A modified with an alkylene oxide and having (Meth) acrylfluorenyl compounds and the like.

Other examples of the compound (c3) having an ethylenically unsaturated double bond (C3) include aminomethyl esters which are reaction products of a diisocyanate compound and a compound having a hydroxyl group and a (meth) acrylic group in one molecule. Ester compounds, etc.
(C) As a commercially available product of a compound having an ethylenically unsaturated double bond, examples of pentaerythritol tetraacrylate include A-TMMT (manufactured by Shin Nakamura Chemical Industry Co., Ltd.), and m-phenoxybenzyl acrylate, Examples include: POB-A (manufactured by Kyoeisha Chemical Co., Ltd.), and as 2- (o-phenylphenoxy) ethyl acrylate, examples include: HRD-01 (manufactured by NISSHOKU TECHNO FINE CHEMICAL) Examples of the polybutylene glycol dimethacrylate include FA-PTG-9M and FA-PTG-28M (manufactured by Hitachi Chemical Co., Ltd.).

The content of the photosensitive resin composition (C) as a compound having an ethylenically unsaturated double bond is from the standpoint of resolvability, reduced adhesiveness of the conductor of the cured film, and reduced moisture permeability, in terms of the quality of the photosensitive resin composition. As a reference, it is preferably 20% by mass to 60% by mass, and more preferably 30% by mass to 50% by mass.

＜ (D) Photopolymerization initiator ＞
The (D) photopolymerization initiator of this embodiment is a compound capable of polymerizing a compound such as an ethylenically unsaturated group-containing compound by generating radicals by active light. The photopolymerization initiator of this embodiment is a compound which can generate a radical by active light, thereby polymerizing an ethylenically unsaturated group-containing compound or the like. Examples of the (D) photopolymerization initiator include benzophenone, N, N, N ', N'-tetramethyl-4,4'-diaminobenzophenone (Michlerone) ), N, N, N ', N'-tetraethyl-4,4'-diaminobenzophenone, 4-methoxy-4'-dimethylaminobenzophenone, 2- Benzyl-2-dimethylamino-1- (4-olinylphenyl) -butanone-1, 2-methyl-1- [4- (methylthio) phenyl] -2-olinyl- Aromatic ketones such as acetone-1, acrylated benzophenone, 4-benzylidene-4'-methyldiphenyl sulfide; benzoin ether compounds such as benzoin methyl ether, benzoin ether, benzoin phenyl ether; benzoin, Benzoin compounds such as methyl benzoin and ethyl benzoin; 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzylidene oxime)], ethyl ketone, 1- [ 9-ethyl-6- (2-methylbenzylidene) -9H-carbazol-3-yl]-, 1- (O-acetamidooxime), 1- [4- (phenylthio) Phenyl] -3-cyclopentylpropane-1,2-dione-2- (O-benzylideneoxime), 1,2-propanedione, 3-cyclohexyl-1- [9-ethyl -6- (2-furylcarbonyl) -9H-carbazol-3-yl]-, 2- (O-ethylammonium oxime) and other oxime ester compounds; Derivatives such as benzoin dimethyl ketal Products; 9-phenylacridine, 1,7-bis (9,9'-acridyl) heptane and other acridine derivatives ; N-phenylglycinic acid derivatives such as N-phenylglycine; coumarin compounds; oxazole compounds; 2,4,6-trimethylbenzylidene-diphenyl-phosphine oxide and other oxidation Phosphine compounds. The photopolymerization initiator may be used alone or in combination of two or more.

Among these, 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, the oxime ester compound is preferred, and among these, 365 nm is more preferred. Compound with higher Mohr absorption coefficient. By using an oxime initiator with a high absorption coefficient at a wavelength of 365 nm, a high-sensitivity protective film can be obtained by i-ray exposure. Among them, from the viewpoint of rust prevention, an oxime ester compound is preferable, and among these, a compound having a higher Mohr absorption coefficient at 365 nm is more preferable. By using an oxime initiator with a high absorption coefficient at a wavelength of 365 nm, a high-sensitivity protective film can be obtained by i-ray exposure. It is speculated that a higher surface hardenability can be obtained by this, and the invasion of sodium ions in the development step as described above can be suppressed, and as a result, a higher rust resistance of the conductor can be obtained.

Specific oxime ester compounds include 1,2-octanedione, 1-[(4-phenylthio) phenyl-, 2- (O-benzylideneoxime)] (BASF Japan (stock) Manufacturing, Irgacure Oxe01, product name), ethyl ketone, 1- [9-ethyl-6- (2-methylbenzyl) -9H-carbazol-3-yl]-, 1- (O-ethyl Fluorenyl oxime) (manufactured by BASF Japan, Irgacure Oxe02), 1- [4- (phenylthio) phenyl] -3-cyclopentylpropane-1,2-dione-2- (O-benzene Formamyl oxime) (TR-PBG-305, product name, manufactured by Changzhou Qiangli Electronic New Materials Co., Ltd.), and 1,2-propanedione, 3-cyclohexyl-1- [9-ethyl-6- (2- Furylcarbonyl) -9H-carbazol-3-yl]-, 2- (O-ethylammonium oxime) (TR-PBG-326, product name, manufactured by Changzhou Qiangli Electronic New Materials Co., Ltd.), (7-nitro- 9,9-dipropyl-9H-fluoren-2-yl) (o-tolyl) methanone O-ethylammonium oxime (DFI-020 manufactured by Daito Chemix (stock)), 1,8-octanedione, 1 , 8-bis [9- (2-ethylhexyl) -6-nitro-9H-carbazol-3-yl]-, 1,8-bis (O-acetamidooxime), 3-cyclohexyl- 1- (6- (2- (benzyloxyimino) octyl) -9-ethyl-9H-carbazol-3-yl) -propane-1,2-dione-2- (O- Benzamidine oxime) (TR-PBG-371, product name, manufactured by Changzhou Qiangli Electronic New Materials Co., Ltd.), 3-cyclohexyl-1- (6- (2- (benzene Formamyloxyimino) hexyl) -9-ethyl-9H-carbazol-3-yl) -propane-1,2-dione-2- (O-benzylideneoxime) (Changzhou Power Electronics New Materials Co., Ltd. manufactures TR-PBG-391 (product name) and so on.

The content in the photosensitive resin composition as the (D) photopolymerization initiator is 0.1% to 10% by mass based on the mass of the photosensitive resin composition. From the viewpoint of sensitivity and resolvability, More preferably, it is 0.3 to 5 mass%. When the content of the photopolymerization initiator is in the range of 0.1% by mass to 10% by mass, the photosensitivity becomes sufficient, and the increase in the absorption of the surface of the composition when the active light is irradiated can be suppressed, so that the internal light hardening becomes Inadequate conditions such as insufficient light transmittance.

＜ (E) Thermal crosslinking agent ＞
From the viewpoint of exhibiting higher rust prevention performance, it is preferable to further blend (E) a thermal crosslinking agent in the photosensitive resin composition. The (E) thermal cross-linking agent refers to (A) an alkali-soluble resin, (B) a compound containing a carboxyl group and an ethylenically unsaturated group, or unreacted (B) an ethylenically unsaturated double bond by heat. The compound and the compound (E) which is added at the same time undergoes an addition reaction or a polycondensation reaction. The temperature at which the addition reaction or the polycondensation reaction occurs is preferably 100 ° C to 150 ° C. The addition reaction or condensation reaction occurs during heat treatment after patterning by development.

Specific examples of the thermal cross-linking agent include blocked isocyanate compounds, diol compounds, epoxy compounds, and the thermal cross-linking agents described in paragraph [0054] of International Publication No. 2016/047691, but are not limited thereto. Etc.

The blocked isocyanate compound refers to 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-hexanediisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, xylylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, 4,4'-hydroxide diisocyanate, isophorone diisocyanate, 1,5-naphthalene diisocyanate, 4,4-diphenyl diisocyanate, 1,3- Bis (isocyanate methyl) cyclohexane, 1,4-benzene diisocyanate, 2,6-benzene diisocyanate, 1,3,6-hexamethylene triisocyanate, and hexamethylene diisocyanate.

Examples of the end-capping agent include alcohols, phenols, ε-caprolactam, oximes, active methylenes, thiols, amines, fluorimines, amidines, imidazoles, Urea, carbamates, imines, and sulfites.

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

The diol compound refers to one containing two hydroxyl groups with respect to one molecular chain. Examples thereof include hydrocarbon groups such as aliphatic, aromatic, and alicyclic groups in the skeleton.
Specific examples of the diol compound include polytetramethylene glycol (for example, P4TMG650, PTMG850, PTMG1000, PTMG1300, PTMG1500, PTMG1800, PTMG2000, and PTMG3000 manufactured by Mitsubishi Chemical Co., Ltd.), and polybutadiene diene. Alcohols (eg, G-1000, G-2000, and G-3000 manufactured by Soda Co., Ltd.), hydrogenated polybutadiene glycols (e.g., GI-1000, GI-2000, and GO- 3000, etc.), polycarbonate diols (e.g., Duranol T5651, Duranol T5652, Duranol T4671, Duranol G4672, Duranol G3452 and Duranol G3450J manufactured by Asahi Kasei Co., Ltd., and Kuraray Polyol C-590, Kuraray Polyol C manufactured by Kuraray Co., Ltd. -1090, Kuraray Polyol C-2090, Kuraray Polyol C-3090, etc.), polycaprolactone diols (e.g. PLACCEL 205PL, PLACCEL 210, PLACCEL 220, PLACCEL 220PL, etc., manufactured by Daicel), polyester diols ( For example, Kuraray Polyol P-530, Kuraray Polyol P-2030 and Kuraray Polyol P-2050 manufactured by Kuraray Co., Ltd., and HS2N-220S manufactured by Toyooka Oil Co., Ltd., etc., and bisphenols (for example, Mitsubishi Chemical Co., Ltd.) Manufacture of bisphenol A, etc.) and hydrogenated bisphenols (for example, Nissin (Rikabinol HB, etc.). These diol compounds may be used alone or in combination of two or more kinds.

From the viewpoints of storage stability of the transfer film and reduction of the moisture permeability of the cured film, the (E) thermal crosslinking agent is preferably a blocked isocyanate compound, and further, the low-temperature developability of the photosensitive resin composition layer From a viewpoint, it is more preferable to use it together with a diol compound.

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

In the heat treatment after the blocked isocyanate compound is patterned by development, it is used in combination with (A) an alkali-soluble resin or (B) a carboxyl group or a hydroxyl group of a compound containing a carboxyl group and an ethylenically unsaturated group, or a diol compound used in combination. The hydroxyl group reacts, so that the moisture permeability of the cured film becomes low, and the rust resistance for protecting the substrate, the electrode, etc. becomes good. Further, it is considered that the blocked isocyanate compound is crosslinked with (A) an alkali-soluble resin and / or (B) a compound containing a carboxyl group and an ethylenically unsaturated group, whereby the crosslinking density of the cured film is increased, and the water diffusivity is reduced. The moisture permeability of the cured film becomes lower, and the rust resistance of the conductor is improved. In addition, in the blocked isocyanate, the isocyanate group is blocked by a blocking agent, so that the reaction with the (A) alkali-soluble resin or diol compound at room temperature is suppressed, and the photosensitive resin composition and the transfer film are maintained. stability.

The diol compound has a hydrophilic hydroxyl group, and therefore has good developability. In addition, in the heat treatment after the pattern is formed by development, the hydroxyl group of the diol compound reacts with the blocked isocyanate compound, so the excellent rust preventive property of the conductor is maintained. From the viewpoint of developability, the molecular weight of the diol compound is preferably 300 to 3,000, and the molecular weight is more preferably 500 to 2,000. On the other hand, if unreacted hydroxyl groups remain after heat curing, the moisture permeability of the cured film may be deteriorated, which may cause damage to 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 added so that it is 15.0 mgKOH / g or less. By setting the hydroxyl value of the photosensitive resin composition to 20 or less, the moisture permeability of the cured product of the photosensitive resin composition can be reduced, and the rust prevention property of the conductor can be improved. The hydroxyl value of the photosensitive resin composition layer is preferably 0.01 mgKOH / g or more.

＜ (F) Rosin ester compound ＞
From the viewpoint of exhibiting lower water permeability, it is preferable to further compound the (F) rosin ester compound in the photosensitive resin composition. The (F) rosin ester compound of the present embodiment refers to a rosin acid, a dimer of rosin acid, a dimer of rosin acid, and a non-volatile component selected from rosin, that is, a tricyclic diterpene having a carbon number of 20, a rosin acid dimer, and a rosin acid. A compound having an ester bond obtained by reacting a compound in a group consisting of a hydride and a disproportion of rosinic acid (hereinafter, collectively referred to as a "pinsolic acid derivative") with a hydroxy compound, a phenol compound, or a glycidyl compound The compound is a compound having an ester bond obtained by reacting a rosinic acid derivative with any of a glycidyl compound, a carboxyl compound, and a phenol compound.

Specific examples of the (F) rosin ester compound include, for example, products of Arakawa Chemical Co., Ltd .: Ester Gum series, Pine Crystal series, Super Ester series, Pensel series, Beamset 101, etc. The company's products include: Hariester series, Neotall series, Haritack series.

(F) The rosin ester compound becomes a compound having higher hydrophobicity by having an alicyclic structure and an ester structure, but it is incompatible with (A) an alkali-soluble resin and (B) a carboxyl group and an ethylenic compound in a photosensitive resin composition Saturated compounds, (C) photopolymerizable compounds, and (D) photopolymerization initiators have good compatibility, so they do not impair the developability of the composition. Therefore, the low-temperature developability of the transfer film and the cured film Excellent balance of moisture permeability and rust resistance of conductors.

From the viewpoint of the rust resistance of the conductor, the acid value of the (F) rosin ester compound is more preferably 20 mgKOH / g or less. Among the products of the Arakawa Chemical Co., Ltd. and Harima Chemical Co., Ltd., For example: Pine Crystal KE-100, Ester Gum 105, Super Ester A-115, Super Ester A-125, Pensel A, Pensel C, Pensel D-125, Pensel D-135, Pensel D-160, Beamset 101, Hariester S, Neotall 125HK, Haritack F105, Haritack FK125, Haritack PCJ, etc.

Furthermore, from the viewpoint of reducing the moisture permeability of the cured film, the softening point of the (F) rosin ester compound is more preferably 100 ° C or higher. Specific compounds meeting these conditions include, for example, Ester Gum 105, Super Ester A -115, Super Ester A-125, Pensel A, Pensel C, Pensel D-125, Pensel D-135, Pensel D-160, Neotall 125HK, etc. The softening point is particularly preferably above 110 ° C, as specific to meet these conditions The compounds include: Super Ester A-115, Super Ester A-125, Pensel A, Pensel C, Pensel D-125, Pensel D-135, Pensel D-160, Neotall 125HK. (F) The rosin ester compound may be used alone or as a mixture of two or more kinds.

(F) The content in the photosensitive resin composition of the rosin ester compound is 1% to 20% by mass based on 100% by mass of the total solid content of the photosensitive resin composition. From the viewpoint of moisture permeability and developability It is more preferable that it is 5 to 20 mass%, and from a viewpoint of the adhesiveness with respect to a base material, it is still more preferable that it is 5 to 15 mass%. When the content of the (F) rosin ester compound is within a range of 1% to 20% by mass, the performance of low-temperature developability of the transfer film and the moisture permeability of the cured film are well balanced.

＜ (G) Anti-rust agent ＞
The rust preventive agent of the present embodiment refers to a compound having a rust preventive effect, for example, a substance that forms a film on a metal surface to prevent metal corrosion or rust.

As the rust preventive, in terms of compatibility and sensitivity with the photosensitive resin composition of the present embodiment, heterocyclic compounds containing N, S, O, and the like are preferred, and examples include tetrazole and derivatives thereof Substances, triazole and its derivatives, imidazole and its derivatives, indazole and its derivatives, pyrazole and its derivatives, imidazoline and its derivatives, oxazole and its derivatives, isoxazole and its derivatives , Oxadiazole and its derivatives, thiazole and its derivatives, isothiazole and its derivatives, thiadiazole and its derivatives, thiophene and its derivatives, and the like. Derivatives described herein include compounds in which a substituent is introduced into the parent structure. For example, in the case of a tetrazole derivative, a compound in which a substituent is introduced into tetrazole is included. The substituent is not particularly limited, and examples thereof include a hydrocarbon group (which may be saturated or unsaturated, linear or branched, and may include a cyclic structure in the structure) or one or more of them Substituents for functional groups having a hetero atom such as a hydroxyl group, a carbonyl group, a carboxyl group, an amine group, a sulfonylamino group, a nitro group, a cyano group, a thiol group, and a halogen (fluorine, chlorine, bromine, iodine, etc.) group.

Furthermore, from the viewpoint of rust resistance, it is preferred that the heterocyclic compound has a heterocyclic ring containing C and N and / or S, and in the same heterocyclic ring, the number of N atoms is 3 or less or the number of S atoms is A compound having 3 or less or a total number of N and S atoms of 3 or less. 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, and thiophene and Its derivatives, etc. From the viewpoint of rust prevention and developability, as the compound, benzotriazole and a derivative thereof, and imidazole and a derivative thereof are more preferable.

The following discloses specific examples of compounds having a heterocyclic ring containing C and N and / or S, and in the same heterocyclic ring, the number of N atoms is 3 or less or the number of S atoms is 3 or less or the total number of N atoms and S atoms is 3 or less example:
Triazoles, for example, 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, etc .;

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 .;
Imidazoline; imidazoline derivatives, such as 2-undecylimidazoline, 2-propyl-2-imidazoline, 2-phenylimidazoline, etc .;
Thiazoles; Thiazole derivatives, such as 2-amino-4-methylthiazole, 5- (2-hydroxyethyl) -4-methylthiazole, benzothiazole, 2-mercaptobenzothiazole, 2-amino Benzothiazole, 2-amino-6-methylbenzothiazole, (2-benzothiazylthio) acetic acid, 3- (2-benzothiazylthio) propionic acid, etc .;

Isothiazole; isothiazole derivatives, such as 3-chloro-1,2-benzoisothiazole, etc .;
Thiadiazole, for example, 1,2,3-thiadiazole, 1,2,5-thiadiazole, 1,3,4-thiadiazole, etc .; Thiadiazole derivatives, for example, 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, 3-amino-2-thiophenecarboxylic acid methyl ester, 3-methylbenzothiophene, and the like.

Among the above-mentioned rust inhibitors, benzotriazole, 5-carboxybenzotriazole, 1-hydroxybenzotriazole, and 5-chlorobenzotriazole.
On the other hand, as the (G) component, from the viewpoints of the rust prevention properties of the conductor and the adhesion between the cured film and the substrate, tetrazole and its derivatives, triazole and its derivatives, and indazole are preferred. And its derivatives and thiadiazoles and their derivatives.

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

Specific examples of indazole include 1H-indazole. Examples of the indazole derivative include 5-aminoindazole, 6-aminoindazole, 1-benzyl-3-hydroxy-1H-indazole, 5-bromoindazole, 6-bromoindazole, 6 -Hydroxyindazole, 3-carboxyindazole and 5-nitroindazole.

Specific examples of the triazole and its derivative and the thiadiazole and its derivative are the same as those described above.
Among these, 5-amine-1H-tetrazole, 5-carboxybenzotriazole, and 5-amine are particularly preferable from the viewpoints of rust prevention of the conductor and adhesion of the cured film to the substrate. Indazole and 5-amino-1,2,3-thiadiazole.
In this embodiment, one of the rust inhibitors described above may be used alone, or two or more of them may be used in combination.

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

＜ Other ingredients ＞
In this embodiment, in addition to the components (A) to (G), the photosensitive resin composition may contain an oligomer having a carboxyl group and an ethylenically unsaturated group, and an addition of 3 moles of nitroso Polymerization inhibitors such as aluminum salts of phenylhydroxylamine, antioxidants, adhesion promoters, leveling agents, fillers, defoamers and flame retardants, etc., as other ingredients (H), these can be used alone or in combination of two or more use.

<Photosensitive resin composition and layer>
The photosensitive resin composition according to this embodiment is characterized in that in a differential molecular weight distribution curve obtained from a GPC dissolution curve by performing gel permeation chromatography (GPC) measurement,
(i) Ratio of dw / d (logM) value of molecular weight M = 20,000 to molecular weight M = 5000: R _{20k / 5k} is in the range of 0.20 to 1.50, and
(ii) In the differential molecular weight distribution curve, when the area of a region with a molecular weight M of 2,000 or more is 100%, the ratio of the area of a region with a molecular weight M of 50,000 or more: S _{≧ 50k} is 1.0 to 9.0%.
Here, the GPC measurement is performed by the same method as described above with respect to the (A) alkali-soluble resin. The method for obtaining the differential molecular weight distribution curve from the GPC dissolution curve obtained by the measurement is, for example, Technical Report No. T1001 (2013.10.1) issued by the analysis center of Tosoh Corporation, "GPC method (SEC (size exclusion chromatography (size exclusion chromatography) method) introductory lecture ".

In the differential molecular weight distribution curve, by setting R _{20k / 5k to} be 0.20 or more, a photosensitive resin composition having excellent tackiness can be provided, and by setting R _{20k / 5k to} be 1.50 or less, a photosensitivity having excellent low-temperature lamination properties can be provided. Sexual resin composition. From the viewpoint of the adhesiveness and low-temperature lamination of the transfer film, a preferred range of R _{20k / 5k} is 0.30 to 1.20.

By setting S _{≧ 50k} in the differential molecular weight distribution curve to be 1.0% or more, it is possible to provide a photosensitive resin composition having excellent adhesion to a conductive substrate. When S _{≧ 50k} is in the range of 1.0 to 9.0%, a photosensitive resin composition excellent in low-temperature developability can be provided. Furthermore, from the viewpoint of low-temperature developability, S _{≧ 50k is} preferably in a range of 2.5 to 6.7%.

From the viewpoints of hydrophobicity, film density, and rust resistance, the component that belongs to the region of molecular weight M ≧ 50,000 in the differential molecular weight distribution curve preferably contains an aromatic ring. The component having a molecular weight M ≧ 50,000 and containing an aromatic ring can be derived from, for example, the components (A1) to (A4) described above.

Organic components constituting the photosensitive resin composition of this embodiment are generally soluble in tetrahydrofuran (THF), but most high molecular weight components having a molecular weight (M) of 2,000 or more are insoluble in tetrahydrofuran (THF) / ring at room temperature. Hexane (Cy) mixed solvent (mass ratio = 1/2). On the other hand, the high-molecular-weight component of the photosensitive resin composition of this embodiment has a feature that it contains an acidic functional group and has a refractive index n2 of 1.560 or more. That is, the photosensitive resin composition of this embodiment is characterized in that (i) the acid value A2 (mgKOH) of a component that is soluble in THF and insoluble in a THF / Cy (mass ratio = 1/2) mixed solvent at 23 ° C. / g) is 95 or more, and (ii) the refractive index n2 is 1.560 or more.
The refractive index of the photosensitive resin composition layer is preferably 1.550 or more. The refractive index of the photosensitive resin composition layer is preferably 1.630 or less.

A method for obtaining a component that is soluble in THF and insoluble in a THF / Cy mixed solvent (mass ratio = 1/2) from a photosensitive resin composition or a layer thereof will be described.
First, accurately weigh 10.0 g of the photosensitive resin composition or a layer thereof as a sample into a 100 mL Erlenmeyer flask, add 30.0 g of tetrahydrofuran (THF), and then seal the container. It takes 1 hour at 23 ° C to Stirrer. After removing insoluble matters by filtration, 60.0 g of cyclohexane (Cy) was added dropwise to the THF solution over 10 minutes, and the mixture was stirred at 23 ° C. for 1 hour. The suspended solution was subjected to solid-liquid separation by a centrifugal separator, and the insoluble matter was washed 3 times with 50 g of cyclohexane, and vacuum-dried at 40 ° C for 6 hours, thereby obtaining an insoluble THF / Cy mixed solvent (mass Ratio = 1/2).

The measuring method of the acid value A2 of the components soluble in THF and insoluble in the mixed solvent of THF / Cy (mass ratio = 1/2) is described below.
First, 1.0 g of the insoluble component after vacuum drying was accurately weighed into a THF / Cy mixed solvent (mass ratio = 1/2), and 30 g of THF was added thereto to dissolve uniformly. Using this solution, the acid value was measured in the same manner as described above for the (A) alkali-soluble resin. The acid value A2 (mgKOH / g) of the components insoluble in the THF / Cy mixed solvent (mass ratio = 1/2) in the photosensitive resin composition of this embodiment is 95 from the viewpoint of low-temperature developability and adhesion. From the viewpoint of low-temperature lamination properties, the above is preferably 200 or less, and more preferably in the range of 105 to 180.

The measurement method of the refractive index n2 of the components insoluble in the THF / Cy mixed solvent (mass ratio = 1/2) is described below. First, prepare a solvent insoluble in a THF / Cy mixed solvent (mass ratio = 1/2). An organic solvent having a boiling point of 200 ° C or lower at 1 atmosphere (dissolved in, for example, ethanol, acetone, methyl ethyl ketone, 1 -Methoxy-2-propanol, propylene glycol-1-monomethyl ether-2-acetate, etc.). At this time, it is prepared so that solid substance content concentration may become 10-70 mass%. The obtained solution can be applied to any substrate having resistance to the solution. For example, the obtained solution is coated on a commercially available polyethylene terephthalate (PET) film (thickness: 16 μm) with a bar coater, and dried in a hot air oven at 100 ° C. for 10 minutes to obtain A layered body having a thickness of 2 μm as a layer of components insoluble in a THF / Cy mixed solvent (mass ratio = 1/2). The refractive index measurement was performed using a Prism Coupler Model 2010 / M (laser light wavelength: 532 nm) manufactured by Metricon, and a layer containing a component insoluble in a THF / Cy mixed solvent (mass ratio = 1/2) was connected to the tritium Status. The refractive index n2 of the components insoluble in the THF / Cy mixed solvent (mass ratio = 1/2) in the photosensitive resin composition of this embodiment is 1.560 or more from the viewpoint of low moisture permeability and the viewpoint of low-temperature developability In particular, it is preferably 1.650 or less, more preferably in the range of 1.570 to 1.600, and still more preferably in the range of 1.574 to 1.590.

When the mass ratio of the tetrahydrofuran (THF) / cyclohexane (Cy) mixed solvent is 1 / 1.3 as the organic component constituting the photosensitive resin composition of this embodiment, the molecular weight (M) of the insoluble component becomes It is a high molecular weight component whose molecular weight (M) is 20,000 or more. The insoluble component is preferably (i) the acid value A1 is 100 mgKOH / g or more and / or (ii) the refractive index n1 is 0.005 or more smaller than the above-mentioned n2. The acid value A1 is preferably 200 mgKOH / g or less.
A method for obtaining a component that is soluble in THF and insoluble in a THF / Cy mixed solvent (mass ratio = 1 / 1.3) from the photosensitive resin composition or a layer thereof will be described.
First, accurately weigh 10.0 g of the photosensitive resin composition or layer thereof as a sample into a 100 mL Erlenmeyer flask, add 39.1 g of tetrahydrofuran (THF), and then seal the container, and spend 1 hour at 23 ° Stirrer. After removing insoluble matters by filtration, 50.9 g of cyclohexane (Cy) was added dropwise to the THF solution over 10 minutes, and the mixture was stirred at 23 ° C. for 1 hour. The suspended solution was subjected to solid-liquid separation by a centrifugal separator, and the insoluble matter was washed 3 times with 50 g of cyclohexane, and vacuum-dried at 40 ° C for 6 hours, thereby obtaining an insoluble THF / Cy mixed solvent (mass Ratio = 1 / 1.3).
The measurement of the acid value A1 and the refractive index n1 of the components soluble in THF and insoluble in the THF / Cy mixed solvent (mass ratio = 1 / 1.3) can be determined by the same method as the method for measuring the acid value A2 and the refractive index n2 described above. get on.

In the photosensitive resin composition of this embodiment, in order to achieve both low-temperature developability and low moisture permeability, it is preferred that any of the following (1) to (5) be satisfied:
(1) In the differential molecular weight distribution curve of GPC, S _{≧ 50k} is in the range of 1.0 to 9.0%.
(2) The acid value A2 (mgKOH / g) of the components insoluble in the THF / Cy mixed solvent (mass ratio = 1/2) is 95 or more,
(3) the refractive index n2 of the components insoluble in the THF / Cy mixed solvent (mass ratio = 1/2) is 1.560 or more,
(4) The acid value A1 of the components insoluble in the THF / Cy mixed solvent (mass ratio = 1 / 1.3) is 100 mgKOH / g or more,
(5) The refractive index n1 of the components insoluble in the THF / Cy mixed solvent (mass ratio = 1 / 1.3) is 0.005 or more smaller than the above-mentioned n2.

In the photosensitive resin composition of this embodiment, in order to take into account the adhesiveness and low-temperature lamination properties as a transfer film, any one of the following (1) and (2) satisfies:
(1) In the differential molecular weight distribution curve of GPC, S _{≧ 50k} is in the range of 1.0 to 9.0%.
(2) In the differential molecular weight distribution curve of GPC, the ratio of dw / d (logM) value of molecular weight M = 20,000 to molecular weight M = 5000: R _{20k / 5k} is in the range of 0.20 to 1.50.

In the photosensitive resin composition of this embodiment, in order to make the adhesiveness with a conductor base material excellent, any of the following (1) and (2) is satisfied:
(1) In the differential molecular weight distribution curve of GPC, S _{≧ 50k} is in the range of 0.2 to 9.0%.
(2) The acid value A2 (mgKOH / g) of the components insoluble in the THF / Cy mixed solvent (mass ratio = 1/2) is 70 or more.

The hydroxyl value (mgKOH / g) of the photosensitive resin composition of this embodiment is preferably 20 or less, and more preferably 15.0 or less. By setting the hydroxyl value of the photosensitive resin composition to 20 or less, the moisture permeability of the cured product of the photosensitive resin composition can be reduced, and the rust prevention property of the conductor can be improved.
The refractive index of the photosensitive resin composition of this embodiment is preferably 1.550 or more. The refractive index of the photosensitive resin composition layer is preferably 1.630 or less.

＜ Transfer Film ＞
The thickness of the photosensitive resin layer in this embodiment is preferably 40 μm or less, and the absorbance of the photosensitive resin layer at a wavelength of 365 nm is 0.01 to 0.05 per 1 μm of the thickness of the photosensitive resin layer. If the film thickness of the photosensitive resin layer is too thick, the flexibility is deteriorated. Therefore, the thickness of the photosensitive resin layer is preferably 40 μm or less. From the viewpoint of following the unevenness of the wiring and the viewpoint of ensuring rust prevention, it is preferable. It is 3 μm or more.

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

As the supporting film used in this embodiment, a transparent film that can transmit light emitted from the exposure light source is desirable. Examples of such a support film include a polyethylene terephthalate film, a polyvinyl alcohol film, a polyvinyl chloride film, a vinyl chloride copolymer film, a polyvinylidene chloride film, and a vinylidene chloride copolymer film. , Polymethyl methacrylate copolymer film, polystyrene film, polyacrylonitrile film, styrene copolymer film, polyamide film, film containing cellulose and its derivatives, etc. These films can also be extended as needed. The haze of the supporting film is preferably 5 or less. The smaller the thickness of the support film is, the more advantageous it is in terms of resolution and economy, but in order to maintain strength, it is preferably 10 μm to 30 μm.

An important characteristic of the protective film used for the transfer film is that the protective film has a sufficiently small adhesion to the photosensitive resin layer and can be easily peeled off compared to the supporting film. As the protective layer, for example, a polyethylene film or a polypropylene film can be preferably used.

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

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

Examples of the coating method include a blade coating method, a Meyer bar coating method, a roll coating method, a screen coating method, a spin coating method, an inkjet coating method, a spray coating method, and a dip coating method. Cloth method, gravure coating method, curtain coating method, nozzle coating method, etc. The drying conditions of the coating liquid are not particularly limited. The drying temperature is preferably 50 ° C to 130 ° C, and the drying time is preferably 30 seconds to 30 minutes.

In this embodiment, the transfer film is preferably a protective film for forming a conductor portion. In this case, the conductor portion is more preferably a copper electrode, an alloy electrode of nickel, palladium, silver, titanium, molybdenum, etc. with copper or transparent electrode. In more detail, the transfer film can be used as a protective film for lead-out wiring in a frame area of a touch panel (touch sensor or force sensor), and a protective film for copper electrodes in a sensing area.

[Resin pattern, cured film pattern, and manufacturing method thereof]
The formation of a resin pattern using a transfer film can be performed by a method of manufacturing a resin pattern including the following steps:
Laminating steps of laminating the above-mentioned transfer film on a substrate;
An exposure step of exposing the laminated photosensitive resin laminate; and a development step of developing the exposed transfer film.
Furthermore, in order to use a resin pattern as a protective film for a conductor portion, it is preferable to include the following steps as a method of manufacturing a resin pattern: After the developing step, the resin pattern is subjected to post-exposure treatment and / or heat treatment to form a hardened film pattern. .

An example of a specific method is described below. As the substrate, a substrate for forming copper wiring on a copper clad laminate, a transparent electrode (for example, ITO, Ag nanowire substrate, etc.) or a metal electrode (for example, Cu) can be formed on a glass substrate or a transparent resin substrate. , Al, Ag, Ni, Mo, and at least two of these alloys, etc.) touch panel substrates or touch sensor substrates (such as force sensors, etc.). Flexible copper-clad laminates, substrates for electrode formation of touch panels, or substrates for electrode formation of touch sensors are formed by forming a copper layer, a transparent electrode, or a metal layer as a raw material of a metal electrode on a flexible film. Substrate.

Examples of the film include a film containing film raw materials such as polyimide, polyester (PET, PEN (Polyethylene naphthalate), and a cycloolefin polymer (COP). The thickness of the film is preferably 10 μm to 100 μm. As the copper, an alloy containing copper as a main component may be used in addition to pure copper. Here, the "main component" means that at least 50% by mass of the alloy is copper. Examples of the alloy metal include an alloy of copper, such as nickel, palladium, silver, titanium, molybdenum, and the like.
The thickness of the copper layer is preferably 50 nm to 2 μm. From the viewpoint of the uniformity of the copper layer, the thickness of the copper layer is more preferably 100 nm or more.

By performing the step of laminating a transfer film on the substrate as described above, a photosensitive resin layer is formed on the copper layer of the substrate. In the case where the transfer film has a protective layer, it is preferable to heat-press the transfer film with a laminator after laminating the protective layer and laminate it on the surface of the substrate. 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 usually about 40 ° C to 160 ° C. The heat and pressure bonding can be performed using a two-stage laminator equipped with a double roller, or can be performed by repeatedly passing the transfer film and the substrate through the roller multiple times. In addition, if a vacuum roll laminator is used, the protective film has good followability to unevenness caused by wiring and the like on the substrate, and can prevent the disadvantage that air is mixed between the transfer film and the substrate. On the other hand, in the case of using a vacuum roll laminator, the concentration of oxygen inhibiting radical polymerization is significantly lowered, so that the photopolymerization initiator is cleaved, and the dark reaction is easy to proceed. Therefore, the temperature of the drum is preferably 40 ° C to 100 ° C, and more preferably 40 ° C to 80 ° C.

Next, the exposure step is performed using an exposure machine. If necessary, the support film is peeled from the transfer film, and the photosensitive resin layer is exposed with active light through a photomask. The exposure amount is determined by the illuminance of the light source and the exposure time. The exposure amount can 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 that adjusts parallelism, and a proximity exposure machine that sets a gap between a mask and a workpiece. Further, as the exposure machine, a projection type exposure machine having a size ratio of a mask to an image of 1: 1, a reduced projection exposure machine called a high-illumination stepper (registered trademark), or An exposure machine using a concave mirror called a specular projection alignment exposure device (registered trademark).

In the exposure step, a direct writing exposure method may be used. The so-called direct writing exposure means a method of directly writing on a substrate for exposure 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 can be used. The engraving pattern is controlled by a computer. The exposure amount in this case is determined by the illuminance of the light source and the moving speed of the substrate.

Next, a developing step is performed using a developing device. When there is a support film on the photosensitive resin layer after exposure, if necessary, the support film is removed, and then the unexposed portion is developed and removed using a developing solution of an alkaline aqueous solution 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, and is usually a Na ₂ CO ₃ aqueous solution having a concentration of about 0.2% to 2% by mass and a temperature of about 20 ° C to 40 ° C. When the temperature of the developing solution is high, moisture tends to volatilize in a negative pressure environment caused by exhaust gas or the like as a countermeasure against odor, and the developing solution tends to condense over time, thereby stabilizing productivity. Therefore, the temperature of the developer is preferably less than 30 ° C. In addition, a surfactant, an antifoaming agent, and a small amount of an organic solvent for promoting development can be mixed into the alkaline aqueous solution. Considering the influence on the substrate, an amine-based alkaline aqueous solution such as a tetramethylammonium hydroxide (TMAH) aqueous solution can also be used. The concentration of the basic compound in the aqueous solution can be appropriately selected according to the developing speed. From the viewpoint of less odor of the developer, excellent operability, and simple management and post-treatment, a Na ₂ CO ₃ aqueous solution of 1% by mass and 25 ° C to 30 ° C is particularly preferred. Examples of the development method include known methods such as alkaline water spraying, spraying, swing dipping, brushing, and scraping.

After development, the alkali of the alkaline aqueous solution remaining in the resin pattern can be subjected to acid treatment by using known methods such as spraying, swing dipping, brushing, and scratching, using organic acids, inorganic acids, or these acid aqueous solutions (medium And processing). After the acid treatment (neutralization treatment), a step of washing with water may be performed.

The resin pattern can be obtained through the above steps, but a post-exposure step and / or a heating step can be further performed. By implementing 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 200 mJ / cm ² to 1,000 mJ / cm ² , and it is preferable to perform the treatment at 40 ° C. to 200 ° C. in the heating step. From the viewpoint of the manufacturing process, heating The processing time is preferably 60 minutes or less. As a method of the heat treatment, a heating furnace of a suitable method such as hot air, infrared rays, or far infrared rays can be used. Examples of the environment of the heat treatment include an N ₂ environment or an N ₂ / O ₂ environment.

According to this embodiment, it is possible to provide a transfer film with good adhesion, low-temperature lamination, low-temperature developability, hardened film moisture permeability, and adhesion to a conductive base material, and can be preferably used for wiring. And a transfer film for protecting a conductive part such as an electrode and an electrode. Such a transfer film can be preferably used as, for example, a protective film for wiring, electrodes, or the like of a touch panel, a touch sensor, or a force sensor, or a solder resist for a printed wiring board.

[A device with a touch panel display device, a touch sensor, or a force sensor]
By forming the hardened film of the transfer film of this embodiment due to the substrate for a touch panel, a touch panel display device having a hardened film of a transfer film, a hardened film with a transfer film, and touch sensing can be provided. Devices and / or force sensors.
Examples of the substrate for a touch panel include substrates generally used for a touch panel, a touch sensor, or a force sensor, such as a glass plate, a plastic plate, a plastic film, and a ceramic plate. Electrodes or metal wirings for touch panels, such as ITO, Cu, Al, Ag, Ni, Mo, and alloys containing at least two of these, are provided on the substrate. An insulating layer is provided between the electrodes.

A substrate for a touch panel having electrodes for a touch panel can be obtained, for example, by the following procedure. After forming a metal film in the order of ITO and Cu by a sputtering method on a substrate for a touch panel such as polyester or COP film, a photosensitive film for etching is attached to the metal film to form a desired resist pattern. Unnecessary Cu is removed with an etching solution such as an aqueous ferric chloride solution, and the resist pattern is removed and removed.

The method for forming a hardened film as a protective film on a substrate for a touch panel preferably includes the following steps in sequence: the first step of laminating the transfer film of this embodiment on the substrate for a touch panel; The second step of hardening a specific part of the protective film by the irradiation of light; the third step of removing the specific part of the protective film (the part of the protective film that is not irradiated with active light) to form a hardened body of the patterned protective film; and Step 4 of exposing and / or heat treating the patterned protective film.

By using the above method to prepare a substrate for a touch panel having a hardened film pattern of a transfer film, a touch panel display device having a hardened film of a transfer film, or a hardened film having a hardened film and Device for touch sensor and / or force sensor.
[Example]

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

First, the production of (A) an alkali-soluble resin will be described.
<Production of acrylic copolymer (A-1)>
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 the temperature was raised to 75 ° C. in a nitrogen atmosphere. 20 mass% of methacrylic acid (MAA), 25 mass% of methyl methacrylate (MMA), 55 mass% of styrene (St), and an azo-based polymerization initiator were added dropwise uniformly over 2 hours. After the dropwise addition, stirring of the reaction system was continued at 75 ° C for 10 hours. After the reaction was completed, the obtained resin solution was diluted with methyl ethyl ketone to obtain a solid content acid value of 130 mgKOH / g and a weight average molecular weight of about 25,000 acrylic copolymer solution (43% by mass of solid content) (A-1).

<Production of acrylic copolymer (A-2)>
By the same method as the above-mentioned acrylic copolymer (A-1), 20% by mass of methacrylic acid, 25% by mass of methyl methacrylate, and 55% by mass of styrene (St) were used to obtain the acid value of the solid component An acrylic copolymer solution (solid content: 41% by mass) of 130 mgKOH / g and a weight average molecular weight of about 13,000 (A-2).

<Production of acrylic copolymer (A-3)>
By the same method as the above-mentioned acrylic copolymer (A-1), 22.5 mass% of methacrylic acid, 60 mass% of styrene, 12.5 mass% of methyl methacrylate, and 5 mass% of butyl acrylate (BA) were used. An acrylic copolymer solution (solid content 50% by mass) (A-3) having an acid value of 147 mgKOH / g and a weight average molecular weight of approximately 22,500 was obtained.

<Production of acrylic copolymer (A'-1)>
By the same method as the above-mentioned acrylic copolymer (A-1), 20% by mass of methacrylic acid, 25% by mass of methyl methacrylate, and 55% by mass of styrene were used to obtain a solid component acid value of 130 mgKOH / g, an acrylic copolymer solution (solid content 50% by mass) (A'-1) having a weight average molecular weight of about 35,000.

<Preparation of acrylic copolymer solution (A'-2)>
By the same method as the above-mentioned acrylic copolymer (A-1), 29% by mass of methacrylic acid, 19% by mass of methyl methacrylate, and 52% by mass of styrene were used to obtain a solid content acid value of 189 mgKOH / g, an acrylic copolymer solution having a weight average molecular weight of about 50,000 (solid content: 49% by mass) (A'-2).

<Preparation of acrylic copolymer solution (A'-3)>
By the same method as the above-mentioned acrylic copolymer (A-1), 15% by mass of methacrylic acid, 75% by mass of benzyl methacrylate (BzMA), and 10% by mass of hydroxyethyl acrylate (HEA) were used to obtain a solid form. Acrylic copolymer solution (solid content 50% by mass) (A'-3) having an acid value of 98 mgKOH / g, a hydroxyl value of 65 mgKOH / g as a solid component, and a weight average molecular weight of about 20,000.

The copolymerization composition, weight average molecular weight, acid value, and hydroxyl value of the obtained acrylic copolymer are shown in Table 1. The measurement of the weight-average molecular weight, acid value, and hydroxyl value of the acrylic copolymer was carried out by the method described in the details of the aforementioned ((A) alkali-soluble resin).

＜ About (B) component ＞
As (B) a compound containing a carboxyl group and an ethylenically unsaturated group, the following solution commercially available was used.
B-1 Acid modified product of epoxy acrylate with biphenyl skeleton
B-2 Acid modified product of epoxy acrylate with biphenyl skeleton
B-3 Acid modified product of epoxy acrylate with fluorenyl skeleton
B-4 Acid modified product of epoxy acrylate with biphenyl skeleton
B'-1 Acid modified product of epoxy acrylate with bisphenol F skeleton
B'-2 Compound having a urethane skeleton and containing a carboxyl group and an ethylenically unsaturated group

Table 2 shows the weight-average molecular weight, acid value, and hydroxyl value of the compound containing a carboxyl group and an ethylenically unsaturated group. The weight average molecular weight, acid value, and hydroxyl value of the compound containing a carboxyl group and an ethylenically unsaturated group were measured by the method described in the details of the above-mentioned "(A) Alkali-soluble resin".
(B) The refractive index measurement of the compound containing a carboxyl group and an ethylenically unsaturated group is performed by the following method.
<Production method for refractive index measurement samples>
Using a doctor blade coater, uniformly apply the solution of the compound containing a carboxyl group and an ethylenically unsaturated group (B) to a 16 μm-thick polyethylene terephthalate film (manufactured by Toray Co., Ltd.) as a support. FB40) surface was dried in a dryer at 100 ° C. for 10 minutes to form a 5 μm thick uniform resin layer on the support and cut it into 5 cm × 5 cm.
<Method for evaluating refractive index>
Using the refractive index measuring device (Prism Coupler Model 2010 / M, manufactured by Metricon Corporation) and the laser light source at 532 nm, the refractive index of the sample produced by the above method was measured at any of four positions in the plane direction of the sample. The refractive index at arbitrary four places was measured in the vertical direction, and the average value was calculated. The refractive index measurement results are shown in Table 2.
Next, the production method of the evaluation transfer film of an Example and a comparative example is demonstrated, and the evaluation method of the obtained transfer film and its evaluation result are demonstrated.

1. Production of Evaluation Transfer Films The evaluation transfer films of Examples and Comparative Examples were produced as follows.
＜ Production of transfer film ＞
According to the composition shown in Tables 4 to 6 below, each component was weighed into a 250 ml plastic bottle, and methyl ethyl ketone was added so that the solid content concentration became 53% by mass, and it took 5 hours to dissolve using a blender. And mixed to obtain a photosensitive resin composition. Thereafter, the photosensitive resin composition was passed through a 3 μm filter to prepare a photosensitive resin composition blending solution (Examples 1 to 22 and Comparative Examples 1 to 10).
Using a doctor blade coater, uniformly coat the photosensitive resin composition preparation liquid on the surface of a 16 μm-thick polyethylene terephthalate film (manufactured by Toray Co., Ltd., FB40) as a support at 95 ° C. Dry in a dryer for 10 minutes to form a uniform photosensitive resin layer on the support. The thickness of the photosensitive resin layer is 8 μm and 40 μm. Then, a 33 μm-thick polyethylene film (manufactured by Tamapoly Co., Ltd., GF-858) was laminated on the surface of the photosensitive resin layer to obtain a transfer film for evaluation. The following evaluation results are shown in Tables 4 and 5. In addition, the names and the like of the material components in the photosensitive resin composition preparation solution shown in Table 4 to Table 6 are shown in Tables 1 to 3.

2. GPC measurement of photosensitive resin composition The protective film of the transfer film obtained as described above was peeled off. 0.30 g of the photosensitive resin layer was weighed from the transfer film and dissolved in 20 g of THF.
The measurement of GPC was performed using a gel permeation chromatography (GPC) manufactured by JASCO Corporation under the following conditions, and a GPC dissolution curve was obtained.
Pump: Gulliver, PU-1580 Column: Shodex (registered trademark) (KF-807, KF-806M, KF-806M, KF-802.5) manufactured by Showa Denko Corporation, 4 detectors in series: RI
Column temperature: 40 ℃
Flow rate: 1.0 mL / min
Injection volume: 0.02 mL
Moving bed solvent: Tetrahydrofuran calibration curve: Calibration curve specified using a polystyrene standard sample {Use calibration curve obtained using a polystyrene standard sample (Shodex STANDARD SM-105 manufactured by Showa Denko Corporation)}

Derive the differential molecular weight distribution curve from the GPC dissolution curve by the above method, and calculate (i) the ratio of the dw / d (logM) value of molecular weight M = 20000 and molecular weight M = 5000; R _{20k / 5k} , and (ii) the molecular weight M When the area of a region of 2,000 or more is set to 100%, the ratio of the area of the region with a molecular weight M ≧ 50,000; S _{≧ 50k} . The differential molecular weight distribution curve of Example 5 is shown in FIG. 1. The R _{20k / 5k} values and S _{≧ 50k} values of Examples 1 to 22 and Comparative Examples 1 to 10 are shown in Tables 4 to 6.

3. Physical properties of THF / Cy (mass ratio = 1/2) insoluble content in the photosensitive resin composition The protective film of the transfer film obtained above was peeled off, and the photosensitive resin layer was weighed in a 100 mL conical flask 10.0 g, 30.0 g of tetrahydrofuran (THF) was added thereto, and the container was closed. The mixture was stirred at 23 ° C. for 1 hour with a stirrer. After removing insoluble matters by filtration, 60.0 g of cyclohexane (Cy) was added dropwise to the THF solution over 10 minutes, and the mixture was stirred at 23 ° C. for 1 hour. The suspended solution was subjected to solid-liquid separation at 5000 rpm by a centrifugal separator for 10 minutes, and the supernatant was removed by decantation. The insoluble matter was washed three times with 50 g of Cy and vacuum-dried at 40 ° C for 6 hours. Thereby, a component insoluble in a THF / Cy mixed solvent (mass ratio = 1/2) was obtained.
(1) Measurement of acid value A2 Accurately weigh 1.0 g of the insoluble component obtained above and dissolve it in 9.0 g of THF. Thereafter, using an automatic titrator ("COM-555" manufactured by Hiranuma Sangyo Co., Ltd.), the acid value was measured by neutralization titration with a 0.1 mol / L potassium hydroxide in ethanol solution.
(2) Measurement of the refractive index n2: 1.0 g of the insoluble component obtained above was dissolved in 9.0 g of a methyl ethyl ketone / propylene glycol-1-monomethyl ether-2-acetate (mass ratio 2/1) mixed solvent. This solution was applied to a 16 μm-thick polyethylene terephthalate film (manufactured by Toray Co., Ltd., FB40) with a bar coater, and dried in an oven at 100 ° C. for 10 minutes to obtain a thickness of 2 μm insoluble component layer. The refractive index measurement was performed using a Prism Coupler (laser refractive index measurement model 2010, laser light wavelength: 532 nm) manufactured by Metricon, in a state in which an insoluble component layer was in contact with thallium.
In addition, as a measurement of the physical properties of the THF / Cy (mass ratio = 1 / 1.3) insoluble content in the photosensitive resin composition, the measurement of the acid value A1 and the refractive index n1 is also performed by comparing the acid value A2 and the refractive index n2. The measurement method was performed in the same manner.

4. Measurement of hydroxyl value of photosensitive resin composition The hydroxyl value of the photosensitive resin composition layer constituting the transfer film was measured as follows.
First, 1 g of a photosensitive resin composition as a measurement target of a hydroxyl value was taken from an transfer film and accurately weighed. To the accurately weighed photosensitive resin composition, 10 mL of a 10% by mass acetic anhydride-pyridine solution was added, and they were uniformly dissolved, and heated at 100 ° C. for 1 hour. After heating, 10 mL of water and 10 mL of pyridine were added and heated at 100 ° C for 10 minutes. Thereafter, using an automatic titrator ("COM-1700" manufactured by Hiranuma Sangyo Co., Ltd.), the hydroxyl value was measured by neutralization titration with an ethanol solution of 0.5 mol / L potassium hydroxide.
The hydroxyl value is calculated by the following formula.
Hydroxyl value = (A－B) × f × 28.05 / sample (g) + acid value
{In the formula, A represents the amount of 0.5 mol / L potassium hydroxide ethanol solution (mL) used in the blank test, and B represents the amount of 0.5 mol / L potassium hydroxide ethanol solution (mL) used in the titration, f Representation factor}
The measurement results of the hydroxyl value of the photosensitive resin composition layer in Examples and Comparative Examples are shown in Tables 4 to 6.

5. Evaluation of viscosity The viscosity of the transfer film was evaluated in the following manner.
First, the prepared transfer film was left to stand in an environment of 23 ° C and 50% RH for 24 hours, and then the protective film was peeled off at a speed of 10 cm / second, and it was visually confirmed whether a photosensitive resin composition was adhered to the surface of the protective film. . Next, the absorbent cotton was rubbed on the surface of the photosensitive resin composition layer after the protective film was peeled off, and the surface of the photosensitive resin composition layer was visually observed.
＜ Evaluation method ＞
A ... There is no adhesion of the photosensitive resin composition on the surface of the peeled protective film, and there is no absorbent cotton on the surface of the photosensitive resin composition layer.
B ... There is no adhesion of the photosensitive resin composition on the surface of the peeled protective film, but the surface of the photosensitive resin composition layer is affixed with cotton wool of absorbent cotton.
C ... The surface of the peeled protective film is adhered to the photosensitive resin composition.

6. Evaluation of lamination property The lamination property of the transfer film was evaluated in the following manner.
One side of the protective film of the transfer film is peeled off, and the other side is laminated with a resin, ITO, and sputtered copper layer in order by using a hot-roller laminator (Taisei Laminator (stock), VA-400III) at a roller temperature of 80 ° C. On the copper surface (size: 5 cm × 10 cm) of the substrate. Set the air pressure to 0.4 MPa and the lamination speed to 1.5 m / min. A case where the transfer film was adhered to the copper surface of the substrate was evaluated as A, and a case where the transfer film was not adhered under conditions of 80 ° C. was evaluated as B.

7. Developability <Sample Preparation Method>
The samples after the above-mentioned lamination evaluation were used directly. Furthermore, regarding the level at which the transfer film was not adhered to the substrate at 80 ° C, a sample laminated at a roller temperature of 100 ° C was prepared.
After laminating the sample for 15 minutes, set the PET mask and the Stouffer 21-stage step exposure meter side by side on the support film (set the optical density 0.00 as the first step, and increase the optical density by 0.15 in each step. ), The optimum exposure of each composition is determined from the surface of the PET mask and stepwise exposure, and exposure is performed by a parallel light exposure machine (manufactured by ORC MANUFACTURING (HMW-801)). As the PET mask, a pattern having an unexposed portion as a circular hole was used. After standing still for more than 15 minutes, the support was peeled off, using a developing device manufactured by FUJI KIKO, using a fullcone-type nozzle at a developing spray pressure of 0.12 MPa, and spraying 1% by mass of 28 ° C to 30 ° C The Na ₂ CO ₃ aqueous solution was developed for 45 seconds, and the unexposed portion of the photosensitive resin layer was dissolved and removed. At this time, the water-washing step was performed by a flat nozzle with a water-washing spray pressure of 0.12 MPa at the same time as the development step, and the water-washed sample was dried by a blower to prepare a sample for evaluation of developability. The above-mentioned so-called optimum exposure amount is defined as an exposure amount in which the number of steps remaining when the exposure is performed through the Stouffer 21-segment exposure meter is 7 to 8 steps.
＜ Evaluation method ＞
The surface state of the base material in the portion where the photosensitive layer of the substrate with the protective film was removed was observed under a microscope, and it was judged in the following manner.
A: There is no developing residue on the copper of the substrate under the developing condition of 28 ° C.
B: Under the developing condition of 28 ° C, there is a developing residue on the copper of the substrate, but under the developing condition of 30 ° C, there is no developing residue on the copper of the substrate.
C: Development residues also occur under the developing conditions of 30 ° C.
In the developability evaluation, it is considered to be a practically good result in the touch panel manufacturing process up to the B grade.

8. Moisture permeability test <Sample preparation method>
The protective film of the transfer film having a thickness of 40 μm of the photosensitive resin layer was peeled off, and laminated on No. 4 filter paper (manufactured by Advantec) using a heat roller laminator (manufactured by Taisei Laminator (Stock), VA-400III). The drum temperature was set to 80 ° C (in the case where the lamination property was evaluated to a level of ×, the temperature was 100 ° C), the air pressure was 0.4 MPa, and the lamination speed was 1.0 m / min. After standing for 15 minutes, the optimum exposure amount of each composition was exposed from the entire support surface of the protective film by a scattered light exposure machine. After standing for 30 minutes, the support film was peeled off and exposed to light at an exposure amount of 350 mJ / cm ² from the photosensitive layer side by a scattered light exposure machine, and then processed in a hot air circulation oven at 150 ° C. for 30 minutes to prepare a sample. The above-mentioned optimum exposure amount is defined in the same manner as the method for preparing a sample for evaluation of developability.
＜ Evaluation method ＞
The measurement of moisture permeability was performed in accordance with the cup method of JIS Z0208, and the moisture permeability conditions were implemented at a temperature of 65 ° C and a humidity of 90%.
A ・ ・ ・ Water permeability 150 ～ 200 g / (m ²・ day)
B ・ ・ ・ Moisture permeability 201 ～ 250 g / (m ²・ day)
C ・ ・ ・ Moisture permeability 251 ～ 300 g / (m ²・ day)

9. Adhesion evaluation (cross cutting test)
＜ Sample production method ＞
The protective film of the transfer film with a thickness of 8 μm was peeled off on one side, and laminated with a resin and sputter-coated copper using a hot-roller laminator (Taisei Laminator (Stock), VA-400III) in order. Nickel alloy substrate on the alloy surface (size: 3 cm x 3 cm). The roller temperature was 80 ° C (the above-mentioned lamination evaluation was 100 ° C as the level of x), the air pressure was 0.4 MPa, and the lamination speed was 1.0 m / min. After standing for 15 minutes, the optimum exposure amount of each composition was exposed from the entire support surface of the protective film by a scattered light exposure machine. The above-mentioned optimum exposure amount is defined in the same manner as the method for preparing a sample for evaluation of developability.
Thereafter, after standing for 30 minutes, the supporting film was peeled off, and using a developing device made by FUJI KIKO, a solid cone nozzle was used to develop a spray pressure of 0.12 MPa and a 1% by mass Na ₂ CO ₃ aqueous solution was sprayed at 30 ° C. Development was performed for 45 seconds, and the unexposed portion of the photosensitive resin layer was dissolved and removed. At this time, the water washing step was performed by a flat nozzle with a water washing spray pressure of 0.12 MPa at the same time as the developing step, and the water washed sample was dried by a blower.
A scattered light exposure machine was used to expose the developed sample from the photosensitive resin layer side at an exposure amount of 350 mJ / cm ² , and then processed in a hot air circulation oven at 150 ° C. for 30 minutes to produce an adhesiveness evaluation sample.
＜ Evaluation method ＞
Using the JIS standard K5400 as a reference, a 100-cell cross-cut test was performed on the above-treated samples. Use a cutter to cut a 1 × 1 mm square grid incision on the test surface, press the invisible tape # 810 (made by 3M (strand)) firmly on the grid portion, and slowly peel off the tape at an angle of almost 0 ° After the end, observe the state of the grid, and evaluate the cross-cut adhesion based on the following scores.
A: In the total area, peeling did not reach 5%.
B: 5 to 35% of the total area was peeled.
C: 35% or more of the total area was peeled.
In the cross-cut test, the grade A was considered to be practical, and a good result was obtained as a protective film for the conductor.

[Table 1]

[Table 2]

[table 3]

[Table 4]

[table 5]

[TABLE 6]

The results shown in Tables 4 and 5 show that Examples 1 to 22 meet the requirements of the present invention as the transfer film's viscosity, low-temperature lamination and low-temperature developability, as the moisture permeability of the cured film, Excellent adhesion to conductive substrates. It can also be seen that Example 5 and Example 6 are all different in the components (B-1) and (B-2), but the cured film was adjusted so that the hydroxyl value of the composition became 15 mgKOH / g or less. Excellent moisture permeability.

On the other hand, in Comparative Examples 1 to 10 shown in Table 5, any one of the elements specified in the present invention was not satisfied, and therefore it was used as the transfer film adhesiveness, low-temperature lamination property or low-temperature developability, and as a cured film. Either the moisture permeability or the adhesiveness with the conductor substrate is degraded. Comparative Examples 1 and 9 are photosensitive resin compositions in which the A / B mass ratio was increased to 6.38. As a result, the low-temperature lamination and low-temperature developability of the transfer film and the moisture permeability of the cured product were inferior to those of Example 1 ,2. Comparative Examples 2 and 3 were photosensitive resin compositions in which the A / B mass ratio was reduced to 0 to 0.12. As a result, the adhesiveness and low-temperature developability of the transfer film, and the adhesion between the cured film and the conductor substrate were deteriorated. Comparative Example 4 was blended with (A'-1) which does not satisfy the molecular weight requirement of the (A) component specified in the present invention. As a result, the low-temperature developability was inferior to that of Example 10. The component (B) was not blended in the photosensitive resin composition of Comparative Example 5. As a result, the low-temperature lamination property and low-temperature developability as a transfer film were deteriorated. In Comparative Example 6, the component (A) was not added, and only the component (B-3) was added. As a result, compared with Example 17 or Example 18, the adhesiveness as a transfer film, low-temperature developability, and the conductor as a cured film were compared. The adhesiveness of the substrate is deteriorated. The component (A) was not added in Comparative Example 7. Instead, a weight average molecular weight and an acid value satisfying the requirements of the component (A) were added. The structure did not include a skeleton of any of the general formulae (1) to (3). As a result of (B'-1) component of an epoxy acrylate acid modified product, the adhesiveness and low-temperature developability as a transfer film deteriorated. From this, it turns out that an epoxy acrylate acid modification is not suitable for the (A) component of this invention. Comparative Example 8 does not satisfy the requirements for the weight average molecular weight and refractive index of the component (B) of the present invention, and further adds (B'-2) to the structure that does not contain any one of the general formulae (1) to (3). ) Component, as a result, the low-temperature developability as a transfer film and the moisture permeability of the cured film were deteriorated. In Comparative Example 10, when the component (A'-3) that did not satisfy the requirement for the acid value of the component (A) of the present invention was added, the low-temperature developability and adhesiveness as a transfer film were deteriorated. In addition, the (A'-3) component has a high hydroxyl value, and as a result, the moisture permeability is also deteriorated.

From the above results, it is known that in order to satisfy the adhesiveness as a transfer film, low-temperature lamination and low-temperature developability, moisture permeability as a cured film, and adhesiveness with a conductor substrate, it is important to satisfy A, which is an element of the present invention. The mass ratio of / B is in the range of 0.18 to 6.0. The present inventors think that there are surprising results regarding the following: When the A / B quality ratio is less than 0.18 and more than 6.0, the low-temperature developability as a transfer film is significantly deteriorated.

In Examples 1 to 22, in order to balance low-temperature developability and low moisture permeability, any one of the following conditions was satisfied:
(1) S _{≧ 50k} in the differential molecular weight distribution curve of GPC is in the range of 1.0 to 9.0%;
(2) The acid value A2 (mgKOH / g) of the components insoluble in the THF / Cy mixed solvent (mass ratio = 1/2) is 95 or more;
(3) the refractive index n2 of the components insoluble in the THF / Cy mixed solvent (mass ratio = 1/2) is 1.560 or more;
(4) The acid value A1 of the components insoluble in the THF / Cy mixed solvent (mass ratio = 1 / 1.3) is 100 mgKOH / g or more;
(5) The refractive index n1 of the components insoluble in the THF / Cy mixed solvent (mass ratio = 1 / 1.3) is 0.005 or more smaller than the above-mentioned n2; either of low-temperature developability and low moisture permeability is good. On the other hand, Comparative Examples 1 to 10 did not satisfy all of the above (1) to (5), and as a result, at least one of low-temperature developability and low moisture permeability was deteriorated.

In Examples 1 to 22 and Comparative Examples 8 and 10, in order to achieve both adhesiveness as a transfer film and low-temperature lamination, any one of the following conditions was satisfied:
(1) S _{≧ 50k} in the differential molecular weight distribution curve of GPC is in the range of 1.0 to 9.0%;
(2) In the differential molecular weight distribution curve of GPC, the ratio of dw / d (logM) value of molecular weight M = 20,000 to molecular weight M = 5000: R _{20k / 5k} is in the range of 0.20 to 1.50;
Both the adhesiveness and the low-temperature lamination property of the transfer film were good. On the other hand, Comparative Examples 1 to 7 and Comparative Example 9 did not satisfy all of the above (1) and (2), and as a result, either of the adhesiveness and low-temperature lamination properties as a transfer film was deteriorated.

In Examples 1 to 22 and Comparative Examples 1, 4, 5, 7 to 9, in order to make the adhesiveness with the conductive base material excellent, any one of the following conditions was satisfied:
(1) S _{≧ 50k} in the differential molecular weight distribution curve of GPC is in the range of 0.2 to 9.0%;
(2) The acid value A2 (mgKOH / g) of the components insoluble in the THF / Cy mixed solvent (mass ratio = 1/2) is 70 or more;
Therefore, the adhesiveness with the conductor substrate is good. In Comparative Example 2, S _{≧ 50k} was 0.2%, and as a result, the adhesiveness with the conductive substrate was slightly deteriorated. In Comparative Examples 3 and 6, S _{≧ 50k} was 0%, and as a result, the adhesiveness with the conductor substrate was deteriorated. In Comparative Example 10, the acid value A2 (mgKOH / g) of the components insoluble in the THF / Cy mixed solvent (mass ratio = 1/2) was 69, and as a result, the adhesiveness with the conductor substrate was deteriorated.

As mentioned above, although embodiment of this invention was described, this invention is not limited to this, It can change suitably in the range which does not deviate from the meaning of invention.
[Industrial availability]

By using the photosensitive resin composition and the transfer film according to the present invention, it has good rust resistance and low-temperature developability, and is suitable for protecting conductor parts such as wiring and electrodes. Protective film for wiring, electrodes, etc. for sensor or force sensor applications and solder resist applications for printed wiring boards.

FIG. 1 is a differential molecular weight distribution curve obtained from a GPC dissolution curve of a photosensitive resin layer contained in a transfer film obtained in Example 5. FIG.

Claims (31)

A transfer film for forming a conductor portion protective film, characterized in that the transfer film includes a support film and a photosensitive resin composition layer, and the photosensitive resin composition layer contains the following components: (A) alkali-soluble resin (except for acid-modified epoxy (meth) acrylate compounds); (B) a compound containing a carboxyl group and an ethylenically unsaturated group; (C) a photopolymerizable compound; and (D) a photopolymerizable initiator; The weight average molecular weight of the (A) alkali-soluble resin is 11,000 to 29,000, and the acid value is 100 mgKOH / g or more. The (B) compound containing a carboxyl group and an ethylenically unsaturated group has a weight average molecular weight of 1,000 or more and 9,500 or less, an acid value of 60 mgKOH / g or more, and a refractive index of 1.570 or more, and The mass ratio (A) / (B) of the (A) alkali-soluble resin to the (B) compound containing a carboxyl group and an ethylenically unsaturated group is 0.18 to 6.0. For example, the transfer film of claim 1, wherein the acid value of the (A) alkali-soluble resin is 200 mgKOH / g or less. For example, the transfer film of claim 1 or 2, wherein the (B) compound containing a carboxyl group and an ethylenically unsaturated group has an acid value of 200 mgKOH / g or less and a refractive index of 1.650 or less. The transfer film according to any one of claims 1 to 3, wherein the hydroxyl value of the photosensitive resin composition layer is 15.0 mgKOH / g or less. The transfer film according to claim 4, wherein the hydroxyl value of the photosensitive resin composition layer is 0.01 mgKOH / g or more. The transfer film according to any one of claims 1 to 5, wherein the refractive index of the photosensitive resin composition layer is 1.550 or more. The transfer film according to claim 6, wherein the refractive index of the photosensitive resin composition layer is 1.630 or less. The transfer film according to any one of claims 1 to 7, wherein the (A) alkali-soluble resin contains a structure derived from (meth) acrylic acid of 12% by mass or more and 30% by mass or less, and 30% by mass or more and 80% by mass % Or less Derived from styrene or its derivatives. The transfer film according to any one of claims 1 to 8, wherein the compound (B) containing a carboxyl group and an ethylenically unsaturated group is an acid-modified epoxy (meth) acrylate compound. The transfer film according to any one of claims 1 to 9, which is used for any of a protective film for a touch panel or a protective film for a force sensor. A transfer film for forming a conductor portion protective film, comprising a support film and a photosensitive resin composition layer, and the photosensitive resin composition layer satisfies the following (I) and (II): (I) on loan The differential molecular weight distribution curve obtained by the GPC dissolution curve obtained by measuring the component dissolved in tetrahydrofuran by gel permeation chromatography (GPC), (i) the value of the dw / d (logM) value of the molecular weight M = 20,000 and the molecular weight M = 5000. The ratio R _{20k / 5k} is in the range of 0.20 to 1.50, and (ii) in the differential molecular weight distribution curve, when the area of a region with a molecular weight M ≧ 2000 is set to 100%, the ratio of the area of the region with a molecular weight M ≧ 50,000 S _{≧ 50k} is 1.0 to 9.0%; and (II) (i) the acid value A2 of the component soluble in tetrahydrofuran and insoluble in the mixed solvent of tetrahydrofuran / cyclohexane (mass ratio = 1/2) at 23 ° C is 95 mgKOH / g or more, and (ii) the refractive index n2 is 1.560 or more. The transfer film for forming a conductive protective film as claimed in claim 11 further satisfies the following (III): (III) Components that are soluble in tetrahydrofuran and insoluble in a mixed solvent of tetrahydrofuran / cyclohexane (mass ratio = 1 / 1.3) at 23 ° C (i) the acid value A1 is 100 mgKOH / g or more, and (ii) The refractive index n1 is 0.005 or more smaller than the above-mentioned n2. For example, the transfer film for forming a conductive protective film according to claim 12, wherein the above-mentioned acid value A1 is 200 mgKOH / g or less. The transfer film according to any one of claims 11 to 13, wherein the component in the region of the molecular weight M ≧ 50,000 in the differential molecular weight distribution curve contains an aromatic ring. The transfer film according to any one of claims 11 to 14, which is used for any of a protective film for a touch panel or a protective film for a force sensor. A transfer film for forming a conductive protective film, comprising a support film and a photosensitive resin composition layer, and the photosensitive resin composition layer satisfies the following (II) and (III): (II) Components that are soluble in tetrahydrofuran and insoluble in a mixed solvent of tetrahydrofuran / cyclohexane (mass ratio = 1/2) at 23 ° C (i) the acid value A2 is above 95 mgKOH / g, and (ii) the refractive index n2 is 1.560 or more; (III) Components that are soluble in tetrahydrofuran and insoluble in a mixed solvent of tetrahydrofuran / cyclohexane (mass ratio = 1 / 1.3) at 23 ° C (i) the acid value A1 is 100 mgKOH / g or more, and (ii) The refractive index n1 is 0.005 or more smaller than the above-mentioned n2. The transfer film for forming a conductive protective film according to claim 16, wherein the above-mentioned acid value A1 is 200 mgKOH / g or less. The transfer film of claim 16 or 17 is used for any of a protective film for a touch panel or a protective film for a force sensor. A transfer film for forming a protective film for a conductor portion, comprising a support film and a photosensitive resin composition layer, wherein the photosensitive resin composition layer contains the following components: (A) an alkali-soluble resin (wherein an acid (Except for modified epoxy (meth) acrylate compounds); (B) compounds containing a carboxyl group and an ethylenically unsaturated group; (C) a photopolymerizable compound; and (D) a photopolymerizable initiator; the (A The weight-average molecular weight of the alkali-soluble resin is 11,000 or more and 29,000 or less, and the acid value is 100 mgKOH / g or more. It is 60 mgKOH / g or more, and contains at least the following general formulae (1) to (3): [化 1] (Wherein R _l is an alkyl group or a halogen atom, l is an integer of 0 to 4; when l is 2 or more, the substituents may be the same or different from each other) (In the formula, R _m is an alkyl group or a halogen atom, and m is an integer of 0 to 3; when m is 2 or more, the substituents may be the same or different.) (Wherein R _n is an alkyl group or a halogen atom, n is an integer of 0 or more and 4 or less; when n is 2 or more, the substituents may be the same or different from each other), and The mass ratio (A) / (B) of the (A) alkali-soluble resin to the (B) compound containing a carboxyl group and an ethylenically unsaturated group is 0.18 to 6.0. The transfer film of claim 19, wherein the acid value of the (A) alkali-soluble resin is 200 mgKOH / g or less. For example, the transfer film of claim 19 or 20, wherein the (B) compound containing a carboxyl group and an ethylenically unsaturated group has an acid value of 200 mgKOH / g or less. The transfer film according to claim 19, wherein the hydroxyl value of the photosensitive resin composition layer is 15.0 mgKOH / g or less. The transfer film according to claim 22, wherein the hydroxyl value of the photosensitive resin composition layer is 0.01 mgKOH / g or more. The transfer film according to any one of claims 19 to 23, wherein the refractive index of the photosensitive resin composition layer is 1.550 or more. The transfer film according to claim 24, wherein the refractive index of the photosensitive resin composition layer is 1.630 or less. The transfer film according to any one of claims 19 to 25, wherein the (A) alkali-soluble resin contains a structure derived from (meth) acrylic acid of 12% by mass or more and 30% by mass or less, and 30% by mass or more and 80% by mass % Or less Derived from styrene or its derivatives. The transfer film according to any one of claims 19 to 26, wherein the compound (B) containing a carboxyl group and an ethylenically unsaturated group is an acid-modified epoxy (meth) acrylate compound. The transfer film according to any one of claims 19 to 27, which is used for any of a protective film for a touch panel or a protective film for a force sensor. A pattern manufacturing method, characterized in that a pattern is produced by laminating a transfer film according to any one of claims 1 to 28 on a substrate, exposing and developing. A method for manufacturing a cured film pattern, which is characterized in that a pattern obtained by the pattern manufacturing method as in claim 29 is subjected to a post-exposure treatment and / or a heat treatment. A method for manufacturing a touch panel display device or a device with a touch sensor, characterized in that a hardened film pattern obtained by a hardened film pattern manufacturing method as claimed in claim 30 is used.