WO2019164016A1

WO2019164016A1 - Transfer film, resin pattern forming method using transfer film, and cured film pattern forming method

Info

Publication number: WO2019164016A1
Application number: PCT/JP2019/007370
Authority: WO
Inventors: 下田　浩一朗; 智史渋井; 誠中出; 華菜子水村; 真由紀吉田
Original assignee: 旭化成株式会社
Priority date: 2018-02-26
Filing date: 2019-02-26
Publication date: 2019-08-29
Also published as: TW201940342A

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, resin pattern manufacturing method using transfer film, and cured film pattern manufacturing method

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

In recent years, as electronic devices have become more sophisticated, diversified, and smaller and lighter, devices with a transparent touch panel (touch sensor) mounted on the entire surface of display elements such as liquid crystals have increased. Increasingly, it is possible to visually recognize and select characters, symbols, patterns, and the like displayed on a display element through a transparent touch panel, and to switch each function of the device by operating the transparent touch panel. Touch panels are used not only for large electronic devices such as personal computers and televisions, but also for small electronic devices such as car navigation systems, mobile phones, and electronic dictionaries, and display devices such as OA / FA devices. An electrode made of a material is provided. As the transparent conductive electrode material, ITO (Indium-Tin-Oxide), indium oxide, and tin oxide are known, and these materials have high visible light transmittance, so that electrode materials for substrates for liquid crystal display elements, etc. It is mainly used as.

Existing touch panel methods include resistive film method, optical method, pressure method, capacitance method, electromagnetic wave induction method, image recognition method, vibration detection method, ultrasonic method, etc. ing. In recent years, the use of capacitive touch panels has been most advanced. In a capacitive touch panel, when a fingertip, which is a conductor, contacts the touch input surface, capacitive coupling occurs between the fingertip and the conductive film, thereby forming a capacitor. For this reason, the capacitive touch panel detects the coordinates of the contact position by capturing a change in charge at the contact position of the fingertip. In particular, the projected capacitive touch panel can detect multiple points on the fingertip, and thus has a good operability to give complicated instructions. Therefore, it can be used for small displays such as mobile phones and portable music players. The use as an input device on a display surface in a device having the device is advancing. In general, in a projected capacitive touch panel, a plurality of X electrodes and a plurality of Y electrodes orthogonal to the plurality of X electrodes have a two-layer structure in order to express two-dimensional coordinates by the X axis and the Y axis. ITO is used as the electrode material.

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

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

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

On the other hand, not only in the touch panel field described above, in recent years, there is an increasing demand for manufacturing various substrates or devices by a roll-to-roll method from the viewpoint of high-speed productivity and high yield. In order to meet this requirement, it is desirable that the photosensitive resin composition for forming the protective film is provided as a transfer film, not as a liquid resist.

A vacuum roll laminator is usually used in the process of attaching the transfer film to the substrate by the roll-to-roll method. However, the temperature is applied to the photosensitive resin composition layer due to the heat of the roll after the transfer film is attached, and oxygen is not present in the environment for suppressing radical polymerization. The photopolymerization initiator is cleaved, and the dark reaction proceeds to cause a significant decrease in developability. Therefore, the roll temperature of the vacuum roll laminate is required to be low, specifically, less than 100 ° C.

In addition to the recent increase in demand for flexible display substrates, as a protective film for protecting the wiring board surface or pattern circuit provided on the substrate, in addition to the protective film, a photosensitive solder resist, a photosensitive film Various film-like photosensitive materials such as dry film resists are also used depending on the application.

In patent document 1, although the composition which combined two types of epoxy acrylate acid modified products is used as a photosensitive coverlay film, the description regarding low temperature developability, low temperature laminating property, or moisture permeability is not made | formed.
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 photosensitive. Used as a conductive dry film solder resist. None of the documents describes low-temperature developability, low-temperature laminating properties, or adhesion to a substrate, and it is assumed that these performances are not all satisfied.
In Patent Document 4, a composition containing an acrylic copolymer having a weight average molecular weight of 12,000 and a modified cresol novolac epoxy acrylate is used as a photosensitive dry film solder resist. There is no description of properties, low-temperature laminating properties or adhesion to a substrate. Moreover, although the solder resist of patent document 4 has provided the moisture resistance of a fixed level, the request | requirement level of the latest moisture resistance has increased further, and is not satisfied with this.

JP 2013-228723 A JP 2009-251286 A JP 2012-215804 A JP 2006-243564 A

The technologies described in Patent Documents 1 to 4 still have room for improvement, as explained above. Therefore, the problem to be solved by the present invention is that the transfer film has a tack property, a low temperature developability, a low temperature laminate property, a moisture permeability as a cured film, and a good adhesion to a conductor substrate, and a conductor portion such as an electrode. It is providing the photosensitive resin composition suitable for protection of a film, a transfer film, and its manufacturing method.

The above problem is solved by the following technical means.
[1]
A transfer film for forming a conductor protective film comprising a support film and a photosensitive resin composition layer, wherein the photosensitive resin composition layer comprises the following components:
(A) 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;
Containing
The (A) alkali-soluble resin has a weight average molecular weight of 11,000 or more and 29,000 or less, and an acid value of 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 to 9,500, an acid value of 60 mgKOH / g or more, and a refractive index of 1.570 or more. ,
A conductor characterized in that the mass ratio (A) / (B) of the (A) alkali-soluble resin to the compound containing (B) a carboxyl group and an ethylenically unsaturated group is 0.18 to 6.0. Transfer film for forming a protective film.
[2]
Item 2. The transfer film according to Item 1, wherein the acid value of the alkali-soluble resin (A) is 200 mgKOH / g or less.
[3]
Item 3. The transfer film according to Item 1 or 2, wherein the acid value of the compound (B) containing a carboxyl group and an ethylenically unsaturated group is 200 mgKOH / g or less and the refractive index is 1.650 or less.
[4]
Item 4. The transfer film according to any one of Items 1 to 3, wherein the photosensitive resin composition layer has a hydroxyl value of 15.0 mgKOH / g or less.
[5]
Item 5. The transfer film according to Item 4, wherein the photosensitive resin composition layer has a hydroxyl value of 0.01 mgKOH / g or more.
[6]
Item 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]
Item 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 (A) alkali-soluble resin contains a structure derived from (meth) acrylic acid in an amount of 12% by mass to 30% by mass and a structure derived from styrene or a derivative thereof in an amount of 30% by mass to 80% by mass. 8. The transfer film according to any one of 7 above.
[9]
Item 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]
Item 10. The transfer film according to any one of Items 1 to 9, which is used for either a protective film for a touch panel or a protective film for a force sensor.
[11]
A conductor part protective film-forming transfer film comprising a support film and a photosensitive resin composition layer, wherein the photosensitive resin composition layer comprises the following (I) and (II):
(I) In a differential molecular weight distribution curve obtained from a GPC elution 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 between the molecular weight M = 20000 and the molecular weight M = 5000 is in the range of 0.20-1.50, and (ii) in the differential molecular weight distribution curve The area ratio S _{≧ 50k} of the region having the molecular weight M ≧ 50000 is 1.0 to 9.0% when the area of the region having the molecular weight M ≧ 2000 is 100%; and (II) tetrahydrofuran at 23 ° C. (I) Acid value A2 is 95 mgKOH / g or more, and (ii) Refractive index n2 is 1.560 or more, which is soluble in water and insoluble in tetrahydrofuran / cyclohexane (mass ratio = 1/2) mixed solvent Is
A transfer film for forming a conductor protective film that satisfies the requirements.
[12]
The transfer film for forming a conductor protective film according to item 11, further comprising the following (III):
(III) A component that is soluble in tetrahydrofuran and insoluble in a tetrahydrofuran / cyclohexane (mass ratio = 1 / 1.3) mixed solvent at 23 ° C. (i) has an acid value A1 of 100 mgKOH / g or more; ii) The transfer film for forming a conductor protective film according to Item 11, wherein the refractive index n1 satisfies 0.005 or more smaller than n2.
[13]
Item 13. The conductor protective film-forming transfer film according to Item 12, wherein the acid value A1 is 200 mgKOH / g or less.
[14]
Item 14. The transfer film according to any one of Items 11 to 13, wherein a component in a region of molecular weight M ≧ 50000 in the differential molecular weight distribution curve includes an aromatic ring.
[15]
Item 15. The transfer film according to any one of Items 11 to 14, which is used for either a protective film for a touch panel or a protective film for a force sensor.
[16]
A transfer film for forming a conductor protective film comprising a support film and a photosensitive resin composition layer, wherein the photosensitive resin composition layer comprises the following (II) and (III):
(II) a component that is soluble in tetrahydrofuran and insoluble in a tetrahydrofuran / cyclohexane (mass ratio = 1/2) mixed solvent at 23 ° C. (i) has an acid value A2 of 95 mgKOH / g or more, and (ii) The refractive index n2 is 1.560 or more;
(III) A component that is soluble in tetrahydrofuran and insoluble in a tetrahydrofuran / cyclohexane (mass ratio = 1 / 1.3) mixed solvent at 23 ° C. (i) has an acid value A1 of 100 mgKOH / g or more; ii) A transfer film for forming a conductor protective film that satisfies a refractive index n1 of 0.005 or more smaller than n2.
[17]
Item 17. The transfer film for forming a conductor protective film according to Item 16, wherein the acid value A1 is 200 mgKOH / g or less.
[18]
Item 18. The transfer film according to Item 16 or 17, which is used for either a touch panel protective film or a force sensor protective film.
[19]
A transfer film for forming a conductor protective film comprising a support film and a photosensitive resin composition layer, wherein the photosensitive resin composition layer comprises the following components:
(A) 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;
Containing
The (A) alkali-soluble resin has a weight average molecular weight of 11,000 or more and 29,000 or less, and an acid value of 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 to 9,500, an acid value of 60 mgKOH / g or more, and the following general formulas (1) to (3): ):

Including at least the structure according to any one of
A conductor characterized in that the mass ratio (A) / (B) of the (A) alkali-soluble resin to the compound containing (B) a carboxyl group and an ethylenically unsaturated group is 0.18 to 6.0. Transfer film for forming a protective film.
[20]
Item 20. The transfer film according to Item 19, wherein the acid value of the (A) alkali-soluble resin is 200 mgKOH / g or less.
[21]
Item 21. The transfer film according to Item 19 or 20, wherein the acid value of the compound containing (B) a carboxyl group and an ethylenically unsaturated group is 200 mgKOH / g or less.
[22]
Item 20. The transfer film according to Item 19, wherein the photosensitive resin composition layer has a hydroxyl value of 15.0 mgKOH / g or less.
[23]
Item 23. The transfer film according to Item 22, wherein the photosensitive resin composition layer has a hydroxyl value of 0.01 mgKOH / g or more.
[24]
24. The transfer film according to any one of items 19 to 23, wherein a refractive index of the photosensitive resin composition layer is 1.550 or more.
[25]
Item 25. The transfer film according to Item 24, wherein the refractive index of the photosensitive resin composition layer is 1.630 or less.
[26]
Items (19) to (19), wherein the (A) alkali-soluble resin contains a structure derived from (meth) acrylic acid in an amount of 12% by mass to 30% by mass and a structure derived from styrene or a derivative thereof in an amount of 30% by mass to 80% by mass. The transfer film according to any one of 25.
[27]
Item 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]
Item 28. The transfer film according to any one of Items 19 to 27, which is used for either a protective film for a touch panel or a protective film for a force sensor.
[29]
29. A pattern production method comprising producing a pattern by laminating, exposing and developing the transfer film according to any one of items 1 to 28 on a substrate.
[30]
30. A cured film pattern manufacturing method, wherein a pattern obtained by the pattern manufacturing method according to item 29 is subjected to post-exposure processing and / or heat treatment.
[31]
A method for manufacturing a device having a touch panel display device or a touch sensor, wherein the cured film pattern obtained by the method for manufacturing a cured film pattern according to Item 30 is used.

According to the present invention, there are provided a photosensitive resin composition and a transfer film in which the transfer film has good tack properties, low-temperature developability, low-temperature laminating properties, moisture permeability as a cured film, and good adhesion to a conductor substrate. be able to.

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

Hereinafter, modes for carrying out the present invention (hereinafter abbreviated as “embodiments”) will be described in detail. In addition, this invention is not limited to the following embodiment, It can implement by changing variously within the range of the summary.

<(A) Alkali-soluble resin>
The (A) alkali-soluble resin according to the present embodiment is not limited as long as it contains a carboxyl group but does not contain an acid-modified epoxy (meth) acrylate compound. For example, (A) (meth) acrylic acid, ( Acrylic copolymers (A1) such as (meth) acrylic acid ester, (meth) acrylonitrile, (meth) acrylamide, polyimide precursor (A2), carboxyl group-containing polyimide (A3), carboxyl group-containing urethane resin (A4), etc. Is mentioned.

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

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

(A) The weight average molecular weight of alkali-soluble resin is 11,000 or more and 29,000 or less from a viewpoint of applicability | paintability, coating-film strength, the tackiness of a transfer film, and developability. The weight-average molecular weight of the alkali-soluble resin is determined based on the properties of the development aggregate, the tack properties when used as a transfer film, the properties of the unexposed film such as edge fuse properties, cut chip properties, etc. It is 11,000 or more from the viewpoint of adhesion to the substrate after film formation and curing on the substrate, and 29,000 or less from the viewpoint of low-temperature developability. Here, the edge fuse property is a phenomenon in which the photosensitive resin composition layer protrudes from the end face of the roll when the transfer film is wound into a roll shape. The cut chip property is a phenomenon in which a chip flies when an unexposed film is cut with a cutter. If the scattered chips adhere to the upper surface of the transfer film or the like, it is transferred to a mask in the subsequent exposure process or the like, causing a defect. (A) The weight average molecular weight of the alkali-soluble resin is more preferably from 13,000 to 27,000, still more preferably from 15,000 to 26,000. The measurement of the weight average molecular weight according to the present embodiment is performed using gel permeation chromatography (GPC) manufactured by JASCO Corporation set under the following conditions. The obtained weight average molecular weight is a polystyrene equivalent value.
Pump: Gulliver, PU-1580 type Column: Shodex (registered trademark) (KF-807, KF-806M, KF-806M, KF-802.5) manufactured by Showa Denko KK Four detectors: RI
Column temperature: 40 ° C
Flow rate: 1.0 mL / min
Injection volume: 0.02 mL
Moving bed solvent: Tetrahydrofuran calibration curve: Calibration curve defined using polystyrene standard sample {Use of calibration curve based on polystyrene standard sample (Shodex STANDARD SM-105 manufactured by Showa Denko KK)}

(A) 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 the photosensitive resin composition is exposed and thermally cured can be lowered, so that the rust prevention property of the conductor is improved.

(A) The hydroxyl value of alkali-soluble resin can be measured as follows.
First, the (A) alkali-soluble resin solution to be measured for hydroxyl value is placed on an aluminum dish and heated at a temperature 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 alkali-soluble resin (A) thus obtained is precisely weighed, and 10 mL of 10% by mass acetic anhydride pyridine solution is added and dissolved uniformly, followed by heating at 100 ° C. for 1 hour. After heating, 10 mL of water and 10 mL of pyridine are added and heated at 100 ° C. for 10 minutes. Then, it is measured by neutralization titration with an ethanol solution of 0.1 mol / L potassium hydroxide using an automatic titrator (“COM-555” manufactured by Hiranuma Sangyo Co., Ltd.).
The hydroxyl value can be calculated by the following formula.
Hydroxyl value = (AB) × f × 28.05 / sample (g) + acid value {wherein A represents the amount (mL) of 0.1 mol / L potassium hydroxide ethanol solution used in the blank test. , B indicates the amount (mL) of 0.1 mol / L potassium hydroxide ethanol solution used for titration, and f indicates a factor. }

(A1) Acrylic copolymer The (A1) acrylic copolymer according to the present embodiment includes, for example, (meth) acrylic acid, (meth) acrylic acid ester, (meth) acrylonitrile, (meth) acrylamide, and styrene. And copolymers such as derivatives thereof.

As an example of the copolymer, in addition to the structural units already described, other monomers copolymerizable with those structural units may be contained as the structural units. Other monomers include, for example, hydroxyalkyl (meth) acrylate, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, maleic anhydride, (meth) acrylic acid tetrahydrofurfuryl ester, dimethylaminoethyl (meth) acrylate Ester, (meth) acrylic acid diethylaminoethyl ester, (meth) acrylic acid glycidyl ester, (meth) acrylic acid benzyl ester, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-tetra Examples thereof include fluoropropyl (meth) acrylate, styrene and derivatives thereof. Examples of the styrene derivative include 4-methylstyrene, 4-hydroxystyrene, 4-methoxystyrene, 4-chlorostyrene, 4- (chloromethyl) styrene, and 4-vinylbenzoic acid.
Among these copolymers, structural units derived from (meth) acrylic acid and (meth) acrylic acid aromatic ester or styrene and derivatives thereof from the viewpoint of reducing moisture permeability and improving the rust prevention property of the conductor. A copolymer containing a structural unit is more preferable.

By copolymerizing the unit having an aromatic group, the hydrophobicity of the acrylic copolymer is increased, and the rust prevention property is improved. Moreover, it is thought that the film density after hardening of the photosensitive resin composition becomes high, and the rust prevention property of a conductor improves because an acrylic copolymer has an aromatic group. The structure derived from (meth) acrylic acid is 12% by mass or more and 30% by mass or less, and the structure derived from styrene or its derivative is 30 as (A1) acrylic copolymer in that both low temperature developability and moisture permeability reduction can be achieved. More preferably, the content is from 80% by weight to 80% by weight.
(A1) The acrylic copolymer is synthesized by radical polymerization by combining the above monomers in a specific weight ratio. In this case, an azo polymerization initiator is preferably used as the photopolymerization initiator. Examples of commercially available azo initiators include V-601 (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.).

(A2) Polyimide Precursor The (A2) polyimide precursor according to the present embodiment does not mean only polyamic acid but also includes imidized part of the polyamic acid.

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

Examples of tetracarboxylic dianhydrides include biphenyl-3,3 ′, 4,4′-tetracarboxylic dianhydride, benzophenone-3,3 ′, 4,4′-tetracarboxylic dianhydride, oxydiphthalic acid Anhydride, diphenylsulfone-3,3 ′, 4,4′-tetracarboxylic dianhydride, ethylene glycol bis (trimellitic acid monoester acid anhydride), p-phenylenebis (trimellitic acid monoester acid anhydride) ), P-biphenylenebis (trimellitic acid monoester acid anhydride), m-phenylenebis (tomellitic acid monoester acid anhydride), o-phenylenebis (trimellitic acid monoester acid anhydride), pentanediol bis (Trimellitic acid monoester acid anhydride), decanediol bis (trimellitic acid monoester acid anhydride), Merit acid, bis (3,4-dicarboxyphenyl) ether dianhydride, 4,4 ′-(2,2-hexafluoroisopropylidene) diphthalic dianhydride, meta-terphenyl-3,3 ′, 4 , 4'-tetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, bicyclo [2,2,2] oct-7-ene-2,3,5,6-tetra Carboxylic dianhydride, cyclobutane-1,2,3,4-tetracarboxylic dianhydride, 1-carboxymethyl-2,3,5-cyclopentatricarboxylic acid-2,6: 3,5-dianhydride 4- (2,5-dioxotetrahydrofuran-3-yl) -1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid anhydride and 5- (2,5-dioxotetrahydrofuryl) ) -3-Me -3-cyclohexene-1,2-dicarboxylic anhydride, and the like. The tetracarboxylic dianhydrides described above may be used alone or in combination of two or more.

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

The main chain terminal of the polyimide precursor is not particularly limited as long as it does not affect the performance, and may be an acid dianhydride or a terminal structure derived from a diamine used for producing the polyimide precursor. The terminal may be sealed with other acid anhydrides or amine compounds.

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

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

The polyimide part can be synthesized by adding a known imidization catalyst or without a catalyst. The imidation catalyst is not particularly limited, but may be an acid anhydride such as acetic anhydride, γ-valerolactone, γ-butyrolactone, γ-tetronic acid, γ-phthalide, γ-coumarin, and γ-phthalido acid. Lactone compounds, and tertiary amines such as pyridine, quinoline, N-methylmorpholine, and triethylamine. Moreover, you may use 1 type, or 2 or more types of these mixtures as needed. Among these, a mixed system of γ-valerolactone and pyridine and non-catalyst are particularly preferable from the viewpoint of high reactivity and reducing the influence on the next reaction.

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

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

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

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

(A3) Carboxyl group-containing polyimide A carboxyl group-containing polyimide is synthesized by mixing tetracarboxylic dianhydride and diamine in an organic solvent at a molar ratio of 0.8: 1 to 1.2: 1 and reacting them. The skeleton is characterized by containing a carboxyl group even after imidization, but the polyamic acid structure may partially remain.

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

Examples of the tetracarboxylic dianhydride, the diamine used in combination with the carboxyl group-containing diamine, the solvent used for the synthesis, and the imidization catalyst are the same as those described above for the (A2) polyimide precursor.

(A4) Carboxyl group-containing polyurethane The carboxyl group-containing polyurethane according to the present embodiment is a known disulfide compound, a carboxyl group-containing diol compound, and other diol compounds in an aprotic solvent having an activity corresponding to the respective reactivity. It is synthesized by adding a catalyst and heating. The molar ratio of the diisocyanate and diol compound to be used is preferably 0.8: 1 to 1.2: 1. When an isocyanate group remains at the end of the polymer, the molar ratio can be determined by treating with an alcohol or an amine. Is synthesized in a form in which no isocyanate group remains.

Diisocyanate compounds include 2,4-tolylene diisocyanate, dimer of 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, p-xylylene diisocyanate, m-xylylene diisocyanate, 4,4'- Aromatic diisocyanate compounds such as diphenylmethane diisocyanate, 1,5-naphthylene diisocyanate, 3,3′-dimethylhyphenyl-4,4′-diisocyanate: hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate, dimer acid diisocyanate, etc. Aliphatic diisocyanate compounds such as: isophorone diisocyanate, 4,4′-methylenebis (cyclohexyl isocyanate), methylcyclohexane-2,4- (or 2 6) Alicyclic diisocyanate compounds such as diisocyanate and 1,3- (isocyanatomethyl) cyclohexane; reaction product of diol and diisocyanate such as an adduct of 1 mol of 1,3-butylene glycol and 2 mol of tolylene diisocyanate The diisocyanate compound etc. which are are mentioned.

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

Other diol compounds used in combination with a carboxyl group-containing diol compound include high molecular weight diols such as polytetramethylene diol, polybutadiene diol, hydrogenated polybutadiene diol, polycarbonate diol, polyester diol, and polycaprolactone diol; or ethylene glycol, 1 , 2-propylene glycol, 1,3-propylene glycol, 1,3-butylene glycol, 2,3-butylene glycol, 1,4-butanediol, 2,2′-dimethyl-1,3-propanediol, diethylene glycol, Triethylene glycol, 1,5-pentamethylene glycol, dipropylene glycol, neopentyl glycol, 1,6-hexamethylene glycol, cyclohexane-1,4-dio , Cyclohexane-1,4-diol, cyclohexane-1,4-dimethanol, 2-butene-1,4-diol, 2,2,4-trimethyl-1,3-pentanediol, xylylene glycol, 1, 4-bis-β-hydroxyethoxycyclohexane, tridichlorodecane dimethanol, hydrogenated bisphenol A, hydrogenated bisphenol F, bisphenol A, bisphenol S, hydroquinone dihydroxyethyl ether, p-xylylene glycol, dihydroxyethyl sulfone, bis (2 -Hydroxyethyl) -2,4-tolylenedicarbamate, 2,4-tolylene-bis (2-hydroxyethylcarbamide), bis (2-hydroxyethyl) -m-xylylenedicarbamate, bis (2-hydroxyethyl) iso Phthalate, 1,4- And low molecular weight diols such as bis (β-hydroxyethoxy) benzene and bis (β-hydroxyethyl) terephthalate.

(B) Compound containing carboxyl group and ethylenically unsaturated group (B) The compound containing carboxyl group and ethylenically unsaturated group according to the present embodiment has one or more carboxyl groups and one in the molecule. Although there will be no restriction | limiting if it is a compound containing the above ethylenically unsaturated group, For example, (B1) epoxy (meth) acrylate acid modified material can be used conveniently.

(B) The acid value (mgKOH / g) of the compound containing a carboxyl group and an ethylenically unsaturated group is 60 or more, 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 prevention property of the conductor, and from the viewpoint of improving the low temperature developability of the photosensitive resin composition layer. From the viewpoint of balance of both performances, 70 to 170 is more preferable, and 80 to 150 is still more preferable. The acid value is measured in the same manner as described above for the (A) alkali-soluble resin.

(B) The weight average molecular weight of the compound containing a carboxyl group and an ethylenically unsaturated group is (A) compatible with an alkali-soluble resin, tackiness when used as a transfer film, and low-temperature developability. 1,000 or more and 9,500 or less. 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 the unexposed film such as tackiness, edge fuse property and cut chip property when used as a transfer film. From the viewpoint of low temperature developability and low temperature laminating property of the photosensitive resin composition layer, it is 9,500 or less, 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 lowered, so that the rust prevention property of the conductor is improved. The measurement of the hydroxyl value is performed in the same manner as described above for the (A) alkali-soluble resin.

In addition, the compound (B) containing a carboxyl group and an ethylenically unsaturated group according to the present embodiment is 1) a refractive index of 1.570 or more, and / or 2) the following general formulas (1) to (3) It includes at least one of the skeletons represented by By satisfying the above 1) and / or 2), the moisture permeability of the cured product obtained from the photosensitive resin composition according to the present embodiment can be lowered, so that the rust prevention property of the conductor is improved. From the viewpoint of moisture permeability, the refractive index of the component (B) is preferably 1.570 or more, and preferably 1.650 or less from the viewpoint of low-temperature developability of the photosensitive resin composition layer.

The refractive index of the component (B) according to the present embodiment is measured by the following method.
First, (B) an organic solvent having a boiling point of 200 ° C. or less at 1 atm that dissolves a compound containing a carboxyl group and an ethylenically unsaturated group (for example, ethanol, acetone, methyl ethyl ketone, 1-methoxy-2-propanol, propylene) Glycol-1-monomethyl ether-2-acetate) is prepared. At this time, the solid content concentration is adjusted to 30 to 70% by mass. The obtained solution was coated on a commercially available polyethylene terephthalate (PET) film (thickness 16 μm) with a bar coater, dried in a hot air oven at 100 ° C. for 10 minutes, and (B) carboxyl group and ethylenically unsaturated group. A layered product having a thickness of 5 μm is obtained. Refractive index measurement is performed using a prism made by Metricon, Prism Coupler Model 2010 / M, laser beam wavelength: 532 nm, and in a state where a layer made of a compound containing (B) a carboxyl group and an ethylenically unsaturated group is in contact with the prism. Is called.

(B1) Epoxy (meth) acrylate acid-modified product (B1) Epoxy (meth) acrylate acid-modified product according to the present embodiment is defined as a compound that satisfies the following two conditions, and is an acid-modified epoxy (meth) acrylate Also called a compound.
i) A compound containing two or more epoxy groups in the molecule can be synthesized as a starting material.
ii) It contains one or more carboxyl groups and one or more (meth) acryloyl groups in the molecule.

<Compound containing two or more epoxy groups in the molecule>
(B1) In order to adjust the refractive index of the modified epoxy (meth) acrylate acid to 1.570 or more, compounds containing two or more epoxy groups in the molecule include those represented by the general formulas (1) to ( Epoxy compounds containing at least any of 3) are preferred from the viewpoint of availability, and commercially available products that contain the general formula (1) include NC-3000 series (manufactured by Nippon Kayaku Co., Ltd.), BPAE (Manufactured by Nippon Steel Chemical Co., Ltd.), HP-4700, 4770, 5000, 6000 (manufactured by DIC), NC-7000, 7300 (manufactured by Nippon Kayaku Co., Ltd.) ESN-175 as containing general formula (2) Epoxy compounds such as OGSOL PG-100 and OGSOL EG-200 (Osaka Gas Chemical Co., Ltd.) may be mentioned as those containing General Formula (3) (manufactured by Nippon Steel Chemical Co., Ltd.).

Two methods for synthesizing (B1) modified epoxy (meth) acrylate acid starting from a compound containing two or more epoxy groups in the molecule are shown below. (B1) Epoxy (B1) according to this embodiment ( The chemical structure and production method of the modified meth) acrylate are not limited thereto.

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

The second reaction is a reaction between the hydroxyl group of the compound produced in the first reaction and a dicarboxylic acid anhydride. As the dicarboxylic acid anhydride, either a saturated dicarboxylic acid anhydride or an unsaturated dicarboxylic acid anhydride can be used. Such dicarboxylic anhydrides include, for example, succinic anhydride, maleic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, endomethylenetetrahydroanhydride. Examples thereof include phthalic acid and methylbutenyl tetrahydrophthalic anhydride. Of these, succinic anhydride, phthalic anhydride, tetrahydrophthalic anhydride and methyltetrahydrophthalic anhydride are particularly preferred. These dicarboxylic acid anhydrides can be used individually by 1 type, and 2 or more types can also be mixed and used for them.
Known reaction conditions can also be used for the second reaction between the hydroxyl group and the anhydride group. By the reaction, the anhydride group is cleaved to produce an ester group and a carboxyl group.

The amount of the acid anhydride group of the dicarboxylic dianhydride in the second reaction is usually 60 to 100 parts by mole, preferably 75 parts by mole or more and 100 parts by mole or less with respect to 100 parts by mole of the hydroxyl group produced in the first reaction. React as follows.
Moreover, the epoxy (meth) acrylate modified product synthesized through the first and second reactions is further reacted with a compound having one epoxy group and one or more radically polymerizable unsaturated groups in the molecule. It is also possible 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 the first reaction, as in the above synthesis method (1), the carboxyl group of a monocarboxylic acid having a (meth) acryloyl group is reacted with the epoxy group of a compound containing two or more epoxy groups in the molecule. . The monocarboxylic acid having a (meth) acryloyl group is, for example, acrylic acid or methacrylic acid. Known reaction conditions can be applied to this reaction. The epoxy group is cleaved by the reaction to generate a hydroxyl group.

The second reaction is a reaction between the hydroxyl group of the compound produced in the first reaction and a tetracarboxylic anhydride. Examples of tetracarboxylic acid anhydrides include biphenyl-3,3 ′, 4,4′-tetracarboxylic dianhydride, benzophenone-3,3 ′, 4,4′-tetracarboxylic dianhydride, oxydiphthalic acid dianhydride , Diphenylsulfone-3,3 ′, 4,4′-tetracarboxylic dianhydride, ethylene glycol bis (trimellitic acid monoester anhydride), p-phenylenebis (trimellitic acid monoester acid anhydride) , P-biphenylenebis (trimellitic acid monoester acid anhydride), m-phenylenebis (tomellitic acid monoester acid anhydride), o-phenylenebis (trimellitic acid monoester acid anhydride), pentanediol bis ( Trimellitic acid monoester anhydride), decanediol bis (trimellitic acid monoester anhydride), pyrome anhydride Oxalic acid, bis (3,4-dicarboxyphenyl) ether dianhydride, 4,4 ′-(2,2-hexafluoroisopropylidene) diphthalic dianhydride, meta-terphenyl-3,3 ′, 4,4′-tetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, bicyclo [2,2,2] oct-7-ene-2,3,5,6- Tetracarboxylic dianhydride, cyclobutane-1,2,3,4-tetracarboxylic dianhydride, 1-carboxymethyl-2,3,5-cyclopentatricarboxylic acid-2,6: 3,5-dianhydride , 4- (2,5-dioxotetrahydrofuran-3-yl) -1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride, and 5- (2,5-dioxotetrahydro Furyl) -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 the residual hydroxyl group of the compound produced in the second reaction and a dicarboxylic acid anhydride. As the dicarboxylic acid anhydride, either a saturated dicarboxylic acid anhydride or an unsaturated dicarboxylic acid anhydride can be used. Such dicarboxylic anhydrides include, for example, succinic anhydride, maleic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, endomethylenetetrahydroanhydride. Examples thereof include phthalic acid and methylbutenyl tetrahydrophthalic anhydride. Of these, succinic anhydride, phthalic anhydride, tetrahydrophthalic anhydride and methyltetrahydrophthalic anhydride are particularly preferred. These dicarboxylic acid anhydrides can be used individually by 1 type, and 2 or more types can also be mixed and used for them.
Known reaction conditions can be used for the third reaction between the hydroxyl group and the dicarboxylic anhydride group. By the reaction, the anhydride group is cleaved to produce an ester group and a carboxyl group, and an epoxy (meth) acrylate acid modified product can be obtained.

The total amount of acid anhydride groups in the tetracarboxylic dianhydride in the second reaction and the dicarboxylic anhydride in the third reaction is usually 60 to 100 moles per 100 moles of the hydroxyl group produced in the first reaction. Part, preferably 75 parts by mole or more and 100 parts by mole or less. The second reaction and the third reaction can also be performed simultaneously. As a specific synthesis method, the method described in JP-A-06-001938 can be used.

In addition, the modified epoxy (meth) acrylate acid synthesized through the first to third reactions is further reacted with a compound having one epoxy group and one or more radically polymerizable unsaturated groups in the molecule. It is also possible to increase the content of ethylenically unsaturated groups (fourth 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) acrylate modified product according to this embodiment can be obtained by the synthesis method (1), the synthesis method (2), or the like, but a commercially available product can also be used. Commercially available epoxy (meth) acrylate modified products containing the general formula (1) include ZCR-1569H, ZCR-1601H, ZCR-1797H, ZCR-1798H (manufactured by Nippon Kayaku Co., Ltd.), etc. Commercially available epoxy (meth) acrylate modified products containing formula (3) include FCA-954, FCA-293, FCA-506 (manufactured by Nagase ChemteX) or TR-B201, TR-B202 (Strong Changzhou) Electronic material company) etc. are mentioned.

Mass ratio A / B of (A) alkali-soluble resin and compound containing (B) carboxyl group and ethylenically unsaturated group according to the present embodiment ((A) mass of alkali-soluble resin / (B) carboxyl group and The mass of the compound containing an ethylenically unsaturated group is 0.18 to 6.0. When A / B is 0.18 or more, the tackiness of the transfer film is improved, and the adhesion to the conductor base material is improved. When A / B is 6.0 or less, the low temperature laminating property and the moisture permeability of the cured film are reduced. Surprisingly, the low temperature developability deteriorates when A / B is less than 0.18 and more than 6.0. From the viewpoint of balance of various performances, a more preferable range of A / B is 0.40 to 1.0.

<(C) Photopolymerizable compound>
The photopolymerizable compound according to the present embodiment is a compound having an ethylenically unsaturated double bond, for example, a compound having polymerizability by having an ethylenically unsaturated group in the structure thereof. The compound having an ethylenically unsaturated double bond preferably includes (c1) a compound having three or more polymerizable groups in the molecule and / or (c2) a compound having one polymerizable group in the molecule. It is more preferable to contain. Moreover, the compound which has an ethylenically unsaturated double bond can be used in combination with compounds other than the above.

(C) Component (c1) contains a compound having three or more polymerizable groups in the molecule, thereby increasing the crosslink density of the protective film, making it difficult for moisture to permeate, and reducing the moisture permeability of the cured film. Can do. (C1) The compound having three or more polymerizable groups in the molecule has at least 3 moles of a group capable of adding an alkylene oxide group in the molecule as a central skeleton, and this group has an ethylene oxide group and a propylene oxide group. Alternatively, it can be obtained by converting an alcohol obtained by adding an alkylene oxide group such as a butylene oxide group into (meth) acrylate. Alternatively, (meth) acrylic acid may be reacted directly with the central skeleton without modifying the central skeleton with an alkylene oxide group. Examples of the compound that can be a central skeleton include glycerin, trimethylolpropane, pentaerythritol, diglycerin, ditrimethylolpropane, dipentaerythritol, and isocyanurate rings. From the viewpoint of reducing the moisture permeability of the cured film, it may contain dipentaerythritol hexa (meth) acrylate, pentaerythritol tetra (meth) acrylate, trimethylolpropane tri (meth) acrylate, or ditrimethylolpropane tri (meth) acrylate. preferable. The photosensitive resin composition further preferably includes (c1) a compound having a molecular weight of 430 or less as the compound having three or more polymerizable groups in the molecule. When the molecular weight of the component (c1) is 430 or less, the low temperature developability of the photosensitive resin composition layer is improved. Examples of the compound having a molecular weight of 430 or less include compounds having glycerin, trimethylolpropane, pentaerythritol and the like as a central skeleton. From the viewpoint of achieving both low-temperature developability of the photosensitive resin composition layer and reduced moisture permeability of the cured film, the component (C) may contain pentaerythritol tetra (meth) acrylate or trimethylolpropane tri (meth) acrylate. preferable.

(C1) Without compound or in addition to (c1) compound, (c2) By including a compound having one polymerizable group in the molecule, (C) the entire compound having an ethylenically unsaturated double bond The reaction rate is improved, and the moisture permeability of the cured film can be expected to be reduced. Moreover, the improvement of the low temperature developability of the photosensitive resin composition layer may be seen. (C2) As a compound having one polymerizable group in the molecule, a compound obtained by adding (meth) acrylic acid to one end of polyalkylene oxide, (meth) acrylic acid added to one end, and the other end And the like, and the like. For example, m-phenoxybenzyl acrylate, o-phenylphenoxyethyl acrylate, 4-methacryloyloxybenzophenone, EO-modified paracumylphenol acrylate, nonylphenoxyethyl acrylate, 4-nonylphenylheptaethylene glycol dipropylene glycol acrylate, 2-hydroxy-3 -Phenoxypropyl acrylate, phenoxyhexaethylene glycol acrylate, 4-normal octylphenoxypentapropylene glycol acrylate, 1,6-hexanediol (meth) acrylate. M-phenoxybenzyl acrylate, o-phenylphenoxyethyl acrylate, 4-methacryloyloxybenzophenone, EO-modified paracumylphenol acrylate, nonylphenoxyethyl acrylate, from the viewpoint of rust prevention of the conductor and moisture permeability of the cured film More preferred.

Further, as other compound (c3) having an ethylenically unsaturated double bond (C), for example, a compound having a (meth) acryloyl group at both ends of a polyalkylene oxide chain, or a polyethylene oxide chain and a polypropylene oxide chain And a compound having a (meth) acryloyl group at both ends of an alkylene oxide chain bonded to each other in a random or block manner, a compound having bisphenol A modified with an alkylene oxide and having a (meth) acryloyl group at both ends It is done.

In addition, (C) The compound (c3) having an ethylenically unsaturated double bond is a urethane which is a reaction product of a diisocyanate compound and a compound having a hydroxyl group and a (meth) acryl group in one molecule. Compounds and the like.
(C) Commercially available compounds having an ethylenically unsaturated double bond include A-TMMT (made by Shin-Nakamura Chemical Co., Ltd.) as pentaerythritol tetraacrylate, and POB-A (Kyoeisha Chemical Co., Ltd.) as m-phenoxybenzyl acrylate. ), 2- (o-phenylphenoxy) ethyl acrylate as HRD-01 (manufactured by Solar Eclipse Fine Chemical Co., Ltd.), and polybutylene glycol dimethacrylate as FA-PTG-9M and FA-PTG-28M (Hitachi Chemical Co., Ltd.) Etc.).

(C) The content of the compound having an ethylenically unsaturated double bond in the photosensitive resin composition is the mass of the photosensitive resin composition from the viewpoints of resolution, conductor adhesion of the cured film, and moisture permeability reduction. The reference is preferably 20% by mass to 60% by mass, and more preferably 30% by mass to 50% by mass.

<(D) Photopolymerization initiator>
The photopolymerization initiator (D) according to the present embodiment is a compound capable of generating radicals with active light and polymerizing an ethylenically unsaturated group-containing compound. The photopolymerization initiator according to the present embodiment is a compound capable of generating radicals with active light and polymerizing an ethylenically unsaturated group-containing compound or the like. (D) As the photopolymerization initiator, for example, benzophenone, N, N, N ′, N′-tetramethyl-4,4′-diaminobenzophenone (Michler ketone), N, N, N ′, N′-tetraethyl- 4,4′-diaminobenzophenone, 4-methoxy-4′-dimethylaminobenzophenone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2-methyl-1- [4- Aromatic ketones such as (methylthio) phenyl] -2-morpholino-propanone-1, acrylated benzophenone, 4-benzoyl-4′-methyldiphenyl sulfide; benzoin ether compounds such as benzoin methyl ether, benzoin ethyl ether and benzoin phenyl ether Benzoins such as benzoin, methylbenzoin and ethylbenzoin Compound: 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)], ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole -3-yl]-, 1- (O-acetyloxime), 1- [4- (phenylthio) phenyl] -3-cyclopentylpropane-1,2-dione-2- (o-benzoyloxime), 1,2 Oxime ester compounds such as propanedione, 3-cyclohexyl-1- [9-ethyl-6- (2-furanylcarbonyl) -9H-carbazol-3-yl]-, 2- (O-acetyloxime); Benzyl derivatives such as dimethyl ketal; acridine derivatives such as 9-phenylacridine and 1,7-bis (9,9′-acridinyl) heptane; N- phenylglycine derivatives such as Shin; coumarin compounds; oxazole compounds; 2,4,6 - diphenyl - phosphine oxide compounds such as phosphine oxide. A photoinitiator can also be used individually or in mixture of 2 or more types.

Among these, oxime ester compounds are preferable from the viewpoints of improving the rust prevention property of the conductor, reducing the moisture permeability of the cured film, and improving the chemical resistance, and among these, compounds having a high molar extinction coefficient of 365 nm are more preferable. By using an oxime initiator having a high absorption coefficient at a wavelength of 365 nm, a highly sensitive protective film can be obtained by i-line exposure. Among these, from the viewpoint of rust prevention, an oxime ester compound is preferable, and among these, a compound having a high molar extinction coefficient of 365 nm is more preferable. By using an oxime initiator having a high extinction coefficient at a wavelength of 365 nm, a highly sensitive protective film can be obtained by i-line exposure. Thereby, high surface curability is obtained, it is speculated that the penetration of sodium ions in the development process as described above can be suppressed, and as a result, high rust prevention property of the conductor can be obtained.

As specific oxime ester compounds, 1,2-octanedione, 1-[(4-phenylthio) phenyl-, 2- (O-benzoyloxime)] (manufactured by BASF Japan Ltd., Irgacure Oxe01, product name) Ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime) (manufactured by BASF Japan Ltd., Irgacure Oxe02), 1 -[4- (phenylthio) phenyl] -3-cyclopentylpropane-1,2-dione-2- (O-benzoyloxime) (TR-PBG-305, product name) from Changzhou Power Electronics New Materials Co., Ltd., and 1, 2-propanedione, 3-cyclohexyl-1- [9-ethyl-6- (2-furanylcarbonyl) -9H-carbazol -3-yl]-, 2- (O-acetyloxime) (TR-PBG-326, product name, Changzhou Power Electronics New Materials Co., Ltd.), (7-nitro-9,9-dipropyl-9H-fluorene-2- Yl) (ortho-tolyl) methanone O-acetyloxime (DFI-020 manufactured by Daitokemix Co., Ltd.), 1,8-octanedione, 1,8-bis [9- (2-ethylhexyl) -6-nitro-9H-carbazole- 3-yl]-, 1,8-bis (O-acetyloxime), 3-cyclohexyl-1- (6- (2- (benzoyloxyimino) octanoyl) -9-ethyl-9H-carbazol-3-yl) -Propane-1,2-dione-2- (O-benzoyloxime) (TR-PBG-371, product name of Changzhou Power Electronics New Materials Co., Ltd.), 3-cyclohexyl-1- ( -(2- (Benzoyloxyimino) hexanoyl) -9-ethyl-9H-carbazol-3-yl) -propane-1,2-dione-2- (O-benzoyloxime) (TR made by Changzhou Power Electronics New Materials Co., Ltd.) -PBG-391, product name).

(D) The content of the photopolymerization initiator in the photosensitive resin composition is 0.1% by mass to 10% by mass based on the mass of the photosensitive resin composition, and is a viewpoint of sensitivity and resolution. Therefore, the content is more preferably 0.3% by mass to 5% by mass. If the content of the photopolymerization initiator is in the range of 0.1% by mass to 10% by mass, the photosensitivity will be sufficient, and the absorption on the surface of the composition will increase when irradiated with actinic rays. Problems such as insufficient internal photocuring and a decrease in visible light transmittance can be suppressed.

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

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

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

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

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

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

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

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

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

The block isocyanate compound is a carboxyl group or hydroxyl group of a compound containing (A) an alkali-soluble resin or (B) a carboxyl group and an ethylenically unsaturated group, or a combined diol compound in a heat treatment after pattern formation by development. Since it reacts with the hydroxyl group, the moisture permeability of the cured film is lowered, and the rust prevention property for protecting the substrate, the electrode and the like is improved. Further, 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, thereby increasing the crosslinking density of the cured film and reducing the water diffusibility. Therefore, it is considered that the moisture permeability of the cured film is lowered and the rust prevention property of the conductor is improved. Moreover, since the isocyanate group is sealed with the blocking agent in the blocked isocyanate, the reaction with the (A) alkali-soluble resin or diol compound at room temperature is suppressed, and the stability of the photosensitive resin composition and the transfer film is improved. Kept.

Since the diol compound has a hydrophilic hydroxyl group, the developability is good. In addition, in the heat treatment after pattern formation by development, the hydroxyl group of the diol compound reacts with the blocked isocyanate compound, so that excellent rust resistance of the conductor is maintained. The molecular weight of the diol compound is preferably from 300 to 3,000, more preferably from 500 to 2,000, from the viewpoint of developability. On the other hand, if unreacted hydroxyl groups remain after thermal curing, the moisture permeability of the cured film is deteriorated, which may be a factor that impairs the rust prevention performance of the conductor. Therefore, the diol compound is preferably added so that the hydroxyl value of the photosensitive resin composition is 20 mgKOH / g or less, and more preferably 15.0 mgKOH / g or less. Since the moisture permeability of the hardened | cured material of the photosensitive resin composition can be reduced because the hydroxyl value of the photosensitive resin composition is 20 or less, the rust prevention property of a conductor improves. Moreover, it is preferable that the hydroxyl value of the photosensitive resin composition layer is 0.01 mgKOH / g or more.

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

(F) Specific examples of rosin ester compounds include, for example, Arakawa Chemical Co., Ltd. products such as the ester gum series, pine crystal series, super ester series, pencel series, beam set 101, etc. ) The company's products include the Harrier Star Series, Neotor Series, and Harituck Series.

(F) The rosin ester compound has a cycloaliphatic structure and an ester structure, so that the hydrophobicity is increased, but (A) an alkali-soluble resin, (B) a carboxyl group and ethylene in the photosensitive resin composition. Since the compatibility with the compound containing a polymerizable unsaturated group, (C) the photopolymerizable compound, and (D) the photopolymerization initiator is good, the developability as a composition is not hindered. It has excellent performance balance of low temperature developability, moisture permeability of cured film, and rust prevention of conductor.

From the viewpoint of the rust prevention property of the conductor, the acid value of the (F) rosin ester compound is more preferably 20 mgKOH / g or less. In the above-mentioned products of Arakawa Chemical Co., Ltd. and Harima Kasei Co., Ltd., For example, Pine Crystal KE-100, Ester Gum 105, Super Ester A-115, Super Ester A-125, Pencel A, Pencel C, Pencel D-125, Pencel D-135, Pencel D-160, Beam Set 101, Harrier Star S, Neotol 125HK, Haritac F105, Haritac FK125, Haritac PCJ, and the like.

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

(F) The content of the rosin ester compound in the photosensitive resin composition is 1% by mass to 20% by mass with respect to 100% by mass of the total solid content of the photosensitive resin composition. From 5% by mass to 20% by mass, more preferably from 5% by mass to 15% by mass from the viewpoint of adhesion to the substrate. (F) When the content of the rosin ester compound is in the range of 1% by mass to 20% by mass, the performance balance between the low temperature developability of the transfer film and the moisture permeability of the cured film is good.

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

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

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

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

Imidazole; Imidazole derivatives such as undecyl imidazole, benzimidazole, 5-carboxybenzimidazole, 6-bromobenzimidazole, 5-chlorobenzimidazole, 2-hydroxybenzimidazole, 2- (1-hydroxymethyl) benzimidazole, 2 -Methylbenzimidazole, 5-nitrobenzimidazole, 2-phenylbenzimidazole, 2-aminobenzimidazole, 5-aminobenzimidazole, 5-amino-2-mercaptobenzimidazole, etc .;
An imidazoline; an imidazoline derivative such as 2-undecylimidazoline, 2-propyl-2-imidazoline, 2-phenylimidazoline;
Thiazole; thiazole derivatives such as 2-amino-4-methylthiazole, 5- (2-hydroxyethyl) -4-methylthiazole, benzothiazole, 2-mercaptobenzothiazole, 2-aminobenzothiazole, 2-amino-6 -Methylbenzothiazole, (2-benzothiazolylthio) acetic acid, 3- (2-benzothiazolylthio) propionic acid, etc .;

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

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

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

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

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

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

<Other ingredients>
In this embodiment, in addition to components (A) to (G), as other component (H), an oligomer having a carboxyl group and an ethylenically unsaturated group, an aluminum salt to which 3 mol of nitrosophenylhydroxylamine has been added, etc. Polymerization inhibitors, antioxidants, adhesion aids, leveling agents, fillers, antifoaming agents, flame retardants, etc. can also be included in the photosensitive resin composition, and these can be used alone or in combination of two or more. Can be used.

<Photosensitive resin composition and its layer>
The photosensitive resin composition in the present embodiment measures gel permeation chromatography (GPC), and in a differential molecular weight distribution curve obtained from a GPC elution curve,
(I) the ratio of dw / d (logM) values of molecular weight M = 20000 and molecular weight M = 5000; R _{20k / 5k} is in the range of 0.20 to 1.50, and (ii) the differential molecular weight distribution curve The ratio of the area of the region having the molecular weight M of 50000 or more when the area of the region having the molecular weight M of 2000 or more is 100%; S _{≧ 50k} is 1.0 to 9.0%.
Here, the GPC measurement is performed in the same manner as described above for the (A) alkali-soluble resin. Regarding the method for obtaining the differential molecular weight distribution curve from the GPC elution curve obtained by the measurement, technical report No. T1001 (2013.10.1), “GPC method (SEC method) introductory course”.

In the differential molecular weight distribution curve, it is possible to provide a photosensitive resin composition having excellent tackiness when R _{20k / 5k} is 0.20 or more, and low temperature laminating property when R _{20k / 5k} is 1.50 or less. It is possible to provide a photosensitive resin composition having excellent resistance. From the viewpoint of tackiness and low-temperature laminating property of the transfer film, a preferable range of R _{20k / 5k} is 0.30 to 1.20.

The photosensitive resin composition excellent in adhesiveness with a conductor base material can be provided because S _{> = 50k} in a differential molecular weight distribution curve is 1.0% or more. In addition, when S _{≧ 50k} is in the range of 1.0 to 9.0%, a photosensitive resin composition having excellent low-temperature developability can be provided. Further, S _{≧ 50k} is preferably in the range of 2.5 to 6.7% from the viewpoint of low-temperature developability.

From the viewpoint of hydrophobicity, film density and rust prevention, it is preferable that the component belonging to the region of molecular weight M ≧ 50000 in the differential molecular weight distribution curve contains an aromatic ring. The component having a molecular weight M ≧ 50000 and containing an aromatic ring can be derived from, for example, the components (A1) to (A4) described above.

The organic components constituting the photosensitive resin composition in the present embodiment are generally soluble in tetrahydrofuran (THF), but most of the high molecular weight components having a molecular weight (M) of 2000 or more are tetrahydrofuran (THF) at room temperature. ) / Cyclohexane (Cy) mixed solvent (mass ratio = 1/2). On the other hand, the high molecular weight component of the photosensitive resin composition in the present embodiment includes an acidic functional group and has a refractive index n2 of 1.560 or more. That is, the photosensitive resin composition in the present embodiment is a component (i) acid value A2 (23) that is soluble in THF and insoluble in a THF / Cy (mass ratio = 1/2) mixed solvent at 23 ° C. mgKOH / 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. Moreover, it is preferable that the refractive index of the photosensitive resin composition layer is 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 the photosensitive resin composition or a layer thereof will be described.
First, 10.0 g of the photosensitive resin composition or its layer was precisely weighed as a sample in a 100 mL Erlenmeyer flask, 30.0 g of tetrahydrofuran (THF) was added thereto, the container was sealed, Stir with a stirrer for 1 hour. After removing insolubles by filtration, 60.0 g of cyclohexane (Cy) is added dropwise to the THF solution over 10 minutes, and the mixture is stirred at 23 ° C. for 1 hour. The suspended solution is solid-liquid separated with a centrifuge, the insoluble matter is washed 3 times with 50 g of cyclohexane, and vacuum-dried at 40 ° C. for 6 hours to obtain a THF / Cy mixed solvent (mass ratio = 1/2). Insoluble components are obtained.

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

A method for measuring the refractive index n2 of a component insoluble in a THF / Cy mixed solvent (mass ratio = 1/2) is shown below. First, an organic solvent (for example, ethanol, acetone, methyl ethyl ketone, 1-methoxy-2-propanol) having a boiling point of 200 ° C. or less at 1 atm that dissolves insoluble components in a THF / Cy mixed solvent (mass ratio = 1/2). A solution dissolved in propylene glycol-1-monomethyl ether-2-acetate). At this time, the solid content concentration is adjusted to 10 to 70% by mass. The resulting solution can be applied to any substrate that is resistant to the solution. For example, the obtained solution was coated on a commercially available polyethylene terephthalate (PET) film (thickness 16 μm) with a bar coater, dried in a hot air oven at 100 ° C. for 10 minutes, and a THF / Cy mixed solvent (mass ratio = A layered product having a thickness of 2 μm consisting of insoluble components in 1/2) is obtained. For refractive index measurement, a prism made by Metricon, Prism Coupler Model 2010 / M, laser beam wavelength: 532 nm was used, and a layer made of a component insoluble in (THF / Cy mixed solvent (mass ratio = 1/2)) was in contact with the prism. The refractive index n2 of the component insoluble in the THF / Cy mixed solvent (mass ratio = 1/2) in the photosensitive resin composition in the present embodiment is 1.560 from the viewpoint of low moisture permeability. From the viewpoint of low-temperature developability, it is preferably 1.650 or less, more preferably in the range of 1.570 to 1.600, and in the range of 1.574 to 1.590. Is more preferable.

Further, the organic component constituting the photosensitive resin composition in the present embodiment has a molecular weight (M) of an insoluble component when the mass ratio of tetrahydrofuran (THF) / cyclohexane (Cy) mixed solvent is 1 / 1.3. ) Is a high molecular weight component having a molecular weight (M) of 20,000 or more. With respect to this insoluble component, it is preferable that (i) the acid value A1 is 100 mgKOH / g or more and / or (ii) the refractive index n1 is 0.005 or less smaller than the n2. Moreover, it is preferable that acid value A1 is 200 mgKOH / g or less.
A method for obtaining a component 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, 10.0 g of the photosensitive resin composition or its layer was precisely weighed as a sample in a 100 mL Erlenmeyer flask, 39.1 g of tetrahydrofuran (THF) was added thereto, the container was sealed, Stir with a stirrer for 1 hour. After removing insolubles by filtration, 50.9 g of cyclohexane (Cy) is added dropwise to the THF solution over 10 minutes, and the mixture is stirred at 23 ° C. for 1 hour. The suspended solution was subjected to solid-liquid separation with a centrifugal separator, the insoluble matter was washed three times with 50 g of cyclohexane, and vacuum-dried at 40 ° C. for 6 hours, whereby a THF / Cy mixed solvent (mass ratio = 1/1. A component insoluble in 3) is obtained.
The acid value A1 and the refractive index n1 of the component soluble in THF and insoluble in the THF / Cy mixed solvent (mass ratio = 1 / 1.3) were measured using the above-mentioned acid value A2 and refractive index n2. It can be performed by the same method as the measurement method.

In the photosensitive resin composition in the present embodiment, in order to achieve both low temperature developability and low moisture permeability, the following (1) to (5):
(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 component insoluble in the THF / Cy mixed solvent (mass ratio = 1/2) is 95 or more,
(3) The refractive index n2 of the component insoluble in the THF / Cy mixed solvent (mass ratio = 1/2) is 1.560 or more,
(4) The acid value A1 of the component 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 component insoluble in the THF / Cy mixed solvent (mass ratio = 1 / 1.3) is 0.005 or more smaller than the n2.
It is preferable to satisfy all of these.

In the photosensitive resin composition in the present embodiment, the following (1) and (2):
(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 the dw / d (log M) value between the molecular weight M = 20000 and the molecular weight M = 5000; R _{20k / 5k} is in the range of 0.20 to 1.50. Both are satisfied.

In the photosensitive resin composition in the present embodiment, the following (1) and (2):
(1) S _{≧ 50k} in the differential molecular weight distribution curve of GPC is in the range of 0.2 to 9.0%,
(2) All satisfy | fill that acid value A2 (mgKOH / g) of the component insoluble in a THF / Cy mixed solvent (mass ratio = 1/2) is 70 or more.

The hydroxyl value (mgKOH / g) of the photosensitive resin composition in the present embodiment is preferably 20 or less, and more preferably 15.0 or less. Since the moisture permeability of the hardened | cured material of the photosensitive resin composition can be reduced because the hydroxyl value of the photosensitive resin composition is 20 or less, the rust prevention property of a conductor improves.
The refractive index of the photosensitive resin composition in the present embodiment is preferably 1.550 or more. Moreover, it is preferable that the refractive index of the photosensitive resin composition layer is 1.630 or less.

<Transfer film>
The photosensitive resin layer according to the present embodiment has a thickness of 40 μm or less, and the absorbance at a wavelength of 365 nm of the photosensitive resin layer is 0.01 to 0.05 per 1 μm of the thickness of the photosensitive resin layer. It is preferable. Since the flexibility deteriorates if the film thickness of the photosensitive resin layer is too thick, the thickness of the photosensitive resin layer is preferably 40 μm or less, from the viewpoint of following the unevenness of the wiring, and from the viewpoint of ensuring rust prevention, 3 μm or more is preferable.

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

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

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

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

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

Application methods include, for example, doctor blade coating method, Meyer bar coating method, roll coating method, screen coating method, spinner coating method, inkjet coating method, spray coating method, dip coating method, gravure coating method, curtain coating method, die coating Examples thereof include a coating method. There are no particular restrictions on the drying conditions of the coating solution, but the drying temperature is preferably 50 ° C. to 130 ° C., and the drying time is preferably 30 seconds to 30 minutes.

In the present embodiment, the transfer film is preferably used to form a protective film for the conductor portion. In this case, the conductor portion is made of a copper electrode, nickel, palladium, silver, titanium, molybdenum, and the like. An alloy electrode with copper or a transparent electrode is more preferable. More specifically, the transfer film can be used as a protective film for the lead-out wiring in the frame area of the touch panel (touch sensor or force sensor) and as a protective film for the copper electrode in the sensing area.

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

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

As said film, the film which consists of film raw materials, such as a polyimide, polyester (PET, PEN), a cycloolefin polymer (COP), is mentioned, for example. The thickness of the film is preferably 10 μm to 100 μm. Moreover, as said copper, the alloy containing copper as a main component other than pure copper can be used. Here, the “main component” means that at least 50% by mass of the alloy is copper. As the alloy metal, for example, an alloy of nickel, palladium, silver, titanium, molybdenum or the like and copper can be cited.
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.

A photosensitive resin layer is formed on the copper layer of the substrate by performing a process of laminating a transfer film on the substrate as described above. When the transfer film has a protective layer, the protective layer is preferably peeled off, and then the transfer film is heat-pressed and laminated on the substrate surface with a laminator. In this case, the transfer film may be laminated only on one side of the substrate surface, or may be laminated on both sides. The heating temperature is generally about 40 ° C to 160 ° C. The thermocompression bonding may be performed using a two-stage laminator provided with two rolls, or may be performed by repeatedly passing the transfer film and the substrate through the roll a plurality of times. . In addition, when a vacuum roll laminator is used, the followability of the protective film to unevenness due to wiring on the substrate is good, and the disadvantage that air is mixed between the transfer film and the substrate can be prevented. On the other hand, when a vacuum roll laminator is used, since the oxygen concentration that suppresses radical polymerization is extremely low, the photopolymerization initiator is cleaved and the dark reaction easily proceeds. Accordingly, the roll temperature is preferably 40 ° C. to 100 ° C., more preferably 40 ° C. to 80 ° C.

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

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

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

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

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

According to this embodiment, the transfer film has good tack, low-temperature laminating properties, low-temperature developability, moisture permeability of the cured film, and adhesion to the conductor base material, and the conductor parts such as wiring and electrodes A photosensitive resin composition and a transfer film suitable for protection can be provided. Such a transfer film is suitable as a solder resist for a protective film such as a wiring for a touch panel, a touch sensor or a force sensor, an electrode, or a printed wiring board.

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

The touch panel substrate having the touch panel electrode can be obtained, for example, by the following procedure. After a metal film is formed on a touch panel substrate such as polyester or COP film by sputtering in the order of ITO and Cu, an etching photosensitive film is pasted on the metal film to form a desired resist pattern, which is unnecessary Cu is removed with an etching solution such as an iron chloride aqueous solution, and the resist pattern is further removed and removed.

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

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

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

First, (A) Preparation of alkali-soluble resin will be described.
<Preparation 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 heated to 75 ° C. in a nitrogen gas atmosphere. Methacrylic acid (MAA) 20% by mass, methyl methacrylate (MMA) 25% by mass, styrene (St) 55% by mass, and an azo polymerization initiator were uniformly added dropwise over 2 hours. After the dropwise addition, the reaction system was continuously stirred at 75 ° C. for 10 hours. After completion of the reaction, the obtained resin solution was diluted with methyl ethyl ketone, the solid content acid value was 130 mgKOH / g, and the weight average molecular weight was about 25,000. An acrylic copolymer solution (solid content: 43% by mass) (A-1) was obtained.

<Preparation of acrylic copolymer (A-2)>
In the same manner as the 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, and the solid content acid value was 130 mgKOH / g, An acrylic copolymer solution (solid content 41% by mass) (A-2) having a weight average molecular weight of about 13,000 was obtained.

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

<Preparation of acrylic copolymer (A'-1)>
Using the same method as the above acrylic copolymer (A-1), using 20% by mass of methacrylic acid, 25% by mass of methyl methacrylate and 55% by mass of styrene, the solid content acid value is 130 mgKOH / g, and the weight average molecular weight. An acrylic copolymer solution (solid content 50% by mass) (A′-1) having an A of about 35,000 was obtained.

<Preparation of acrylic copolymer solution (A'-2)>
Using the same method as the acrylic copolymer (A-1), using 29% by mass of methacrylic acid, 19% by mass of methyl methacrylate, and 52% by mass of styrene, the solid content acid value was 189 mgKOH / g, and the weight average molecular weight An acrylic copolymer solution (solid content: 49 mass%) (A′-2) having an A of about 50,000 was obtained.

<Preparation of acrylic copolymer solution (A'-3)>
In the same manner as for the acrylic copolymer (A-1), solid acid was obtained using 15% by mass of methacrylic acid, 75% by mass of benzyl methacrylate (BzMA), and 10% by mass of hydroxyethyl acrylate (HEA). An acrylic copolymer solution (solid content 50 mass%) (A′-3) having a value of 98 mg KOH / g, a solid content hydroxyl value of 65 mg KOH / g, and a weight average molecular weight of about 20,000 was obtained.

The copolymer composition, weight average molecular weight, acid value, and hydroxyl value of the resulting acrylic copolymer are shown in Table 1. In addition, the measurement of the weight average molecular weight of an acrylic copolymer, an acid value, and a hydroxyl value was performed by the method described in the detail of said <(A) alkali-soluble resin>.

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

Table 2 shows the weight average molecular weight, acid value, and hydroxyl value of the compound containing the carboxyl group and the ethylenically unsaturated group. In addition, the measurement of the weight average molecular weight of the compound containing a carboxyl group and an ethylenically unsaturated group, an acid value, and a hydroxyl value was performed by the method described in the detail of said <(A) alkali-soluble resin>.
(B) The refractive index measurement of the compound containing a carboxyl group and an ethylenically unsaturated group was performed by the following method.
<Refractive index measurement sample preparation method>
(B) A solution of a compound containing a carboxyl group and an ethylenically unsaturated group is uniformly applied to the surface of a 16 μm-thick polyethylene terephthalate film (FB40, manufactured by Toray Industries, Inc.) using a blade coater. It was applied and dried in a dryer at 100 ° C. for 10 minutes to form a uniform resin layer having a thickness of 5 μm on the support, which was cut into 5 cm × 5 cm.
<Refractive index evaluation method>
Using the 532 nm laser light source with the refractive index measuring device (Prism Coupler Model 2010 / M, manufactured by Metricon), the sample produced by the above method was used at any four locations in the plane direction of the sample, and any four in the vertical direction. The refractive index of the place was measured and the average value was computed. The refractive index measurement results are shown in Table 2.
Next, a method for producing an evaluation transfer film of Examples and Comparative Examples will be described, and further, an evaluation method for the obtained transfer film and an evaluation result thereof will be shown.

1. Preparation of Evaluation Transfer Film Evaluation transfer films in Examples and Comparative Examples were prepared as follows.
<Production of transfer film>
In accordance with the composition shown in Tables 4 to 6 below, each component was weighed into a 250 ml plastic bottle, charged with methyl ethyl ketone so that the solid content concentration became 53% by mass, dissolved and stirred for 5 hours using a stirrer. Mixing was performed to obtain a photosensitive resin composition. Thereafter, the photosensitive resin composition was passed through a 3 μm filter to prepare photosensitive resin composition preparation solutions (Examples 1 to 22 and Comparative Examples 1 to 10).
The photosensitive resin composition preparation liquid was uniformly applied to the surface of a 16 μm-thick polyethylene terephthalate film (FB40, manufactured by Toray Industries, Inc.) as a support using a blade coater, and 10% in a dryer at 95 ° C. It was dried for a minute to form a uniform photosensitive resin layer on the support. The thickness of the photosensitive resin layer was 8 μm and 40 μm. Next, a transfer film for evaluation was obtained by laminating a 33 μm thick polyethylene film (manufactured by Tamapoly Co., Ltd., GF-858) as a protective film on the surface of the photosensitive resin layer. The following evaluation results are shown in Tables 4 and 5. Tables 1 to 3 show the names of the material components in the photosensitive resin composition preparations represented by abbreviations in Tables 4 to 6.

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

A differential molecular weight distribution curve is derived from the GPC elution curve by the above-described method, and (i) the ratio of the molecular weight M = 20000 to the molecular weight M = 5000 dw / d (logM) value; R _{20k / 5k} , and (ii) the molecular weight M = The ratio of the area of the region having a molecular weight M ≧ 50000 when the area of the region of 2000 or more is 100%; S _{≧ 50k} was calculated. The differential molecular weight distribution curve of Example 5 is shown in FIG. Tables 4 to 6 show R _{20k / 5k} values and S _{≧ 50k} values of Examples 1 to 22 and Comparative Examples 1 to 10.

3. Physical property measurement of THF / Cy (mass ratio = 1/2) insoluble component in photosensitive resin composition The protective film of the transfer film obtained above is peeled off, and 10.0 g of the photosensitive resin layer is placed in a 100 mL Erlenmeyer flask. The sample was weighed, 30.0 g of tetrahydrofuran (THF) was added thereto, the container was sealed, and the mixture was stirred with a stirrer at 23 ° C. for 1 hour. After removing insolubles 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 with a high-speed centrifuge at 5000 rpm for 10 minutes, and the supernatant was removed by decantation. The insoluble component was washed 3 times with 50 g of Cy, and vacuum-dried at 40 ° C. for 6 hours to obtain a component insoluble in the THF / Cy mixed solvent (mass ratio = 1/2).
(1) Measurement of acid value A2 1.0 g of the insoluble component obtained above was precisely weighed and dissolved in 9.0 g of THF. Then, the acid value was measured by neutralization titration with an ethanol solution of 0.1 mol / L potassium hydroxide using an automatic titrator (“COM-555” manufactured by Hiranuma Sangyo Co., Ltd.).
(2) Refractive Index n2 Measurement 1.0 g of the insoluble component obtained above was dissolved in 9.0 g of a mixed solvent of methyl ethyl ketone / propylene glycol-1-monomethyl ether-2-acetate (mass ratio 2/1). This solution was applied on a 16 μm-thick polyethylene terephthalate film (manufactured by Toray Industries, Inc., FB40) with a bar coater and dried in an oven at 100 ° C. for 10 minutes to obtain an insoluble component layer having a thickness of 2 μm. The refractive index was measured using a prism coupler (laser refractive index measurement model 2010, laser light wavelength: 532 nm) manufactured by Metricon, with the insoluble component layer in contact with the prism.
In addition, as the measurement of the physical properties of the THF / Cy (mass ratio = 1 / 1.3) insoluble component in the photosensitive resin composition, the acid value A1 and the refractive index n1 are also measured by the acid value A2 and the refractive index. The same method as that for measuring n2 was used.

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 the photosensitive resin composition which is a measurement target of the hydroxyl value was collected from the transfer film and precisely weighed. 10 mL of a 10% by mass acetic anhydride pyridine solution was added to the precisely weighed photosensitive resin composition to dissolve it uniformly and heated at 100 ° C. for 1 hour. After heating, 10 mL of water and 10 mL of pyridine are added and heated at 100 ° C. for 10 minutes. Thereafter, the measurement was performed by neutralization titration with an ethanol solution of 0.5 mol / L potassium hydroxide using an automatic titrator (“COM-1700” manufactured by Hiranuma Sangyo Co., Ltd.).
The hydroxyl value was calculated by the following formula.
Hydroxyl value = (A−B) × f × 28.05 / sample (g) + acid value {where A represents the amount (mL) of 0.5 mol / L potassium hydroxide ethanol solution used in the blank test. , B represents the amount (mL) of 0.5 mol / L potassium hydroxide ethanol solution used for titration, and f represents a factor. }
Tables 4 to 6 show the hydroxyl value measurement results of the photosensitive resin composition layers in Examples and Comparative Examples.

5. Evaluation of tack property The tack property of the transfer film was evaluated as follows.
First, the prepared transfer film is allowed to stand for 24 hours in an environment of 23 ° C. and 50% RH, and then the protective film is peeled off at a speed of 10 cm / second, so that the photosensitive resin composition is attached to the surface of the protective film. Was confirmed visually. Next, absorbent cotton was rubbed on the surface of the photosensitive resin composition layer after peeling the protective film, and the surface of the photosensitive resin composition layer was visually observed.
<Evaluation method>
A: The photosensitive resin composition does not adhere to the surface of the peeled protective film, and the absorbent cotton does not stick to the surface of the photosensitive resin composition layer.
B: The photosensitive resin composition does not adhere to the surface of the peeled protective film, but the lint of absorbent cotton sticks to the surface of the photosensitive resin composition layer.
C: The photosensitive resin composition adheres to the surface of the peeled protective film.

6). Evaluation of Laminating Property The laminating property of the transfer film was evaluated as follows.
While removing the protective film of the transfer film, a hot roll laminator (VA-400III, manufactured by Taisei Laminator Co., Ltd.) is formed on the copper surface (size: 5 cm × 10 cm) of the substrate on which the resin, ITO and sputtered copper are laminated in this order. Was laminated under the condition of a roll temperature of 80 ° C. The air pressure was set to 0.4 MPa, and the laminating speed was set to 1.5 m / min. Evaluation was carried out as A when the transfer film was adhered to the copper surface of the substrate and as B when it was not adhered at 80 ° C.

7). Developability <Sample preparation method>
The sample after the evaluation of the laminate property was used as it was. For the level at which the transfer film did not adhere to the substrate at 80 ° C., a sample laminated at a roll temperature of 100 ° C. was prepared.
The laminated sample was allowed to stand for 15 minutes, and then a PET mask and a stuber 21-step tablet on the support film (optical density 0.00 was the first step, and the optical density was 0.15 for each step. Incremental step tablets) were placed side by side, the optimum exposure amount of each composition was determined from the PET mask and step tablet side, and exposure was performed with a parallel light exposure machine (HMW-801, manufactured by Oak Manufacturing Co., Ltd.). As the PET mask, a mask having a pattern in which an unexposed portion becomes a circular hole was used. Next, after leaving still for 15 minutes or more, the support is peeled off, and using a developing device manufactured by Fuji Kiko Co., Ltd., a 1% by mass Na of 28 ° C. to 30 ° C. at a developing spray pressure of 0.12 MPa with a full cone type nozzle. _{A 2} CO ₃ aqueous solution was sprayed for 45 seconds and developed to dissolve and remove the unexposed portions of the photosensitive resin layer. At that time, the water washing step is carried out at the same time as the development step with a flat type nozzle at a water washing spray pressure of 0.12 MPa, and the water washed sample is dried by air blow to prepare a sample for evaluation of developability. Produced. The optimum exposure amount is defined as an exposure amount such that the number of steps remaining in the film when the exposure is performed through the stuber 21-step tablet becomes 7 to 8 steps.
<Evaluation method>
The base material surface state of the part where the photosensitive layer of the produced protective film-coated substrate was removed was observed with a microscope, and determined as follows.
A: No development residue on the copper of the base material under development conditions of 28 ° C.
B: Although there is a development residue on the base copper under the development conditions of 28 ° C., there is no development residue on the base copper under the development conditions of 30 ° C.
C: Development residue is generated even under development conditions of 30 ° C.
In developability evaluation, it is considered that the results up to rank B are practically good results in the touch panel manufacturing process.

8). Moisture permeability test <sample preparation method>
While peeling off the protective film of the transfer film having a thickness of the photosensitive resin layer of 40 μm, Lamination was performed on 4 filter papers (manufactured by Advantech) using a hot roll laminator (manufactured by Taisei Laminator Co., Ltd., VA-400III). The roll temperature was set to 80 ° C. (100 ° C. when the above-described evaluation of the laminate property was “x”), the air pressure was set to 0.4 MPa, and the lamination speed was set to 1.0 m / min. After leaving still for 15 minutes, the optimal exposure amount of each composition was exposed to the whole surface with the scattered light exposure machine from the support film side of the protective film. After leaving still for 30 minutes, the support film is peeled off, exposed with an exposure amount of 350 mJ / cm ² from the photosensitive layer side with a scattered light exposure machine, and then processed at 150 ° C. for 30 minutes in a hot air circulating oven. A sample was prepared. The optimum exposure amount has the same definition as in the sample preparation method for developing property evaluation.
<Evaluation method>
The measurement of moisture permeability was performed according to the cup method of JIS Z0208, and the moisture permeability conditions were a temperature of 65 ° C./a humidity of 90%.
A: Moisture permeability of 150 to 200 g / (m ² · day)
B ... moisture permeability 201-250 g / (m ² · day)
C: Moisture permeability of 251 to 300 g / (m ² · day)

9. Adhesion evaluation (cross cut test)
<Sample preparation method>
While peeling off the protective film of the transfer film having a photosensitive resin layer thickness of 8 μm, a hot roll laminator (Daisei Laminator (3cm × 3cm)) is formed on the alloy surface (size: 3 cm × 3 cm) of the substrate on which the resin and sputtered copper nickel alloy are laminated in this order. Laminate using VA-400III) manufactured by KK The roll temperature was 80 ° C. (the level of the above-mentioned laminating evaluation is 100 ° C.), the air pressure was 0.4 MPa, and the laminating speed was 1.0 m / min. After leaving still for 15 minutes, the optimal exposure amount of each composition was exposed to the whole surface with the scattered light exposure machine from the support film side of the protective film. The optimum exposure amount has the same definition as in the sample preparation method for developing property evaluation.
Then, after leaving still for 30 minutes, the support film was peeled off, and using a developing device manufactured by Fuji Kiko Co., Ltd., a 1% by mass Na ₂ CO at 30 ° C. with a developing spray pressure of 0.12 MPa using a full cone type nozzle. _Three aqueous solutions were sprayed for 45 seconds and developed, and the unexposed portion of the photosensitive resin layer was dissolved and removed. At that time, the water washing step was performed at the same time as the development step with a water spray pressure of 0.12 MPa with a flat type nozzle, and the washed sample was dried by air blow.
The developed sample is exposed with a light exposure of 350 mJ / cm ² from the photosensitive resin layer side with a scattered light exposure machine, and then processed at 150 ° C. for 30 minutes in a hot air circulating oven for evaluation of adhesion. A sample was made.
<Evaluation method>
The sample after the above treatment was subjected to a 100 mass cross-cut test with reference to JIS standard K5400. Using a cutter knife on the test surface, make a 1 x 1 mm square cut on the grid, and firmly press Mending Tape # 810 (manufactured by 3M Co., Ltd.) on the grid, so that the end of the tape is approximately 0 °. After gently peeling off at an angle, the cross-cut state was observed, and cross-cut adhesion was evaluated according to the following score.
A: Peeling is less than 5% in the entire area.
B: There is peeling of 5 to 35% in the entire area.
C: There is peeling of 35% or more in the entire area.
In the cross-cut test, Rank A is considered to be a good result as a protective film for conductors in practice.

From the results shown in Tables 4 and 5, Examples 1 to 22 satisfy the requirements specified in the present invention, so that tackiness as a transfer film, low-temperature laminating property and low-temperature developability, and moisture permeability as a cured film are achieved. It is shown that the adhesiveness with the conductor base material is excellent. Further, Example 5 and Example 6 are the difference between the component (B-1) and the component (B-2). By adjusting the hydroxyl value of the composition to 15 mgKOH / g or less, the cured film It turns out that it is excellent in moisture permeability.

On the other hand, Comparative Examples 1 to 10 shown in Table 5 do not satisfy any of the requirements stipulated in the present invention. Therefore, tackiness as a transfer film, low temperature laminating or low temperature developability, and as a cured film It has been shown that either the moisture permeability or the adhesion to the conductor base material is inferior. Comparative Example 1 and Comparative Example 9 are photosensitive resin compositions having an A / B mass ratio increased to 6.38. The low-temperature laminating property and low-temperature developability of the transfer film and the moisture permeability of the cured product were each Example 1. The result was inferior to 2. Comparative Examples 2 and 3 are photosensitive resin compositions in which the A / B mass ratio was lowered to 0 to 0.12, but the tackiness and low-temperature developability of the transfer film, and the close contact with the conductor substrate as a cured film The result was inferior. Comparative Example 4 contains (A′-1), which does not satisfy the molecular weight definition of the component (A) defined in the present invention, but the low-temperature developability is inferior to Example 10. became. Although the component (B) was not blended in the photosensitive resin composition of Comparative Example 5, the results were inferior in low-temperature laminating properties and low-temperature developability as a transfer film. In Comparative Example 6, the component (A) was not added and only the component (B-3) was increased. However, compared with Example 17 or Example 18, the tackiness as a transfer film, the low temperature developability, and It became a result inferior to adhesiveness with the conductor base material as a cured film. In Comparative Example 7, the component (A) was not added, and instead the weight average molecular weight and acid value satisfied the definition of the component (A), and the skeleton of any one of the general formulas (1) to (3) The component (B′-1), which is a modified epoxy acrylate acid not included in the structure, was added, but the tackiness and low-temperature developability as a transfer film were poor. From this, it was found that the epoxy acrylate modified product is not compatible with the component (A) of the present invention. Comparative Example 8 does not satisfy the requirements of the weight average molecular weight and refractive index of the component (B) of the present invention, and does not contain any skeleton of the general formulas (1) to (3) in the structure (B′-2 ) Component was added, but the low temperature developability as a transfer film and the moisture permeability of the cured film were inferior. In Comparative Example 10, the component (A′-3) that does not satisfy the acid value of the component (A) of the present invention was added, but the results were poor in low-temperature developability and adhesion as a transfer film. . Further, since the component (A′-3) has a high hydroxyl value, the moisture permeability was inferior.

From the above results, the A / B mass ratio, which is a requirement defined in the present invention, is in the range of 0.18 to 6.0, as tackiness as a transfer film, low-temperature laminating property, low-temperature developability, and curing. It was found to be important for satisfying the moisture permeability as a film and the adhesion to the conductor base material. In particular, the present inventors believe that the low-temperature developability as a transfer film is a surprising result in that both the A / B mass ratio is significantly deteriorated when the A / B mass ratio is less than 0.18 and more than 6.0. Think.

In Examples 1 to 22, in order to achieve both low-temperature developability and low moisture permeability, the following conditions:
(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 (mg KOH / g) of the component insoluble in THF / Cy (mass ratio = 1/2) is 95 or more;
(3) The refractive index n2 of the component insoluble in THF / Cy (mass ratio = 1/2) is 1.560 or more;
(4) The acid value A1 of the component 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 component insoluble in the THF / Cy mixed solvent (mass ratio = 1 / 1.3) is 0.005 or less smaller than the above n2; Humidity was good. On the other hand, since Comparative Examples 1 to 10 did not satisfy all of the above (1) to (5), at least one of low temperature developability and low moisture permeability was inferior.

Examples 1 to 22 and Comparative Examples 8 and 10 have the following conditions in order to achieve both tackiness as a transfer film and low-temperature laminating properties:
(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 the dw / d (log M) values of the molecular weight M = 20000 and the molecular weight M = 5000; R _{20k / 5k} is in the range of 0.20 to 1.50;
Both the tackiness and the low-temperature laminating property as a transfer film were satisfactory. On the other hand, Comparative Examples 1 to 7 and Comparative Example 9 did not satisfy all of the above (1) and (2), and therefore either the tack property as a transfer film or the low temperature laminate property was inferior.

Examples 1 to 22 and Comparative Examples 1, 4, 5, and 7 to 9 are excellent in adhesion to the conductor base material.
(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 component insoluble in the THF / Cy mixed solvent (mass ratio = 1/2) is 70 or more;
Therefore, the adhesion to the conductor base material was good. In Comparative Example 2, S _{≧ 50k} was 0.2%, but the adhesion with the conductor base material was slightly inferior. In Comparative Examples 3 and 6, S _{≧ 50k} was 0%, but the adhesion to the conductor substrate was inferior. In Comparative Example 10, the acid value A2 (mg KOH / g) of the component insoluble in the THF / Cy mixed solvent (mass ratio = 1/2) was 69, but the adhesion to the conductor substrate was inferior.

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

By using the photosensitive resin composition and the transfer film according to the present invention, both the rust prevention property and the low-temperature developability are good, and it is suitable for the protection of conductor parts such as wiring and electrodes, and the touch panel, touch sensor, or force. It can be widely used as a protective film for wiring, electrodes and the like for sensor applications and solder resist applications for printed wiring boards.

Claims

A transfer film for forming a conductor protective film comprising a support film and a photosensitive resin composition layer, wherein the photosensitive resin composition layer comprises the following components:
(A) 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;
Containing
The (A) alkali-soluble resin has a weight average molecular weight of 11,000 or more and 29,000 or less, and an acid value of 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 to 9,500, an acid value of 60 mgKOH / g or more, and a refractive index of 1.570 or more. ,
A conductor characterized in that the mass ratio (A) / (B) of the (A) alkali-soluble resin to the compound containing (B) a carboxyl group and an ethylenically unsaturated group is 0.18 to 6.0. Transfer film for forming a protective film.
The transfer film according to claim 1, wherein the acid value of the (A) alkali-soluble resin is 200 mgKOH / g or less.
The transfer film according to claim 1 or 2, wherein the acid value of the compound (B) containing a carboxyl group and an ethylenically unsaturated group is 200 mgKOH / g or less and a refractive index is 1.650 or less.
The transfer film according to any one of claims 1 to 3, wherein the photosensitive resin composition layer has a hydroxyl value of 15.0 mgKOH / g or less.
The transfer film according to claim 4, wherein the photosensitive resin composition layer has a hydroxyl value of 0.01 mg KOH / 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 (A) alkali-soluble resin contains a structure derived from (meth) acrylic acid in an amount of 12% by mass to 30% by mass and a structure derived from styrene or a derivative thereof in an amount of 30% by mass to 80% by mass. 8. The transfer film according to any one of 1 to 7.
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 either a protective film for a touch panel or a protective film for a force sensor.
A conductor part protective film-forming transfer film comprising a support film and a photosensitive resin composition layer, wherein the photosensitive resin composition layer comprises the following (I) and (II):
(I) In a differential molecular weight distribution curve obtained from a GPC elution 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 between the molecular weight M = 20000 and the molecular weight M = 5000 is in the range of 0.20-1.50, and (ii) in the differential molecular weight distribution curve The area ratio S ≧ 50k of the region having the molecular weight M ≧ 50000 is 1.0 to 9.0% when the area of the region having the molecular weight M ≧ 2000 is 100%; and (II) tetrahydrofuran at 23 ° C. (I) Acid value A2 is 95 mgKOH / g or more, and (ii) Refractive index n2 is 1.560 or more, which is soluble in water and insoluble in tetrahydrofuran / cyclohexane (mass ratio = 1/2) mixed solvent Is
A transfer film for forming a conductor protective film that satisfies the requirements.
The transfer film for forming a conductor protective film according to claim 11, further comprising the following (III):
(III) A component that is soluble in tetrahydrofuran and insoluble in a tetrahydrofuran / cyclohexane (mass ratio = 1 / 1.3) mixed solvent at 23 ° C. (i) has an acid value A1 of 100 mgKOH / g or more; ii) The transfer film for forming a conductor protective film according to claim 11, wherein the refractive index n1 satisfies 0.005 or more smaller than the n2.
The transfer film for forming a conductor protective film according to claim 12, wherein the 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 molecular weight M≥50000 in the differential molecular weight distribution curve includes an aromatic ring.
The transfer film according to any one of claims 11 to 14, which is used for either a protective film for a touch panel or a protective film for a force sensor.
A transfer film for forming a conductor protective film comprising a support film and a photosensitive resin composition layer, wherein the photosensitive resin composition layer comprises the following (II) and (III):
(II) a component that is soluble in tetrahydrofuran and insoluble in a tetrahydrofuran / cyclohexane (mass ratio = 1/2) mixed solvent at 23 ° C. (i) has an acid value A2 of 95 mgKOH / g or more, and (ii) The refractive index n2 is 1.560 or more;
(III) A component that is soluble in tetrahydrofuran and insoluble in a tetrahydrofuran / cyclohexane (mass ratio = 1 / 1.3) mixed solvent at 23 ° C. (i) has an acid value A1 of 100 mgKOH / g or more; ii) A transfer film for forming a conductor protective film that satisfies a refractive index n1 of 0.005 or more smaller than n2.
The transfer film for forming a conductor protective film according to claim 16, wherein the acid value A1 is 200 mgKOH / g or less.
The transfer film according to claim 16 or 17, which is used for either a protective film for a touch panel or a protective film for a force sensor.
A transfer film for forming a conductor protective film comprising a support film and a photosensitive resin composition layer, wherein the photosensitive resin composition layer comprises the following components:
(A) 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;
Containing
The (A) alkali-soluble resin has a weight average molecular weight of 11,000 or more and 29,000 or less, and an acid value of 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 to 9,500, an acid value of 60 mgKOH / g or more, and the following general formulas (1) to (3): ):

Including at least the structure according to any one of
A conductor characterized in that the mass ratio (A) / (B) of the (A) alkali-soluble resin to the compound containing (B) a carboxyl group and an ethylenically unsaturated group is 0.18 to 6.0. Transfer film for forming a protective film.
The transfer film according to claim 19, wherein the acid value of the (A) alkali-soluble resin is 200 mgKOH / g or less.
The transfer film according to claim 19 or 20, wherein an acid value of the compound (B) containing a carboxyl group and an ethylenically unsaturated group is 200 mgKOH / g or less.
The transfer film according to claim 19, wherein the photosensitive resin composition layer has a hydroxyl value of 15.0 mg KOH / g or less.
The transfer film according to claim 22, wherein the photosensitive resin composition layer has a hydroxyl value of 0.01 mgKOH / g or more.
The transfer film according to any one of claims 19 to 23, wherein a 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 (A) alkali-soluble resin contains a structure derived from (meth) acrylic acid in an amount of 12% by mass to 30% by mass and a structure derived from styrene or a derivative thereof in an amount of 30% by mass to 80% by mass. The transfer film according to any one of 1 to 25.
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 as either a protective film for a touch panel or a protective film for a force sensor.
A pattern production method, wherein a pattern is produced by laminating, exposing and developing the transfer film according to any one of claims 1 to 28 on a substrate.
A method for producing a cured film pattern, comprising subjecting a pattern obtained by the pattern production method according to claim 29 to post-exposure treatment and / or heat treatment.
A method for manufacturing a device having a touch panel display device or a touch sensor, wherein the cured film pattern obtained by the method for manufacturing a cured film pattern according to claim 30 is used.