KR20240090361A - Transfer film, laminate having a conductor pattern and method of manufacturing the laminate having a conductor pattern, method of manufacturing the transfer film - Google Patents

Abstract

The object of the present invention is to provide a transfer film in which winding defects in the protective film are unlikely to occur when peeling and winding the protective film, and occurrence of pattern defects is suppressed during pattern formation. The transfer film of the present invention is a transfer film having a temporary support, a photosensitive composition layer, and a protective film in this order, wherein the protective film contains polypropylene, and the surface of the protective film on the photosensitive composition layer side is The arithmetic mean roughness Ra1 is smaller than the arithmetic mean roughness Ra2 of the surface of the protective film on the side opposite to the photosensitive composition layer.

Description

Transfer film, laminate having a conductor pattern and method of manufacturing the laminate having a conductor pattern, method of manufacturing the transfer film

The present invention relates to a transfer film, a laminate with a conductor pattern, a method of manufacturing the laminate with a conductor pattern, and a method of manufacturing the transfer film.

In display devices equipped with a touch panel such as a capacitive input device (organic electroluminescence (EL) display devices, liquid crystal display devices, etc.), an electrode pattern corresponding to a sensor in the viewing area and a peripheral wiring portion are used. and conductive layer patterns such as wiring of the extraction wiring portion are provided inside the touch panel. Also, in printed circuit board wiring, etc., wiring patterns are formed through etching and plating processes.

In general, the formation of a patterned layer requires a small number of steps to obtain the required pattern shape, so a photosensitive composition layer is placed on an arbitrary substrate using a transfer film, and a mask is applied to the photosensitive composition layer. The method of developing after exposing to light is widely used.

For example, Patent Document 1 discloses a photosensitive element (transfer film) made of a support film (support), a photosensitive resin composition layer (photosensitive composition layer), and a protective film, and a photosensitive element that satisfies predetermined requirements.

Patent Document 1: Japanese Patent Publication No. 2003-248320

When using a transfer film with a protective film, the protective film is peeled. At this time, the peeled protective film is often wound into a roll, but from the viewpoint of productivity, it is preferable that winding defects are unlikely to occur.

Additionally, when forming a pattern using a transfer film, it is required that the occurrence of pattern defects be suppressed.

As a result of the present inventor's examination of the transfer film disclosed in Patent Document 1, it was found that there was room for improvement in both the ease of winding up the protective film and the suppression of pattern defect occurrence.

Therefore, the object of the present invention is to provide a transfer film in which defective winding of the protective film is unlikely to occur when peeling and winding the protective film, and occurrence of pattern defects is suppressed during pattern formation.

In addition, the present invention also aims to provide a laminate with a conductor pattern, a method for manufacturing a laminate with a conductor pattern, and a method for manufacturing a transfer film.

The present inventor has completed the present invention as a result of intensive studies to solve the above problems. In other words, it was found that the above problem can be solved by the following configuration.

[1] A transfer film having a support, a photosensitive composition layer, and a protective film in this order,

The protective film includes polypropylene,

A transfer film wherein the arithmetic mean roughness Ra1 of the surface of the protective film on the photosensitive composition layer side is smaller than the arithmetic mean roughness Ra2 of the surface of the protective film on the side opposite to the photosensitive composition layer.

[2] The transfer film according to [1], wherein the arithmetic mean roughness Ra1 is 0.050 μm or less.

[3] The transfer film according to [1] or [2], wherein the arithmetic mean roughness Ra2 is greater than 0.050 μm.

[4] The transfer film according to any one of [1] to [3], wherein the arithmetic mean roughness Ra2 is less than 0.150 μm.

[5] The transfer film according to any one of [1] to [4], wherein the protective film has a thickness of 10 to 30 μm.

[6] A laminate having a conductor pattern formed using the transfer film according to any one of [1] to [5].

[7] a peeling process of peeling off the protective film from the transfer film according to any one of [1] to [5] to expose the surface of the photosensitive composition layer;

A bonding step of bonding the transfer film and the substrate having the conductive layer so that the exposed surface of the photosensitive composition layer is in contact with the conductive layer of the substrate having the conductive layer on the surface;

An exposure process of exposing the photosensitive composition layer,

A development process of performing a development treatment on the exposed photosensitive composition layer to form a resist pattern;

an etching process of performing an etching process on the conductive layer in a region where the resist pattern is not disposed, and a plating process of performing a plating process;

a resist pattern peeling process for peeling off the resist pattern;

In addition, in the case of having the plating process, the method of manufacturing a laminate with a conductor pattern includes a removal process of removing the conductive layer exposed by the resist pattern peeling process and forming a conductor pattern on the substrate. As,

A method for producing a laminate with a conductor pattern, further comprising a provisional support peeling step of peeling off the provisional support between the bonding step and the exposure step, or between the exposure step and the development step.

[8] A process of forming a photosensitive composition layer on a support,

A method for producing a transfer film comprising the step of bonding a protective film to a side of the photosensitive composition layer opposite to the support,

The protective film includes polypropylene,

A method for producing a transfer film, wherein the arithmetic average roughness Ra1 of the surface of the protective film on the photosensitive composition layer side is smaller than the arithmetic average roughness Ra2 of the surface of the protective film on the side opposite to the photosensitive composition layer.

According to the present invention, it is possible to provide a transfer film in which defective winding of the protective film is unlikely to occur when peeling and winding the protective film, and occurrence of pattern defects is suppressed during pattern formation.

Moreover, according to the present invention, a laminated body with a conductor pattern, a method for manufacturing a laminated body with a conductor pattern, and a method for manufacturing a transfer film can also be provided.

1 is a schematic diagram showing an example of the structure of the transfer film of the first embodiment.
Fig. 2 is a schematic diagram showing an example of the structure of the transfer film of the second embodiment.

Hereinafter, the present invention will be described in detail.

The description of the structural requirements described below may be based on representative embodiments of the present invention, but the present invention is not limited to such embodiments.

Below, the meaning of each description in this specification is shown.

In this specification, the numerical range indicated using “~” means a range that includes the numerical values written before and after “~” as the lower limit and upper limit.

In this specification, in the numerical range described stepwise, the upper limit or lower limit value described as a predetermined numerical range may be replaced with the upper limit or lower limit value of another numerical range described stepwise. In addition, in the numerical range described in this specification, the upper limit or lower limit described in the predetermined numerical range may be replaced with the value shown in the examples.

In this specification, the term "process" is included in this term not only as an independent process, but also when the intended purpose of the process is achieved even if it cannot be clearly distinguished from other processes.

In this specification, “transparent” means that the average transmittance of visible light with a wavelength of 400 to 700 nm is 80% or more, and is preferably 90% or more.

In this specification, the transmittance is a value measured using a spectrophotometer, and can be measured, for example, using a spectrophotometer U-3310 manufactured by Hitachi Seisakusho Co., Ltd.

In this specification, unless otherwise specified, the weight average molecular weight (Mw) and number average molecular weight (Mn) are TSKgel GMHxL, TSKgel G4000HxL, or TSKgel G2000HxL (all product names of Tosoh Corporation) as the column, and as the eluent. This is a value converted using polystyrene as a standard material measured by a gel permeation chromatography (GPC) analysis device using THF (tetrahydrofuran), a differential refractometer as a detector, and polystyrene as a standard material.

In this specification, unless otherwise specified, the ratio of polymer structural units is a mass ratio.

In this specification, unless otherwise specified, the molecular weight of a compound with a molecular weight distribution is the weight average molecular weight (Mw).

In this specification, unless otherwise specified, the content of metal elements is a value measured using an inductively coupled plasma (ICP: Inductively Coupled Plasma) spectroscopic analysis device.

In this specification, unless otherwise specified, the refractive index is a value measured using an ellipsometer at a wavelength of 550 nm.

In this specification, unless otherwise specified, color is a value measured using a colorimeter (CR-221, manufactured by Minolta Corporation).

In this specification, “(meth)acryl” is a concept that includes both acrylic and methacryl, and “(meth)acryloxy group” is a concept that includes both an acryloxy group and a methacryloxy group. .

In addition, in this specification, “alkali solubility” means that the solubility of 100 g of a 1% by mass aqueous solution of sodium carbonate at 22°C is 0.1 g or more.

In this specification, “water-soluble” means that the solubility in 100 g of water at pH 7.0 with a liquid temperature of 22°C is 0.1 g or more. Therefore, for example, water-soluble resin refers to a resin that satisfies the above-mentioned solubility conditions.

As used herein, “solid content” of a composition refers to components that form a composition layer formed using the composition, and when the composition includes a solvent (organic solvent, water, etc.), it refers to all components except the solvent. do. In addition, if it is a component that forms a composition layer, the liquid component is also considered a solid content.

[Transfer film]

The transfer film of the present invention has a support, a photosensitive composition layer, and a protective film in this order. Characteristic points of the transfer film of the present invention include that the protective film contains polypropylene, and the arithmetic mean roughness Ra1 of the surface on the photosensitive composition layer side of the protective film is the arithmetic average of the surface on the opposite side to the photosensitive composition layer side of the protective film. The illuminance may be smaller than Ra2.

The mechanism by which the transfer film of the present invention facilitates winding of the protective film when peeling and winding the protective film and suppresses the occurrence of pattern defects during pattern formation is not necessarily clear, but the present inventor speculates as follows. .

It is believed that the transfer film of the present invention has the above characteristic points, so that when peeling and winding the protective film, blocking is unlikely to occur even if the protective film is rolled up in a roll, and winding defects are unlikely to occur.

In addition, by providing the transfer film with the above characteristic points, the occurrence of the above-mentioned winding defect is made difficult, and the irregularities on the surface of the photosensitive composition layer on the protective film side resulting from the above-mentioned arithmetic mean roughness Ra1 become small. As a result, it is thought that when the photosensitive composition layer is transferred to another member using a transfer film, bubbles, etc. are unlikely to be generated at the interface between the other member and the photosensitive composition layer, and pattern defects are unlikely to occur.

Hereinafter, the transfer film of the present invention will be described.

The transfer film of the present invention has a temporary support, a composition layer disposed on the temporary support, and a protective film in this order.

The composition layer is not particularly limited as long as it includes a photosensitive composition layer.

The photosensitive composition layer may be a negative photosensitive composition layer or a chemically amplified photosensitive composition layer, but is preferably a negative photosensitive composition layer.

Additionally, the composition layer may have a single-layer structure or a two-layer or more structure. When the composition layer includes a composition layer other than the photosensitive composition layer, examples of the other composition layer include a thermoplastic resin layer, an intermediate layer, and a refractive index adjustment layer.

An example of an aspect of the transfer film of the present invention is shown below, but is not limited thereto.

(1) “Branched support/photosensitive composition layer/refractive index adjustment layer/protective film”

(2) “Branched support/photosensitive composition layer/protective film”

(3) “Branched support/middle layer/photosensitive composition layer/protective film”

(4) “Branched support/thermoplastic resin layer/middle layer/photosensitive composition layer/protective film”

In addition, in each of the above structures, it is preferable that the photosensitive composition layer is a negative photosensitive composition layer. Moreover, it is preferable that the photosensitive composition layer is a colored resin layer.

The transfer film of the present invention may be used as a transfer film for a wiring protective film or may be used as a transfer film for an etching resist, as will be described later.

When using a transfer film for a wiring protective film, the structure of the transfer film is preferably, for example, the structure (1) or (2) described above. Moreover, when using it as a transfer film for etching resist, it is preferable that the structure of the transfer film is, for example, the structures (2) to (4) mentioned above.

In the case where the composition layer of the transfer film further has another composition layer on the side opposite to the support side of the photosensitive composition layer, the total thickness of the other layers disposed on the side opposite to the support side of the photosensitive composition layer. It is preferably 0.1 to 30%, and more preferably 0.1 to 20%, relative to the thickness of the photosensitive composition layer.

From the viewpoint of suppressing bubble generation in the bonding process described later, the maximum width of the waveform of the transfer film is preferably 300 μm or less, more preferably 200 μm or less, and still more preferably 60 μm or less. Additionally, the lower limit of the maximum width of the waveform is 0 μm or more, preferably 0.1 μm or more, and more preferably 1 μm or more.

The maximum width of the waveform of the transfer film is a value measured by the following procedure.

First, the transfer film is cut in a direction perpendicular to the main surface to a size of 20 cm in height x 20 cm in width, and the protective film is peeled off to produce a test sample. Next, the test sample is placed on a stage with a smooth and horizontal surface so that the surface of the support faces the stage. After standing still, the surface of the test sample is scanned with a laser microscope (for example, VK-9700SP manufactured by Keyence Co., Ltd.) over a square area with one side of the center of the test sample being 10 cm, and a three-dimensional surface image is acquired. The lowest concave height is subtracted from the highest convex height observed in the obtained three-dimensional surface image. The above operation is performed on 10 test samples, and the arithmetic average value is taken as the “maximum waveform width of the transfer film.”

Below, an example of a specific embodiment will be given and the transfer film of the present invention will be described. In addition, the transfer film of the first embodiment below has a structure that can be suitably used as a transfer film for a wiring protective film, and the transfer film of the second embodiment below has a structure that can be used as a transfer film for a wiring protective film and an etching resist. This configuration is suitable for use as a transfer film.

Hereinafter, the fact that winding defects of the protective film are unlikely to occur when peeling and winding the protective film is also referred to as “excellent winding properties of the protective film,” and the suppression of pattern defects during pattern formation is referred to as “pattern defect.” It is also said to have “excellent deterrence properties.”

[Transfer film of first embodiment]

Below, an example of an embodiment of the transfer film of the first embodiment is described.

The transfer film 10 shown in FIG. 1 includes a temporary support 1, a composition layer 2 including a photosensitive composition layer 3 and a refractive index adjustment layer 5, and a protective film 7 in this order. It has

In addition, the transfer film 10 shown in FIG. 1 is in a form in which the refractive index adjustment layer 5 is disposed, but the refractive index adjustment layer 5 does not need to be disposed.

Below, each element constituting the transfer film is explained.

<<Branched body>>

The transfer film has a branched support.

The temporary support is a member that supports the composition layer, and is ultimately removed through peeling treatment.

The branch support may have a single-layer structure or a multi-layer structure.

The temporary support is preferably a film, and more preferably a resin film. As the support, a film that has flexibility and does not cause significant deformation, shrinkage, or elongation under pressure or under pressure and heating is preferable.

Examples of the film include polyethylene terephthalate film (e.g., biaxially stretched polyethylene terephthalate film), polymethyl methacrylate film, cellulose triacetate film, polystyrene film, polyimide film, and polycarbonate film. can be mentioned.

Among them, polyethylene terephthalate film is preferable as the support.

In addition, it is preferable that the film used as a temporary support does not have wrinkles or other deformation, or scratches, etc.

The branched support preferably has high transparency in that pattern exposure can be performed through the branched support, and the transmittance at 313nm, 365nm, 313nm, 405nm, and 436nm is preferably 60% or more, and more preferably 70% or more. , 80% or more is more preferable, and 90% or more is most preferable. Preferred values of transmittance include, for example, 87%, 92%, and 98%.

In terms of pattern formation during pattern exposure through the branched support and transparency of the branched support, it is preferable that the haze of the branched support is small. Specifically, the haze value of the branched support is preferably 2% or less, more preferably 0.5% or less, more preferably 0.4% or less, and especially preferably 0.1% or less. However, in the case where the branched support is peeled off and exposed during the exposure described in the latter part, the haze of the branched support is not limited to this.

In addition, the haze of the branched support is preferably 0.05% or more, and more preferably 0.1% or more from the viewpoint of transportability during production of the branched support.

In addition, the above haze is total light haze (%) based on JIS K 7136:2000, and can be measured as total light haze using a haze meter (device name: HZ-2, manufactured by Suga Shikenki Co., Ltd.) .

As described later, when surface treatment or undercoating treatment is performed on the temporary support, the haze is measured using the value obtained by measuring the temporary support after the above treatment.

In terms of pattern formation during pattern exposure through the branch support and transparency of the branch support, it is preferable that the number of fine particles, foreign substances, and defects contained in the branch support be small. The number of fine particles, foreign substances, and defects with a diameter of 1 μm or more in the support is preferably 50 pieces/10 mm ² or less, more preferably 10 pieces/10 mm ² or less, and even more preferably 3 pieces/10 mm ² or less. , 0/10mm ² is particularly preferred.

The thickness of the branched support is not particularly limited, but is preferably 5 to 300 μm, more preferably 5 to 150 μm, more preferably 5 to 50 μm, and most preferably 5 to 25 μm in terms of ease of handling and versatility.

The thickness of the branched body is calculated as the average value of five arbitrary points measured by cross-sectional observation using a SEM (Scanning Electron Microscope).

In order to improve the adhesion between the temporary support and the composition layer, the side of the temporary support in contact with the composition layer may be surface modified by UV irradiation, corona discharge, plasma, etc.

When the surface is modified by UV irradiation, the exposure amount is preferably 10 to 2000 mJ/cm ² , and more preferably 50 to 1000 mJ/cm ² .

Light sources for UV irradiation include low-pressure mercury lamps, high-pressure mercury lamps, ultra-high pressure mercury lamps, carbon arc lamps, metal halide lamps, xenon lamps, chemical lamps, electrodeless discharge lamps, and light-emitting diodes that emit light in the 150 to 450 nm wavelength band. (LED), etc. may be mentioned. As long as the light irradiation amount can be within this range, there are no particular restrictions on lamp output or illuminance.

In addition, from the viewpoint of adhesion to the composition layer, etc., the temporary support may be subjected to an undercoating treatment to form an undercoating layer containing polyvinylidene chloride resin, styrene butadiene rubber, or gelatin.

Examples of the support include a biaxially stretched polyethylene terephthalate film with a film thickness of 16 μm, a biaxially stretched polyethylene terephthalate film with a film thickness of 12 μm, and a biaxially stretched polyethylene terephthalate film with a film thickness of 9 μm.

Preferred forms of the branchial support include, for example, paragraphs [0017] to [0018] of Japanese Patent Application Laid-Open No. 2014-085643, paragraphs [0019] to [0026] of Japanese Patent Application Publication No. 2016-027363, and International Publication No. 2012. Paragraphs [0041] to [0057] of /081680, and paragraphs [0029] to [0040] of International Publication No. 2018/179370 are mentioned, and the contents of these publications are incorporated herein by reference.

In terms of providing handling properties, a layer (lubricant layer) containing fine particles may be provided on the surface of the support. The lubricant layer may be provided on one side of the branch support or on both sides. The diameter of the particles contained in the lubricant layer is preferably 0.05 to 0.8 μm.

Additionally, the thickness of the lubricant layer is preferably 0.05 to 1.0 μm. Commercially available products of the branch include Lumiror 16KS40, Lumiror 16FB40 (manufactured by Toray Corporation), Cosmoshine A4100, Cosmoshine A4160, Cosmoshine A4300, and Cosmoshine A8300 (manufactured by Toyobo Corporation).

<<Photosensitive composition layer>>

The transfer film has a photosensitive composition layer.

After transferring the photosensitive composition layer onto the transfer target, a pattern can be formed on the transfer target by exposing and developing.

As the photosensitive composition layer, a negative type is preferable. In addition, the negative photosensitive composition layer is a photosensitive composition layer in which the solubility of the exposed portion in the developing solution decreases due to exposure. When the photosensitive composition layer is a negative photosensitive composition layer, the pattern formed corresponds to the cured layer.

Hereinafter, components that may be included in the photosensitive composition layer will be described in detail.

<Binder polymer>

The photosensitive composition layer may contain a binder polymer.

Binder polymers include, for example, (meth)acrylic resin, styrene resin, epoxy resin, amide resin, amide epoxy resin, alkyd resin, phenol resin, ester resin, urethane resin, epoxy resin, and (meth)acrylic acid. Examples include epoxy acrylate resin obtained by reaction, and acid-modified epoxy acrylate resin obtained by reaction of epoxy acrylate resin and an acid anhydride.

One of the preferred embodiments of the binder polymer is (meth)acrylic resin because it is excellent in alkali developability and film formation.

In addition, in this specification, (meth)acrylic resin means resin which has structural units derived from a (meth)acrylic compound. The content of the structural unit derived from the (meth)acrylic compound is preferably 50% by mass or more, more preferably 70% by mass or more, and still more preferably 90% by mass or more, based on the total structural units of the (meth)acrylic resin. do.

The (meth)acrylic resin may be comprised only of structural units derived from the (meth)acrylic compound, or may have structural units derived from polymerizable monomers other than the (meth)acrylic compound. That is, the upper limit of the content of the structural unit derived from the (meth)acrylic compound is 100% by mass or less with respect to all structural units of the (meth)acrylic resin.

Examples of (meth)acrylic compounds include (meth)acrylic acid, (meth)acrylic acid ester, (meth)acrylamide, and (meth)acrylonitrile.

Examples of (meth)acrylic acid ester include (meth)acrylic acid alkyl ester, (meth)acrylic acid tetrahydrofurfuryl ester, (meth)acrylic acid dimethylaminoethyl ester, (meth)acrylic acid diethylaminoethyl ester, (meth)acrylic acid. ) Acrylic acid glycidyl ester, (meth)acrylic acid benzyl ester, 2,2,2-trifluoroethyl (meth)acrylate, and 2,2,3,3-tetrafluoropropyl (meth)acrylate These include, and (meth)acrylic acid alkyl ester is preferable.

Examples of (meth)acrylamide include acrylamide such as diacetone acrylamide.

The alkyl group of the (meth)acrylic acid alkyl ester may be linear or branched. Specific examples include, for example, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, ( Alkyl groups with 1 to 12 carbon atoms, such as octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, undecyl (meth)acrylate, and dodecyl (meth)acrylate. (meth)acrylic acid alkyl esters having .

As the (meth)acrylic acid ester, an alkyl (meth)acrylate having an alkyl group having 1 to 4 carbon atoms is preferable, and methyl (meth)acrylate or ethyl (meth)acrylate is more preferable.

The (meth)acrylic resin may have structural units other than those derived from the (meth)acrylic compound.

The polymerizable monomer forming the structural unit is not particularly limited as long as it is a compound other than a (meth)acrylic compound that can be copolymerized with a (meth)acrylic compound, and examples include styrene, vinyltoluene, and α-methylstyrene. Styrene compounds that may have a substituent on the α position or aromatic ring, vinyl alcohol esters such as acrylonitrile and vinyl-n-butyl ether, maleic acid, maleic anhydride, monomethyl maleate, monomethyl maleate Examples include ethyl, maleic acid monoesters such as monoisopropyl maleate, fumaric acid, cinnamic acid, α-cyanocinnamic acid, itaconic acid, and crotonic acid.

These polymerizable monomers may be used alone or in combination of two or more types.

Moreover, it is preferable that the (meth)acrylic resin has a structural unit which has an acid group from the point of improving alkali developability more. Examples of the acid group include a carboxy group, a sulfo group, a phosphoric acid group, and a phosphonic acid group.

Among them, it is more preferable that the (meth)acrylic resin has a structural unit having a carboxy group, and it is more preferable that it has a structural unit derived from the above-mentioned (meth)acrylic acid.

The content of the structural unit having an acid group (preferably a structural unit derived from (meth)acrylic acid) in the (meth)acrylic resin is 10% relative to the total mass of the (meth)acrylic resin because of excellent developability. Mass % or more is preferable. Moreover, the upper limit is not particularly limited, but from the viewpoint of excellent alkali resistance, 50% by mass or less is preferable, and 40% by mass or less is more preferable.

Moreover, it is more preferable that the (meth)acrylic resin has a structural unit derived from the above-mentioned (meth)acrylic acid alkyl ester.

When having a structural unit derived from an alkyl (meth)acrylic acid, the content of the structural unit derived from an alkyl (meth)acrylic acid in the (meth)acrylic acid is based on the total structural units of the (meth)acrylic resin. 1-90 mass % is preferable, 1-50 mass % is more preferable, and 1-30 mass % is more preferable.

As the (meth)acrylic resin, a resin having both a structural unit derived from (meth)acrylic acid and a structural unit derived from a (meth)acrylic acid alkyl ester is preferable, and a structural unit derived from (meth)acrylic acid is preferable. And a resin composed only of structural units derived from (meth)acrylic acid alkyl ester is more preferable.

Moreover, as the (meth)acrylic resin, an acrylic resin having a structural unit derived from methacrylic acid, a structural unit derived from methyl methacrylate, and a structural unit derived from ethyl acrylate is also preferable.

In addition, the (meth)acrylic resin has at least one type selected from the group consisting of a structural unit derived from methacrylic acid and a structural unit derived from a methacrylic acid alkyl ester in that the effect of the present invention is more excellent. It is preferable to have both a structural unit derived from methacrylic acid and a structural unit derived from a methacrylic acid alkyl ester.

The total content of the structural units derived from methacrylic acid and the structural units derived from methacrylic acid alkyl esters in the (meth)acrylic resin is the overall composition of the (meth)acrylic resin because the effect of the present invention is more excellent. With respect to the unit, 40% by mass or more is preferable, and 60% by mass or more is more preferable. The upper limit is not particularly limited, and may be 100% by mass or less, and is preferably 80% by mass or less.

In addition, since the effect of the present invention is more excellent, the (meth)acrylic resin contains at least one selected from the group consisting of structural units derived from methacrylic acid and structural units derived from methacrylic acid alkyl esters, and acrylic acid. It is also preferable to have at least one type selected from the group consisting of structural units derived from and structural units derived from acrylic acid alkyl esters.

Since the effect of the present invention is more excellent, the total content of the structural units derived from methacrylic acid and the structural units derived from methacrylic acid alkyl esters is the ratio of the structural units derived from acrylic acid and the structural units derived from acrylic acid alkyl esters. With respect to the total content, a mass ratio of 60/40 to 80/20 is preferable.

The (meth)acrylic resin preferably has an ester group at its terminal because it is excellent in the developability of the photosensitive composition layer after transfer.

Additionally, the terminal portion of the (meth)acrylic resin is composed of a portion derived from the polymerization initiator used in the synthesis. (meth)acrylic resin having an ester group at the terminal can be synthesized by using a polymerization initiator that generates a radical having an ester group.

Moreover, as another suitable aspect of the binder polymer, alkali-soluble resin can be mentioned.

For example, from the viewpoint of developability, the binder polymer is preferably a binder polymer with an acid value of 60 mgKOH/g or more.

In addition, the binder polymer is more likely to be a resin having a carboxy group (so-called carboxy group-containing resin) with an acid value of 60 mgKOH/g or more because it is easy to form a strong film by heat cross-linking with the cross-linking component by heating, for example. Preferred, it is more preferable that it is a (meth)acrylic resin having a carboxy group with an acid value of 60 mgKOH/g or more (so-called carboxy group-containing (meth)acrylic resin).

If the binder polymer is a resin having a carboxy group, for example, the three-dimensional crosslinking density can be increased by adding a heat crosslinkable compound such as a block isocyanate compound and heat crosslinking. Additionally, if the carboxy group of the resin having a carboxy group is anhydrized and hydrophobized, wet heat resistance can be improved.

The carboxyl group-containing (meth)acrylic resin with an acid value of 60 mgKOH/g or more is not particularly limited as long as it satisfies the conditions for the acid value, and can be appropriately selected from known (meth)acrylic resins.

For example, among the polymers described in paragraph [0025] of Japanese Patent Application Laid-Open No. 2011-095716, an acrylic resin containing a carboxyl group with an acid value of 60 mgKOH/g or more is described in paragraphs [0033] to [0052] of Japanese Patent Application Laid-Open No. 2010-237589. Among polymers, acrylic resin containing a carboxy group with an acid value of 60 mgKOH/g or more can be preferably used.

Another suitable embodiment of the binder polymer includes styrene-acrylic copolymer.

In addition, in this specification, the styrene-acrylic copolymer refers to a resin having a structural unit derived from a styrene compound and a structural unit derived from a (meth)acrylic compound, and the structural unit derived from the styrene compound. , and, the total content of structural units derived from the (meth)acrylic compound is preferably 30% by mass or more, and more preferably 50% by mass or more, based on the total structural units of the copolymer.

Moreover, the content of the structural unit derived from the styrene compound is preferably 1% by mass or more, more preferably 5% by mass or more, and still more preferably 5 to 80% by mass, based on the total structural units of the copolymer. .

In addition, the content of the structural unit derived from the (meth)acrylic compound is preferably 5% by mass or more, more preferably 10% by mass or more, and 20 to 95% by mass, based on the total structural units of the copolymer. It is more desirable.

The binder polymer preferably has an aromatic ring structure, and more preferably has a structural unit with an aromatic ring structure, because the effect of the present invention is more excellent.

As monomers forming structural units having an aromatic ring structure, monomers having an aralkyl group, styrene, and polymerizable styrene derivatives (e.g., methylstyrene, vinyltoluene, tert-butoxystyrene, acetoxystyrene) rene, 4-vinylbenzoic acid, styrene dimer, and styrene trimer, etc.). Among them, a monomer having an aralkyl group or styrene is preferable. Examples of the aralkyl group include substituted or unsubstituted phenylalkyl groups (excluding benzyl groups), substituted or unsubstituted benzyl groups, and substituted or unsubstituted benzyl groups are preferred.

Examples of monomers having a phenylalkyl group include phenylethyl (meth)acrylate.

Examples of the monomer having a benzyl group include (meth)acrylate having a benzyl group, such as benzyl (meth)acrylate, chlorobenzyl (meth)acrylate, etc.; Vinyl monomers having a benzyl group, such as vinylbenzyl chloride and vinylbenzyl alcohol, are included. Among them, benzyl (meth)acrylate is preferable.

Moreover, it is more preferable that the binder polymer has a structural unit (a structural unit derived from styrene) represented by the following formula (S) because the effect of the present invention is more excellent.

[Formula 1]

When the binder polymer has a structural unit having an aromatic ring structure, the content of the structural unit having an aromatic ring structure is 5 to 90% by mass based on the total structural units of the binder polymer because the effect of the present invention is more excellent. It is preferable, 10 to 70 mass% is more preferable, and 20 to 60 mass% is more preferable.

In addition, the content of the structural unit having an aromatic ring structure in the binder polymer is preferably 5 to 70 mol%, and 10 to 60 mol%, relative to all structural units of the binder polymer, because the effect of the present invention is more excellent. % is more preferable, and 20 to 60 mol% is more preferable.

In addition, the content of the structural unit represented by the above formula (S) in the binder polymer is preferably 5 to 70 mol%, and 10 to 70 mol%, relative to all structural units of the binder polymer, because the effect of the present invention is more excellent. 60 mol% is more preferable, 20 to 60 mol% is more preferable, and 20 to 50 mol% is particularly preferable.

In addition, in this specification, when the content of the "structural unit" is defined as a molar ratio, the "structural unit" is assumed to have the same meaning as the "monomer unit." In addition, in this specification, the "monomer unit" may be modified after polymerization through a polymer reaction or the like. The same applies below.

The binder polymer preferably has an aliphatic hydrocarbon ring structure because the effect of the present invention is more excellent. That is, it is preferable that the binder polymer has structural units having an aliphatic hydrocarbon ring structure. The aliphatic hydrocarbon ring structure may be monocyclic or polycyclic. Among them, it is more preferable that the binder polymer has a ring structure in which two or more aliphatic hydrocarbon rings are fused.

Examples of rings constituting the aliphatic hydrocarbon ring structure in the structural unit having the aliphatic hydrocarbon ring structure include tricyclodecane ring, cyclohexane ring, cyclopentane ring, norbornene ring, and isophorone ring. You can.

Among them, since the effect of the present invention is more excellent, a ring in which two or more aliphatic hydrocarbon rings are fused is preferable, and a tetrahydrodicyclopentadiene ring (tricyclo[5.2.1.0 ^2,6 ]decane ring) is preferable. It is more desirable.

Monomers that form structural units having an aliphatic hydrocarbon ring structure include dicyclopentanyl (meth)acrylate, cyclohexyl (meth)acrylate, and isobornyl (meth)acrylate.

In addition, since the effect of the present invention is more excellent, the binder polymer preferably has a structural unit represented by the formula (Cy) below, and a structural unit represented by the formula (S) and the formula (Cy) below. It is more desirable to have structural units that appear.

[Formula 2]

In formula (Cy), R ^M represents a hydrogen atom or a methyl group, and R ^Cy represents a monovalent group having an aliphatic hydrocarbon ring structure.

R ^M in formula (Cy) is preferably a methyl group.

R ^Cy in the formula (Cy) is preferably a monovalent group having an aliphatic hydrocarbon ring structure of 5 to 20 carbon atoms, and has an aliphatic hydrocarbon ring structure of 6 to 16 carbon atoms, because the effect of the present invention is more excellent. It is more preferable that it is a monovalent group having an aliphatic hydrocarbon ring structure of 8 to 14 carbon atoms.

In addition, the aliphatic hydrocarbon ring structure in R ^Cy of formula (Cy) has a cyclopentane ring structure, a cyclohexane ring structure, and a tetrahydrodicyclopentadiene ring structure because the effect of the present invention is more excellent. , it is preferably a norbornene ring structure, or an isophorone ring structure, and more preferably a cyclohexane ring structure, or a tetrahydrodicyclopentadiene ring structure, and a tetrahydrodicyclopentadiene ring structure. It is more desirable.

In addition, the aliphatic hydrocarbon ring structure in R ^Cy of the formula (Cy) is preferably a ring structure in which two or more aliphatic hydrocarbon rings are condensed because the effect of the present invention is more excellent, and the aliphatic hydrocarbon ring structure has 2 to 4 rings. It is more preferable that the aliphatic hydrocarbon ring is a fused ring.

In addition, R ^Cy in the formula (Cy) is a direct bond between the oxygen atom of -C(=O)O- in the formula (Cy) and the aliphatic hydrocarbon ring structure in that the effect of the present invention is more excellent. It is preferable that the group is an aliphatic hydrocarbon ring group, more preferably a cyclohexyl group or a dicyclopentanyl group, and even more preferably a dicyclopentanyl group.

The binder polymer may have one type of structural unit having an aliphatic hydrocarbon ring structure, or may have two or more types thereof.

When the binder polymer has a structural unit having an aliphatic hydrocarbon ring structure, the content of the structural unit having an aliphatic hydrocarbon ring structure is 5 to 5 based on all structural units of the binder polymer because the effect of the present invention is more excellent. 90 mass% is preferable, 10 to 80 mass% is more preferable, and 20 to 70 mass% is more preferable.

In addition, the content of the structural unit having an aliphatic hydrocarbon ring structure in the binder polymer is preferably 5 to 70 mol%, and 10 to 70 mol%, relative to all structural units of the binder polymer, because the effect of the present invention is more excellent. 60 mol% is more preferable, and 20 to 50 mol% is more preferable.

In addition, the content of the structural unit represented by the above formula (Cy) in the binder polymer is preferably 5 to 70 mol%, and 10 to 70 mol%, relative to all structural units of the binder polymer, because the effect of the present invention is more excellent. 60 mol% is more preferable, and 20 to 50 mol% is more preferable.

When the binder polymer has a structural unit having an aromatic ring structure and a structural unit having an aliphatic hydrocarbon ring structure, the total content of the structural unit having an aromatic ring structure and the structural unit having an aliphatic hydrocarbon ring structure is the effect of the present invention. Since it is superior, 10 to 90% by mass is preferable, 20 to 80% by mass is more preferable, and 40 to 75% by mass is more preferable, relative to the total structural units of the binder polymer.

In addition, the total content of the structural units having an aromatic ring structure and the structural units having an aliphatic hydrocarbon ring structure in the binder polymer is 10 to 10 based on all structural units of the binder polymer because the effect of the present invention is more excellent. 80 mol% is preferable, 20 to 70 mol% is more preferable, and 40 to 60 mol% is more preferable.

In addition, the total content of the structural units represented by the formula (S) and the structural units represented by the formula (Cy) in the binder polymer is, relative to all structural units of the binder polymer, in that the effect of the present invention is more excellent. 10 to 80 mol% is preferable, 20 to 70 mol% is more preferable, and 40 to 60 mol% is more preferable.

In addition, the molar amount nS of the structural unit represented by the above formula (S) and the molar amount nCy of the structural unit represented by the above formula (Cy) in the binder polymer are expressed in the following formula (SCy) because the effect of the present invention is more excellent. It is preferable to satisfy the relationship shown, more preferably to satisfy the following formula (SCy-1), and more preferably to satisfy the following formula (SCy-2).

0.2≤nS/(nS+nCy)≤0.8 equation (SCy)

0.30≤nS/(nS+nCy)≤0.75 equation (SCy-1)

0.40≤nS/(nS+nCy)≤0.70 Equation (SCy-2)

The binder polymer preferably has a structural unit having an acid group because the effect of the present invention is more excellent.

Examples of the acid group include a carboxyl group, a sulfo group, a phosphonic acid group, and a phosphoric acid group, with a carboxy group being preferable.

As the structural unit having the acid group, structural units derived from (meth)acrylic acid shown below are preferable, and structural units derived from methacrylic acid are more preferable.

[Formula 3]

The binder polymer may have one type of structural unit having an acid group, or may have two or more types thereof.

When the binder polymer has a structural unit having an acidic group, the content of the structural unit having an acidic group is preferably 5 to 50% by mass based on the total structural units of the binder polymer because the effect of the present invention is more excellent, and 5 ~40 mass% is more preferable, and 10-30 mass% is more preferable.

In addition, the content of the structural unit having an acid group in the binder polymer is preferably 5 to 70 mol%, and 10 to 50 mol%, relative to all structural units of the binder polymer, because the effect of the present invention is more excellent. It is more preferable, and 20 to 40 mol% is more preferable.

In addition, the content of the structural unit derived from (meth)acrylic acid in the binder polymer is preferably 5 to 70 mol%, and 10 to 50 mol%, relative to all structural units of the binder polymer, because the effect of the present invention is more excellent. Mol% is more preferable, and 20 to 40 mol% is more preferable.

The binder polymer preferably has a reactive group, and more preferably has a structural unit having a reactive group, because the effect of the present invention is more excellent.

As the reactive group, a radical polymerizable group is preferable and an ethylenically unsaturated group is more preferable. Moreover, when the binder polymer has an ethylenically unsaturated group, it is preferable that the binder polymer has a structural unit which has an ethylenically unsaturated group in a side chain.

In this specification, “main chain” refers to the relatively longest bond chain among the molecules of the polymer compound constituting the resin, and “side chain” refers to the atomic group branching from the main chain.

As the ethylenically unsaturated group, allyl group or (meth)acryloxy group is more preferable.

Examples of structural units having a reactive group include those shown below, but are not limited to these.

[Formula 4]

The binder polymer may have one type of structural unit having a reactive group, or may have two or more types of structural units having a reactive group.

When the binder polymer has a structural unit having a reactive group, the content of the structural unit having a reactive group is preferably 5 to 70% by mass based on the total structural units of the binder polymer because the effect of the present invention is more excellent, and 10 -50% by mass is more preferable, and 20-40% by mass is more preferable.

In addition, the content of the structural unit having a reactive group in the binder polymer is preferably 5 to 70 mol%, and 10 to 60 mol%, relative to all structural units of the binder polymer, because the effect of the present invention is more excellent. It is more preferable, and 20 to 50 mol% is more preferable.

As a means of introducing a reactive group into the binder polymer, functional groups such as hydroxy group, carboxy group, primary amino group, secondary amino group, acetoacetyl group, and sulfo group, epoxy compound, block isocyanate compound, A method of reacting compounds such as an isocyanate compound, a vinyl sulfone compound, an aldehyde compound, a methylol compound, and a carboxylic acid anhydride can be mentioned.

As a preferred example of a means for introducing a reactive group into a binder polymer, a polymer having a carboxyl group is synthesized through a polymerization reaction, and then a portion of the carboxyl group of the obtained polymer is reacted with glycidyl (meth)acrylate through a polymer reaction, A means for introducing a (meth)acryloxy group into a polymer may be mentioned. By this means, a binder polymer having a (meth)acryloxy group in the side chain can be obtained.

The polymerization reaction is preferably performed under temperature conditions of 70 to 100°C, and more preferably performed under temperature conditions of 80 to 90°C. As a polymerization initiator used in the above polymerization reaction, an azo-based initiator is preferable, and for example, V-601 (brand name) or V-65 (brand name) manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. is more preferable. The polymer reaction is preferably performed under temperature conditions of 80 to 110°C. In the above polymer reaction, it is preferable to use a catalyst such as ammonium salt.

As the binder polymer, the polymer shown below is preferable because the effect of the present invention is more excellent. In addition, the content ratio (a to d) and weight average molecular weight (Mw) of each structural unit shown below can be appropriately changed depending on the purpose.

[Formula 5]

Among the above polymers, a: 20 to 60 wt%, b: 10 to 50 wt%, c: 5.0 to 25 wt%, and d: 10 to 50 wt% are preferable.

[Formula 6]

Among the above polymers, a: 20 to 60 wt% b: 10 to 50 wt% c: 5.0 to 25 wt% d: 10 to 50 wt% are preferred.

[Formula 7]

Among the above polymers, a: 30 to 65 wt%, b: 1.0 to 20 wt%, c: 5.0 to 25 wt%, and d: 10 to 50 wt% are preferable.

[Formula 8]

Among the above polymers, a: 1.0 to 20 wt%, b: 20 to 60 wt%, c: 5.0 to 25 wt%, and d: 10 to 50 wt% are preferred.

In addition, the binder polymer may contain a polymer (hereinafter also referred to as “polymer X”) having a structural unit having a carboxylic acid anhydride structure.

The carboxylic acid anhydride structure may be either a linear carboxylic acid anhydride structure or a cyclic carboxylic acid anhydride structure, but is preferably a cyclic carboxylic acid anhydride structure.

As a ring of a cyclic carboxylic acid anhydride structure, a 5- to 7-membered ring is preferable, a 5-membered ring or a 6-membered ring is more preferable, and a 5-membered ring is still more preferable.

The structural unit having a carboxylic acid anhydride structure is a structural unit containing in the main chain a divalent group obtained by removing two hydrogen atoms from a compound represented by the formula P-1 below, or a structural unit containing one hydrogen atom from a compound represented by the formula P-1 below. It is preferable that the removed monovalent group is a structural unit that is bonded to the main chain directly or through a divalent linking group.

[Formula 9]

In formula P-1, R ^A1a represents a substituent, n ^1a pieces of R ^A1a may be the same or different, and Z ^1a represents a ring containing -C(=O)-OC(=O)-. It represents the divalent group formed, and n ^1a represents an integer of 0 or more.

Examples of the substituent represented by R ^A1a include an alkyl group.

As Z ^1a , an alkylene group with 2 to 4 carbon atoms is preferable, an alkylene group with 2 or 3 carbon atoms is more preferable, and an alkylene group with 2 carbon atoms is still more preferable.

n ^1a represents an integer of 0 or more. When Z ^1a represents an alkylene group having 2 to 4 carbon atoms, n ^1a is preferably an integer of 0 to 4, more preferably an integer of 0 to 2, and still more preferably 0.

When n ^1a represents an integer of 2 or more, the plural R ^A1a may be the same or different. In addition, multiple R ^A1a may be bonded to each other to form a ring, but it is preferable that they are not bonded to each other to form a ring.

As the structural unit having a carboxylic acid anhydride structure, a structural unit derived from an unsaturated carboxylic acid anhydride is preferable, a structural unit derived from an unsaturated cyclic carboxylic acid anhydride is more preferable, and a structural unit derived from an unsaturated aliphatic carboxylic acid anhydride is more preferable, Structural units derived from maleic anhydride or itaconic anhydride are particularly preferred, and structural units derived from maleic anhydride are most preferred.

Hereinafter, specific examples of structural units having a carboxylic acid anhydride structure will be given, but the structural units having a carboxylic acid anhydride structure are not limited to these specific examples. Among the structural units below, Rx represents a hydrogen atom, a methyl group, CH ₂ OH group, or CF ₃ group, and Me represents a methyl group.

[Formula 10]

[Formula 11]

The structural units having a carboxylic acid anhydride structure in the polymer X may be one type or two or more types.

The total content of structural units having a carboxylic acid anhydride structure is preferably 0 to 60 mol%, more preferably 5 to 40 mol%, and still more preferably 10 to 35 mol%, relative to the total structural units of polymer X.

The photosensitive composition layer may contain only one type of polymer X, or may contain two or more types of polymer X.

When the photosensitive composition layer contains polymer It is more preferable, 0.5 to 20 mass% is more preferable, and 1 to 20 mass% is more preferable.

The weight average molecular weight (Mw) of the binder polymer is preferably 5,000 or more, more preferably 10,000 or more, more preferably 10,000 to 50,000, and especially preferably 15,000 to 30,000, because the effect of the present invention is more excellent.

The acid value of the binder polymer is preferably 10 to 200 mgKOH/g, more preferably 60 to 200 mgKOH/g, more preferably 60 to 150 mgKOH/g, and especially preferably 70 to 130 mgKOH/g.

In addition, the acid value of the binder polymer is a value measured according to the method described in JIS K0070:1992. From the viewpoint of developability, the dispersion degree of the binder polymer is preferably 1.0 to 6.0, more preferably 1.0 to 5.0, more preferably 1.0 to 4.0, and especially preferably 1.0 to 3.0.

The photosensitive composition layer may contain only one type of binder polymer or may contain two or more types.

Since the effect of the present invention is more excellent, the content of the binder polymer is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, and more preferably 30 to 70% by mass, relative to the total mass of the photosensitive composition layer. desirable.

<Polymerizable compound>

The photosensitive composition layer may contain a polymerizable compound.

A polymerizable compound is a compound having a polymerizable group. Examples of the polymerizable group include a radical polymerizable group and a cationic polymerizable group, with a radical polymerizable group being preferred.

The polymerizable compound preferably contains a radically polymerizable compound having an ethylenically unsaturated group (hereinafter also simply referred to as an "ethylenically unsaturated compound").

As the ethylenically unsaturated group, (meth)acryloxy group is preferable.

In addition, the ethylenically unsaturated compound in this specification is a compound other than the binder polymer, and preferably has a molecular weight of less than 5,000.

One of the preferred embodiments of the polymerizable compound includes a compound represented by the following formula (M) (also simply referred to as “compound M”).

Q ² -R ¹ -Q ¹ Equation (M)

In formula (M), Q ¹ and Q ² each independently represent a (meth)acryloyloxy group, and R ¹ represents a divalent linking group having a chain structure.

From the viewpoint of ease of synthesis, Q ¹ and Q ² in formula (M) ^are preferably the ^same group.

Moreover, Q ¹ and Q ² in the formula (M) are preferably an acryloyloxy group from the viewpoint of reactivity.

As R ¹ in the formula (M), an alkylene group, an alkyleneoxyalkylene group (-L ¹ -OL ¹ -), or a polyalkyleneoxyalkylene group (-( L ¹ -O) _p -L ¹ -) is preferable, a hydrocarbon group having 2 to 20 carbon atoms, or a polyalkyleneoxyalkylene group is more preferable, and an alkylene group having 4 to 20 carbon atoms is more preferable. Straight chain alkylene groups of 6 to 18 are particularly preferred.

The hydrocarbon group may have a chain structure at least in part, and there is no particular limitation on the parts other than the chain structure. For example, branched chain, cyclic, or straight chain alkylene group having 1 to 5 carbon atoms, aryl group. Any of a lene group, an ether bond, and a combination thereof may be used, and an alkylene group or a group combining two or more alkylene groups and one or more arylene groups is preferable, an alkylene group is more preferable, and a straight-chain alkylene group is more preferable. .

In addition, the L ¹ each independently represents an alkylene group, preferably an ethylene group, a propylene group, or a butylene group, and more preferably an ethylene group or a 1,2-propylene group. p represents an integer of 2 or more, and is preferably an integer of 2 to 10.

In addition, the number of atoms of the shortest linking chain connecting Q ¹ and Q ² in compound M is preferably 3 to 50, and 4 to 40 in view of the superior effect of the present invention. It is more preferable, 6 to 20 is more preferable, and 8 to 12 is particularly preferable.

In this specification, “the number of atoms in the shortest chain connecting Q ¹ and Q ² ” means from the atom in R ¹ connected to Q ¹ to the atom in R ¹ connected to Q ² It is the shortest number of atoms connecting .

Specific examples of compound M include 1,3-butane diol di(meth)acrylate, tetramethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, and 1,6-hex. Seinediol di(meth)acrylate, 1,7-heptane diol di(meth)acrylate, 1,8-octane diol di(meth)acrylate, 1,9-nonane diol diol ( Meth)acrylate, 1,10-decanediol di(meth)acrylate, di(meth)acrylate of hydrogenated bisphenol A, di(meth)acrylate of hydrogenated bisphenol F, polyethylene glycol di( Meth)acrylate, polypropylene glycol di(meth)acrylate, poly(ethylene glycol/propylene glycol) di(meth)acrylate, and polybutylene glycol di(meth)acrylate. can be mentioned. The ester monomers can also be used as a mixture.

Among the above compounds, 1,6-hexanedioldi(meth)acrylate, 1,9-nonanedioldi(meth)acrylate, and 1,10-decane are used in that the effect of the present invention is more excellent. It is preferable that it is at least one compound selected from the group consisting of diol di(meth)acrylate and neopentyl glycol di(meth)acrylate, and 1,6-hexanediol di(meth)acrylate. It is more preferable that it is at least one compound selected from the group consisting of late, 1,9-nonanedioldi(meth)acrylate, and 1,10-decanedioldi(meth)acrylate, 1 It is more preferable that it is at least one compound selected from the group consisting of 9-nonanedioldi(meth)acrylate, and 1,10-decanedioldi(meth)acrylate.

Moreover, as one of the suitable embodiments of the polymerizable compound, an ethylenically unsaturated compound having two or more functions can be mentioned.

In this specification, “bifunctional or more ethylenically unsaturated compound” means a compound having two or more ethylenically unsaturated groups in one molecule.

As the ethylenically unsaturated group in the ethylenically unsaturated compound, a (meth)acryloyl group is preferable.

As the ethylenically unsaturated compound, a (meth)acrylate compound is preferable.

The bifunctional ethylenically unsaturated compound is not particularly limited and can be appropriately selected from known compounds.

As bifunctional ethylenically unsaturated compounds other than the above compound M, tricyclodecane dimethanol di(meth)acrylate, dioxane glycol di(meth)acrylate, and 1,4-cyclohexanediol. Di(meth)acrylate can be mentioned.

Commercially available products of difunctional ethylenically unsaturated compounds include tricyclodecanedimethanoldiacrylate (brand name: NK Ester A-DCP, manufactured by Shinnakamura Chemical Industry Co., Ltd.) and tricyclodecanedimethanoldimethacrylate. (Product name: NK Ester DCP, manufactured by Shin-Nakamura Chemical Industries, Ltd.), 1,9-nonanediol diacrylate (Product name: NK Ester A-NOD-N, manufactured by Shin-Nakamura Chemical Industry Corporation) , 1,6-hexanediol diacrylate (Product name: NK Ester A-HD-N, manufactured by Shinnakamura Chemical Co., Ltd.), dioxane glycol diacrylate (manufactured by Nippon Kayaku Co., Ltd.) KAYARAD R-604) may be mentioned.

There is no particular limitation on the trifunctional or more ethylenically unsaturated compound, and it can be appropriately selected from known compounds.

Examples of trifunctional or more ethylenically unsaturated compounds include dipentaerythritol (tri/tetra/penta/hexa)(meth)acrylate, pentaerythritol (tri/tetra)(meth)acrylate, and trimethylolpropane tri(meth)acrylate. ) acrylate, ditrimethylolpropane tetra(meth)acrylate, isocyanuric acid (meth)acrylate, and (meth)acrylate compounds with a glycerin tri(meth)acrylate skeleton.

Here, “(tri/tetra/penta/hexa)(meth)acrylate” refers to tri(meth)acrylate, tetra(meth)acrylate, penta(meth)acrylate, and hexa(meth)acrylate. It is a concept including, and “(tri/tetra)(meth)acrylate” is a concept including tri(meth)acrylate and tetra(meth)acrylate.

As polymerizable compounds, caprolactone-modified compounds of (meth)acrylate compounds (KAYARAD (registered trademark) DPCA-20, manufactured by Nippon Kayaku Co., Ltd., A-9300-1CL, manufactured by Shinnakamura Chemical Co., Ltd., etc.), Alkylene oxide modified compounds of (meth)acrylate compounds (KAYARAD (registered trademark) RP-1040 manufactured by Nippon Kayaku Co., Ltd., ATM-35E, A-9300 manufactured by Shinnakamura Chemical Industry Co., Ltd., Daicel All NEX's EBECRYL (registered trademark) 135, etc.) and ethoxylated glycerol triacrylate (NK ester A-GLY-9E, manufactured by Shinnakamura Chemical Co., Ltd., etc.) can also be mentioned.

Examples of polymerizable compounds include urethane (meth)acrylate compounds.

Examples of urethane (meth)acrylate include urethane di(meth)acrylate, for example, propylene oxide-modified urethane di(meth)acrylate, and ethylene oxide and propylene oxide-modified oil. Retain die(meth)acrylate can be mentioned.

Moreover, examples of urethane (meth)acrylate include urethane (meth)acrylate having three or more functional groups. As the lower limit of the number of functional groups, 6 or more functional groups are more preferable, and 8 or more functional groups are more preferable. Additionally, the upper limit of the number of functional groups is preferably 20 or less. Examples of trifunctional or higher urethane (meth)acrylate include 8UX-015A (manufactured by Taisei Fine Chemical Co., Ltd.), UA-32P (manufactured by Shinnakamura Chemical Co., Ltd.), and U-15HA (manufactured by Shinnakamura Chemical Co., Ltd.). (manufactured by Shinnakamura Kagaku Kogyo Co., Ltd.), UA-1100H (manufactured by Shinnakamura Kagaku Kogyo Co., Ltd.), AH-600 (brand name) manufactured by Kyoeisha Kagaku Co., Ltd., and UA-306H, UA -306T, UA-306I, UA-510H, and UX-5000 (all manufactured by Nippon Kayaku Co., Ltd.).

One of the preferred embodiments of the polymerizable compound is an ethylenically unsaturated compound having an acid group.

Examples of the acid group include a phosphate group, a sulfo group, and a carboxy group.

Among these, as the acid group, a carboxy group is preferable.

As ethylenically unsaturated compounds having an acid group, 3- to 4-functional ethylenically unsaturated compounds having an acid group [those with a carboxyl group introduced into the pentaerythritol tri and tetraacrylate (PETA) skeleton (acid value: 80-120 mgKOH/g)] , 5- to 6-functional ethylenically unsaturated compounds having an acid group [dipentaerythritol penta and hexaacrylate (DPHA) skeleton with a carboxy group introduced (acid value: 25-70 mgKOH/g)], etc.

These tri- or higher-functional ethylenically unsaturated compounds having an acid group may be used in combination with a bi-functional ethylenically unsaturated compound having an acid group, as needed.

As the ethylenically unsaturated compound having an acid group, at least one type selected from the group consisting of bifunctional or more ethylenically unsaturated compounds having a carboxyl group and their carboxylic acid anhydrides is preferable.

If the ethylenically unsaturated compound having an acid group is at least one selected from the group consisting of bifunctional or more ethylenically unsaturated compounds having a carboxyl group and their carboxylic acid anhydrides, developability and film strength are further increased.

The bifunctional or higher ethylenically unsaturated compound having a carboxyl group is not particularly limited and can be appropriately selected from known compounds.

Examples of difunctional or more ethylenically unsaturated compounds having a carboxyl group include Aronix (registered trademark) TO-2349 (manufactured by Toa Kosei Co., Ltd.), Aronix (registered trademark) M-520 (manufactured by Toa Kosei Co., Ltd.), and Aronix (registered trademark) M-520 (manufactured by Toa Kosei Co., Ltd.). (Registered trademark) M-510 (manufactured by Toa Kosei Co., Ltd.).

As the ethylenically unsaturated compound having an acid group, polymerizable compounds having an acid group described in paragraphs [0025] to [0030] of Japanese Patent Application Laid-Open No. 2004-239942 are preferable, and the content described in this publication is incorporated herein by reference.

Polymerizable compounds include, for example, compounds obtained by reacting an α,β-unsaturated carboxylic acid with a polyhydric alcohol, compounds obtained by reacting an α,β-unsaturated carboxylic acid with a glycidyl group-containing compound, and (meth) having a urethane bond. ) Acrylate compounds such as urethane monomer, γ-chloro-β-hydroxypropyl-β'-(meth)acryloyloxyethyl-o-phthalate, β-hydroxyethyl-β'-(meth)acryl Phthalic acid-based compounds such as loyloxyethyl-o-phthalate and β-hydroxypropyl-β'-(meth)acryloyloxyethyl-o-phthalate, and (meth)acrylic acid alkyl esters can also be mentioned. .

These are used individually or in combination of two or more types.

Compounds obtained by reacting an α,β-unsaturated carboxylic acid with a polyhydric alcohol include, for example, 2,2-bis(4-((meth)acryloxypolyethoxy)phenyl)propane, 2,2-bis(4) -Bisphenol A series (meth) such as ((meth)acryloxypolypropoxy)phenyl)propane and 2,2-bis(4-((meth)acryloxypolyethoxypolypropoxy)phenyl)propane ) Acrylate compound, polyethylene glycol di(meth)acrylate having 2 to 14 ethylene oxide groups, polypropylene glycol di(meth)acrylate having 2 to 14 propylene oxide groups, ethylene oxide group polyethylene polypropylene glycol di(meth)acrylate, trimethylolpropane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, and the number of propylene oxide groups is 2 to 14. ) Acrylate, trimethylolpropane ethoxytri(meth)acrylate, trimethylolpropane diethoxytri(meth)acrylate, trimethylolpropane triethoxytri(meth)acrylate, trimethyl Allpropane tetraethoxytri(meth)acrylate, trimethylolpropane pentaethoxytri(meth)acrylate, di(trimethylolpropane)tetraacrylate, tetramethylolmethane tri(meth)acrylate tetramethylolmethane tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, and dipentaerythritol hexa(meth)acrylate. You can.

Among them, ethylenically unsaturated compounds having a tetramethylolmethane structure or a trimethylolpropane structure are preferable, such as tetramethylolmethane tri(meth)acrylate, tetramethylolmethane tetra(meth)acrylate, trimethyl All-propane tri(meth)acrylate or di(trimethylolpropane)tetraacrylate is more preferable.

As the polymerizable compound, caprolactone-modified compounds of ethylenically unsaturated compounds (e.g., KAYARAD (registered trademark) DPCA-20 manufactured by Nippon Kayaku Co., Ltd., A-9300-1CL manufactured by Shinnakamura Chemical Co., Ltd., etc. ), alkylene oxide modified compounds of ethylenically unsaturated compounds (e.g., KAYARAD RP-1040 manufactured by Nippon Kayaku Co., Ltd., ATM-35E, A-9300 manufactured by Shinnakamura Chemical Industry Co., Ltd., Daicel All EBECRYL (registered trademark) 135, manufactured by NEX, etc.), ethoxylated glycerin triacrylate (A-GLY-9E, manufactured by Shinnakamura Chemical Co., Ltd., etc.), etc. can also be mentioned.

As a polymerizable compound (particularly, an ethylenically unsaturated compound), one containing an ester bond is also preferable because the developability of the photosensitive composition layer after transfer is excellent.

The ethylenically unsaturated compound containing an ester bond is not particularly limited as long as it contains an ester bond in the molecule, but because the effect of the present invention is excellent, an ethylenically unsaturated compound having a tetramethylolmethane structure or a trimethylolpropane structure is used. Preferred compounds include tetramethylolmethane tri(meth)acrylate, tetramethylolmethane tetra(meth)acrylate, trimethylolpropane tri(meth)acrylate, or di(trimethylolpropane). ) Tetraacrylate is more preferable.

In terms of providing reliability, examples of ethylenically unsaturated compounds include ethylenically unsaturated compounds having an aliphatic group of 6 to 20 carbon atoms and ethylenically unsaturated compounds having the above-mentioned tetramethylolmethane structure or trimethylolpropane structure. desirable.

Examples of ethylenically unsaturated compounds having an aliphatic structure of 6 or more carbon atoms include 1,9-nonanedioldi(meth)acrylate, 1,10-decanedioldi(meth)acrylate, and tricyclodecanedioldi(meth)acrylate. and methanol di(meth)acrylate.

One of the preferred embodiments of the polymerizable compound is a polymerizable compound (preferably a bifunctional ethylenically unsaturated compound) having an aliphatic hydrocarbon ring structure.

As the polymerizable compound, a polymerizable compound having a ring structure in which two or more aliphatic hydrocarbon rings are fused (preferably a structure selected from the group consisting of a tricyclodecane structure and a tricyclodecene structure) is preferred, A bifunctional ethylenically unsaturated compound having a ring structure in which two or more aliphatic hydrocarbon rings are fused is more preferable, and tricyclodecane dimethanol di(meth)acrylate is more preferable.

The aliphatic hydrocarbon ring structure includes a cyclopentane structure, a cyclohexane structure, a tricyclodecane structure, a tricyclodecene structure, a norbornene structure, or an isophorone structure in that the effect of the present invention is more excellent. desirable.

The molecular weight of the polymerizable compound is preferably 200 to 3,000, more preferably 250 to 2,600, more preferably 280 to 2,200, and especially preferably 300 to 2,200.

Among the polymerizable compounds contained in the photosensitive composition layer, the content ratio of the polymerizable compound with a molecular weight of 300 or less is preferably 30% by mass or less, and is preferably 25% by mass, relative to the content of all polymerizable compounds contained in the photosensitive composition layer. The amount below is more preferable, and 20% by mass or less is more preferable.

As one of the preferred embodiments of the photosensitive composition layer, the photosensitive composition layer preferably contains a bifunctional or higher ethylenically unsaturated compound, more preferably contains a trifunctional or higher ethylenically unsaturated compound, and trifunctional or tetrafunctional It is more preferable to contain an ethylenically unsaturated compound.

In addition, as one of the preferred embodiments of the photosensitive composition layer, the photosensitive composition layer preferably contains a difunctional ethylenically unsaturated compound having an aliphatic hydrocarbon ring structure and a binder polymer having a structural unit having an aliphatic hydrocarbon ring. .

In addition, as one of the preferred embodiments of the photosensitive composition layer, the photosensitive composition layer preferably contains a compound represented by formula (M) and an ethylenically unsaturated compound having an acid group, 1,9-nonanediol diacryl It is more preferable to include 1,9-nonanediol diacrylate, tricyclodecane dimethanol diacrylate, and a polyfunctional ethylenically unsaturated compound having a carboxylic acid group, and tricyclodecane dimethanol. It is more preferable that it contains diacrylate and a succinic acid modified form of dipentaerythritol pentaacrylate.

In addition, as one of the preferred embodiments of the photosensitive composition layer, the photosensitive composition layer preferably contains a compound represented by the formula (M), an ethylenically unsaturated compound having an acid group, and a heat crosslinkable compound described later, and the formula (M) It is more preferable to include a compound represented by ), an ethylenically unsaturated compound having an acid group, and a block isocyanate compound described later.

In addition, as one of the preferred embodiments of the photosensitive composition layer, the photosensitive composition layer contains a bifunctional ethylenically unsaturated compound (preferably a bifunctional (meth)acrylate compound) from the viewpoint of development residue inhibition and rust prevention properties. ) and a trifunctional or higher ethylenically unsaturated compound (preferably a trifunctional or higher (meth)acrylate compound).

In the photosensitive composition layer, the mass ratio of the content of the bifunctional ethylenically unsaturated compound and the content of the trifunctional or higher ethylenically unsaturated compound is preferably 10:90 to 90:10, and is more preferably 30:70 to 70:30. desirable.

The content of the bifunctional ethylenically unsaturated compound relative to the total amount of all ethylenically unsaturated compounds is preferably 20 to 80 mass%, and more preferably 30 to 70 mass%.

The amount of the bifunctional ethylenically unsaturated compound in the photosensitive composition layer is preferably 10 to 60% by mass, and more preferably 15 to 40% by mass.

In addition, as one of the preferred embodiments of the photosensitive composition layer, the photosensitive composition layer preferably contains compound M and a bifunctional ethylenically unsaturated compound having an aliphatic hydrocarbon ring structure from the viewpoint of rust prevention properties.

In addition, as one of the preferred embodiments of the photosensitive composition layer, the photosensitive composition layer preferably contains compound M and an ethylenically unsaturated compound having an acid group in terms of substrate adhesion, development residue suppression, and rust prevention. , Compound M, a bifunctional ethylenically unsaturated compound having an aliphatic hydrocarbon ring structure, and, It is more preferable to include an ethylenically unsaturated compound having an acid group, and Compound M, a bifunctional ethylenically unsaturated compound having an aliphatic hydrocarbon ring structure. It is more preferable to include a compound, a trifunctional or more ethylenically unsaturated compound, and an ethylenically unsaturated compound having an acid group, and compound M, a bifunctional ethylenically unsaturated compound having an aliphatic hydrocarbon ring structure, a trifunctional or more ethylenically unsaturated compound. It is particularly preferable to include a compound, an ethylenically unsaturated compound having an acid group, and a urethane (meth)acrylate compound.

In addition, as one of the preferred embodiments of the photosensitive composition layer, the photosensitive composition layer includes 1,9-nonanediol diacrylate in terms of substrate adhesion, development residue inhibition, and rust prevention, and , It is preferable to include a polyfunctional ethylenically unsaturated compound having a carboxylic acid group, such as 1,9-nonanediol diacrylate, tricyclodecane dimethanol diacrylate, and a polyfunctional ethylenically unsaturated compound having a carboxylic acid group. It is preferable to include 1,9-nonanediol diacrylate, tricyclodecane dimethanol diacrylate, dipentaerythritol hexaacrylate, and an ethylenically unsaturated compound having a carboxylic acid group. It is more preferable, and it is especially preferable that it contains 1,9-nonanediol diacrylate, tricyclodecane dimethanol diacrylate, an ethylenically unsaturated compound having a carboxylic acid group, and a urethane acrylate compound.

The photosensitive composition layer may contain a monofunctional ethylenically unsaturated compound as an ethylenically unsaturated compound.

The content of the bifunctional or higher ethylenically unsaturated compound in the ethylenically unsaturated compound is preferably 60 to 100% by mass, and 80 to 100% by mass, based on the total content of all ethylenically unsaturated compounds contained in the photosensitive composition layer. is more preferable, and 90 to 100 mass% is more preferable.

Polymerizable compounds (especially ethylenically unsaturated compounds) may be used individually or in combination of two or more.

The content of the polymerizable compound (especially ethylenically unsaturated compound) in the photosensitive composition layer is preferably 1 to 70% by mass, more preferably 5 to 70% by mass, based on the total mass of the photosensitive composition layer, and 5 to 70% by mass. 60% by mass is more preferable, and 5 to 50% by mass is particularly preferable.

<Polymerization initiator>

The photosensitive composition layer may contain a polymerization initiator.

As a polymerization initiator, a photopolymerization initiator is preferable.

There is no particular limitation as a photopolymerization initiator, and a known photopolymerization initiator can be used.

As a photopolymerization initiator, a photopolymerization initiator having an oxime ester structure (hereinafter also referred to as “oxime-based photopolymerization initiator”), a photopolymerization initiator having an α-aminoalkylphenone structure (hereinafter also referred to as “α-aminoalkylphenone-based photopolymerization initiator”) .), a photopolymerization initiator having an α-hydroxyalkylphenone structure (hereinafter also referred to as “α-hydroxyalkylphenone polymerization initiator”), a photopolymerization initiator having an acylphosphine oxide structure (hereinafter referred to as “acylphosphine oxide”) and photopolymerization initiators having an N-phenylglycine structure (hereinafter also referred to as “N-phenylglycine-based photopolymerization initiators”).

The photopolymerization initiator includes at least one selected from the group consisting of an oxime-based photopolymerization initiator, an α-aminoalkylphenone-based photopolymerization initiator, an α-hydroxyalkylphenone-based polymerization initiator, and an N-phenylglycine-based photopolymerization initiator. Preferred, it is more preferable that it contains at least one type selected from the group consisting of an oxime-based photopolymerization initiator, an α-aminoalkylphenone-based photopolymerization initiator, and an N-phenylglycine-based photopolymerization initiator.

In addition, as the photopolymerization initiator, for example, the polymerization initiators described in paragraphs [0031] to [0042] of Japanese Patent Application Laid-Open No. 2011-95716 and paragraphs [0064] to [0081] of Japanese Patent Application Laid-Open No. 2015-014783. You may use it.

Commercially available photopolymerization initiators include 1-[4-(phenylthio)phenyl]-1,2-octanedione-2-(O-benzoyloxime) [brand name: IRGACURE (registered trademark) OXE-01, manufactured by BASF. ], 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone-1-(O-acetyloxime) [Product name: IRGACURE (registered trademark) OXE-02, BASF], IRGACURE (registered trademark) OXE03 (manufactured by BASF), IRGACURE (registered trademark) OXE04 (manufactured by BASF), 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4- (4-morpholinyl)phenyl]-1-butanone [Product name: Omnirad (registered trademark) 379EG, manufactured by IGM Resins B.V.], 2-methyl-1-(4-methylthiophenyl)-2-morpholino Propan-1-one [brand name: Omnirad (registered trademark) 907, manufactured by IGM Resins B.V.], 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionyl)benzyl]phenyl} -2-Methylpropan-1-one [Brand name: Omnirad (registered trademark) 127, manufactured by IGM Resins B.V.], 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone-1 [ Brand name: Omnirad (registered trademark) 369, manufactured by IGM Resins B.V.], 2-hydroxy-2-methyl-1-phenylpropan-1-one [Brand name: Omnirad (registered trademark) 1173, manufactured by IGM Resins B.V.], 1- Hydroxycyclohexylphenylketone [brand name: Omnirad (registered trademark) 184, manufactured by IGM Resins B.V.], 2,2-dimethoxy-1,2-diphenylethan-1-one [brand name: Omnirad (registered trademark) 651 , manufactured by IGM Resins B.V.], etc., oxime ester series [brand name: Lunar (registered trademark) 6, manufactured by DKSH Japan Co., Ltd.], 1-[4-(phenylthio)phenyl]-3-cyclopentylpropane- 1,2-Dione-2-(O-benzoyloxime) (Product name: TR-PBG-305, manufactured by Changzhou Tronly New Electronic Materials Co., Ltd.), 1,2 -Propanedione, 3-cyclohexyl-1-[9-ethyl-6-(2-furanylcarbonyl)-9H-carbazol-3-yl]-, 2-(O-acetyloxime) (Product name : TR-PBG-326, Changzhou Strong Electronic New Materials Co., Ltd.), 3-cyclohexyl-1-(6-(2-(benzoyloxyimino)hexanoyl)-9-ethyl-9H-carbazole-3 -1)-Propane-1,2-dione-2-(O-benzoyloxime) (Product name: TR-PBG-391, manufactured by Changzhou Strong Electronic New Materials Co., Ltd.), APi-307 (1-(Bai) and phenyl-4-yl)-2-methyl-2-morpholinopropan-1-one, manufactured by Shenzhen UV-ChemTech Ltd.).

Photopolymerization initiators may be used individually by 1 type, or 2 or more types may be used. When using two or more types, it is preferable to use at least one type selected from an oxime-based photopolymerization initiator, an α-aminoalkylphenone-based photopolymerization initiator, and an α-hydroxyalkylphenone-based polymerization initiator.

When the photosensitive composition layer contains a photopolymerization initiator, the content of the photopolymerization initiator is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and still more preferably 1.0% by mass or more, based on the total mass of the photosensitive composition layer. . Moreover, the upper limit is preferably 10% by mass or less, and more preferably 5% by mass or less, based on the total mass of the photosensitive composition layer.

<Heterocyclic compounds>

The photosensitive composition layer may contain a heterocyclic compound.

The heterocycle of the heterocyclic compound may be either a monocyclic ring or a polycyclic ring.

Examples of heteroatoms contained in heterocyclic compounds include nitrogen atoms, oxygen atoms, and sulfur atoms. The heterocyclic compound preferably has at least one atom selected from the group consisting of a nitrogen atom, an oxygen atom, and a sulfur atom, and more preferably has a nitrogen atom.

As heterocyclic compounds, for example, triazole compounds, benzotriazole compounds, tetrazole compounds, thiadiazole compounds, triazine compounds, rhodanine compounds, thiazole compounds, benzothiazole compounds, benzimidazole compounds, A benzoxazole compound and a pyrimidine compound can be mentioned.

Among the above, heterocyclic compounds include triazole compounds, benzotriazole compounds, tetrazole compounds, thiadiazole compounds, triazine compounds, rhodanine compounds, thiazole compounds, benzimidazole compounds, and benzoxazole compounds. At least one compound selected from the group consisting of is preferred, a triazole compound, a benzotriazole compound, a tetrazole compound, a thiadiazole compound, a thiazole compound, a benzothiazole compound, a benzimidazole compound, and, At least one compound selected from the group consisting of benzoxazole compounds is more preferable.

Preferred specific examples of heterocyclic compounds are shown below. Examples of triazole compounds and benzotriazole compounds include the following compounds.

[Formula 12]

[Formula 13]

Examples of tetrazole compounds include the following compounds.

[Formula 14]

[Formula 15]

As a thiadiazole compound, the following compounds can be exemplified.

[Formula 16]

Examples of triazine compounds include the following compounds.

[Formula 17]

Examples of rhodanine compounds include the following compounds.

[Formula 18]

As a thiazole compound, the following compounds can be exemplified.

[Formula 19]

Examples of benzothiazole compounds include the following compounds.

[Formula 20]

As benzimidazole compounds, the following compounds can be exemplified.

[Formula 21]

[Formula 22]

As benzoxazole compounds, the following compounds can be exemplified.

[Formula 23]

Heterocyclic compounds may be used individually, or two or more types may be used in combination.

When the photosensitive composition layer contains a heterocyclic compound, the content of the heterocyclic compound is preferably 0.01 to 20.0% by mass, more preferably 0.10 to 10.0% by mass, and 0.30 to 8.0% by mass, based on the total mass of the photosensitive composition layer. % is more preferable, and 0.50 to 5.0 mass % is especially preferable.

<Aliphatic thiol compounds>

The photosensitive composition layer may contain an aliphatic thiol compound.

When the photosensitive composition layer contains an aliphatic thiol compound, an enthiol reaction occurs between the aliphatic thiol compound and the radically polymerizable compound having an ethylenically unsaturated group, thereby suppressing curing shrinkage of the formed film and relieving stress. .

As the aliphatic thiol compound, a monofunctional aliphatic thiol compound or a polyfunctional aliphatic thiol compound (i.e., a bifunctional or more aliphatic thiol compound) is preferable.

Among the above, polyfunctional aliphatic thiol compounds are preferred as the aliphatic thiol compound from the viewpoint of adhesion to the formed pattern (particularly, adhesion after exposure).

As used herein, “polyfunctional aliphatic thiol compound” refers to an aliphatic compound having two or more thiol groups (also referred to as “mercapto groups”) in the molecule.

As the polyfunctional aliphatic thiol compound, a low molecular weight compound with a molecular weight of 100 or more is preferable. Specifically, the molecular weight of the polyfunctional aliphatic thiol compound is more preferably 100 to 1,500, and further preferably 150 to 1,000.

The number of functional groups of the polyfunctional aliphatic thiol compound is preferably 2 to 10 functional groups, more preferably 2 to 8 functional groups, and even more preferable 2 to 6 functional groups, for example, from the viewpoint of adhesion of the formed pattern. .

Examples of polyfunctional aliphatic thiol compounds include trimethylolpropanetris(3-mercaptobutyrate), 1,4-bis(3-mercaptobutyryloxy)butane, and pentaerythritol tetrakis. (3-mercaptobutyrate), 1,3,5-tris(3-mercaptobutyryloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-tri On, trimethylol ethane tris(3-mercaptobutyrate), tris[(3-mercaptopropionyloxy)ethyl]isocyanurate, trimethylol propane tris(3-mercaptopropionate), Pentaerythritol tetrakis (3-mercaptopropionate), tetraethylene glycol bis (3-mercaptopropionate), dipentaerythritol hexakis (3-mercaptopropionate), ethylene glycol Colbisthiopropionate, 1,4-bis(3-mercaptobutyryloxy)butane, 1,2-ethane dithiol, 1,3-propane dithiol, 1,6-hexamethylene Dithiol, 2,2'-(ethylene dithio)diethanethiol, meso-2,3-dimercaptosuccinic acid, and di(mercaptoethyl)ether are included.

Among the above, examples of polyfunctional aliphatic thiol compounds include trimethylolpropanetris(3-mercaptobutyrate), 1,4-bis(3-mercaptobutyryloxy)butane, and 1,3, At least one compound selected from the group consisting of 5-tris(3-mercaptobutyryloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione desirable.

Monofunctional aliphatic thiol compounds include, for example, 1-octanethiol, 1-dodecanethiol, β-mercaptopropionic acid, methyl-3-mercaptopropionate, and 2-ethylhexyl-3-. Mercaptopropionate, n-octyl-3-mercaptopropionate, methoxybutyl-3-mercaptopropionate, and stearyl-3-mercaptopropionate can be mentioned.

The photosensitive composition layer may contain one type of aliphatic thiol compound, or may contain two or more types of aliphatic thiol compounds.

When the photosensitive composition layer contains an aliphatic thiol compound, the content of the aliphatic thiol compound is preferably 5% by mass or more, more preferably 5 to 50% by mass, based on the total mass of the photosensitive composition layer, and 5 to 30% by mass. The mass % is more preferable, and 8 to 20 mass % is particularly preferable.

<Thermal crosslinking compound>

The photosensitive composition layer preferably contains a heat crosslinkable compound from the viewpoint of the strength of the cured film obtained and the adhesiveness of the uncured film obtained. In addition, in this specification, the heat-crosslinkable compound having an ethylenically unsaturated group described later is not handled as an ethylenically unsaturated compound, but rather as a heat-crosslinkable compound.

Examples of thermally crosslinkable compounds include epoxy compounds, oxetane compounds, methylol compounds, and block isocyanate compounds. Among them, block isocyanate compounds are preferable from the viewpoint of the strength of the cured film obtained and the adhesiveness of the uncured film obtained.

Since block isocyanate compounds react with hydroxy groups and carboxyl groups, for example, at least one of the binder polymer and the radically polymerizable compound having an ethylenically unsaturated group has at least one of a hydroxy group and a carboxyl group. In this case, the hydrophilicity of the formed film tends to be lowered and its function as a protective film is strengthened.

In addition, the block isocyanate compound refers to "a compound having a structure in which the isocyanate group of isocyanate is protected (so-called masked) with a blocking agent."

The dissociation temperature of the block isocyanate compound is not particularly limited, but is preferably 90 to 160°C, and more preferably 100 to 150°C.

The dissociation temperature of block isocyanate refers to "the temperature of the endothermic peak resulting from the deprotection reaction of block isocyanate when measured by DSC (Differential scanning calorimetry) analysis using a differential scanning calorimeter." it means.

As a differential scanning calorimeter, for example, a differential scanning calorimeter (model: DSC6200) manufactured by Seiko Instruments Co., Ltd. can be suitably used. However, the differential scanning calorimeter is not limited to this.

Blocking agents with a dissociation temperature of 100 to 160°C include active methylene compounds [malonic acid diesters (dimethyl malonate, diethyl malonate, din-butyl malonate, di2-ethylhexyl malonate, etc.)], oximes. Compounds (compounds having a structure represented by -C(=N-OH)- in the molecule such as formaldoxime, acetaldoxime, acetoxime, methylethylketoxime, and cyclohexanone oxime) can be mentioned.

Among these, as a blocking agent with a dissociation temperature of 90 to 160°C, for example, at least one type selected from oxime compounds and pyrazole compounds is preferable from the viewpoint of storage stability.

The block isocyanate compound preferably has an isocyanurate structure in terms of, for example, improving the brittleness of the film and improving adhesion to the transfer target.

A block isocyanate compound having an isocyanurate structure is obtained, for example, by isocyanurating hexamethylene diisocyanate and protecting it.

Among the block isocyanate compounds having an isocyanurate structure, compounds having an oxime structure using an oxime compound as a blocking agent are more likely to set the dissociation temperature in a desirable range than compounds not having an oxime structure, and furthermore, the compounds having an oxime structure are more likely to maintain the development residue. This is desirable in that it is easy to do less.

The block isocyanate compound may have a polymerizable group.

The polymerizable group is not particularly limited, and known polymerizable groups can be used, with radical polymerizable groups being preferred.

Examples of the polymerizable group include groups having ethylenically unsaturated groups such as (meth)acryloxy group, (meth)acrylamide group, and styryl group, and epoxy groups such as glycidyl group.

Among them, as the polymerizable group, an ethylenically unsaturated group is preferable, a (meth)acryloxy group is more preferable, and an acryloxy group is still more preferable.

As the block isocyanate compound, a commercial product can be used.

Examples of commercially available block isocyanate compounds include Karenz (registered trademark) AOI-BM, Karenz (registered trademark) MOI-BM, Karenz (registered trademark) MOI-BP, etc. (above, Showa Denko Co., Ltd.) (made), block-type Duranate series (for example, Duranate (registered trademark) TPA-B80E, Duranate (registered trademark) SBN-70D, Duranate (registered trademark) WT32-B75P, etc., Asahi Kasei Chemicals ( Co., Ltd.) can be mentioned. As a block isocyanate compound, a block isocyanate compound with an NCO value of 4.5 mmol/g or more (hereinafter sometimes referred to as a first block isocyanate compound) has the effect of the present invention. It is preferable in that it is superior. The NCO value of the first block isocyanate compound is preferably 5.0 mmol/g or more, and more preferably 5.3 mmol/g or more.

The upper limit of the NCO value of the first block isocyanate compound is preferably 8.0 mmol/g or less, more preferably 6.0 mmol/g or less, and more preferably less than 5.8 mmol/g because the effect of the present invention is more excellent. It is preferred, and 5.7 mmol/g or less is particularly preferred.

The NCO value of the block isocyanate compound in the present invention means the number of moles of isocyanate groups contained per 1 g of the block isocyanate compound, and is a value calculated from the structural formula of the block isocyanate compound.

The first block isocyanate compound preferably has a ring structure because the effect of the present invention is more excellent. Ring structures include aliphatic hydrocarbon rings, aromatic hydrocarbon rings, and heterocycles. Since the effect of the present invention is more excellent, aliphatic hydrocarbon rings and aromatic hydrocarbon rings are preferred, and aliphatic hydrocarbon rings are more preferred. desirable.

Specific examples of the aliphatic hydrocarbon ring include a cyclopentane ring and a cyclohexane ring, and among them, a cyclohexane ring is preferable.

Specific examples of the aromatic hydrocarbon ring include a benzene ring and a naphthalene ring, and among them, a benzene ring is preferable.

Specific examples of heterocycles include isocyanurate rings.

When the first block isocyanate compound has a ring structure, the number of rings is preferably 1 to 2, and 1 is more preferable because the effect of the present invention is more excellent. In addition, when the first block isocyanate compound contains a condensed ring, the number of rings constituting the condensed ring is counted. For example, the number of rings in a naphthalene ring is counted as 2.

The number of block isocyanate groups in the first block isocyanate compound is preferably 2 to 5, from the viewpoint of excellent strength of the formed pattern and more excellent effects of the present invention, and 2 to 5. 3 is more preferable, and 2 is more preferable.

The first block isocyanate compound is preferably a block isocyanate compound represented by formula Q because the effect of the present invention is more excellent.

B ¹ -A ¹ -L ¹ -A ² -B ² Equation Q

In formula Q, B ¹ and B ² each independently represent a block isocyanate group.

The blocked isocyanate group is not particularly limited, but in view of the superior effect of the present invention, a group in which the isocyanate group is blocked with an oxime compound is preferable, and a group in which the isocyanate group is blocked with methyl ethyl ketoxime is preferred. (Specifically, a group represented by *-NH-C(=O)-ON=C(CH ₃ )-C ₂ H _5. * represents the bonding position with A ¹ or A ^2. ) is more preferable. .

B ¹ and B ² are preferably the same group.

In formula Q, A ¹ and A ² each independently represent a single bond or an alkylene group with 1 to 10 carbon atoms, and an alkylene group with 1 to 10 carbon atoms is preferable.

The alkylene group may be linear, branched, or cyclic, but is preferably linear.

The carbon number of the alkylene group is 1 to 10, but since the effect of the present invention is more excellent, 1 to 5 are preferable, 1 to 3 are more preferable, and 1 is still more preferable.

A ¹ and A ² are preferably the same group.

In formula Q, L ¹ represents a divalent linking group.

Specific examples of the divalent linking group include a divalent hydrocarbon group.

Specific examples of the divalent hydrocarbon group include a divalent saturated hydrocarbon group, a divalent aromatic hydrocarbon group, and a group formed by connecting two or more of these groups.

The divalent saturated hydrocarbon group may be linear, branched, or cyclic, and is preferably cyclic because the effect of the present invention is more excellent. The number of carbon atoms of the divalent saturated hydrocarbon group is preferably 4 to 15, more preferably 5 to 10, and still more preferably 5 to 8, since the effect of the present invention is more excellent.

The divalent aromatic hydrocarbon group preferably has 5 to 20 carbon atoms, and examples include phenylene groups. The divalent aromatic hydrocarbon group may have a substituent (for example, an alkyl group).

Among them, the divalent linking group includes a linear, branched or cyclic divalent saturated hydrocarbon group having 5 to 10 carbon atoms, a cyclic saturated hydrocarbon group having 5 to 10 carbon atoms and a linear alkylene group having 1 to 3 carbon atoms. A group, a divalent aromatic hydrocarbon group that may have a substituent, or a group in which a divalent aromatic hydrocarbon group is linked to a linear alkylene group having 1 to 3 carbon atoms is preferred, and a cyclic divalent saturated hydrocarbon group having 5 to 10 carbon atoms is preferable. A group or a phenylene group which may have a substituent is more preferable, a cyclohexylene group or a phenylene group which may have a substituent is more preferable, and a cyclohexylene group is particularly preferable.

The block isocyanate compound represented by the formula Q is particularly preferably a block isocyanate compound represented by the formula QA because the effect of the present invention is more excellent.

B ^1a -A ^1a -L ^1a -A ^2a -B ^2a Formula QA

In the formula QA, B ^1a and B ^2a each independently represent a block isocyanate group. The suitable embodiments of B ^1a and B ^2a are the same as B ¹ and B ² in Formula Q.

In the formula QA, A ^1a and A ^2a each independently represent a divalent linking group. The suitable form of the divalent linking group in A ^1a and A ^2a is the same as that for A ¹ and A ² in formula Q.

In the formula QA, L ^1a represents a cyclic divalent saturated hydrocarbon group or a divalent aromatic hydrocarbon group.

The number of carbon atoms of the cyclic divalent saturated hydrocarbon group in L ^1a is preferably 5 to 10, more preferably 5 to 8, more preferably 5 to 6, and especially preferably 6.

The suitable form of the divalent aromatic hydrocarbon group in L ^1a is the same as that for L ¹ in the formula Q.

Among them, L ^1a is preferably a cyclic divalent saturated hydrocarbon group, more preferably a cyclic divalent saturated hydrocarbon group having 5 to 10 carbon atoms, and even more preferably a cyclic divalent saturated hydrocarbon group having 5 to 10 carbon atoms. , a cyclic divalent saturated hydrocarbon group having 5 to 6 carbon atoms is particularly preferable, and a cyclohexylene group is most preferable.

When L ^1a is a cyclohexylene group, the block isocyanate compound represented by formula QA may be an isomer mixture of cis and trans isomers (hereinafter also referred to as “cis-trans isomer mixture”).

The mass ratio of the cis form and the trans form is preferably cis form/trans form = 10/90 to 90/10, and more preferably cis form/trans form = 40/60 to 60/40.

Specific examples of the first block isocyanate compound are shown below, but the first block isocyanate compound is not limited to this.

[Formula 24]

Heat-crosslinkable compounds may be used individually, or two or more types may be used in combination.

When the photosensitive composition layer contains a thermally crosslinkable compound, the content of the thermally crosslinkable compound is preferably 1 to 50% by mass, more preferably 5 to 30% by mass, based on the total mass of the photosensitive composition layer.

<Surfactant>

The photosensitive composition layer may contain a surfactant.

Examples of the surfactant include the surfactants described in paragraph [0017] of Japanese Patent Application Publication No. 4502784, and paragraphs [0060] to [0071] of Japanese Patent Application Publication No. 2009-237362.

Examples of the surfactant include hydrocarbon-based surfactants, fluorine-based surfactants, or silicone-based surfactants. From the viewpoint of improving environmental compatibility, it is preferable that the surfactant does not contain a fluorine atom. As the surfactant, a hydrocarbon-based surfactant or a silicone-based surfactant is preferable. Moreover, as the surfactant, a nonionic surfactant is preferable.

Commercially available fluorine-based surfactants include, for example, Megapak F-171, F-172, F-173, F-176, F-177, F-141, F-142, F-143, F-144, F -437, F-475, F-477, F-479, F-482, F-551-A, F-552, F-554, F-555-A, F-556, F-557, F-558 , F-559, F-560, F-561, F-565, F-563, F-568, F-575, F-780, EXP. MFS-330, EXP. MFS-578, EXP. MFS-578-2, EXP. MFS-579, EXP. MFS-586, EXP. MFS-587, EXP. MFS-628, EXP. MFS-631, EXP. MFS-603, R-41, R-41-LM, R-01, R-40, R-40-LM, RS-43, TF-1956, RS-90, R-94, RS-72-K, DS-21 (above, manufactured by DIC Corporation), Fluorad FC430, FC431, FC171 (above, manufactured by Sumitomo 3M Corporation), Surfron S-382, SC-101, SC-103, SC-104, SC-105 , SC-1068, SC-381, SC-383, S-393, KH-40 (above, manufactured by AGC Corporation), PolyFox PF636, PF656, PF6320, PF6520, PF7002 (above, manufactured by OMNOVA Corporation), Ftergent 710FL , 710FM, 610FM, 601AD, 601ADH2, 602A, 215M, 245F, 251, 212M, 250, 209F, 222F, 208G, 710LA, 710FS, 730LM, 650AC, 681, 683 (or more, made by NEOS) ),U- 120E (Unichem Co., Ltd.), etc.

Additionally, as a fluorine-based surfactant, an acrylic compound that has a molecular structure having a functional group containing a fluorine atom, and when heated, the portion of the functional group containing a fluorine atom is cut and the fluorine atom volatilizes can also be suitably used. Examples of such fluorine-based surfactants include the Megapaak DS series manufactured by DIC Corporation (Kagaku Kogyo Nippo (February 22, 2016), Nikkei Sangyo Shinbun (February 23, 2016)), for example, Megapaak DS. -21.

Additionally, as the fluorine-based surfactant, it is also preferable to use a polymer of a fluorine atom-containing vinyl ether compound having a fluorinated alkyl group or a fluorinated alkylene ether group and a hydrophilic vinyl ether compound.

Additionally, block polymers can also be used as fluorine-based surfactants.

Moreover, as a fluorine-based surfactant, it has a structural unit derived from a (meth)acrylate compound having a fluorine atom and 2 or more (preferably 5 or more) alkyleneoxy groups (preferably ethyleneoxy groups and propyleneoxy groups). Fluorinated polymer compounds containing structural units derived from (meth)acrylate compounds can also be preferably used.

Additionally, as the fluorine-based surfactant, a fluorinated polymer having an ethylenically unsaturated bond-containing group in the side chain can also be used. Megapak RS-101, RS-102, RS-718K, RS-72-K (above, manufactured by DIC Corporation), etc.

As a fluorine-based surfactant, from the viewpoint of improving environmental compatibility, it can be used as an alternative to compounds having a linear perfluoroalkyl group with 7 or more carbon atoms, such as perfluorooctanoic acid (PFOA) and perfluorooctanesulfonic acid (PFOS). It is preferable that it is a surfactant derived from a surfactant.

Hydrocarbon-based surfactants include glycerol, trimethylolpropane, trimethylolethane and their ethoxylates and propoxylates (e.g., glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl. Ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate. , sorbitan fatty acid ester, etc. Specific examples include Pluronic L10, L31, L61, L62, 10R5, 17R2, 25R2, Tetronic 304, 701, 704, 901, 904, 150R1, HYDROPALAT WE 3323 (manufactured by BASF), Solsperse 20000 (above, Nippon Lubrizol Co., Ltd. product, NCW-101, NCW-1001, NCW-1002 (above, Fujifilm Wako Pure Chemical Co., Ltd. product), Pionin D-1105, D-6112, D-6112-W , D-6315 (above, manufactured by Takemoto Yushi Co., Ltd.), Allfin E1010, Surfinol 104, 400, 440 (above, manufactured by Nisshin Chemical Industry Co., Ltd.), etc.

Examples of silicone-based surfactants include linear polymers composed of siloxane bonds and modified siloxane polymers with organic groups introduced into side chains or terminals.

Specific examples of silicone-based surfactants include:

EXP. S-309-2, EXP. S-315, EXP. S-503-2, EXP. S-505-2 (above, manufactured by DIC Corporation), DOWSIL 8032 ADDITIVE, Toray Silicon DC3PA, Toray Silicon SH7PA, Toray Silicon DC11PA, Toray Silicon SH21PA, Toray Silicon SH28PA, Toray Silicon SH29PA, Toray Silicon SH30PA, Toray Silicon SH8400 (above , manufactured by Toray Dow Corning Co., Ltd., and X-22-4952, -642, KF-643, X-22-6191, , KP-109, KP-112, KP-120, KP-121, KP-124, KP-125, KP-301, KP-306, KP-310, KP-322, KP-323, KP-327, KP -341, KP-368, KP-369, KP-611, KP-620, KP-621, KP-626, KP-652 (above, manufactured by Shin-Etsu Silicone Co., Ltd.), F-4440, TSF-4300, TSF- 4445, TSF-4460, TSF-4452 (manufactured by Momentive Performance Materials), BYK300, BYK306, BYK307, BYK310, BYK320, BYK323, BYK325, BYK330, BYK313, BYK315N, BYK331, BYK333, BYK345, 347, Examples include BYK348, BYK349, BYK370, BYK377, and BYK378 (manufactured by Big Chemistry).

Surfactants may be used individually or in combination of two or more.

When the photosensitive composition layer contains a surfactant, the content of the surfactant is preferably 0.01 to 3.0% by mass, more preferably 0.01 to 1.0% by mass, and 0.05 to 0.80% by mass, based on the total mass of the photosensitive composition layer. It is more desirable.

<Polymerization inhibitor>

The photosensitive composition layer may contain a polymerization inhibitor.

A polymerization inhibitor refers to a compound that has the function of delaying or inhibiting a polymerization reaction. As the polymerization inhibitor, for example, known compounds used as polymerization inhibitors can be used.

Examples of polymerization inhibitors include phenothiazine compounds such as phenothiazine, bis-(1-dimethylbenzyl)phenothiazine, and 3,7-dioctylphenothiazine; Bis[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionic acid][ethylenebis(oxyethylene)], 2,4-bis[(laurylthio)methyl]-o-cresol, 1,3,5-tris(3,5-di-t-butyl-4-hydroxybenzyl), 1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethyl Benzyl), 2,4-bis-(n-octylthio)-6-(4-hydroxy-3,5-di-t-butylanilino)-1,3,5-triazine, and penta Hindered phenol compounds such as erythritoltetrakis 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate; Nitroso compounds or salts thereof such as 4-nitrosophenol, N-nitrosodiphenylamine, N-nitrosocyclohexylhydroxylamine, and N-nitrosophenylhydroxylamine; Quinone compounds such as methylhydroquinone, t-butylhydroquinone, 2,5-di-t-butylhydroquinone, and 4-benzoquinone; Phenol compounds such as 4-methoxyphenol, 4-methoxy-1-naphthol, and t-butylcatechol; Metal salt compounds such as copper dibutyl dithiocarbamate, copper diethyl dithiocarbamate, manganese diethyl dithiocarbamate, and manganese diphenyl dithiocarbamate can be mentioned.

Among them, since the effect of the present invention is more excellent, the polymerization inhibitor is preferably at least one selected from the group consisting of phenothiazine compounds, nitroso compounds or salts thereof, and hindered phenol compounds, and phenothiazine compounds or salts thereof are preferred. Azine, bis[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionic acid], [ethylenebis(oxyethylene)] 2,4-bis[(laurylthio)methyl]-o- Cresol, 1,3,5-tris(3,5-di-t-butyl-4-hydroxybenzyl), p-methoxyphenol, and N-nitrosophenylhydroxylamine aluminum salt are more preferred. .

Polymerization inhibitors may be used individually, or two or more types may be used in combination.

When the photosensitive composition layer contains a polymerization inhibitor, the content of the polymerization inhibitor is preferably 0.001 to 5.0% by mass, more preferably 0.01 to 3.0% by mass, and 0.02 to 2.0% by mass, based on the total mass of the photosensitive composition layer. % is more preferable. The content of the polymerization inhibitor is preferably 0.005 to 5.0 mass%, more preferably 0.01 to 3.0 mass%, and still more preferably 0.01 to 1.0 mass%, based on the total mass of the polymerizable compound.

<Hydrogen Donating Compound>

The photosensitive composition layer may contain a hydrogen donating compound.

The hydrogen donating compound has functions such as further improving the sensitivity of the photopolymerization initiator to actinic light and suppressing inhibition of polymerization of the polymerizable compound by oxygen.

Examples of hydrogen donating compounds include amines and amino acid compounds.

As amines, for example, M. R. Sander et al., "Journal of Polymer Society", volume 10, page 3173 (1972), Japanese Patent Publication No. 44-020189, Japanese Patent Application Publication No. 51-082102, Japanese Patent Publication No. Japanese Patent Application Laid-Open No. 52-134692, Japanese Patent Application Publication No. 59-138205, Japanese Patent Application Publication No. 60-084305, Japanese Patent Application Publication No. 62-018537, Japanese Patent Application Publication No. 64-033104, and Research Disclosure Compounds described in No. 33825 and the like can be mentioned. More specifically, 4,4'-bis(diethylamino)benzophenone, tris(4-dimethylaminophenyl)methane (aka: Leuco Crystal Violet), triethanolamine, and p-dimethylaminobenzoic acid ethyl ester. , p-formyldimethylaniline, and p-methylthiodimethylaniline.

Among them, since the effect of the present invention is more excellent, the amines include at least one selected from the group consisting of 4,4'-bis(diethylamino)benzophenone and tris(4-dimethylaminophenyl)methane. Paper is preferred.

Examples of amino acid compounds include N-phenylglycine, N-methyl-N-phenylglycine, and N-ethyl-N-phenylglycine.

Among them, N-phenylglycine is preferable as the amino acid compound because the effect of the present invention is more excellent.

In addition, examples of the hydrogen donating compound include organometallic compounds (tributyl tin acetate, etc.) described in Japanese Patent Publication No. 48-042965, hydrogen donors described in Japanese Patent Publication No. 55-034414, and, Sulfur compounds (such as tricyan) described in Japanese Patent Application Laid-Open No. 6-308727 can also be mentioned.

Hydrogen donating compounds may be used individually, or two or more types may be used in combination.

When the photosensitive composition layer contains a hydrogen donating compound, the content of the hydrogen donating compound is 0.01 to 10.0 with respect to the total mass of the photosensitive composition layer in terms of improving the curing speed by balancing the polymerization growth rate and chain transfer. The mass % is preferable, 0.01 to 8.0 mass % is more preferable, and 0.03 to 5.0 mass % is more preferable.

<Impurities, etc.>

The photosensitive composition layer may contain a predetermined amount of impurities.

Specific examples of impurities include sodium, potassium, magnesium, calcium, iron, manganese, copper, aluminum, titanium, chromium, cobalt, nickel, zinc, tin, halogen, and ions thereof. Among them, halide ions (chloride ions, bromide ions, iodide ions), sodium ions, and potassium ions are likely to be incorporated as impurities, so the contents are preferably set to the following.

The content of impurities in the photosensitive composition layer is preferably 80 ppm or less, more preferably 10 ppm or less, and still more preferably 2 ppm or less, based on mass. The content of impurities in the photosensitive composition layer can be 1 ppb or more or 0.1 ppm or more on a mass basis. A specific example of the content of impurities in the photosensitive composition layer includes an embodiment in which all of the above impurities are 0.6 ppm on a mass basis.

Methods for keeping the impurities within the above range include selecting a raw material with a low content of impurities as a raw material for the photosensitive composition layer, preventing mixing of impurities during formation of the photosensitive composition layer, and removing them by washing. . By this method, the amount of impurities can be within the above range.

Impurities can be quantified by known methods such as ICP (Inductively Coupled Plasma) emission spectroscopy, atomic absorption spectroscopy, and ion chromatography, for example.

In the photosensitive composition layer, benzene, formaldehyde, trichlorethylene, 1,3-butadiene, carbon tetrachloride, chloroform, N,N-dimethylformamide, N,N-dimethylacetamide, and hexane. It is preferable that the content of compounds such as cein is small. The content of these compounds in the photosensitive composition layer is preferably 100 ppm or less, more preferably 20 ppm or less, and even more preferably 4 ppm or less on a mass basis. The lower limit can be 10 ppb or more based on mass, and can be 100 ppb or more. The content of these compounds can be suppressed in the same manner as the above-mentioned metal impurities. Additionally, it can be quantified using a known measurement method.

The water content in the photosensitive composition layer is preferably 0.01 to 1.0 mass%, and more preferably 0.05 to 0.5 mass%, from the viewpoint of improving reliability and lamination properties.

<Residual monomer>

The photosensitive composition layer may contain residual monomers of each structural unit of the alkali-soluble resin described above.

From the viewpoint of patterning properties and reliability, the content of the remaining monomer is preferably 5,000 ppm by mass or less, more preferably 2,000 ppm by mass or less, and still more preferably 500 ppm by mass or less, relative to the total mass of the alkali-soluble resin. The lower limit is not particularly limited, but is preferably 1 ppm by mass or more, and more preferably 10 ppm by mass or more.

The residual monomer of each structural unit of the alkali-soluble resin is preferably 3,000 ppm by mass or less, more preferably 600 ppm by mass or less, and 100 ppm by mass, relative to the total mass of the photosensitive composition layer, from the viewpoint of patterning properties and reliability. The following is more preferable. The lower limit is not particularly limited, but is preferably 0.1 ppm by mass or more, and more preferably 1 ppm by mass or more.

It is preferable that the amount of residual monomers when synthesizing an alkali-soluble resin by polymer reaction is within the above range. For example, when synthesizing an alkali-soluble resin by reacting glycidyl acrylate with a carboxylic acid side chain, it is preferable that the content of glycidyl acrylate is within the above range.

The amount of remaining monomer can be measured by known methods such as liquid chromatography and gas chromatography.

<Other ingredients>

The photosensitive composition layer may contain components (hereinafter also referred to as “other components”) other than the components described above. Other components include, for example, colorants, antioxidants, and particles (for example, metal oxide particles). Additionally, other components include other additives described in paragraphs [0058] to [0071] of Japanese Patent Application Laid-Open No. 2000-310706.

(particle)

As the particles, metal oxide particles are preferable.

Metals in metal oxide particles also include semimetals such as B, Si, Ge, As, Sb, and Te.

From the viewpoint of transparency of the cured film, for example, the average primary particle diameter of the particles is preferably 1 to 200 nm, and more preferably 3 to 80 nm.

The average primary particle diameter of particles is calculated by measuring the particle diameters of 200 arbitrary particles using an electron microscope and taking the arithmetic average of the measurement results. Additionally, when the shape of the particle is not spherical, the longest side is taken as the particle diameter.

When the photosensitive composition layer contains particles, it may contain only one type or two or more types of particles different in metal species, size, etc.

The photosensitive composition layer does not contain particles, or when the photosensitive composition layer contains particles, the particle content is preferably greater than 0% by mass and 35% by mass or less with respect to the total mass of the photosensitive composition layer, and the particles are preferably It is more preferable that the particle content is more than 0% by mass and 10% by mass or less based on the total mass of the photosensitive composition, and that the particle content is not included or the particle content is 0% by weight with respect to the total mass of the photosensitive composition layer. It is more preferable that the mass% exceeds 5% by mass or less and does not contain particles, or the particle content is more preferably more than 0% by mass and 1% by mass or less relative to the total mass of the photosensitive composition layer, and it does not contain particles. Particularly desirable.

(coloring agent)

The photosensitive composition layer may contain a trace amount of colorant (pigment, dye, etc.), but, for example, from the viewpoint of transparency, it is preferable that the photosensitive composition layer does not contain a colorant substantially.

When the photosensitive composition layer contains a colorant, the content of the colorant is preferably less than 1% by mass, and more preferably less than 0.1% by mass, based on the total mass of the photosensitive composition layer.

(antioxidant)

Antioxidants include, for example, 1-phenyl-3-pyrazolidone (aka phenidone), 1-phenyl-4,4-dimethyl-3-pyrazolidone, and 1-phenyl-4-methyl. 3-pyrazolidone such as -4-hydroxymethyl-3-pyrazolidone; polyhydroxybenzenes such as hydroquinone, catechol, pyrogallol, methylhydroquinone, and chlorohydroquinone; Paramethylaminophenol, paraaminophenol, parahydroxyphenylglycine, and paraphenylenediamine can be mentioned.

Among them, since the effect of the present invention is more excellent, 3-pyrazolidone is preferable as the antioxidant, and 1-phenyl-3-pyrazolidone is more preferable.

When the photosensitive composition layer contains an antioxidant, the content of the antioxidant is preferably 0.001% by mass or more, more preferably 0.005% by mass or more, and still more preferably 0.01% by mass or more, based on the total mass of the photosensitive composition layer. . The upper limit is not particularly limited, but is preferably 1% by mass or less.

<Thickness of photosensitive composition layer>

The thickness of the photosensitive composition layer is not particularly limited, but is often 30 μm or less. Since the effect of the present invention is more excellent, 20 μm or less is preferable, 15 μm or less is more preferable, 10 μm or less is still more preferable, and 5.0 μm or less. The following is particularly preferable. As a lower limit, 0.60 μm or more is preferable, and 1.5 μm or more is more preferable because the strength of the film obtained by curing the photosensitive composition layer is excellent.

The thickness of the photosensitive composition layer can be calculated, for example, as the average value of five arbitrary points measured by cross-sectional observation using a scanning electron microscope (SEM).

<Refractive index of photosensitive composition layer>

The refractive index of the photosensitive composition layer is preferably 1.41 to 1.59, and more preferably 1.47 to 1.56.

<Color of photosensitive composition layer>

The photosensitive composition layer is preferably achromatic. Specifically, total reflection (angle of incidence 8°, light source: D-65 (2° field of view)) is preferably in the CIE1976 (L*, a*, b*) color space, and the L ^* value is 10 to 90. The a ^* value is preferably -1.0 to 1.0, and the b ^* value is preferably -1.0 to 1.0.

Additionally, the pattern obtained by curing the photosensitive composition layer (cured film of the photosensitive composition layer) is preferably achromatic.

Specifically, total reflection (angle of incidence 8°, light source: D-65 (2° field of view)) is in the CIE1976 (L*, a*, b*) color space, and the L ^* value of the pattern is 10 to 90. It is preferable that the a ^* value of the pattern is -1.0 to 1.0, and the b ^* value of the pattern is preferably -1.0 to 1.0.

<Transmittance of photosensitive composition layer>

The visible light transmittance per 1.0 μm film thickness of the photosensitive composition layer is preferably 80% or more, more preferably 90% or more, and most preferably 95% or more. As for the visible light transmittance, it is desirable that the average transmittance with a wavelength of 400 nm to 800 nm, the minimum transmittance with a wavelength of 400 nm to 800 nm, and the transmittance with a wavelength of 400 nm all satisfy the above. Preferred values of transmittance include, for example, 87%, 92%, and 98%. The transmittance per 1 μm film thickness of the cured film of the photosensitive composition layer is also the same.

<Water permeability of photosensitive composition layer>

The moisture permeability of the pattern (cured film of the photosensitive composition layer) obtained by curing the photosensitive composition layer at a film thickness of 40 μm is preferably 500 g/m ² /24 hr or less from the viewpoint of rust prevention of the electrode or wiring and reliability of the device. And, it is more preferable that it is 300g/ ^m2 /24hr or less, and it is more preferable that it is 100g/ ^m2 /24hr or less.

The moisture permeability is measured with a cured film obtained by curing the photosensitive composition layer by exposing the photosensitive composition layer to an i-line at an exposure amount of 300 mJ/cm ² and then post-baking the photosensitive composition layer at 145°C for 30 minutes. Measurement of moisture permeability is performed according to the cup method of JIS Z0208. In any of the test conditions of temperature 40°C/humidity 90%, temperature 65°C/humidity 90%, and temperature 80°C/humidity 95%, the above water vapor transmission rate is preferable. Specific preferable values include, for example, 80 g/m ² /24hr, 150 g/m ² /24hr, 220 g/m ² /24hr, etc.

<Dissolution rate of photosensitive composition layer>

The dissolution rate of the photosensitive composition layer in the 1.0% sodium carbonate aqueous solution is preferably 0.01 μm/sec or more, more preferably 0.10 μm/sec or more, and more preferably 0.20 μm/sec or more from the viewpoint of suppressing residues during development. desirable. From the viewpoint of the edge shape of the pattern, 5.0 μm/sec or less is preferable, 4.0 μm/sec or less is more preferable, and 3.0 μm/sec or less is still more preferable. Specific preferable values include, for example, 1.8 μm/sec, 1.0 μm/sec, and 0.7 μm/sec. The dissolution rate per unit time of the photosensitive composition layer in a 1.0 mass% sodium carbonate aqueous solution is measured as follows.

A photosensitive composition layer (within a film thickness of 1.0 to 10 μm) formed on a glass substrate from which the solvent has been sufficiently removed is subjected to a shower phenomenon at 25°C using a 1.0 mass% sodium carbonate aqueous solution until the photosensitive composition layer is completely dissolved. (However, the maximum is 2 minutes).　The film thickness of the photosensitive composition layer is determined by dividing it by the time required for the photosensitive composition layer to completely dissolve. In addition, if it is not completely dissolved in 2 minutes, the same calculation is made from the amount of change in film thickness so far.

The dissolution rate of the cured film of the photosensitive composition layer (within a film thickness of 1.0 to 10 μm) in a 1.0% sodium carbonate aqueous solution is preferably 3.0 μm/sec or less, more preferably 2.0 μm/sec or less, and 1.0 μm/sec. Second or less is more preferable, and 0.2 μm/second or less is most preferable. The cured film of the photosensitive composition layer is a film obtained by exposing the photosensitive composition layer to i-line at an exposure amount of 300 mJ/cm ² . Specific preferable values include, for example, 0.8 μm/sec, 0.2 μm/sec, and 0.001 μm/sec. For development, a 1/4MINJJX030PP shower nozzle manufactured by Ikeuchi Co., Ltd. was used, and the spray pressure of the shower was set to 0.08 MPa. Under the above conditions, the shower flow rate per unit time is 1,800 mL/min.

<Swelling rate of photosensitive composition layer>

From the viewpoint of improving pattern formation, the swelling ratio of the photosensitive composition layer after exposure with respect to the 1.0 mass% sodium carbonate aqueous solution is preferably 100% or less, more preferably 50% or less, and still more preferably 30% or less. The swelling ratio of the photosensitive resin layer after exposure to a 1.0 mass% sodium carbonate aqueous solution is measured as follows.

A photosensitive resin layer (within a film thickness of 1.0 to 10 μm) formed on a glass substrate from which the solvent has been sufficiently removed is exposed to light at 500 mJ/cm ² (i-line measurement) with an ultra-high pressure mercury lamp. A glass substrate is immersed in a 1.0 mass% sodium carbonate aqueous solution at 25°C, and the film thickness is measured after 30 seconds. Then, the rate at which the film thickness after immersion increases with respect to the film thickness before immersion is calculated. Specific preferable values include, for example, 4%, 13%, and 25%.

<Foreign matter in photosensitive composition layer>

From the viewpoint of pattern formation, the number of foreign substances with a diameter of 1.0 μm or more in the photosensitive composition layer is preferably 10 pieces/mm ² or less, and more preferably 5 pieces/mm ² or less. The number of foreign substances is measured as follows. From the direction normal to the surface of the photosensitive composition layer, five arbitrary areas (1 mm x 1 mm) on the surface of the photosensitive composition layer were visually observed using an optical microscope, and each area had a diameter of 1.0 μm or more. The number of foreign substances is measured, and the arithmetic average of them is calculated as the number of foreign substances. Specific preferable values include, for example, 0 pieces/mm ² , 1 piece/mm ² , 4 pieces/mm ² , and 8 pieces/mm ² .

<Haze of dissolved material in photosensitive composition layer>

From the viewpoint of suppressing the generation of aggregates during development, the haze of the solution obtained by dissolving a 1.0 cm ³ photosensitive resin layer in 1.0 liter of a 1.0 mass % sodium carbonate aqueous solution at 30°C is preferably 60% or less, and more preferably 30% or less. It is preferable, more preferably 10% or less, and most preferably 1% or less. Haze is measured as follows. First, a 1.0% by mass aqueous solution of sodium carbonate is prepared, and the liquid temperature is adjusted to 30°C. Add 1.0 cm ³ photosensitive resin layer to 1.0 L of sodium carbonate aqueous solution. Stir for 4 hours at 30°C, being careful not to introduce air bubbles. After stirring, the haze of the solution in which the photosensitive resin layer is dissolved is measured. Haze is measured using a haze meter (product name "NDH4000", manufactured by Nippon Denshoku Industries, Ltd.) using a liquid measurement unit and a liquid measurement cell with an optical path length of 20 mm. Specific preferable values include, for example, 0.4%, 1.0%, 9%, 24%, etc.

<<Protective Film>>

The transfer film has a protective film.

The protective film contains polypropylene.

The protective film is not particularly limited as long as it contains polypropylene, and may contain a resin other than polypropylene. Examples of other resins include polyolefin resins such as polyethylene, polyester resins such as polyethylene terephthalate, polycarbonate resins, and polystyrene resins.

Among them, as a protective film, a polyolefin film containing polypropylene is preferable, a polypropylene film or a polyethylene film containing polypropylene is more preferable, and a polypropylene film is still more preferable.

Moreover, the arithmetic mean roughness Ra1 of the surface on the photosensitive composition layer side of the protective film is smaller than the arithmetic mean roughness Ra2 of the surface on the opposite side to the photosensitive composition layer side of the protective film.

The arithmetic mean roughness Ra1 is not particularly limited as long as it is smaller than the arithmetic mean roughness Ra2, but since pattern defect suppression is excellent, the arithmetic mean roughness Ra1 is preferably 0.090 μm or less, and more preferably 0.050 μm or less. The lower limit of the arithmetic mean roughness Ra1 is 0.000 μm or more, and is often 0.005 μm or more.

The arithmetic mean roughness Ra2 is not particularly limited as long as it is greater than the arithmetic mean roughness Ra1, but from the viewpoint of excellent winding properties of the protective film, it is preferably greater than 0.050 μm, more preferably greater than 0.060 μm, and still more preferably greater than 0.070 μm, Greater than 0.080 μm is particularly preferred. The upper limit of the arithmetic mean roughness Ra2 is preferably 0.200 μm or less, more preferably less than 0.150 μm, and still more preferably 0.120 μm or less, in view of excellent inspection performance when inspecting defects in the transfer film, etc. 0.100 μm or less is particularly preferred.

Moreover, the ratio of the arithmetic mean illuminance Ra2 to the arithmetic mean illuminance Ra1 (arithmetic mean illuminance Ra2/arithmetic mean illuminance Ra1) is greater than 1, preferably 1.3 or more, and more preferably 1.7 or more. The upper limit of the ratio is not particularly set, but is preferably 5.0 or less, and more preferably 3.0 or less.

The arithmetic mean roughness Ra2 of the protective film is obtained by measuring the surface roughness of the surface on the opposite side to the photosensitive composition layer of the transfer film.

In this specification, the arithmetic mean roughness Ra2 is the arithmetic mean roughness Ra based on JIS B 0601:2001 from the contour curve obtained by measuring the irregularities of the surface with a fine shape measuring device (ET-350K, manufactured by Kosaka Kenkyusho Co., Ltd.). It is assumed that . In addition, 3D analysis software (TDA-22, manufactured by Kosaka Kenkyusho Co., Ltd.) is used to calculate the arithmetic mean illuminance Ra.

In addition, the arithmetic mean roughness Ra1 of the protective film is the arithmetic mean roughness Ra1 of the transfer film, which is the arithmetic mean roughness of the surface of the protective film on the side that was in contact with the photosensitive composition layer when the protective film is peeled off at the interface between the protective film and the photosensitive composition layer. It is obtained by measuring in the same way as Ra2.

The thickness of the protective film is preferably 1 to 100 μm, more preferably 5 to 50 μm, more preferably 5 to 40 μm, and especially preferably 10 to 30 μm.

Since the thickness of the protective film is excellent in mechanical strength, it is preferably 1 μm or more, and more preferably 10 μm or more. Moreover, from the viewpoint of relatively low cost and the ability to reduce bubbles during manufacturing, which will be described later, 100 μm or less is preferable, and 30 μm or less is more preferable. By reducing the number of bubbles during manufacturing, pattern defect suppression can also be improved.

Moreover, in the protective film, it is preferable that the number of fish eyes with a diameter of 80 μm or more contained in the protective film is 5/m ² or less.

In addition, "fish eye" refers to the fact that when a material is heat-melted and a film is manufactured by methods such as kneading, extrusion, biaxial stretching, and casting, foreign substances, undissolved substances, and oxidation-deteriorated substances of the material are removed from the film. It was introduced during

The number of particles with a diameter of 3 μm or more contained in the protective film is preferably 30 particles/mm ² or less, more preferably 10 particles/mm ² or less, and even more preferably 5 particles/mm ² or less.

As a result, defects that occur when irregularities caused by particles contained in the protective film are transferred to the photosensitive composition layer or conductive layer can be suppressed.

<<Relationship between branch support, photosensitive composition layer, and protective film>>

The transfer film has a fracture elongation of 15% or more at 120°C of the cured film obtained by curing the photosensitive composition layer, the arithmetic mean roughness Ra of the surface on the photosensitive composition layer side of the support is 50 nm or less, and the photosensitive composition layer of the protective film has an arithmetic mean roughness Ra of 50 nm or less. It is also preferable that the arithmetic mean roughness Ra of the side surface is 150 nm or less.

Moreover, it is preferable that the transfer film satisfies the following formula (1).

X×Y<1500 equation (1)

Here, in formula (1), Indicates the value (nm) of roughness Ra. The above X×Y is more preferably 750 or less. Specific values of X include 18%, 25%, 30%, and 35%. Specific values of X×Y include 4nm, 8nm, 15nm, 30nm, etc. Specific values of X×Y include 150, 200, 300, 360, and 900.

It is preferable that the breaking elongation at 120°C is at least twice as large as the breaking elongation at 23°C of the cured film obtained by curing the photosensitive composition layer.

The breaking elongation is obtained by curing a 20 μm-thick photosensitive composition layer by exposing it to 120 mJ/cm ² with an ultra-high pressure mercury lamp, then further exposing it to 400 mJ/cm ² with a high pressure mercury lamp, and heating it at 145°C for 30 minutes. It is measured by a tensile test.

Moreover, it is also preferable that the transfer film satisfies the following formula (2).

Y≤Z equation (2)

Here, in formula (2), Y represents the arithmetic mean roughness Ra value (nm) of the surface on the photosensitive composition layer side of the support, and Z represents the arithmetic average roughness of the surface on the photosensitive composition layer side of the protective film. Indicates the value of Ra (nm).

<<Refractive index adjustment layer>>

The transfer film may have a refractive index adjustment layer.

As the refractive index adjustment layer, a known refractive index adjustment layer can be applied. Materials contained in the refractive index adjustment layer include, for example, binder polymers, polymerizable compounds, metal salts, and particles.

The method of controlling the refractive index of the refractive index adjustment layer is not particularly limited, and examples include a method using a resin of a predetermined refractive index alone, a method using a resin and particles, and a method using a complex of a metal salt and a resin. You can.

Examples of the binder polymer and polymerizable compound include the binder polymer and polymerizable compound described in the above section "Photosensitive composition layer."

Examples of particles include metal oxide particles and metal particles.

The type of metal oxide particles is not particularly limited and includes known metal oxide particles. Metals in metal oxide particles also include semimetals such as B, Si, Ge, As, Sb, and Te.

From the viewpoint of transparency of the cured film, for example, the average primary particle diameter of the particles is preferably 1 to 200 nm, and more preferably 3 to 80 nm.

The average primary particle diameter of particles is calculated by measuring the particle diameters of 200 arbitrary particles using an electron microscope and taking the arithmetic average of the measurement results. Additionally, when the shape of the particle is not spherical, the longest side is taken as the particle diameter.

Metal oxide particles specifically include zirconium oxide particles (ZrO ₂ particles), Nb ₂ O ₅ particles, titanium oxide particles (TiO ₂ particles), silicon dioxide particles (SiO ₂ particles), and composite particles thereof. At least one type selected from the group is preferred.

Among these, as the metal oxide particles, for example, at least one type selected from the group consisting of zirconium oxide particles and titanium oxide particles is more preferable because it is easy to adjust the refractive index.

Commercially available metal oxide particles include calcined zirconium oxide particles (manufactured by CIK Nanotech Co., Ltd., product name: ZRPGM15WT%-F04), calcined zirconium oxide particles (manufactured by CIK Nanotech Co., Ltd., product name: ZRPGM15WT%-F74), and calcined zirconium oxide particles (CIK Nanotech Co., Ltd., product name: ZRPGM15WT%-F74). Co., Ltd., product name: ZRPGM15WT%-F75), calcined zirconium oxide particles (CIK Nanotech Co., Ltd., product name: ZRPGM15WT%-F76), zirconium oxide particles (Nano Youth OZ-S30M, Nissan Chemical Industries, Ltd.), and , zirconium oxide particles (Nano Youth OZ-S30K, manufactured by Nissan Chemical Industries, Ltd.).

Particles may be used individually, or two or more types may be used in combination.

The content of particles in the refractive index adjustment layer is preferably 1 to 95% by mass, more preferably 20 to 90% by mass, and still more preferably 40 to 85% by mass, relative to the total mass of the refractive index adjustment layer.

When using titanium oxide as the metal oxide particle, the content of the titanium oxide particle is preferably 1 to 95% by mass, more preferably 20 to 90% by mass, and 40 to 85% by mass, relative to the total mass of the refractive index adjustment layer. It is more desirable.

The refractive index of the refractive index adjustment layer is preferably higher than that of the photosensitive composition layer.

The refractive index of the refractive index adjustment layer is preferably 1.50 or more, more preferably 1.55 or more, more preferably 1.60 or more, and especially preferably 1.65 or more. The upper limit of the refractive index of the refractive index adjustment layer is preferably 2.10 or less, more preferably 1.85 or less, and still more preferably 1.78 or less.

The thickness of the refractive index adjustment layer is preferably 50 to 500 nm, more preferably 55 to 110 nm, and still more preferably 60 to 100 nm.

The thickness of the refractive index adjustment layer is calculated as the average value of five arbitrary points measured by cross-sectional observation using a scanning electron microscope (SEM).

<<Method for producing the transfer film of the first embodiment>>

The manufacturing method of the transfer film of the first embodiment is not particularly limited, and a known method can be used.

As a method for producing the transfer film 10, for example, a step of applying a photosensitive composition to the surface of the support 1 to form a coating film, and drying the coating film to further form a photosensitive composition layer 3. A process of applying a composition for forming a refractive index adjusting layer to the surface of the photosensitive composition layer 3 to form a coating film, drying the coating film to further form a refractive index adjusting layer 5, and forming a coating film on the refractive index adjusting layer 5. For example, a method including the step of pressing the protective film 7 is mentioned.

By the above process, the transfer film 10 including the support (1), the photosensitive composition layer (3), the refractive index adjustment layer (5), and the protective film (7) can be manufactured.

After manufacturing the transfer film 10 by the above manufacturing method, a roll-shaped transfer film may be produced and stored by winding the transfer film 10. The roll-shaped transfer film can be provided in its original form to the roll-to-roll bonding process with the substrate described later.

In addition, in the method for manufacturing the transfer film 10, the refractive index adjusting layer 5 is formed on the protective film 7, and then the photosensitive resin layer 3 is formed on the surface of the refractive index adjusting layer 5. It can be done any way.

In addition, as a method for producing the transfer film 10, the photosensitive composition layer 3 is formed on the support 1, and the refractive index adjustment layer 5 is separately formed on the protective film 7, A method of forming the photosensitive composition layer 3 and the refractive index adjustment layer 5 by bonding them may be used.

<Method of forming photosensitive composition and photosensitive composition layer>

Because productivity is excellent and the photosensitive composition layer described above is easy to form, the photosensitive composition layer in the transfer film contains the components constituting the photosensitive composition layer described above (e.g., binder polymer, polymerizable compound, and It is preferably formed by a coating method using a photosensitive composition containing a polymerization initiator, etc.) and a solvent. As a method for producing the transfer film of the first embodiment, specifically, a photosensitive composition is applied onto a temporary support to form a coating film, and the coating film is subjected to a drying treatment at a predetermined temperature to form a photosensitive composition layer. desirable.

As a solvent that can be included in the photosensitive composition, an organic solvent is preferable. Organic solvents include, for example, methyl ethyl ketone, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate (aka: 1-methoxy-2-propyl acetate), and diethylene glycol ethyl. Examples include methyl ether, cyclohexanone, methyl isobutyl ketone, ethyl lactate, methyl lactate, caprolactam, n-propanol, and 2-propanol.

Additionally, as a solvent, an organic solvent (high boiling point solvent) with a boiling point of 180 to 250°C can be used as needed.

Solvents may be used individually or in combination of two or more.

The total solid content of the photosensitive composition is preferably 5 to 80% by mass, more preferably 5 to 40% by mass, and still more preferably 5 to 30% by mass, relative to the total mass of the photosensitive composition.

That is, the content of the solvent in the photosensitive composition is preferably 20 to 95% by mass, more preferably 60 to 95% by mass, and still more preferably 70 to 95% by mass, relative to the total mass of the photosensitive composition.

For example, from the viewpoint of applicability, the viscosity of the photosensitive composition at 25°C is preferably 1 to 50 mPa·s, more preferably 2 to 40 mPa·s, and still more preferably 3 to 30 mPa·s. Viscosity is measured using a viscometer. As a viscometer, for example, a viscometer (brand name: VISCOMETER TV-22) manufactured by Toki Sangyo Co., Ltd. can be suitably used. However, the viscometer is not limited to the above viscometer.

For example, the surface tension of the photosensitive composition at 25°C is preferably 5 to 100 mN/m, more preferably 10 to 80 mN/m, and still more preferably 15 to 40 mN/m from the viewpoint of coatability. Surface tension is measured using a surface tensiometer. As a surface tension meter, for example, a surface tension meter manufactured by Kyowa Kaimen Chemical Co., Ltd. (brand name: Automatic Surface Tensiometer CBVP-Z) can be suitably used. However, the surface tension meter is not limited to the surface tension meter described above.

Examples of application methods for the photosensitive composition include printing, spraying, roll coating, bar coating, curtain coating, spin coating, and die coating (i.e., slit coating).

As a drying method for the coating film of the photosensitive composition, heat drying and reduced pressure drying are preferred. In addition, in this specification, “drying” means removing at least part of the solvent contained in the composition. Drying methods include, for example, natural drying, heat drying, and reduced pressure drying. The above methods can be applied singly or in combination. As a drying temperature, 80 degreeC or more is preferable, and 90 degreeC or more is more preferable. Moreover, as the upper limit, 130°C or lower is preferable, and 120°C or lower is more preferable. Drying can also be done by continuously changing the temperature.

Moreover, as drying time, 20 seconds or more is preferable, 40 seconds or more is more preferable, and 60 seconds or more is still more preferable. The upper limit is not particularly limited, but is preferably 600 seconds or less, and more preferably 300 seconds or less.

<Composition for forming a refractive index adjustment layer and method for forming a refractive index adjustment layer>

The composition for forming the refractive index adjusting layer preferably contains various components and a solvent for forming the refractive index adjusting layer described above. In addition, in the composition for forming a refractive index adjusting layer, the suitable range of the content of each component with respect to the total solid content of the composition is the same as the suitable range of the content of each component with respect to the total mass of the refractive index adjusting layer described above.

The solvent is not particularly limited as long as it can dissolve or disperse the components contained in the refractive index adjustment layer, and at least one selected from the group consisting of water and water-miscible organic solvents is preferable, and water or water-miscible organic solvents are preferred. Mixed solvents are more preferable.

Examples of water-miscible organic solvents include alcohols having 1 to 3 carbon atoms, acetone, ethylene glycol, and glycerin, with alcohols having 1 to 3 carbon atoms being preferable, and methanol or ethanol being more preferable.

Solvents may be used individually by one type, or two or more types may be used.

The content of the solvent is preferably 50 to 2,500 parts by mass, more preferably 50 to 1,900 parts by mass, and still more preferably 100 to 900 parts by mass, based on 100 parts by mass of the total solid content of the composition.

The method of forming the refractive index adjustment layer is not particularly limited as long as it can form a layer containing the above components, and examples include known coating methods (slit coating, spin coating, curtain coating, and inkjet coating, etc.). You can.

<Method of pressing the protective film>

Moreover, the transfer film of 1st Embodiment can be manufactured by bonding a protective film to a refractive index adjustment layer.

The method of bonding the protective film to the refractive index adjustment layer is not particularly limited and includes known methods.

Examples of devices for bonding the protective film to the refractive index adjustment layer include known laminators such as a vacuum laminator and an auto-cut laminator.

The laminator is preferably provided with any heatable roller such as a rubber roller, and is capable of pressurizing and heating.

In addition, a protective film in which the arithmetic mean roughness Ra1 of the surface on the side of the photosensitive composition layer described above is smaller than the arithmetic mean roughness Ra2 of the surface on the side opposite to the photosensitive composition layer can be manufactured by a known method, and the manufacturing method thereof is not particularly limited.

For example, methods for controlling the arithmetic mean roughness Ra1 and Ra2 include a method using a physical action and a method using a chemical action. More specifically, a method of contacting the surface of a member having the desired surface roughness with the surface of the protective film, a method of cutting or polishing the surface of the protective film, a method of irradiating actinic rays or plasma to the surface of the protective film, and heat treatment. A method using the temperature difference between the crystal transformation temperature and melting point of polypropylene, a method of mixing polypropylene with a low melting point resin such as olefin to cause segregation, and a method combining the above methods. there is. If the method is applied to only one side of the protective film, or is applied to a different degree from the one side, a protective film in which the arithmetic mean roughness Ra1 is smaller than the arithmetic mean roughness Ra2 can be produced.

[Transfer film of second embodiment]

Below, an example of an embodiment of the transfer film of the second embodiment is described.

The transfer film 20 shown in FIG. 2 includes a temporary support 11, a composition layer 12 including a thermoplastic resin layer 13, an intermediate layer 15, and a photosensitive composition layer 17, and a protective film ( 19) in this order.

In addition, the transfer film 20 shown in FIG. 2 has the thermoplastic resin layer 13 and the intermediate layer 15 disposed, but the thermoplastic resin layer 13 and the intermediate layer 15 do not need to be disposed.

Below, each element constituting the transfer film is explained.

In the transfer film of the second embodiment, the temporary support 11 and the protective film 17 may be the same as the temporary support 1 and the protective film 9 of the first embodiment described above, and are suitable embodiments. Since it is the same, its description is omitted.

<<Photosensitive composition layer>>

The transfer film has a photosensitive composition layer.

In display devices equipped with a touch panel such as a capacitive input device (organic electroluminescence (EL) display devices, liquid crystal display devices, etc.), the electrode pattern corresponding to the sensor in the visible area, the peripheral wiring portion, and the extraction wiring portion are A conductive layer pattern such as wiring is provided inside the touch panel. In general, to form a patterned layer, a negative photosensitive composition layer (photosensitive layer) is provided on a substrate using a transfer film, etc., the photosensitive layer is exposed through a mask with a desired pattern, and then developed. The method is widely adopted. Therefore, the photosensitive composition layer is preferably a negative photosensitive composition layer. When the photosensitive composition layer is a negative photosensitive composition layer, the pattern formed corresponds to the cured layer.

When the photosensitive composition layer is a negative photosensitive composition layer, the negative photosensitive composition layer preferably contains a resin, a polymerizable compound, and a polymerization initiator. Moreover, when the photosensitive composition layer is a negative photosensitive composition layer, it is also preferable that an alkali-soluble resin (polymer A, which is an alkali-soluble resin, etc.) is included as part or all of the resin, as will be described later. That is, in one aspect, the photosensitive composition layer preferably contains a resin containing an alkali-soluble resin, a polymerizable compound, and a polymerization initiator.

This photosensitive composition layer (negative photosensitive composition layer) contains, based on the total mass of the photosensitive composition layer, resin: 10 to 90% by mass; Polymerizable compound: 5 to 70% by mass; Polymerization initiator: It is preferable to contain 0.01 to 20 mass%.

Below, each component is explained in order.

<Polymer A (resin)>

When the photosensitive composition layer is a negative photosensitive composition layer, the resin contained in the photosensitive composition layer is also specifically referred to as polymer A. Resin A is not particularly limited, but includes, for example, (meth)acrylic resin, styrene resin, epoxy resin, amide resin, amide epoxy resin, alkyd resin, phenol resin, ester resin, urethane resin, and epoxy. and acid-modified epoxy acrylate resin obtained by reaction of an acrylate resin and an acid anhydride.

As resin A, (meth)acrylic resin is preferable. In addition, in this specification, (meth)acrylic resin means resin which has structural units derived from a (meth)acrylic compound. In the (meth)acrylic resin, the content of the structural unit derived from the (meth)acrylic compound is preferably 30% by mass or more, and more preferably 50% by mass or more, based on the total structural units of the (meth)acrylic resin. , 60% by mass or more is more preferable. As the resin A, a polymer having a structural unit derived from a (meth)acrylic compound and a structural unit derived from a styrene compound is also preferable.

Polymer A is preferably an alkali-soluble resin.

The acid value of polymer A is preferably 220 mgKOH/g or less, more preferably less than 200 mgKOH/g, and less than 190 mgKOH/g from the viewpoint of better resolution by suppressing swelling of the negative photosensitive composition layer due to the developer. It is more desirable.

The lower limit of the acid value of polymer A is not particularly limited, but from the viewpoint of better developability, 60 mgKOH/g or more is preferable, 120 mgKOH/g or more is more preferable, 150 mgKOH/g or more is still more preferable, and 170 mgKOH/g or more is preferable. This is particularly desirable.

Additionally, the acid value (mgKOH/g) is the mass [mg] of potassium hydroxide required to neutralize 1 g of sample. The acid value can be calculated, for example, from the average content of acid groups in the compound.

The acid value of polymer A may be adjusted depending on the type of structural unit constituting polymer A and the content of the structural unit containing an acid group.

The weight average molecular weight of polymer A is preferably 5,000 to 500,000. A weight average molecular weight of 500,000 or less is preferable from the viewpoint of improving resolution and developability. The weight average molecular weight is more preferably 100,000 or less, and more preferably 60,000 or less. On the other hand, when the weight average molecular weight is 5,000 or more, it is preferable from the viewpoint of controlling the properties of the developed aggregate and the properties of the unexposed film, such as edge fuse properties and cut chip properties in the case of a negative photosensitive resin laminate. As for the weight average molecular weight, 10,000 or more is more preferable, 20,000 or more is more preferable, and 30,000 or more is especially preferable. Edge fusing property refers to the degree of ease with which the negative photosensitive composition layer protrudes from the end face of the roll when wound into a roll as a negative photosensitive resin laminate. Cut chip resistance refers to the degree of ease of scattering of chips when the unexposed film is cut with a cutter. If this chip adheres to the upper surface of the negative photosensitive resin laminate, etc., it will be transferred to the mask in the subsequent exposure process, etc., causing defective products. The dispersion degree of polymer A is preferably 1.0 to 6.0, more preferably 1.0 to 5.0, more preferably 1.0 to 4.0, and especially preferably 1.0 to 3.0. In the present disclosure, the degree of dispersion is the ratio of the weight average molecular weight to the number average molecular weight (weight average molecular weight/number average molecular weight). In the present disclosure, the weight average molecular weight and the number average molecular weight are values measured using gel permeation chromatography.

In the negative photosensitive composition layer, the polymer A preferably contains a structural unit based on a monomer having an aromatic hydrocarbon group from the viewpoint of suppressing the increase in line width and deterioration of resolution when the focus position during exposure is shifted. do. Examples of such aromatic hydrocarbon groups include substituted or unsubstituted phenyl groups and substituted or unsubstituted aralkyl groups. The content of the structural unit based on the monomer having an aromatic hydrocarbon group in the polymer A is preferably 20% by mass or more, and more preferably 30% by mass or more, with respect to the total mass of the polymer A. The upper limit is not particularly limited, but is preferably 95% by mass or less, and more preferably 85% by mass or less. In addition, when multiple types of polymer A are included, it is preferable that the average content of structural units based on monomers having an aromatic hydrocarbon group falls within the above range.

Examples of monomers having an aromatic hydrocarbon group include monomers having an aralkyl group, styrene, and polymerizable styrene derivatives (e.g., methylstyrene, vinyltoluene, tert-butoxystyrene, and acetoxystyrene). rene, 4-vinylbenzoic acid, styrene dimer, and styrene trimer, etc.). Among them, a monomer having an aralkyl group or styrene is preferable. In one aspect, when the monomer component having an aromatic hydrocarbon group in polymer A is styrene, the content of structural units based on styrene is preferably 20 to 70% by mass with respect to the total mass of polymer A. , 25 to 65 mass% is more preferable, 30 to 60 mass% is more preferable, and 30 to 55 mass% is particularly preferable. In addition, when the photosensitive resin layer contains multiple types of polymer A, the content of the structural unit derived from a monomer having an aromatic hydrocarbon group is determined as a weight average value.

Examples of the aralkyl group include substituted or unsubstituted phenylalkyl groups (excluding benzyl groups), substituted or unsubstituted benzyl groups, and substituted or unsubstituted benzyl groups are preferred.

Examples of monomers having a phenylalkyl group include phenylethyl (meth)acrylate.

Examples of the monomer having a benzyl group include (meth)acrylate having a benzyl group, such as benzyl (meth)acrylate, chlorobenzyl (meth)acrylate, etc.; Vinyl monomers having a benzyl group, such as vinylbenzyl chloride and vinylbenzyl alcohol, can be mentioned. Among them, benzyl (meth)acrylate is preferable. In one aspect, when the monomer component having an aromatic hydrocarbon group in polymer A is benzyl (meth)acrylate, the content of structural units based on benzyl (meth)acrylate is, relative to the total mass of polymer A, 50-95 mass% is preferable, 60-90 mass% is more preferable, 70-90 mass% is more preferable, and 75-90 mass% is especially preferable.

Polymer A, which contains a structural unit based on a monomer having an aromatic hydrocarbon group, is polymerized with a monomer having an aromatic hydrocarbon group and at least one type of a first monomer described later and/or at least one type of a second monomer described later. It is desirable to obtain

The polymer A, which does not contain a structural unit based on a monomer having an aromatic hydrocarbon group, is preferably obtained by polymerizing at least one type of the first monomer described later, and is obtained by polymerizing at least one type of the first monomer and a second monomer described later. It is more preferable to obtain it by copolymerizing at least one type.

The first monomer is a monomer that has a carboxyl group in the molecule. Examples of the first monomer include (meth)acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, 4-vinylbenzoic acid, maleic anhydride, and maleic acid half ester. Among these, (meth)acrylic acid is preferable.

The content of the structural unit based on the first monomer in polymer A is preferably 5 to 50% by mass, more preferably 10 to 40% by mass, and 15 to 30% by mass, relative to the total mass of polymer A. It is more desirable.

It is preferable that the content is 5% by mass or more from the viewpoint of developing good developability, controlling edge fusing properties, etc. It is preferable that the content is 50% by mass or less from the viewpoint of high resolution and footing shape of the resist pattern, and further from the viewpoint of chemical resistance of the resist pattern.

The second monomer is non-acidic and has at least one polymerizable unsaturated group in the molecule. Examples of the second monomer include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, and iso. Butyl (meth)acrylate, tert-butyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, cyclohexyl (meth)acrylate, and 2-ethyl. (meth)acrylates such as hexyl (meth)acrylate; Esters of vinyl alcohol such as vinyl acetate; and (meth)acrylonitrile. Among them, methyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, or n-butyl (meth)acrylate is preferable, and methyl (meth)acrylate is more preferable.

The content of the structural unit based on the second monomer in polymer A is preferably 5 to 60% by mass, more preferably 15 to 50% by mass, and 17 to 45% by mass, relative to the total mass of polymer A. It is more desirable.

When the polymer A contains a structural unit based on a monomer having an aralkyl group and/or a structural unit based on a styrene monomer, the point of view of suppressing line width thickening and deterioration of resolution when the focus position during exposure is shifted. It is desirable in For example, copolymers containing structural units based on methacrylic acid, structural units based on benzyl methacrylate, and structural units based on styrene, and structural units based on methacrylic acid and methyl methacrylate. A copolymer containing a structural unit based on benzyl methacrylate and a structural unit based on styrene is preferable.

In one aspect, the polymer A contains 25 to 55% by mass of structural units based on a monomer having an aromatic hydrocarbon group, 20 to 35% by mass of structural units based on the first monomer, and structural units based on the second monomer. It is preferable that it is a polymer containing 15 to 45% by mass. Moreover, in another aspect, it is preferable that it is a polymer containing 70-90 mass % of structural units based on a monomer having an aromatic hydrocarbon group, and 10-25 mass % of structural units based on a 1st monomer.

Polymer A may have any of a linear structure, a branched structure, and an alicyclic structure in its side chain. By using a monomer containing a group having a branched structure in the side chain, or a monomer containing a group having an alicyclic structure in the side chain, a branched structure or an alicyclic structure can be introduced into the side chain of the polymer A. The group having an alicyclic structure may be monocyclic or polycyclic.

Specific examples of monomers containing a group having a branched structure in the side chain include isopropyl (meth)acrylate, isobutyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, and isoamyl (meth)acrylate. , tert-amyl (meth)acrylic acid, sec-amyl (meth)acrylic acid, 2-octyl (meth)acrylic acid, 3-octyl (meth)acrylic acid, and tert-octyl (meth)acrylic acid. Among these, isopropyl (meth)acrylate, isobutyl (meth)acrylate, and tert-butyl methacrylate are preferable, and isopropyl methacrylate or tert-butyl methacrylate is more preferable.

Specific examples of the monomer containing a group having an alicyclic structure in the side chain include a monomer having a monocyclic aliphatic hydrocarbon group, and a monomer having a polycyclic aliphatic hydrocarbon group. Moreover, (meth)acrylate which has an alicyclic hydrocarbon group with 5 to 20 carbon atoms can be mentioned. More specific examples include (meth)acrylic acid (bicyclo[2.2.1]heptyl-2), (meth)acrylic acid-1-adamantyl, (meth)acrylic acid-2-adamantyl, (meth)acrylic acid-3- Methyl-1-adamantyl, (meth)acrylic acid-3,5-dimethyl-1-adamantyl, (meth)acrylic acid-3-ethyladamantyl, (meth)acrylic acid-3-methyl-5-ethyl -1-adamantyl, (meth)acrylic acid-3,5,8-triethyl-1-adamantyl, (meth)acrylic acid-3,5-dimethyl-8-ethyl-1-adamantyl, ( Meth)acrylic acid 2-methyl-2-adamantyl, (meth)acrylic acid 2-ethyl-2-adamantyl, (meth)acrylic acid 3-hydroxy-1-adamantyl, (meth)acrylic acid octahydro-4 ,7-mentanoinden-5-yl, (meth)acrylic acid octahydro-4,7-mentanoinden-1-yl methyl, (meth)acrylic acid-1-menthyl, (meth)acrylic acid tricyclodecane, ( Meth)acrylic acid-3-hydroxy-2,6,6-trimethyl-bicyclo[3.1.1]heptyl, (meth)acrylic acid-3,7,7-trimethyl-4-hydroxy-bicyclo[4.1] .0〕Heptyl, (meth)acrylic acid (nor)bornyl, (meth)acrylic acid isobornyl, (meth)acrylic acid pentyl, (meth)acrylic acid-2,2,5-trimethylcyclohexyl, and (meth)acrylic acid cyclo Hexyl, etc. can be mentioned. Among these (meth)acrylic acid esters, (meth)acrylic acid cyclohexyl, (meth)acrylic acid (nor)bornyl, (meth)acrylic acid isobornyl, (meth)acrylic acid-1-adamantyl, (meth)acrylic acid-2- Adamantyl, pentyl (meth)acrylate, 1-menthyl (meth)acrylate, or tricyclodecane (meth)acrylate are preferred, cyclohexyl (meth)acrylate, (nor)bornyl (meth)acrylate, and (meth)acrylic acid are preferred. ) Isobornyl acrylate, 2-adamantyl (meth)acrylate, or tricyclodecane (meth)acrylate are more preferred.

Polymer A may be used individually by 1 type, or may be used in combination of 2 or more types.

When using two or more types, use a mixture of two types of Polymer A containing structural units based on monomers having an aromatic hydrocarbon group, or Polymer A containing structural units based on monomers having an aromatic hydrocarbon group. It is preferable to use a mixture of polymer A and which does not contain a structural unit based on a monomer having an aromatic hydrocarbon group. In the latter case, the usage ratio of polymer A containing structural units based on monomers having an aromatic hydrocarbon group is preferably 50% by mass or more, more preferably 70% by mass or more, with respect to the total mass of polymer A, 80 mass% or more is preferable, and 90 mass% or more is more preferable.

The synthesis of polymer A involves adding an appropriate amount of a radical polymerization initiator such as benzoyl peroxide and azoisobutyronitrile to a solution of the above-mentioned single or plural monomers diluted with a solvent such as acetone, methyl ethyl ketone, and isopropanol. It is preferably carried out by adding, heating and stirring. In some cases, synthesis is performed by dropping part of the mixture into the reaction solution. After completion of the reaction, an additional solvent may be added to adjust the concentration to the desired concentration. As a synthetic means, in addition to solution polymerization, block polymerization, suspension polymerization, or emulsion polymerization may be used.

The glass transition temperature Tg of polymer A is preferably 30 to 135°C. By using polymer A having a Tg of 135°C or lower, thickening of the line width and deterioration of resolution when the focus position during exposure is shifted can be suppressed. From this viewpoint, the Tg of polymer A is more preferably 130°C or lower, more preferably 120°C or lower, and particularly preferably 110°C or lower. Additionally, it is preferable to use polymer A having a Tg of 30°C or higher from the viewpoint of improving edge fuse resistance. From this viewpoint, the Tg of polymer A is more preferably 40°C or higher, more preferably 50°C or higher, particularly preferably 60°C or higher, and most preferably 70°C or higher.

The negative photosensitive composition layer may contain other resins than those described above as polymer A.

Other resins include acrylic resin, styrene-acrylic copolymer, polyurethane resin, polyvinyl alcohol, polyvinyl formal, polyamide resin, polyester resin, polyamide resin, epoxy resin, polyacetal resin, and polyhydride. Examples include oxystyrene resin, polyimide resin, polybenzoxazole resin, polysiloxane resin, polyethyleneimine, polyallylamine, and polyalkylene glycol.

As the polymer A, you may use an alkali-soluble resin described in the description of the thermoplastic resin layer described later.

The content of polymer A is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, more preferably 30 to 70% by mass, and 40 to 60% by mass, relative to the total mass of the negative photosensitive composition layer. % is particularly preferred. It is preferable that the content of polymer A is 90% by mass or less from the viewpoint of controlling the development time. On the other hand, it is preferable that the content of polymer A is 10% by mass or more from the viewpoint of improving fuse resistance.

<Polymerizable compound>

When the photosensitive composition layer is a negative photosensitive composition layer, it is preferable that the negative photosensitive composition layer contains a polymerizable compound having a polymerizable group. In addition, in this specification, “polymerizable compound” means a compound that polymerizes under the action of a polymerization initiator described later, and is different from the polymer A described above.

The polymerizable group possessed by the polymerizable compound is not particularly limited as long as it is a group involved in the polymerization reaction, and examples include those having ethylenically unsaturated groups such as vinyl group, acryloyl group, methacryloyl group, styryl group, and maleimide group. energy; and groups having cationic polymerizable groups such as epoxy groups and oxetane groups.

As the polymerizable group, a group having an ethylenically unsaturated group is preferable, and an acryloyl group or a methacryloyl group is more preferable.

As the polymerizable compound, a compound having one or more ethylenically unsaturated groups (ethylenically unsaturated compound) is preferable because the photosensitivity of the negative photosensitive composition layer is more excellent, and a compound having two or more ethylenically unsaturated groups in one molecule ( polyfunctional ethylenically unsaturated compounds) are more preferable.

Moreover, from the viewpoint of superior resolution and peelability, the number of ethylenically unsaturated groups in one molecule of the ethylenically unsaturated compound is preferably 6 or less, more preferably 3 or less, and even more preferably 2 or less. desirable.

In view of the better balance of photosensitivity, resolution, and peelability of the negative photosensitive composition layer, it is preferable to include a bi- or tri-functional ethylenically unsaturated compound having 2 or 3 ethylenically unsaturated groups in one molecule, 1 It is more preferable to include a bifunctional ethylenically unsaturated compound having two ethylenically unsaturated groups in the molecule.

The content of the bifunctional ethylenically unsaturated compound relative to the total mass of the polymerizable compound is preferably 20% by mass or more, and more than 40% by mass, from the viewpoint of excellent peelability, relative to the total mass of the negative photosensitive composition layer. It is preferable, and 55% by mass or more is more preferable. The upper limit is not particularly limited and may be 100% by mass. That is, the polymerizable compounds may all be difunctional ethylenically unsaturated compounds.

Moreover, as an ethylenically unsaturated compound, a (meth)acrylate compound which has a (meth)acryloyl group as a polymerizable group is preferable.

(Polymerizable Compound B1)

The negative photosensitive composition layer also preferably contains polymerizable compound B1 having an aromatic ring and two ethylenically unsaturated groups. Polymerizable compound B1 is a bifunctional ethylenically unsaturated compound that has one or more aromatic rings per molecule among the polymerizable compounds B described above.

In the negative photosensitive composition layer, the mass ratio of the content of polymerizable compound B1 to the total mass of polymerizable compounds is preferably 40% by mass or more, more preferably 50% by mass or more, from the viewpoint of better resolution, and 55 % by mass or more is more preferable, and 60 % by mass or more is particularly preferable. The upper limit is not particularly limited, but from the viewpoint of peelability, for example, it is 100 mass% or less, preferably 99 mass% or less, more preferably 95 mass% or less, more preferably 90 mass% or less, and 85 mass% or less. The following is particularly preferable.

Examples of aromatic rings possessed by polymerizable compound B1 include aromatic hydrocarbon rings such as benzene rings, naphthalene rings, and anthracene rings, thiophene rings, furan rings, pyrrole rings, imidazole rings, triazole rings, and pyridine rings. aromatic heterocycles, and condensed rings thereof. An aromatic hydrocarbon ring is preferable, and a benzene ring is more preferable. Additionally, the aromatic ring may have a substituent.

Polymerizable compound B1 may have only one aromatic ring or may have two or more aromatic rings.

Polymerizable compound B1 preferably has a bisphenol structure from the viewpoint of improving resolution by suppressing swelling of the photosensitive composition layer due to the developer.

Examples of bisphenol structures include the bisphenol A structure derived from bisphenol A (2,2-bis (4-hydroxyphenyl) propane), bisphenol F (2,2-bis (4-hydroxyphenyl) methane ), and the bisphenol B structure derived from bisphenol B (2,2-bis(4-hydroxyphenyl)butane), with the bisphenol A structure being preferred.

Examples of the polymerizable compound B1 having a bisphenol structure include a compound having a bisphenol structure and two polymerizable groups (preferably (meth)acryloyl groups) bonded to both ends of the bisphenol structure. there is.

Both ends of the bisphenol structure and the two polymerizable groups may be bonded directly or may be bonded through one or more alkyleneoxy groups. As the alkyleneoxy group added to both ends of the bisphenol structure, an ethyleneoxy group or a propyleneoxy group is preferable, and an ethyleneoxy group is more preferable. The number of alkyleneoxy groups added to the bisphenol structure is not particularly limited, but is preferably 4 to 16 per molecule, and more preferably 6 to 14.

The polymerizable compound B1 having a bisphenol structure is described in paragraphs 0072 to 0080 of Japanese Patent Application Laid-Open No. 2016-224162, and the content described in this publication is incorporated herein by reference.

As the polymerizable compound B1, a bifunctional ethylenically unsaturated compound having a bisphenol A structure is preferable, and 2,2-bis(4-((meth)acryloxypolyalkoxy)phenyl)propane is more preferable.

Examples of 2,2-bis(4-((meth)acryloxypolyalkoxy)phenyl)propane include 2,2-bis(4-(methacryloxydiethoxy)phenyl)propane (FA- 324M, manufactured by Hitachi Kasei Corporation), 2,2-bis(4-(methacryloxyethoxypropoxy)phenyl)propane, 2,2-bis(4-(methacryloxypentaethoxy)phenyl)propane (BPE-500, manufactured by Shinnakamura Chemical Co., Ltd.), 2,2-bis(4-(methacryloxydodecaethoxytetrapropoxy)phenyl)propane (FA-3200MY, manufactured by Hitachi Chemical Industries, Ltd.), 2, 2-bis(4-(methacryloxypentadecaethoxy)phenyl)propane (BPE-1300, manufactured by Shinnakamura Chemical Co., Ltd.), 2,2-bis(4-(methacryloxydiethoxy)phenyl) Propane (BPE-200, manufactured by Shin-Nakamura Chemical Industries, Ltd.), and ethoxylated (10) bisphenol A diacrylate (NK Ester A-BPE-10, manufactured by Shin-Nakamura Chemical Industries, Ltd.).

As the polymerizable compound B1, a compound represented by the following general formula (B1) is also preferable.

[Formula 25]

In general formula (B1), R ₁ and R ₂ each independently represent a hydrogen atom or a methyl group. A represents C ₂ H ₄ . B represents C ₃ H ₆ . n1 and n3 are each independently integers from 1 to 39, and n1+n3 is an integer from 2 to 40. n2 and n4 are each independently integers from 0 to 29, and n2+n4 is an integer from 0 to 30. The arrangement of the structural units of -(AO)- and -(BO)- may be random or block. In the case of a block, either -(AO)- or -(BO)- may be on the bisphenyl group side.

In one aspect, n1+n2+n3+n4 is preferably 2 to 20, more preferably 2 to 16, and still more preferably 4 to 12. Moreover, as for n2+n4, 0-10 are preferable, 0-4 are more preferable, 0-2 are more preferable, and 0 is especially preferable.

Polymerizable compound B1 may be used individually, or may be used in combination of two or more types.

The content of polymerizable compound B1 is preferably 10% by mass or more, and more preferably 20% by mass or more, relative to the total mass of the negative photosensitive composition layer, from the viewpoint of better resolution. The upper limit is not particularly limited, but from the viewpoint of transferability and edge fusion (a phenomenon in which the photosensitive resin oozes out from the end of the transfer member), 70 mass% or less is preferable, and 60 mass% or less is more preferable.

The negative photosensitive composition layer may contain a polymerizable compound other than the polymerizable compound B1 described above.

Polymerizable compounds other than polymerizable compound B1 are not particularly limited and can be appropriately selected from known compounds. For example, compounds having one ethylenically unsaturated group per molecule (monofunctional ethylenically unsaturated compounds), bifunctional ethylenically unsaturated compounds without an aromatic ring, and trifunctional or more ethylenically unsaturated compounds.

Examples of monofunctional ethylenically unsaturated compounds include ethyl (meth)acrylate, ethylhexyl (meth)acrylate, 2-(meth)acryloyloxyethyl succinate, and polyethylene glycol mono(meth)acrylic. salt, polypropylene glycol mono(meth)acrylate, and phenoxyethyl(meth)acrylate.

Examples of bifunctional ethylenically unsaturated compounds without an aromatic ring include alkylene glycol di(meth)acrylate, polyalkylene glycol di(meth)acrylate, urethane di(meth)acrylate, and trimethylolpropane diacrylate.

Examples of alkylene glycol di(meth)acrylate include tricyclodecanedimethanoldiacrylate (A-DCP, manufactured by Shinnakamura Chemical Co., Ltd.) and tricyclodecanedimethanoldimethacrylate (DCP). , manufactured by Shinnakamura Chemical Industries, Ltd.), 1,9-nonanediol diacrylate (A-NOD-N, manufactured by Shinnakamura Chemical Industries, Ltd.), 1,6-hexanedioldiacrylate (A-HD) -N, manufactured by Shinnakamura Chemical Co., Ltd.), ethylene glycol dimethacrylate, 1,10-decanediol diacrylate, and neopentyl glycol di(meth)acrylate.

Examples of polyalkylene glycol di(meth)acrylate include polyethylene glycol di(meth)acrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, and polypropylene glycol. Lycol die(meth)acrylate can be mentioned.

Examples of urethane di(meth)acrylate include propylene oxide modified urethane di(meth)acrylate, and ethylene oxide and propylene oxide modified urethane di(meth)acrylate. Commercially available products include, for example, 8UX-015A (manufactured by Taisei Fine Chemical Co., Ltd.), UA-32P (manufactured by Shin-Nakamura Chemical Co., Ltd.), and UA-1100H (manufactured by Shin-Nakamura Chemical Co., Ltd.).

Examples of trifunctional or more ethylenically unsaturated compounds include dipentaerythritol (tri/tetra/penta/hexa)(meth)acrylate, pentaerythritol (tri/tetra)(meth)acrylate, and trimethylolprop. Paint tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, trimethylol ethane tri(meth)acrylate, isocyanuric acid tri(meth)acrylate, glycerin tri(meth)acrylate esters, and alkylene oxide modified products thereof.

Here, "(tri/tetra/penta/hexa)(meth)acrylate" refers to tri(meth)acrylate, tetra(meth)acrylate, penta(meth)acrylate, and hexa(meth)acrylate. It is a concept that includes, and “(tri/tetra)(meth)acrylate” is a concept that includes tri(meth)acrylate and tetra(meth)acrylate.

In one aspect, the negative photosensitive composition layer preferably includes the above-described polymerizable compound B1 and a trifunctional or higher ethylenically unsaturated compound, and the above-described polymerizable compound B1 and two or more trifunctional or higher ethylenically unsaturated compounds. It is more preferable to include. In this case, the mass ratio of polymerizable compound B1 and the trifunctional or higher ethylenically unsaturated compound is (total mass of polymerizable compound B1) : (total mass of trifunctional or higher ethylenically unsaturated compounds) = 1:1 to 5:1. Preferred, 1.2:1 to 4:1 is more preferable, and 1.5:1 to 3:1 is more preferable.

Moreover, in one aspect, the negative photosensitive composition layer preferably contains the above-mentioned polymerizable compound B1 and two or more types of trifunctional ethylenically unsaturated compounds.

Examples of alkylene oxide modified products of trifunctional or higher ethylenically unsaturated compounds include caprolactone-modified (meth)acrylate compounds (KAYARAD (registered trademark) DPCA-20 manufactured by Nippon Kayaku Co., Ltd., A-9300-1CL manufactured by Shinnakamura Chemical Co., Ltd., etc. ), alkylene oxide-modified (meth)acrylate compounds (KAYARAD RP-1040 manufactured by Nippon Kayaku Co., Ltd., ATM-35E and A-9300 manufactured by Shinnakamura Chemical Co., Ltd., EBECRYL (registered trademark) 135 manufactured by Daicel and Allnex Co., Ltd., etc.) , ethoxylated glycerin triacrylate (A-GLY-9E, manufactured by Shinnakamura Chemical Co., Ltd., etc.), Aronix (registered trademark) TO-2349 (manufactured by Toa Kosei Co., Ltd.), Aronix M-520 (manufactured by Toa Kosei Co., Ltd.), and Aro. Examples include Nyx M-510 (manufactured by Toa Kosei Corporation).

Additionally, as the polymerizable compound, a polymerizable compound having an acid group (carboxy group, etc.) may be used. The acid group may form an acid anhydride group. As a polymerizable compound having an acid group, Aronix (registered trademark) TO-2349 (manufactured by Toagosei Corporation), Aronix (registered trademark) M-520 (manufactured by Toagosei Corporation), and Aronix (registered trademark) M-510 (manufactured by Toa Kosei Corporation) (manufactured by Kosei Corporation).

As a polymerizable compound having an acid group, for example, a polymerizable compound having an acid group described in paragraphs 0025 to 0030 of Japanese Patent Application Laid-Open No. 2004-239942 may be used.

Polymerizable compounds may be used individually or in combination of two or more.

The content of the polymerizable compound is preferably 10 to 70% by mass, more preferably 15 to 70% by mass, and still more preferably 20 to 70% by mass, relative to the total mass of the negative photosensitive composition layer.

The molecular weight (weight average molecular weight in the case of having a molecular weight distribution) of the polymerizable compound (including polymerizable compound B1) is preferably 200 to 3,000, more preferably 280 to 2,200, and even more preferably 300 to 2,200.

<Polymerization initiator>

When the photosensitive composition layer is a negative photosensitive composition layer, it is also preferable that the negative photosensitive composition layer contains a polymerization initiator.

The polymerization initiator is selected depending on the type of polymerization reaction, and examples include a thermal polymerization initiator and a photopolymerization initiator.

The polymerization initiator may be a radical polymerization initiator or a cationic polymerization initiator.

The negative photosensitive composition layer preferably contains a photopolymerization initiator.

A photopolymerization initiator is a compound that initiates polymerization of a polymerizable compound by receiving actinic rays such as ultraviolet rays, visible rays, and X-rays. The photopolymerization initiator is not particularly limited, and known photopolymerization initiators can be used.

Examples of photopolymerization initiators include radical photopolymerization initiators and cationic photopolymerization initiators, and radical photopolymerization initiators are preferred.

Examples of the radical photopolymerization initiator include a photopolymerization initiator with an oxime ester structure, a photopolymerization initiator with an α-aminoalkylphenone structure, a photopolymerization initiator with an α-hydroxyalkylphenone structure, and a photopolymerization initiator with an acylphosphine oxide structure. , and a photopolymerization initiator having an N-phenylglycine structure.

In addition, the negative photosensitive composition layer is a group consisting of 2,4,5-triarylimidazole dimer and its derivatives as a radical photopolymerization initiator from the viewpoint of photosensitivity, visibility of exposed and unexposed areas, and resolution. It is preferable to include at least one type selected from the following. In addition, the two 2,4,5-triarylimidazole structures in the 2,4,5-triarylimidazole dimer and its derivatives may be the same or different.

Derivatives of 2,4,5-triarylimidazole dimer include, for example, 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(o-chlorophenyl) -4,5-di(methoxyphenyl)imidazole dimer, 2-(o-fluorophenyl)-4,5-diphenylimidazole dimer, 2-(o-methoxyphenyl)-4, 5-diphenylimidazole dimer, and 2-(p-methoxyphenyl)-4,5-diphenylimidazole dimer.

As a radical photopolymerization initiator, for example, you may use the polymerization initiator described in Paragraphs 0031-0042 of Unexamined-Japanese-Patent No. 2011-95716, and Paragraphs 0064-0081 of Unexamined-Japanese-Patent No. 2015-14783.

As a radical photopolymerization initiator, for example, ethyl dimethylaminobenzoate (DBE, CAS No. 10287-53-3), benzoinmethyl ether, anisyl (p,p'-dimethoxybenzyl), TAZ- 110 (brand name: manufactured by Midori Chemical Co., Ltd.), benzophenone, 4,4'-bis(diethylamino)benzophenone, TAZ-111 (brand name: manufactured by Midori Chemical Co., Ltd.), IrgacureOXE01, OXE02, OXE03, OXE04 (manufactured by BASF Co., Ltd.) , Omnirad651 and 369 (trade name: IGM Resins B.V.), and 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole (Tokyo) Kasei High School teacher).

Commercially available radical photopolymerization initiators include, for example, 1-[4-(phenylthio)]-1,2-octanedione-2-(O-benzoyloxime) (brand name: IRGACURE (registered trademark) OXE -01, manufactured by BASF), 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone-1-(O-acetyloxime) (Product name: IRGACURE OXE-02 , manufactured by BASF), IRGACURE OXE-03 (manufactured by BASF), IRGACURE OXE-04 (manufactured by BASF), 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4- Morpholinyl)phenyl]-1-butanone (product name: Omnirad 379EG, manufactured by IGM Resins B.V.), 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one (product name) : Omnirad 907, manufactured by IGM Resins B.V.), 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionyl)benzyl]phenyl}-2-methylpropan-1-one (product name) : Omnirad 127, manufactured by IGM Resins B.V.), 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone-1 (brand name: Omnirad 369, manufactured by IGM Resins B.V.), 2-hydroxy -2-methyl-1-phenylpropan-1-one (trade name: Omnirad 1173, manufactured by IGM Resins B.V.), 1-hydroxycyclohexylphenylketone (brand name: Omnirad 184, manufactured by IGM Resins B.V.), 2,2-die Methoxy-1,2-diphenylethan-1-one (Product name: Omnirad 651, manufactured by IGM Resins B.V.), 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (Product name: Omnirad TPO H, IGM Resins B.V.), bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (Product name: Omnirad 819, IGM Resins B.V.), Oxime ester photopolymerization initiator (Product name: Lunar 6, DKSH Japan), 2 ,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbisimidazole (2-(2-chlorophenyl)-4,5-diphenylimidazole dimer) ( Product name: B-CIM, manufactured by Hampford, and 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer (brand name: BCTB, manufactured by Tokyo Chemical Industry Co., Ltd.), 1-[4-(phenylcyl) O)phenyl]-3-cyclopentylpropane-1,2-dione-2-(O-benzoyloxime) (Product name: TR-PBG-305, Changzhou Strong Electronic New Materials Co., Ltd.), 1,2 -Propanedione, 3-cyclohexyl-1-[9-ethyl-6-(2-furanylcarbonyl)-9H-carbazol-3-yl]-,2-(O-acetyloxime) (Product name : TR-PBG-326, Changzhou Strong Electronic New Materials Co., Ltd.), and 3-cyclohexyl-1-(6-(2-(benzoyloxyimino)hexanoyl)-9-ethyl-9H-carbazole- 3-yl)-propane-1,2-dione-2-(O-benzoyloxime) (trade name: TR-PBG-391, manufactured by Changzhou Strong Electronic New Materials Co., Ltd.).

A photocationic polymerization initiator (photoacid generator) is a compound that generates acid when exposed to actinic light. As a photocationic polymerization initiator, a compound that generates acid in response to actinic rays with a wavelength of 300 nm or more, preferably 300 to 450 nm, is preferred, but its chemical structure is not limited. In addition, photocationic polymerization initiators that do not directly respond to actinic rays with a wavelength of 300 nm or more can also be preferably used in combination with a sensitizer, as long as they are compounds that respond to actinic rays with a wavelength of 300 nm or more and generate acid when used in combination with a sensitizer. .

As a photocationic polymerization initiator, a photocationic polymerization initiator that generates an acid with a pKa of 4 or less is preferable, a photocationic polymerization initiator that generates an acid with a pKa of 3 or less is more preferable, and a photocationic polymerization initiator that generates an acid with a pKa of 2 or less is more preferable. Initiators are particularly preferred. The lower limit of pKa is not particularly determined, but for example, -10.0 or more is preferable.

Examples of the photocationic polymerization initiator include ionic photocationic polymerization initiators and nonionic photocationic polymerization initiators.

Examples of the ionic photocationic polymerization initiator include onium salt compounds such as diaryliodonium salts and triarylsulfonium salts, and quaternary ammonium salts.

As the ionic photocationic polymerization initiator, you may use the ionic photocationic polymerization initiator described in paragraphs 0114 to 0133 of Japanese Patent Application Laid-Open No. 2014-085643.

Examples of nonionic photocationic polymerization initiators include trichloromethyl-s-triazines, diazomethane compounds, imide sulfonate compounds, and oxime sulfonate compounds. As trichloromethyl-s-triazine, diazomethane compound, and imide sulfonate compound, the compounds described in paragraphs 0083 to 0088 of Japanese Patent Application Laid-Open No. 2011-221494 may be used. Additionally, as the oxime sulfonate compound, you may use the compounds described in paragraphs 0084 to 0088 of International Publication No. 2018/179640.

The negative photosensitive composition layer preferably contains a radical photopolymerization initiator, and more preferably contains at least one selected from the group consisting of 2,4,5-triarylimidazole dimer and its derivatives. .

The polymerization initiator may be used individually by one type, or may be used of two or more types.

The content of the polymerization initiator (preferably a photopolymerization initiator) is not particularly limited, but is preferably 0.1 mass% or more, more preferably 0.5 mass% or more, and 1.0 mass% or more relative to the total mass of the negative photosensitive composition layer. This is more preferable. The upper limit is not particularly limited, but is preferably 20% by mass or less, more preferably 15% by mass or less, and still more preferably 10% by mass or less, relative to the total mass of the negative photosensitive composition layer.

<Pigment>

The photosensitive composition layer has a maximum absorption wavelength of 450 nm or more in the wavelength range of 400 to 780 nm at the time of color development from the viewpoint of visibility of exposed and unexposed areas, pattern visibility after development, and resolution, and also contains acid, base, or It is also preferable to include a dye whose maximum absorption wavelength changes due to radicals (also referred to as “dye N”). When dye N is included, although the detailed mechanism is unclear, adhesion to an adjacent layer (for example, a water-soluble resin layer) is improved, and resolution is more excellent.

In this specification, the term "the maximum absorption wavelength of a dye changes due to an acid, base, or radical" refers to a state in which a dye in a color developing state is decolorized by an acid, base, or radical, or the state in which a dye in a color developing state is decolorized by an acid, base, or radical. It may refer to any of the modes in which a dye in a colored state develops color by an acid, base, or radical, and a mode in which a dye in a colored state changes into a colored state of a different color.

Specifically, the dye N may be a compound that changes from a color developing state upon exposure and develops color, or may be a compound that changes from a color developing state and decolorizes upon exposure. In this case, the dye may be a colorant that changes the state of coloring or fading as an acid, base, or radical is generated and acts within the photosensitive composition layer upon exposure, or the state within the photosensitive composition layer due to the acid, base, or radical (e.g. For example, it may be a dye whose state of color development or disappearance changes as pH changes. Additionally, the dye may be a dye that changes the state of color development or disappearance by directly receiving an acid, base, or radical as a stimulus, without exposure to light.

Among them, from the viewpoint of visibility and resolution of exposed and unexposed areas, the dye N is preferably a dye whose maximum absorption wavelength changes due to an acid or radical, and a dye whose maximum absorption wavelength changes due to a radical is more preferable.

When the photosensitive composition layer is a negative photosensitive composition layer, the negative photosensitive composition layer contains, from the viewpoint of visibility and resolution of exposed and unexposed areas, a dye whose maximum absorption wavelength changes due to radicals as a dye N, and a light radical. It is preferable to include both polymerization initiators.

Moreover, from the viewpoint of visibility of the exposed portion and the non-exposed portion, it is preferable that the pigment N is a pigment that develops color by an acid, a base, or a radical.

As an example of the color development mechanism of the dye N, a photoradical polymerization initiator, a photocationic polymerization initiator (photoacid generator), or a photobase generator is added to the photosensitive composition layer, and after exposure, the photoradical polymerization initiator, the photocationic polymerization initiator, or the photobase generator is added to the photosensitive composition layer. An example is an embodiment in which a radical reactive dye, an acid reactive dye, or a base reactive dye (for example, a leuco dye) develops color due to a radical, acid, or base generated from a base generator.

From the viewpoint of visibility of exposed and unexposed areas, the pigment N preferably has a maximum absorption wavelength of 550 nm or more in the wavelength range of 400 to 780 nm at the time of color development, more preferably 550 to 700 nm, and 550 to 650 nm. It is more desirable.

In addition, the dye N may have only one maximum absorption wavelength in the wavelength range of 400 to 780 nm at the time of color development, or may have two or more. When the dye N has two or more maximum absorption wavelengths in the wavelength range of 400 to 780 nm at the time of color development, the maximum absorption wavelength with the highest absorbance among the two or more maximum absorption wavelengths may be 450 nm or more.

The maximum absorption wavelength of dye N is determined by measuring the transmission spectrum of a solution containing dye N (liquid temperature 25°C) in the range of 400 to 780 nm using a spectrophotometer: UV3100 (manufactured by Shimadzu Seisakusho Co., Ltd.) in an air atmosphere. It is obtained by measuring and detecting the wavelength at which the intensity of light becomes minimum (maximum absorption wavelength).

Examples of pigments that develop or lose color upon exposure to light include leuco compounds.

Examples of dyes that are discolored by exposure include leuco compounds, diarylmethane dyes, oxazine dyes, xanthene dyes, iminonaphthoquinone dyes, azomethane dyes, and anthraquinone dyes. .

As the dye N, a leuco compound is preferable from the viewpoint of visibility of the exposed portion and the non-exposed portion.

Examples of leuco compounds include leuco compounds having a triarylmethane skeleton (triarylmethane-based dye), leuco compounds having a spiropyran skeleton (spiropyran-based dye), and leuco compounds having a fluorane skeleton (fluorine-based dye). egg-based pigment), leuco compound having a diarylmethane skeleton (diarylmethane-based pigment), leuco compound having a rhodamine lactam skeleton (rhodamine lactam-based pigment), leuco compound having an indolylphthalide skeleton (indolyl Phthalide-based pigments), and leuco compounds (leucoauramine-based pigments) having a leucoauramine skeleton.

Among them, triarylmethane-based dyes or fluorane-based dyes are preferable, and leuco compounds (triphenylmethane-based dyes) or fluorane-based dyes having a triphenylmethane skeleton are more preferable.

The leuco compound preferably has a lactone ring, a sultine ring, or a sultone ring from the viewpoint of visibility in exposed and non-exposed areas. As a result, the lactone ring, sultine ring, or sultone ring of the leuco compound is reacted with a radical generated from a photoradical polymerization initiator or an acid generated from a photocationic polymerization initiator, and the leuco compound is changed to a ring-closed state to decolorize, or Color can be developed by changing the leuco compound to a ring-opened state. The leuco compound is preferably a compound that has a lactone ring, sultine ring, or sultone ring and develops color by ring-opening the lactone ring, sultine ring, or sultone ring by a radical or acid. It has a lactone ring and is converted to lactone by a radical or acid. Compounds that develop color by ring opening are more preferable.

Examples of the dye N include the following dyes and leuco compounds.

Specific examples of dyes among pigment N include brilliant green, ethyl violet, methyl green, crystal violet, basic fuchsin, methyl violet 2B, quinaldine red, rose bengal, methyl yellow, thymol sulfonephthalein, xylenol blue, methyl orange, Paramethyl Red, Congo Red, Benzoperpurine 4B, α-Naphthyl Red, Nile Blue 2B, Nile Blue A, Methyl Violet, Malachite Green, Parafuxin, Victoria Pure Blue-Naphthalenesulfonate, Victoria Pure Blue BOH (Hodogaya) Oil Blue #603 (made by Orient Chemical High School), Oil Pink #312 (made by Orient Chemical High School), Oil Red 5B (made by Orient Chemical High School), Oil Scarlet #308 (made by Orient Chemical High School) (manufactured by Orient Chemical), Oil Red OG (made by Orient Chemical Industries), Oil Red RR (made by Orient Chemical Industries), Oil Green #502 (made by Orient Chemical Industries), Spiron Red BEH Special (made by Hodogaya Chemical Industries) , m-cresol purple, cresol red, rhodamine B, rhodamine 6G, sulforhodamine B, auramine, 4-p-diethylaminophenyliminonaphthoquinone, 2-carboxyanilino-4-p-diethyl Aminophenyliminonaphthoquinone, 2-carboxystearylamino-4-p-N,N-bis(hydroxyethyl)amino-phenyliminonaphthoquinone, 1-phenyl-3-methyl-4-p-diethylaminophenyl Imino-5-pyrazolone, and 1-β-naphthyl-4-p-diethylaminophenylimino-5-pyrazolone.

Specific examples of leuco compounds among pigment N include p,p',p"-hexamethyltriaminotriphenylmethane (leuco crystal violet), Pergascript Blue SRB (manufactured by Chiba Geigi), crystal violet lactone, malachite green lactone, and benzoyl. Leucomethylene blue, 2-(N-phenyl-N-methylamino)-6-(N-p-tolyl-N-ethyl)aminofluorane, 2-anilino-3-methyl-6-(N-ethyl-p- Toluidino) fluorane, 3,6-dimethoxyfluorane, 3-(N,N-diethylamino)-5-methyl-7-(N,N-dibenzylamino)fluorane, 3-( N-cyclohexyl-N-methylamino)-6-methyl-7-anilinofluorane, 3-(N,N-diethylamino)-6-methyl-7-anilinofluorane, 3-(N, N-diethylamino)-6-methyl-7-xylidinofluorane, 3-(N,N-diethylamino)-6-methyl-7-chlorofluorane, 3-(N,N-diethylamino )-6-methoxy-7-aminofluorane, 3-(N,N-diethylamino)-7-(4-chloroanilino)fluorane, 3-(N,N-diethylamino)-7 -Chlorofluorane, 3-(N,N-diethylamino)-7-benzylaminofluorane, 3-(N,N-diethylamino)-7,8-benzofluorane, 3-(N,N -Dibutylamino)-6-methyl-7-anilinofluorane, 3-(N,N-dibutylamino)-6-methyl-7-xylidinofluorane, 3-piperidino-6-methyl- 7-anilinofluorane, 3-pyrrolidino-6-methyl-7-anilinofluorane, 3,3-bis(1-ethyl-2-methylindol-3-yl)phthalide, 3,3- Bis(1-n-butyl-2-methylindol-3-yl)phthalide, 3,3-bis(p-dimethylaminophenyl)-6-dimethylaminophthalide, 3-(4-diethyl Amino-2-ethoxyphenyl)-3-(1-ethyl-2-methylindol-3-yl)-4-azaphthalide, 3-(4-diethylaminophenyl)-3-(1-ethyl- 2-methylindol-3-yl)phthalide, and 3',6'-bis(diphenylamino)spiroisobenzofuran-1(3H),9'-[9H]xanthene-3-one. there is.

From the viewpoints of visibility of exposed and unexposed areas, pattern visibility after development, and resolution, the dye N is preferably a dye whose maximum absorption wavelength changes due to radicals, and is more preferably a dye that develops color by radicals.

As the pigment N, leuco crystal violet, crystal violet lactone, brilliant green, or Victoria Pure Blue-naphthalenesulfonate is preferable.

Pigment N may be used individually by 1 type, or may be used in combination of 2 or more types.

The content of pigment N is preferably 0.1% by mass or more, and more preferably 0.1 to 10% by mass, relative to the total mass of the photosensitive composition layer, from the viewpoints of visibility of exposed areas and non-exposed areas, pattern visibility after development, and resolution. 0.1 to 5 mass% is more preferable, and 0.1 to 1 mass% is particularly preferable.

The content of dye N means the content of the dye when all of the dye N contained in the total mass of the photosensitive composition layer is in a color developing state. Below, a method for quantifying the content of pigment N will be explained using a pigment that develops color by radicals as an example.

Prepare a solution in which 0.001 g and 0.01 g of pigment are dissolved in 100 mL of methyl ethyl ketone. To each obtained solution, a radical photopolymerization initiator Irgacure OXE01 (brand name, BASF Japan Co., Ltd.) is added, and radicals are generated by irradiating light at 365 nm to bring all pigments into a coloring state. Thereafter, the absorbance of each solution with a liquid temperature of 25°C is measured using a spectrophotometer (UV3100, manufactured by Shimadzu Seisakusho Co., Ltd.) under an atmospheric atmosphere, and a calibration curve is prepared.

Next, the absorbance of the solution in which all the dyes were developed was measured in the same manner as above, except that 3 g of the photosensitive composition layer was dissolved in methyl ethyl ketone instead of the dye. From the absorbance of the solution containing the obtained photosensitive composition layer, the content of the pigment contained in the photosensitive composition layer is calculated based on a calibration curve.

In addition, 3 g of the photosensitive composition layer is equivalent to 3 g of the total solid content in the photosensitive resin composition.

<Thermal crosslinking compound>

When the photosensitive composition layer is a negative photosensitive composition layer, it is preferable to include a heat crosslinkable compound from the viewpoint of the strength of the cured film obtained and the adhesiveness of the uncured film obtained. In addition, in this specification, the heat-crosslinkable compound having an ethylenically unsaturated group described later is not handled as a polymerizable compound, but rather as a heat-crosslinkable compound.

Examples of thermally crosslinkable compounds include methylol compounds and block isocyanate compounds. Among them, block isocyanate compounds are preferable from the viewpoint of the strength of the cured film obtained and the adhesiveness of the uncured film obtained.

Since block isocyanate compounds react with hydroxy groups and carboxy groups, for example, when resins and/or polymerizable compounds, etc. have at least one of hydroxy groups and carboxy groups, the hydrophilicity of the formed film As this decreases, the function tends to be strengthened when the film obtained by curing the negative photosensitive composition layer is used as a protective film.

In addition, the block isocyanate compound refers to "a compound having a structure in which the isocyanate group of isocyanate is protected (so-called masked) with a blocking agent."

The dissociation temperature of the block isocyanate compound is not particularly limited, but is preferably 100 to 160°C, and more preferably 130 to 150°C.

The dissociation temperature of block isocyanate refers to "the temperature of the endothermic peak resulting from the deprotection reaction of block isocyanate when measured by DSC (Differential scanning calorimetry) analysis using a differential scanning calorimeter." it means.

As a differential scanning calorimeter, for example, a differential scanning calorimeter (model: DSC6200) manufactured by Seiko Instruments can be suitably used. However, the differential scanning calorimeter is not limited to this.

Blocking agents with a dissociation temperature of 100 to 160°C include active methylene compounds [malonic acid diesters (dimethyl malonate, diethyl malonate, din-butyl malonate, di2-ethylhexyl malonate, etc.)], oximes. Compounds (compounds having a structure represented by -C(=N-OH)- in the molecule such as formaldoxime, acetaldoxime, acetoxime, methylethylketoxime, and cyclohexanone oxime) can be mentioned.

Among these, as a blocking agent with a dissociation temperature of 100 to 160°C, for example, at least one type selected from oxime compounds is preferable from the viewpoint of storage stability.

The block isocyanate compound preferably has an isocyanurate structure, for example, from the viewpoints of improving the brittleness of the film and improving adhesion to the transferred body.

A block isocyanate compound having an isocyanurate structure is obtained, for example, by isocyanurating hexamethylene diisocyanate and protecting it.

Among the block isocyanate compounds having an isocyanurate structure, compounds having an oxime structure using an oxime compound as a blocking agent are more likely to set the dissociation temperature in a desirable range than compounds not having an oxime structure, and furthermore, the compounds having an oxime structure are more likely to maintain the development residue. This is desirable from the viewpoint of being easy to do less.

The block isocyanate compound may have a polymerizable group.

The polymerizable group is not particularly limited, and known polymerizable groups can be used, with radical polymerizable groups being preferred.

Examples of the polymerizable group include groups having ethylenically unsaturated groups such as (meth)acryloxy group, (meth)acrylamide group, and styryl group, and epoxy groups such as glycidyl group.

Among them, as the polymerizable group, an ethylenically unsaturated group is preferable, a (meth)acryloxy group is more preferable, and an acryloxy group is still more preferable.

As the block isocyanate compound, a commercial product can be used.

Examples of commercially available block isocyanate compounds include Karenz (registered trademark) AOI-BM, Karenz (registered trademark) MOI-BM, Karenz (registered trademark) MOI-BP, etc. (all manufactured by Showa Denko), Block-type Duranate series (for example, Duranate (registered trademark) TPA-B80E, Duranate (registered trademark) WT32-B75P, etc., manufactured by Asahi Kasei Chemicals) can be mentioned.

Additionally, as the block isocyanate compound, a compound having the following structure can also be used.

[Formula 26]

The heat crosslinkable compound may be used individually by 1 type, or may be used in combination of 2 or more types.

When the photosensitive composition layer contains a thermally crosslinkable compound, the content of the thermally crosslinkable compound is preferably 1 to 50% by mass, more preferably 5 to 30% by mass, relative to the total mass of the photosensitive composition layer.

<Other additives>

In addition to the above components, the photosensitive composition layer may contain known additives as needed.

As additives, for example, radical polymerization inhibitors, sensitizers, plasticizers, heterocyclic compounds (triazoles, etc.), benzotriazoles, carboxybenzotriazoles, pyridines (isonicotinamide, etc.), purine bases (adenine) etc.), and surfactants.

Each additive may be used individually by 1 type, or may be used in combination of 2 or more types.

The photosensitive composition layer may contain a radical polymerization inhibitor.

Examples of the radical polymerization inhibitor include the thermal polymerization inhibitor described in paragraph 0018 of Japanese Patent Publication No. 4502784. Among them, phenothiazine, phenoxazine, or 4-methoxyphenol are preferred. Other radical polymerization inhibitors include naphthylamine, cuprous chloride, N-nitrosophenylhydroxylamine aluminum salt, and diphenylnitrosoamine. In order not to impair the sensitivity of the photosensitive composition layer, it is preferable to use N-nitrosophenylhydroxylamine aluminum salt as a radical polymerization inhibitor.

The preferable content of the radical polymerization inhibitor is the same as in the first embodiment.

Examples of benzotriazoles include 1,2,3-benzotriazole, 1-chloro-1,2,3-benzotriazole, bis(N-2-ethylhexyl)aminomethylene-1,2, 3-benzotriazole, bis(N-2-ethylhexyl)aminomethylene-1,2,3-tolyltriazole, and bis(N-2-hydroxyethyl)aminomethylene-1,2,3-benzotriazole Azole, etc. can be mentioned.

As carboxybenzotriazoles, for example, 4-carboxy-1,2,3-benzotriazole, 5-carboxy-1,2,3-benzotriazole, N-(N,N-di-2- Ethylhexyl)aminomethylenecarboxybenzotriazole, N-(N,N-di-2-hydroxyethyl)aminomethylenecarboxybenzotriazole, and N-(N,N-di-2-ethylhexyl)aminoethylenecarboxy Benzotriazole, etc. can be mentioned. As carboxybenzotriazoles, commercial products such as CBT-1 (Johoku Chemical Industry Co., Ltd., brand name) can be used, for example.

Examples of benzotriazoles include 1,2,3-benzotriazole, 1-chloro-1,2,3-benzotriazole, bis(N-2-ethylhexyl)aminomethylene-1,2, 3-benzotriazole, bis(N-2-ethylhexyl)aminomethylene-1,2,3-tolyltriazole, and bis(N-2-hydroxyethyl)aminomethylene-1,2,3-benzotriazole Azole, etc. can be mentioned.

As carboxybenzotriazoles, for example, 4-carboxy-1,2,3-benzotriazole, 5-carboxy-1,2,3-benzotriazole, N-(N,N-di-2- Ethylhexyl)aminomethylenecarboxybenzotriazole, N-(N,N-di-2-hydroxyethyl)aminomethylenecarboxybenzotriazole, and N-(N,N-di-2-ethylhexyl)aminoethylenecarboxy Benzotriazole, etc. can be mentioned. As carboxybenzotriazoles, commercial products such as CBT-1 (Johoku Chemical Industry Co., Ltd., brand name) can be used, for example.

The total content of benzotriazoles and carboxybenzotriazoles is preferably 0.01 to 3% by mass, more preferably 0.05 to 1% by mass, relative to the total mass of the photosensitive composition layer. When the content is 0.01% by mass or more, the storage stability of the photosensitive composition layer is more excellent. On the other hand, when the content is 3% by mass or less, maintenance of sensitivity and suppression of discoloration of the dye are more excellent.

The photosensitive composition layer may contain a sensitizer.

The sensitizer is not particularly limited, and known sensitizers, dyes, and pigments can be used. As sensitizers, for example, dialkylaminobenzophenone compounds, pyrazoline compounds, anthracene compounds, coumarin compounds, xanthone compounds, thioxanthone compounds, acridone compounds, oxazole compounds, benzoxazole compounds, and thiazole compounds. , benzothiazole compounds, triazole compounds (e.g., 1,2,4-triazole), stilbene compounds, triazine compounds, thiophene compounds, naphthalimide compounds, triarylamine compounds, and amino acids. A chridine compound may be mentioned.

Sensitizers may be used individually or in combination of two or more.

When the photosensitive composition layer contains a sensitizer, the content of the sensitizer can be appropriately selected depending on the purpose, but from the viewpoint of improving sensitivity to a light source and improving the curing rate by balancing the polymerization rate and chain transfer, Relative to the total mass of the photosensitive composition layer, 0.01 to 5 mass% is preferable, and 0.05 to 1 mass% is more preferable.

The photosensitive composition layer may contain at least one selected from the group consisting of a plasticizer and a heterocyclic compound.

Plasticizers and heterocyclic compounds include compounds described in paragraphs 0097 to 0103 and 0111 to 0118 of International Publication No. 2018/179640.

The photosensitive composition layer preferably contains a surfactant. Examples of the surfactant include those similar to the surfactant in the first embodiment, and the preferred embodiments are also the same.

In addition, the photosensitive composition layer may further contain known additives such as metal oxide particles, antioxidants, dispersants, acid increasing agents, development accelerators, conductive fibers, ultraviolet absorbers, thickeners, crosslinking agents, and organic or inorganic precipitation inhibitors. .

The additives contained in the photosensitive composition layer are described in paragraphs 0165 to 0184 of Japanese Patent Application Laid-Open No. 2014-085643, the contents of which are incorporated herein by reference.

The water content in the photosensitive composition layer is preferably 0.01 to 1.0 mass%, and more preferably 0.05 to 0.5 mass% from the viewpoint of improving reliability and lamination properties.

The layer thickness (film thickness) of the photosensitive composition layer is generally 0.1 to 300 μm, preferably 0.2 to 100 μm, more preferably 0.5 to 50 μm, more preferably 0.5 to 15 μm, and especially preferably 0.5 to 10 μm. , 0.5 to 8 μm is most preferable. As a result, the developability of the photosensitive composition layer can be improved, and resolution can be improved.

Moreover, in one aspect, 0.5 to 5 μm is preferable, 0.5 to 4 μm is more preferable, and 0.5 to 3 μm is still more preferable.

Moreover, from the viewpoint of superior adhesion, the light transmittance of the photosensitive composition layer with a wavelength of 365 nm is preferably 10% or more, more preferably 30% or more, and still more preferably 50% or more. The upper limit is not particularly limited, but is preferably 99.9% or less.

<Impurities, etc.>

The photosensitive composition layer may contain a predetermined amount of impurities.

Specific examples of impurities include sodium, potassium, magnesium, calcium, iron, manganese, copper, aluminum, titanium, chromium, cobalt, nickel, zinc, tin, halogen, and ions thereof. Among them, halide ions, sodium ions, and potassium ions are likely to be incorporated as impurities, so the contents are preferably set to the following.

The content of impurities in the photosensitive composition layer is preferably 80 ppm or less, more preferably 10 ppm or less, and still more preferably 2 ppm or less, based on mass. The content of impurities can be 1 ppb or more, and may be 0.1 ppm or more, based on mass.

Methods for keeping the impurities within the above range include selecting a material with a low content of impurities as a raw material for the composition, preventing impurities from being mixed in during production of the photosensitive composition layer, and removing them by washing. By this method, the amount of impurities can be within the above range.

Impurities can be quantified by known methods such as ICP (Inductively Coupled Plasma) emission spectroscopy, atomic absorption spectroscopy, and ion chromatography, for example.

In the photosensitive composition layer, benzene, formaldehyde, trichlorethylene, 1,3-butadiene, carbon tetrachloride, chloroform, N,N-dimethylformamide, N,N-dimethylacetamide, and hexane. It is preferable that the content of compounds such as cein is small. The content of these compounds relative to the total mass of the photosensitive composition layer is preferably 100 ppm or less, more preferably 20 ppm or less, and still more preferably 4 ppm or less, based on mass.

The lower limit can be 10 ppb or more, and can be 100 ppb or more, based on mass, with respect to the total mass of the photosensitive composition layer. The content of these compounds can be suppressed in the same manner as the above-mentioned metal impurities. Additionally, it can be quantified using a known measurement method.

The water content in the photosensitive composition layer is preferably 0.01 to 1.0 mass%, and more preferably 0.05 to 0.5 mass% from the viewpoint of improving reliability and lamination properties.

<Pigment>

The photosensitive composition layer may be a colored resin layer containing a pigment.

Liquid crystal displays in recent electronic devices may be equipped with a cover glass with a black frame-shaped light-shielding layer formed on the periphery of the back surface of a transparent glass substrate, etc., to protect the liquid crystal display window. A colored resin layer may be used to form such a light blocking layer.

The pigment may be appropriately selected according to the desired color, and may be selected from among black pigment, white pigment, and pigments of chromatic colors other than black and white. Among them, when forming a black pattern, a black pigment is suitably selected as the pigment.

As a black pigment, a known black pigment (organic pigment, inorganic pigment, etc.) can be appropriately selected as long as it does not impair the effect of the present invention. Among them, from the viewpoint of optical density, suitable examples of black pigments include carbon black, titanium oxide, titanium carbide, iron oxide, and graphite, and carbon black is particularly preferable. As the carbon black, from the viewpoint of surface resistance, carbon black whose surface is at least partially covered with resin is preferable.

From the viewpoint of dispersion stability, the particle size of the black pigment is preferably 0.001 to 0.1 μm, more preferably 0.01 to 0.08 μm in number average particle size.

Here, the particle size refers to the diameter of a circle when the area of the pigment particle is obtained from a photographic image of the pigment particle taken with an electron microscope and a circle with the same area as the area of the pigment particle is considered. The number average particle size is an arbitrary number. This is the average value obtained by calculating the above-mentioned particle diameters for 100 particles and averaging the determined particle diameters of 100 particles.

As a pigment other than the black pigment, the white pigment described in paragraphs 0015 and 0114 of Japanese Patent Application Laid-Open No. 2005-007765 can be used. Specifically, among the white pigments, the inorganic pigment is preferably titanium oxide, zinc oxide, lithopone, light calcium carbonate, white carbon, aluminum oxide, aluminum hydroxide, or barium sulfate, and titanium oxide or zinc oxide is more preferable. , titanium oxide is more preferred. As the inorganic pigment, rutile-type or anatase-type titanium oxide is more preferable, and rutile-type titanium oxide is particularly preferable.

Additionally, the surface of titanium oxide may be subjected to silica treatment, alumina treatment, titania treatment, zirconia treatment, or organic substance treatment, or two or more treatments may be performed. As a result, the catalytic activity of titanium oxide is suppressed, and heat resistance, light fading properties, etc. are improved.

From the viewpoint of thinning the thickness of the photosensitive composition layer after heating, as a surface treatment for the surface of titanium oxide, at least one of alumina treatment and zirconia treatment is preferable, and both alumina treatment and zirconia treatment are particularly preferable.

Moreover, when the photosensitive composition layer is a colored resin layer, from the viewpoint of transferability, it is preferable that the photosensitive composition layer further contains a chromatic pigment other than the black pigment and the white pigment. When a chromatic pigment is included, the particle size of the chromatic pigment is preferably 0.1 μm or less, and more preferably 0.08 μm or less, from the viewpoint of better dispersibility.

As chromatic pigments, for example, Victoria Pure Blue BO (Color Index (hereinafter C.I.) 42595), Auramin (C.I. 41000), Fat Black HB (C.I. 26150), Mono Light Yellow GT (C.I. Pigment, Yellow 12), Permanent/Yellow GR (C.I. Pigment/Yellow 17), Permanent/Yellow HR (C.I. Pigment/Yellow 83), Permanent/Carmine FBB (C.I. Pigment/Red 146), Hostabum Red ESB (C.I. Pigment/Red 146). Pigment·Violet 19), Permanent·Ruby FBH (C.I. Pigment·Red 11), Pastel·Pink B Spray (C.I. Pigment·Red 81), Monastral·First Blue (C.I. Pigment·Blue 15), Mono Light·First·Black B (C.I. Pigment·Black 1) and Carbon, C.I. Pigment·Red 97, C. I. Pigment·Red 122, C. I. Pigment·Red 149, C. I. Pigment·Red 168, C. I. Pigment· Red 177, C. I. Pigment·Red 180, C. I. Pigment·Red 192, C. I. Pigment·Red 215, C. I. Pigment·Green 7, C. I. Pigment·Blue 15: 1, C. I. Pigment·Blue 15: 4, C. I. Pigment Blue 22, C. I. Pigment Blue 60, C. I. Pigment Blue 64, and C. I. Pigment Violet 23. Among them, C.I. Pigment Red 177 is preferable.

When the photosensitive composition layer contains a pigment, the content of the pigment is preferably more than 3% by mass and 40% by mass or less, more preferably more than 3% by mass and 35% by mass or less, with respect to the total mass of the photosensitive composition layer. The mass % exceeding 35 mass % or less is more preferable, and the mass % is 10 mass % or more and 35 mass % or less is particularly preferable.

When the photosensitive composition layer contains pigments other than the black pigment (white pigment and chromatic pigment), the content of the pigment other than the black pigment is preferably 30% by mass or less relative to the black pigment, and is 1 to 20% by mass. It is more preferable, and 3 to 15 mass% is more preferable.

In addition, when the photosensitive composition layer contains a black pigment and the photosensitive composition layer is formed of a photosensitive resin composition, the black pigment (preferably carbon black) is preferably introduced into the photosensitive resin composition in the form of a pigment dispersion. do.

The dispersion may be prepared by adding a mixture obtained by pre-mixing a black pigment and a pigment dispersant to an organic solvent (or vehicle) and dispersing it with a disperser. The pigment dispersant may be selected depending on the pigment and solvent, and for example, a commercially available dispersant can be used. In addition, the vehicle refers to the part of the medium in which the pigment is dispersed in the case of a pigment dispersion, and is liquid, comprising a binder component that maintains the black pigment in a dispersed state, and a solvent component (organic solvent) that dissolves and dilutes the binder component. Includes.

Examples of dispersants include urethane-based dispersants such as polyurethane, polycarboxylic acid esters such as polyacrylates, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid (partial) amine salts, polycarboxylic acid ammonium salts, and polycarboxylic acid alkylamines. Salts, polysiloxanes, long-chain polyaminoamide phosphates, hydroxyl group-containing polycarboxylic acid esters, their modified products, amides formed by the reaction of poly(lower alkyleneimine) and polyesters with free carboxyl groups, and their salts, etc. Oil-based dispersants, (meth)acrylic acid-styrene copolymer, (meth)acrylic acid-(meth)acrylic acid ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, polyvinylpyrrolidone, etc. or water-soluble resins Examples include polymer compounds, polyester-based, modified polyacrylate-based, ethylene oxide/propylene oxide addition compounds, and phosphoric acid ester-based. The aspect of the dispersant may be selected from the matters described in paragraphs [0021] to [0065] of Japanese Patent Application Laid-Open No. 2021-012355.

Preferred dispersants include, for example, basic polymer-type dispersants. Examples of basic polymer-type dispersants include polymers containing nitrogen atoms. The nitrogen atom may be contained in the main chain of the polymer, may be contained in the side chain of the polymer, or may be contained in the main chain and side chains of the polymer. Among them, it is preferable that the basic polymer-type dispersant is a polymer containing a nitrogen atom in the side chain. Since the surface of carbon black is generally acidic, when carbon black is used as a pigment, a basic polymer-type dispersant is particularly preferred as the dispersant.

Examples of the polymer containing a nitrogen atom (preferably a polymer containing a nitrogen atom in the side chain) include primary amino group, secondary amino group, tertiary amino group, quaternary ammonium base, and nitrogen-containing heterocyclic group. and a polymer containing at least one type of atomic group selected from the group consisting of. For example, polymers containing quaternary ammonium bases are preferred. The atomic group is preferably introduced into the side chain of the polymer. For example, a polymer containing at least one atomic group selected from the group consisting of primary amino group, secondary amino group, tertiary amino group, quaternary ammonium base, and nitrogen-containing heterocyclic group in the side chain is preferred, A polymer containing a quaternary ammonium base in the side chain is more preferable. Examples of the counter ion of the quaternary ammonium cation in the quaternary ammonium base include carboxylic acid ions. Examples of carboxylic acid ions include aliphatic carboxylic acid ions and aromatic carboxylic acid ions.

The polymer containing a nitrogen atom (preferably a polymer containing a nitrogen atom in the side chain) is preferably a polymer containing a structural unit derived from styrene and a structural unit derived from a maleimide derivative, and is preferably a polymer containing a structural unit derived from styrene and a maleimide derivative. Copolymers of mead derivatives are more preferred.

A maleimide derivative has a structure in which at least one hydrogen atom of maleimide is replaced by a substituent. Examples of maleimide derivatives include maleimides containing at least one atomic group selected from the group consisting of primary amino group, secondary amino group, tertiary amino group, quaternary ammonium base, and nitrogen-containing heterocyclic group. Derivatives may be mentioned. The maleimide derivative is preferably a maleimide derivative containing a quaternary ammonium base.

The dispersant may be a commercially available dispersant, for example, BYK-2012 (Big Chemi Japan Co., Ltd.).

The composition may contain a dispersing aid (also referred to as a pigment dispersing aid) in addition to the pigment. The dispersion aid may be selected from known dispersion aids.

Examples of dispersion aids include compounds having an organic dye residue. Examples of organic pigments include phthalocyanine pigments, diketopyrrolopyrrole pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, perinone pigments, perylene pigments, and thiazine indigo pigments. , triazine-based pigments, benzimidazolone-based pigments, indole-based pigments such as benzisoindole, isoindoline-based pigments, isoindolinone-based pigments, quinophthalone-based pigments, naphthol-based pigments, trene-based pigments, and metal complex systems. Pigments, azo-based pigments such as azo, disazo, and polyazo, etc. can be mentioned. The compound having an organic dye residue may have an acidic substituent, a basic substituent, or a neutral substituent. Examples of acidic substituents include sulfo groups, carboxy groups, and phosphoric acid groups. Examples of basic substituents include sulfonamide groups and amino groups. Examples of the neutral substituent include a phenyl group and a phthalimide alkyl group. The mode of dispersion aid may be selected from the matters described in paragraphs [0067] to [0084] of Japanese Patent Application Publication No. 2021-012355.

Preferred dispersion aids include, for example, compounds having a phthalocyanine residue. Specifically, the dispersion aid is preferably a phthalocyanine pigment derivative or a salt thereof having an acidic substituent, and phthalocyanine having at least one acidic substituent selected from the group consisting of a sulfo group, a carboxyl group, and a phosphoric acid group. It is more preferable that it is a phthalocyanine-based pigment derivative or a salt thereof, and it is more preferable that it is a phthalocyanine-based pigment derivative or a salt thereof having a sulfo group. Phthalocyanine pigment derivatives are described, for example, in Japanese Patent Application Laid-Open No. 2007-226161, International Publication No. 2016/163351, Japanese Patent Application Publication No. 2017-165820, and Japanese Patent Application Publication No. 5753266. . These publications are incorporated herein by reference.

There is no particular limitation on the disperser, and examples include known dispersers such as a kneader, roll mill, attritor, super mill, resolver, homomixer, and sand mill. Additionally, it may be finely pulverized using frictional force through mechanical grinding. For dispersers and fine grinding, reference may be made to the description in “Dictionary of Pigments” (by Kunizo Asakura, 1st edition, Asakura Shoten, 2000, pages 438, 310).

<<Relationship between branch support, photosensitive composition layer, and protective film>>

Also in the second embodiment, it is preferable to satisfy the relationship between the temporary support, the photosensitive composition layer, and the protective film described in the first embodiment.

<<thermoplastic resin layer>>

The transfer film may have a thermoplastic resin layer.

The thermoplastic resin layer is usually disposed between the support and the photosensitive composition layer. When the transfer film is provided with a thermoplastic resin layer, followability to the substrate in the bonding process of the transfer film and the substrate is improved, and mixing of air bubbles between the substrate and the transfer film can be suppressed. As a result, adhesion to the thermoplastic resin layer and the adjacent layer (for example, branch support) can be ensured.

The thermoplastic resin layer contains resin. The resin includes, in whole or in part, a thermoplastic resin. That is, in one aspect, it is preferable that the thermoplastic resin layer is a thermoplastic resin.

<Alkali-soluble resin (thermoplastic resin)>

The thermoplastic resin is preferably an alkali-soluble resin.

Examples of alkali-soluble resin include acrylic resin, polystyrene resin, styrene-acrylic copolymer, polyurethane resin, polyvinyl alcohol, polyvinyl formal, polyamide resin, polyester resin, polyamide resin, and epoxy resin. , polyacetal resin, polyhydroxystyrene resin, polyimide resin, polybenzoxazole resin, polysiloxane resin, polyethyleneimine, polyallylamine, and polyalkylene glycol.

As the alkali-soluble resin, acrylic resin is preferable from the viewpoint of developability and adhesion to adjacent layers.

Here, the acrylic resin is at least one structural unit selected from the group consisting of structural units derived from (meth)acrylic acid, structural units derived from (meth)acrylic acid ester, and structural units derived from (meth)acrylic acid amide. It means a resin having .

As an acrylic resin, the total content of structural units derived from (meth)acrylic acid, structural units derived from (meth)acrylic acid ester, and structural units derived from (meth)acrylic acid amide is 50 mass based on the total mass of the acrylic resin. It is preferable that it is % or more.

Among them, the total content of structural units derived from (meth)acrylic acid and structural units derived from (meth)acrylic acid ester is preferably 30 to 100% by mass, and 50 to 100% by mass, relative to the total mass of the acrylic resin. It is more desirable.

Moreover, it is preferable that the alkali-soluble resin is a polymer having an acid group.

Examples of the acid group include carboxyl group, sulfo group, phosphoric acid group, and phosphonic acid group, with carboxyl group being preferred.

From the viewpoint of developability, the alkali-soluble resin is more preferably an alkali-soluble resin with an acid value of 60 mgKOH/g or more, and a carboxyl group-containing acrylic resin with an acid value of 60 mgKOH/g or more is more preferable.

The upper limit of the acid value of the alkali-soluble resin is not particularly limited, but is preferably 300 mgKOH/g or less, more preferably 250 mgKOH/g or less, more preferably 200 mgKOH/g or less, and especially preferably 150 mgKOH/g or less.

The acrylic resin containing a carboxyl group with an acid value of 60 mgKOH/g or more is not particularly limited, and can be appropriately selected from known resins and used.

For example, among the polymers described in paragraph 0025 of Japanese Patent Application Laid-Open No. 2011-095716, an alkali-soluble resin is an acrylic resin containing a carboxyl group with an acid value of 60 mgKOH/g or more, and an acid value among the polymers described in paragraphs 0033 to 0052 of Japanese Patent Application Laid-Open No. 2010-237589. An acrylic resin containing a carboxyl group of 60 mgKOH/g or more, and an acrylic resin containing a carboxyl group of an acid value of 60 mgKOH/g or more in the binder polymer described in paragraphs 0053 to 0068 of Japanese Patent Application Laid-Open No. 2016-224162.

The copolymerization ratio of the structural unit having a carboxyl group in the carboxyl group-containing acrylic resin is preferably 5 to 50% by mass, more preferably 10 to 40% by mass, and 12 to 30% by mass, based on the total mass of the acrylic resin. % is more preferable.

As the alkali-soluble resin, an acrylic resin having a structural unit derived from (meth)acrylic acid is particularly preferable from the viewpoint of developability and adhesion to adjacent layers.

The alkali-soluble resin may have a reactive group. The reactive group may be any group capable of addition polymerization, and may include an ethylenically unsaturated group; Polycondensation groups such as hydroxy groups and carboxy groups; Examples include polyvalent reactive groups such as epoxy groups and (block)isocyanate groups.

The weight average molecular weight (Mw) of the alkali-soluble resin is preferably 1,000 or more, more preferably 10,000 to 100,000, and more preferably 20,000 to 50,000.

Alkali-soluble resins may be used individually or in combination of two or more.

The content of the alkali-soluble resin is preferably 10 to 99% by mass, more preferably 20 to 90% by mass, and 40 to 90% by mass, relative to the total mass of the thermoplastic resin layer, from the viewpoint of developability and adhesion to adjacent layers. 80% by mass is more preferable, and 50 to 75% by mass is particularly preferable.

<Pigment>

The thermoplastic resin layer has a maximum absorption wavelength of 450 nm or more in the wavelength range of 400 to 780 nm at the time of color development, and contains a dye (also simply referred to as “pigment B”) whose maximum absorption wavelength changes due to acids, bases, or radicals. It is desirable to include it.

The preferred embodiment of the pigment B is the same as the preferred embodiment of the pigment N described above, except for the points described later.

From the viewpoint of visibility and resolution of exposed and unexposed areas, the dye B is preferably a dye whose maximum absorption wavelength changes due to an acid or radical, and more preferably a dye whose maximum absorption wavelength changes due to an acid.

From the viewpoint of visibility and resolution of exposed and unexposed areas, the thermoplastic resin layer preferably contains both a dye whose maximum absorption wavelength changes depending on the acid as dye B and a compound that generates acid by light, which will be described later. do.

Pigment B may be used individually or in combination of two or more types.

The content of pigment B is preferably 0.2% by mass or more, more preferably 0.2 to 6% by mass, and 0.2 to 5% by mass, relative to the total mass of the thermoplastic resin layer, from the viewpoint of visibility of exposed and non-exposed areas. It is more preferable, and 0.25 to 3.0 mass% is particularly preferable.

Here, the content of dye B means the content of the dye when all of the dye B contained in the thermoplastic resin layer is in a color developing state. Below, a method for quantifying the content of pigment B will be explained using a pigment that develops color by radicals as an example.

Prepare a solution in which 0.001 g and 0.01 g of pigment are dissolved in 100 mL of methyl ethyl ketone. To each obtained solution, a radical photopolymerization initiator Irgacure OXE01 (brand name, BASF Japan Co., Ltd.) is added, and radicals are generated by irradiating light at 365 nm to bring all pigments into a coloring state. Thereafter, the absorbance of each solution with a liquid temperature of 25°C is measured using a spectrophotometer (UV3100, manufactured by Shimadzu Seisakusho Co., Ltd.) under an atmospheric atmosphere, and a calibration curve is prepared.

Next, the absorbance of the solution in which all the pigments were developed was measured in the same manner as above, except that 0.1 g of the thermoplastic resin layer was dissolved in methyl ethyl ketone instead of the pigment. From the absorbance of the solution containing the obtained thermoplastic resin layer, the amount of pigment contained in the thermoplastic resin layer is calculated based on a calibration curve.

In addition, 3 g of the thermoplastic resin layer is equivalent to 3 g of the solid content of the composition.

<Compounds that generate acids, bases, or radicals when exposed to light>

The thermoplastic resin layer may contain a compound (also simply referred to as “compound C”) that generates an acid, a base, or a radical when exposed to light.

As compound C, a compound that generates an acid, a base, or a radical when exposed to actinic rays such as ultraviolet rays and visible rays is preferable.

As compound C, known photoacid generators, photobase generators, and photoradical polymerization initiators (photoradical generators) can be used.

(mine-generating agent)

The thermoplastic resin layer may contain a photoacid generator from the viewpoint of resolution.

Examples of the photoacid generator include photocationic polymerization initiators that the negative photosensitive composition layer may contain, and the preferred embodiments are the same except for the points described later.

The photo acid generator preferably contains at least one compound selected from the group consisting of onium salt compounds and oxime sulfonate compounds from the viewpoint of sensitivity and resolution, and from the viewpoint of sensitivity, resolution, and adhesion, the oxime It is more preferable to include a sulfonate compound.

Additionally, as the photoacid generator, a photoacid generator having the following structure is also preferable.

[Formula 27]

(Optical radical polymerization initiator)

The thermoplastic resin layer may contain a radical photopolymerization initiator.

As a radical photopolymerization initiator, the radical photopolymerization initiator which the above-mentioned negative photosensitive composition layer may contain is mentioned, and the preferable aspect is also the same.

(Photobase generator)

The thermoplastic resin composition may contain a photobase generator.

The photobase generator is not particularly limited as long as it is a known photobase generator, and examples include 2-nitrobenzylcyclohexylcarbamate, triphenylmethanol, O-carbamoylhydroxylamide, O-carbamoyloxime, [[(2,6-dinitrobenzyl)oxy]carbonyl]cyclohexylamine, bis[[(2-nitrobenzyl)oxy]carbonyl]hexane 1,6-diamine, 4-(methylcy Obenzoyl)-1-methyl-1-morpholinoethane, (4-morpholinobenzoyl)-1-benzyl-1-dimethylaminopropane, N-(2-nitrobenzyloxycarbonyl)pyrroli Dean, hexaaminecobalt(III)tris(triphenylmethylborate), 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone, 2,6-dimethyl-3,5 -Diacetyl-4-(2-nitrophenyl)-1,4-dihydropyridine, and 2,6-dimethyl-3,5-diacetyl-4-(2,4-dinitrophenyl)- and 1,4-dihydropyridine.

Compound C may be used individually or in combination of two or more types.

The content of compound C is preferably 0.1 to 10% by mass, more preferably 0.5 to 5% by mass, relative to the total mass of the thermoplastic resin layer, from the viewpoint of visibility and resolution of exposed and non-exposed areas.

<Plasticizer>

The thermoplastic resin layer preferably contains a plasticizer from the viewpoints of resolution, adhesion to adjacent layers, and developability.

The plasticizer preferably has a molecular weight (weight average molecular weight if it is an oligomer or polymer and has a molecular weight distribution) smaller than that of the alkali-soluble resin. The molecular weight (weight average molecular weight) of the plasticizer is preferably 200 to 2,000.

The plasticizer is not particularly limited as long as it is a compound that is compatible with the alkali-soluble resin and exhibits plasticity. However, from the viewpoint of imparting plasticity, the plasticizer preferably has an alkyleneoxy group in the molecule, and is a polyalkylene glycol compound. This is more preferable. The alkyleneoxy group contained in the plasticizer more preferably has a polyethyleneoxy structure or a polypropyleneoxy structure.

Moreover, it is preferable that the plasticizer contains a (meth)acrylate compound from the viewpoint of resolution and storage stability. From the viewpoints of compatibility, resolution, and adhesion to adjacent layers, it is more preferable that the alkali-soluble resin is an acrylic resin and that the plasticizer contains a (meth)acrylate compound.

Examples of the (meth)acrylate compound used as a plasticizer include the (meth)acrylate compound described as the polymerizable compound contained in the negative photosensitive composition layer described above.

In the transfer film, when the thermoplastic resin layer and the negative photosensitive composition layer are laminated in direct contact, it is preferable that both the thermoplastic resin layer and the negative photosensitive composition layer contain the same (meth)acrylate compound. This is because the thermoplastic resin layer and the negative photosensitive composition layer each contain the same (meth)acrylate compound, thereby suppressing diffusion of components between layers and improving storage stability.

When the thermoplastic resin layer contains a (meth)acrylate compound as a plasticizer, it is preferable that the (meth)acrylate compound does not polymerize even in the exposed area after exposure from the viewpoint of adhesion between the thermoplastic resin layer and the adjacent layer.

In addition, the (meth)acrylate compound used as a plasticizer is a polyfunctional compound having two or more (meth)acryloyl groups in one molecule from the viewpoint of resolution of the thermoplastic resin layer, adhesion to adjacent layers, and developability. (meth)acrylate compounds are preferred.

Moreover, as a (meth)acrylate compound used as a plasticizer, a (meth)acrylate compound or a urethane (meth)acrylate compound having an acid group is also preferable.

Plasticizers may be used individually or in combination of two or more.

The content of the plasticizer is preferably 1 to 70% by mass, and is more preferably 10 to 60% by mass, relative to the total mass of the thermoplastic resin layer, from the viewpoint of resolution of the thermoplastic resin layer, adhesion to adjacent layers, and developability. It is preferable, and 20 to 50 mass% is more preferable.

<Sensitizer>

The thermoplastic resin layer may contain a sensitizer.

The sensitizer is not particularly limited and includes sensitizers that the negative photosensitive composition layer described above may contain.

Sensitizers may be used individually or in combination of two or more.

The content of the sensitizer can be appropriately selected depending on the purpose, but from the viewpoint of improving sensitivity to the light source and visibility of exposed and non-exposed areas, 0.01 to 5% by mass is preferable with respect to the total mass of the thermoplastic resin layer. And 0.05 to 1 mass% is more preferable.

<Additives, etc.>

In addition to the above components, the thermoplastic resin layer may contain known additives such as surfactants as needed.

In addition, the thermoplastic resin layer is described in paragraphs 0189 to 0193 of Japanese Patent Application Publication No. 2014-085643, and the content described in this publication is incorporated herein by reference.

The layer thickness of the thermoplastic resin layer is not particularly limited, but is preferably 1 μm or more, and more preferably 2 μm or more from the viewpoint of adhesion to adjacent layers. The upper limit is not particularly limited, but from the viewpoint of developability and resolution, 20 μm or less is preferable, 10 μm or less is more preferable, and 8 μm or less is still more preferable.

<<middle layer>>

The transfer film may have an intermediate layer.

In the transfer film 10, the intermediate layer 5 exists between the thermoplastic resin layer 3 and the photosensitive composition layer 7, so that it is formed by applying the thermoplastic resin layer 3 and the photosensitive composition layer 7. And mixing of components that may occur during storage after application formation can be suppressed.

As the intermediate layer, a water-soluble resin layer containing a water-soluble resin can be used.

Additionally, as the intermediate layer, an oxygen blocking layer with an oxygen blocking function, described as a "separation layer" in Japanese Patent Application Laid-Open No. 5-072724, can also be used. It is preferable that the intermediate layer is an oxygen blocking layer because sensitivity during exposure is improved, the time load on the exposure machine is reduced, and productivity is improved.

The oxygen blocking layer used as the intermediate layer may be appropriately selected from known layers described in the above publication and the like. Among them, an oxygen barrier layer that exhibits low oxygen permeability and is dispersed or dissolved in water or an aqueous alkaline solution (1% by mass aqueous solution of sodium carbonate at 22°C) is preferable.

Hereinafter, each component that the water-soluble resin layer (middle layer) may contain will be described.

The water-soluble resin layer (middle layer) contains resin.

The resin includes, in whole or in part, a water-soluble resin.

Resins that can be used as water-soluble resins include, for example, polyvinyl alcohol-based resin, polyvinylpyrrolidone-based resin, cellulose-based resin, acrylamide-based resin, polyethylene oxide-based resin, gelatin, vinyl ether-based resin, polyamide resin, and resins such as copolymers thereof.

Additionally, as the water-soluble resin, a copolymer of (meth)acrylic acid/vinyl compound, etc. can also be used. As a copolymer of (meth)acrylic acid/vinyl compound, a copolymer of (meth)acrylic acid/allyl (meth)acrylate is preferable, and a copolymer of methacrylic acid/allyl methacrylate is more preferable.

When the water-soluble resin is a copolymer of (meth)acrylic acid/vinyl compound, the composition ratio (mol%) is preferably, for example, 90/10 to 20/80, and more preferably 80/20 to 30/70.

The lower limit of the weight average molecular weight of the water-soluble resin is preferably 5,000 or more, more preferably 7,000 or more, and even more preferably 10,000 or more. Moreover, as the upper limit, 200,000 or less is preferable, 100,000 or less is more preferable, and 50,000 or less is still more preferable.

The dispersion degree (Mw/Mn) of the water-soluble resin is preferably 1 to 10, and more preferably 1 to 5.

In addition, in order to further improve the ability to suppress interlayer mixing of the water-soluble resin layer (middle layer), the resin in the water-soluble resin layer (middle layer) is the resin contained in the layer disposed on one side of the water-soluble resin layer (middle layer) and the other side. It is preferable that the resin is different from the resin contained in the layer disposed on the surface side. For example, when polymer A is contained in the photosensitive composition layer 17 and a thermoplastic resin (alkali-soluble resin) is contained in the thermoplastic resin layer 13, the resin of the water-soluble resin layer (middle layer) 15 is the polymer. It is preferable that it is a different resin from A and a thermoplastic resin (alkali-soluble resin).

The water-soluble resin preferably contains polyvinyl alcohol, and more preferably contains both polyvinyl alcohol and polyvinylpyrrolidone, from the viewpoint of further improving oxygen barrier properties and interlayer mixing inhibition ability.

Water-soluble resins may be used individually or in combination of two or more.

The content of the water-soluble resin is not particularly limited, but is preferably 50% by mass or more, and 70% by mass or more, relative to the total mass of the water-soluble resin layer (middle layer), from the viewpoint of further improving the oxygen barrier property and the ability to inhibit interlayer mixing. This is more preferable, 80 mass% or more is more preferable, and 90 mass% or more is particularly preferable. In addition, the upper limit is not particularly limited, but for example, 99.9 mass% or less is preferable, and 99.8 mass% or less is more preferable.

The intermediate layer may contain known additives such as surfactants as needed.

The layer thickness of the water-soluble resin layer (middle layer) is not particularly limited, but is preferably 0.1 to 5 μm, and more preferably 0.5 to 3 μm. If the thickness of the water-soluble resin layer (middle layer) is within the above range, the oxygen barrier property is not reduced and the ability to inhibit interlayer mixing is excellent. In addition, an increase in the water-soluble resin layer (middle layer) removal time during development can be further suppressed.

Moreover, when the transfer film of 2nd Embodiment has an intermediate layer, it is also preferable to satisfy the following relationship with respect to the adhesive force between layers.

· Relationship between adhesion 1: The adhesion between the intermediate layer and the photosensitive composition layer is greater than the adhesion between the photosensitive composition layer and the protective film.

· Adhesion relationship 2: The adhesion between the support and the intermediate layer is greater than the adhesion between the photosensitive composition layer and the protective film.

When the above adhesion relationships 1 and 2 are satisfied, when peeling the protective film from the transfer film, peeling occurs at the interface between the photosensitive composition layer and the protective film, making it suitable for use as a transfer film.

Additionally, regarding the adhesion of the intermediate layer, it is also desirable to satisfy the following relationship.

· Relationship between adhesion 3: The adhesion between the middle layer and the photosensitive composition layer is greater than the adhesion between the branch support and the middle layer.

When the above adhesion relationship 3 is satisfied, in the step of peeling off the support, which will be explained in detail later, peeling occurs between the support and the middle layer, and the middle layer tends to remain on the photosensitive composition layer side. As a result, the intermediate layer tends to function as an oxygen blocking layer or the like.

<<Method for producing the transfer film of the second embodiment>>

The manufacturing method of the transfer film of the second embodiment is not particularly limited, and a known method can be used.

As a method for producing the transfer film 20, for example, a thermoplastic resin composition is applied to the surface of the support 11 to form a coating film, and the coating film is dried to further form a thermoplastic resin layer 13. A process of applying a water-soluble resin composition to the surface of the thermoplastic resin layer 13 to form a coating film, drying the coating film to further form an intermediate layer 15, and applying a photosensitive composition to the surface of the intermediate layer 15. A method including the step of forming a coating film, drying the coating film to further form the photosensitive composition layer 17, and pressing the protective film 19 on the photosensitive composition layer 17. .

By the above-described manufacturing method, the transfer film 20 having the support 11, the thermoplastic resin layer 13, the intermediate layer 15, the photosensitive composition layer 17, and the protective film 19 can be manufactured. there is.

After manufacturing the transfer film 20 by the above manufacturing method, a roll-shaped transfer film may be produced and stored by winding the transfer film 20. The roll-shaped transfer film can be provided in its original form to the roll-to-roll bonding process with the substrate described later.

In addition, as a manufacturing method of the transfer film 20, after forming the photosensitive resin layer 17 and the intermediate layer 15 on the protective film 19, a thermoplastic resin layer 3 is formed on the surface of the intermediate layer 15. ) may be a method of forming.

<Composition for forming thermoplastic resin layer and method for forming thermoplastic resin layer>

The method for forming the thermoplastic resin layer on the support is not particularly limited, and known methods can be used. For example, it can be formed by applying a composition for forming a thermoplastic resin layer on a temporary support and drying it as necessary.

The composition for forming a thermoplastic resin layer preferably contains various components and a solvent for forming the thermoplastic resin layer described above. In addition, in the composition for forming a thermoplastic resin layer, the suitable range of the content of each component with respect to the total solid content of the composition is the same as the suitable range of the content of each component with respect to the total mass of the thermoplastic resin layer described above.

The solvent is not particularly limited as long as it can dissolve or disperse each component other than the solvent, and a known solvent can be used. Examples of the solvent include the same solvent as the solvent contained in the photosensitive composition described later, and the preferred embodiments are also the same.

The content of the solvent is preferably 50 to 1,900 parts by mass, and more preferably 100 to 900 parts by mass, based on 100 parts by mass of the total solid content of the composition.

The method of forming the thermoplastic resin layer is not particularly limited as long as it is a method capable of forming a layer containing the above components, and examples include known coating methods (slit coating, spin coating, curtain coating, and inkjet coating, etc.). You can.

<Water-soluble resin composition and method of forming intermediate layer (water-soluble resin layer)>

The water-soluble resin composition preferably contains various components and solvents that form the intermediate layer (water-soluble resin layer) described above. In addition, in the water-soluble resin composition, the suitable range of the content of each component with respect to the total solid content of the composition is the same as the suitable range of the content of each component with respect to the total mass of the water-soluble resin layer described above.

The solvent is not particularly limited as long as it can dissolve or disperse the water-soluble resin, and at least one selected from the group consisting of water and water-miscible organic solvents is preferable, and water or a mixed solvent of water and water-miscible organic solvents is more preferable. do.

Examples of water-miscible organic solvents include alcohols having 1 to 3 carbon atoms, acetone, ethylene glycol, and glycerin, with alcohols having 1 to 3 carbon atoms being preferable, and methanol or ethanol being more preferable.

One type of solvent may be used individually, or two or more types may be used.

The content of the solvent is preferably 50 to 2,500 parts by mass, more preferably 50 to 1,900 parts by mass, and still more preferably 100 to 900 parts by mass, based on 100 parts by mass of the total solid content of the composition.

The method of forming the water-soluble resin layer is not particularly limited as long as it is a method capable of forming a layer containing the above components, and examples include known coating methods (slit coating, spin coating, curtain coating, and inkjet coating, etc.). You can.

<Method of forming photosensitive composition and photosensitive composition layer>

Because productivity is excellent and the above-mentioned photosensitive composition layer is easy to form, the components constituting the above-described photosensitive composition layer (e.g., binder polymer, polymerizable compound, and polymerization initiator, etc.), and solvent It is preferably formed by a coating method using a photosensitive composition containing.

As a method for producing the transfer film of the second embodiment, specifically, it is preferable to apply a photosensitive composition on an intermediate layer to form a coating film, and subject the coating film to a drying treatment at a predetermined temperature to form a photosensitive composition layer. do.

The photosensitive composition preferably contains various components and solvents that form the photosensitive composition layer described above. In addition, in the photosensitive composition, the suitable range of the content of each component with respect to the total solid content of the composition is the same as the suitable range of the content of each component with respect to the total mass of the photosensitive composition layer described above.

The solvent is not particularly limited as long as it can dissolve or disperse each component other than the solvent, and a known solvent can be used. Specifically, for example, alkylene glycol ether solvent, alkylene glycol ether acetate solvent, alcohol solvent (methanol, ethanol, etc.), ketone solvent (acetone, methyl ethyl ketone, etc.), aromatic hydrocarbon solvent ( toluene, etc.), aprotic polar solvents (N,N-dimethylformamide, etc.), cyclic ether solvents (tetrahydrofuran, etc.), ester solvents (n-propyl acetate, etc.), amide solvents, lactone solvents, and these. A mixed solvent containing two or more types can be mentioned.

The solvent preferably contains at least one selected from the group consisting of alkylene glycol ether solvents and alkylene glycol ether acetate solvents. Among them, a mixed solvent containing at least one type selected from the group consisting of alkylene glycol ether solvents and alkylene glycol ether acetate solvents, and at least one type selected from the group consisting of ketone solvents and cyclic ether solvents. More preferably, a mixed solvent containing at least three types of solvents: at least one selected from the group consisting of an alkylene glycol ether solvent and an alkylene glycol ether acetate solvent, a ketone solvent, and a cyclic ether solvent is more preferred. do.

Examples of alkylene glycol ether solvents include ethylene glycol monoalkyl ether, ethylene glycol dialkyl ether, propylene glycol monoalkyl ether (propylene glycol monomethyl ether acetate, etc. ), propylene glycol dialkyl ether, diethylene glycol dialkyl ether, dipropylene glycol monoalkyl ether, and dipropylene glycol dialkyl ether.

Examples of alkylene glycol ether acetate solvents include ethylene glycol monoalkyl ether acetate, propylene glycol monoalkyl ether acetate, diethylene glycol monoalkyl ether acetate, and dipropylene glycol. Colmonoalkyl ether acetate can be mentioned.

As the solvent, the solvent described in paragraphs 0092 to 0094 of International Publication No. 2018/179640 and the solvent described in paragraph 0014 of Japanese Patent Application Publication No. 2018-177889 may be used, and these contents are incorporated in this specification.

One type of solvent may be used individually, or two or more types may be used.

The content of the solvent is preferably 50 to 1,900 parts by mass, more preferably 100 to 1,200 parts by mass, and still more preferably 100 to 900 parts by mass, based on 100 parts by mass of the total solid content of the composition.

Examples of application methods for the photosensitive composition include printing, spraying, roll coating, bar coating, curtain coating, spin coating, and die coating (i.e., slit coating).

As a drying method for the coating film of the photosensitive composition, heat drying and reduced pressure drying are preferable. As a drying temperature, 80 degreeC or more is preferable, and 90 degreeC or more is more preferable. Moreover, as the upper limit, 130°C or lower is preferable, and 120°C or lower is more preferable. Drying can also be done by continuously changing the temperature.

Moreover, as a drying time, 20 seconds or more is preferable, 40 seconds or more is more preferable, and 60 seconds or more is still more preferable. The upper limit is not particularly limited, but is preferably 600 seconds or less, and more preferably 300 seconds or less.

<How to press the protective film>

Additionally, the transfer film of the second embodiment can be manufactured by bonding the protective film to the photosensitive composition layer.

The method of bonding the protective film to the photosensitive composition layer is not particularly limited and includes known methods.

Examples of devices for bonding the protective film to the photosensitive composition layer include known laminators such as a vacuum laminator and an autocut laminator.

The laminator is preferably provided with any heatable roller such as a rubber roller, and is capable of pressurizing and heating.

In addition, a protective film in which the arithmetic mean roughness Ra1 of the surface on the side of the photosensitive composition layer described above is smaller than the arithmetic mean roughness Ra2 of the surface on the side opposite to the photosensitive composition layer can be manufactured by a known method, and the manufacturing method thereof is not particularly limited. The method is as described in the transfer film of the first embodiment.

[Uses of transfer film]

The transfer film of the present invention can be applied to various uses. For example, it can be applied to an electrode protective film, insulating film, planarization film, overcoat film, hard coat film, passivation film, partition, spacer, micro lens, optical filter, anti-reflection film, etching resist, and plating member. More specific examples include a protective film or insulating film for a touch panel electrode, a protective film or insulating film for a printed wiring board, a protective film or insulating film for a TFT substrate, a color filter, an overcoat film for a color filter, and an etching resist for forming wiring.

[Method for manufacturing a laminate with a conductor pattern]

Using the above-described transfer film, a laminate having a conductor pattern can be manufactured. The manufacturing method of the laminate with a conductor pattern is not particularly limited as long as it is a method using the transfer film described above, but the following manufacturing method is preferable for the manufacturing method of the laminate with a conductor pattern of the present invention.

A peeling process of peeling the protective film from the transfer film to expose the surface of the photosensitive composition layer;

A bonding process of bonding the transfer film and the substrate having a conductive layer so that the exposed surface of the photosensitive composition layer is in contact with the conductive layer of the substrate having a conductive layer on the surface;

An exposure process of exposing the photosensitive composition layer,

A development process of performing development treatment on the exposed photosensitive composition layer to form a resist pattern;

One of an etching process in which an etching process is performed on the conductive layer in the area where the resist pattern is not disposed, and a plating process in which a plating process is performed;

A resist pattern peeling process for peeling off the resist pattern,

A method of manufacturing a laminate with a conductor pattern, in the case of having a plating process, further comprising a removal process of removing the exposed conductive layer by a resist pattern peeling process and forming a conductor pattern on the substrate,

A method for producing a laminate with a conductor pattern, further comprising a provisional support peeling step of peeling off the provisional support between the bonding process and the exposure process, or between the exposure process and the development process.

Hereinafter, specific procedures for manufacturing a laminate with a conductor pattern will be described.

Additionally, the steps that may be included in the method for manufacturing a laminate having the above-mentioned preferred conductor pattern will also be described.

[Peeling process]

The peeling process is a process of peeling the protective film from the transfer film.

When the peeling process is performed, the surface of the photosensitive composition layer of the transfer film is exposed.

The method of peeling the protective film is not particularly limited and can be performed by a known method. For example, the protective film can be peeled while being wound into a roll.

[Bonding process]

The bonding process is a process of bonding the transfer film and the substrate having a conductive layer so that the exposed surface of the photosensitive composition layer is in contact with the conductive layer of the substrate having a conductive layer on the surface.

When the bonding process is performed, a laminated body (substrate with a photosensitive composition layer) having the substrate, the conductive layer, the photosensitive composition layer, and the temporary support in this order is obtained.

The substrate having a conductive layer has a conductive layer on the substrate, and an arbitrary layer may be formed as needed. That is, a substrate with a conductive layer is a conductive substrate that has at least a substrate and a conductive layer disposed on the substrate.

Examples of the substrate include a resin substrate, a glass substrate, and a semiconductor substrate.

As a preferred embodiment of the substrate, for example, there is a description in paragraph [0140] of International Publication No. 2018/155193, the content of which is incorporated herein by reference. As materials for the resin substrate, cycloolefin polymers and polyimides are preferable. The thickness of the resin substrate is preferably 5 to 200 μm, and more preferably 10 to 100 μm.

The conductive layer is preferably at least one layer selected from the group consisting of a metal layer, a conductive metal oxide layer, a graphene layer, a carbon nanotube layer, and a conductive polymer layer, in terms of conductivity and fine wire formation.

Additionally, only one conductive layer may be disposed on the substrate, or two or more layers may be disposed. When disposing two or more conductive layers, it is preferable to have conductive layers of different materials.

As a preferable aspect of the conductive layer, for example, there is description in paragraph [0141] of International Publication No. 2018/155193, the content of which is incorporated herein by reference.

The conductive layer may be a transparent conductive layer capable of forming a transparent electrode through a process described later. The transparent conductive layer is preferably comprised of a metal oxide film such as ITO (indium tin oxide) and IZO (indium zinc oxide), a metal mesh, and metal fine wires such as a metal nanowire.

Examples of fine metal wires include fine wires such as silver and copper. Among them, silver conductive materials such as silver mesh and silver nanowire are preferable.

The thickness of the conductive layer is not particularly limited, and is preferably 50 nm or more, and more preferably 100 nm or more. The upper limit is preferably 10 μm or less, and more preferably 2 μm or less.

In the above bonding, it is preferable to press so that the surfaces of the conductive layer and the photosensitive composition layer come into contact.

There is no particular limitation as to the pressing method, and known transfer methods and laminating methods can be used. Among them, it is preferable that the surface of the photosensitive composition layer is overlapped with a substrate having an electrically conductive portion, and pressurization and heating are performed using a roll or the like.

For bonding, known laminators such as a vacuum laminator and an autocut laminator can be used.

The laminating temperature is not particularly limited, but is preferably, for example, 70 to 130°C.

[Exposure process]

The exposure process is a process of pattern exposing the photosensitive composition layer.

By performing an exposure process and a development process described later, a resist pattern that protects at least part of the conductive layer is formed on the conductive layer on the substrate.

In addition, here, “pattern exposure” refers to a form of exposure in a pattern, that is, a form of exposure in which an exposed part and a non-exposed part exist.

The positional relationship between the exposed area and the unexposed area in pattern exposure is not particularly limited and is adjusted appropriately.

You may expose from the side opposite to the substrate of the photosensitive composition layer, or you may expose from the substrate side of the photosensitive composition layer.

As a light source for pattern exposure, any light source that can irradiate at least a wavelength range capable of curing the photosensitive composition layer (for example, 365 nm or 405 nm) can be appropriately selected and used. Among them, the dominant wavelength of exposure light for pattern exposure is preferably 365 nm. Additionally, the dominant wavelength is the wavelength with the highest intensity.

Examples of light sources include various lasers, light-emitting diodes (LEDs), ultra-high pressure mercury lamps, high-pressure mercury lamps, and metal halide lamps.

The exposure amount is preferably 5 to 200 mJ/cm ² and more preferably 10 to 200 mJ/cm ² .

Preferred aspects of the light source, exposure amount, and exposure method used for exposure are, for example, described in paragraphs [0146] to [0147] of International Publication No. 2018/155193, and these contents are incorporated herein by reference.

[Branched support peeling process]

The provisional support peeling process is a process of peeling the provisional support from the substrate with the photosensitive composition layer between the bonding process and the exposure process, or between the exposure process and the development process described later.

The peeling method is not particularly limited, and the same mechanism as the cover film peeling mechanism described in paragraphs [0161] to [0162] of Japanese Patent Application Laid-Open No. 2010-072589 can be used.

[Development process]

The development process is a process of developing the exposed photosensitive composition layer to form a resist pattern.

Development of the photosensitive composition layer can be performed using a developing solution.

As a developer, an alkaline aqueous solution is preferred. Examples of alkaline compounds that can be contained in an alkaline aqueous solution include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, tetramethylammonium hydroxide, tetraethylammonium hydroxide, and tetrapropyl. Examples include ammonium hydroxide, tetrabutylammonium hydroxide, and choline (2-hydroxyethyltrimethylammonium hydroxide).

Examples of the development method include puddle development, shower development, spin development, and dip development.

Examples of a developer suitably used in this specification include the developer described in paragraph [0194] of International Publication No. 2015/093271, and examples of a development method suitably used include, for example, International Publication No. 2015/093271. An example is the development method described in paragraph [0195] of No. 2015/093271.

After development, before moving to the next step, it is also preferable to perform a rinse treatment to remove the developing solution remaining on the substrate with a conductive layer. For rinsing treatment, water or the like can be used.

After development and/or rinsing, a drying process may be performed to remove excess liquid from the substrate with a conductive layer.

[Etching process]

In the above manufacturing method, either an etching process or a plating treatment process described later is performed.

In the etching process, an etching process is performed on the conductive layer in the area where the resist pattern is not disposed.

Through the etching process, a conductor pattern corresponding to the pattern of the resist pattern is formed.

As a method of etching treatment, known methods can be applied, for example, the method described in paragraphs [0209] to [0210] of Japanese Patent Application Laid-Open No. 2017-120435, and paragraph [0048] of Japanese Patent Application Laid-Open No. 2010-152155. ] to [0054], a wet etching method of immersing in an etchant, and a dry etching method such as plasma etching.

The etching solution used for wet etching may be an acidic or alkaline etching solution appropriately selected according to the object of etching.

Acidic etching solutions include, for example, an aqueous solution containing only an acidic component selected from hydrochloric acid, sulfuric acid, nitric acid, acetic acid, hydrofluoric acid, oxalic acid, and phosphoric acid, and an acidic component including ferric chloride, ammonium fluoride, and potassium permanganate. and a mixed aqueous solution of selected salts. The acidic component may be a component that combines multiple acidic components.

As an alkaline etching solution, an aqueous solution of only an alkaline component selected from sodium hydroxide, potassium hydroxide, ammonia, organic amines, and salts of organic amines (tetramethylammonium hydroxide, etc.), and an alkali component and a salt (potassium permanganate) etc.) may be a mixed aqueous solution. The alkaline component may be a component combining multiple alkaline components.

[Plating treatment process]

The plating process is a process of performing plating treatment on the conductive layer in the area where the resist pattern is not disposed.

Examples of the plating treatment include electrolytic plating and electroless plating, and from the viewpoint of productivity, electrolytic plating is preferable.

When the plating process is performed, a plating layer having the same pattern shape as the area where the resist pattern is not disposed (opening portion of the resist pattern) is obtained on the substrate with a conductive layer.

When performing a plating treatment process, it is preferable that the conductive layer is a metal layer.

Examples of metals contained in the plating layer include known metals.

Specifically, metals such as copper, chromium, lead, nickel, gold, silver, tin, and zinc, and alloys of these metals can be mentioned.

Among them, it is preferable that the plating layer contains copper or an alloy thereof because the conductivity of the conductive pattern is more excellent. Moreover, since the conductivity of the conductor pattern is more excellent, it is preferable that the plating layer contains copper as a main component.

The thickness of the plating layer is preferably 0.1 μm or more, and more preferably 1 μm or more. The upper limit is preferably 20 μm or less.

[Resist pattern peeling process]

The resist pattern peeling process is a process of peeling off the remaining resist pattern.

The method for removing the remaining resin pattern is not particularly limited, but includes a method of removing it by chemical treatment, and a method of removing it using a removal liquid is preferable.

As a method of removing the photosensitive resin layer, a method of immersing the substrate with the remaining resin pattern in a removal liquid while stirring, the liquid temperature of which is preferably 30 to 80°C, more preferably 50 to 80°C, is used for 1 to 30 minutes. You can.

Examples of the removal liquid include a removal liquid in which an inorganic alkali component or an organic alkali component is dissolved in water, dimethyl sulfoxide, N-methylpyrrolidone, or a mixed solution thereof. Examples of the inorganic alkaline component include sodium hydroxide and potassium hydroxide. Examples of the organic alkaline component include primary amine compounds, secondary amine compounds, tertiary amine compounds, and quaternary ammonium salt compounds.

Moreover, you may use a removal liquid and remove it by a well-known method, such as a spray method, a shower method, and a puddle method.

[Removal process]

The removal process is a process of removing the conductive layer exposed by the resist pattern peeling process and forming a conductor pattern on the substrate.

In the removal process, the plating layer formed by the plating process is used as an etching resist, and the conductive layer located in the non-pattern formation area (in other words, the area not protected by the plating layer) is etched.

The method for removing part of the conductive layer is not particularly limited, but it is preferable to use a known etching solution.

Examples of known etching solutions include ferric chloride solution, cupric chloride solution, ammonia alkaline solution, sulfuric acid-hydrogen peroxide mixed solution, and phosphoric acid-hydrogen peroxide mixed solution.

When the removal process is performed, the conductive layer exposed to the surface on the substrate is removed, and the plating layer (conductor pattern) having a pattern shape remains, thereby obtaining a laminate having a conductor pattern.

The upper limit of the line width of the formed conductor pattern is preferably 8 μm or less, and more preferably 6 μm or less. The lower limit is not particularly limited, but is often 1 μm or more.

[Other processes]

The method for manufacturing a laminate having a conductor pattern may include any process (other processes) other than the above-described processes.

For example, the process of lowering the visible light reflectance described in paragraph [0172] of International Publication No. 2019/022089, the process of forming a new conductive layer on the insulating film described in paragraph [0172] of International Publication No. 2019/022089. and the like, but are not limited to these processes.

<Process to reduce visible light reflectance>

The method of manufacturing a laminate having a conductor pattern may include a step of performing a treatment to reduce the visible light reflectance of some or all of the plurality of conductive layers included in the substrate.

An example of a treatment that reduces visible light reflectance is oxidation treatment. When the base material has a conductive layer containing copper, the visible light reflectance of the conductive layer can be reduced by oxidizing the copper to obtain copper oxide and blackening the conductive layer.

Treatment for lowering the visible light reflectance is described in paragraphs 0017 to 0025 of Japanese Patent Application Laid-Open No. 2014-150118, and paragraphs 0041, 0042, 0048 and 0058 of Japanese Patent Application Laid-Open No. 2013-206315. The contents described in the publication are incorporated herein by reference.

<Process of forming an insulating film, process of forming a new conductive layer on the surface of the insulating film>

The method of manufacturing a laminate having a conductor pattern preferably includes a step of forming an insulating film on the surface of the conductor pattern and a step of forming a new conductive layer on the surface of the insulating film.

Through the above process, a second electrode pattern insulated from the first electrode pattern can be formed.

The process for forming the insulating film is not particularly limited and includes known methods of forming a permanent film. Additionally, an insulating film with a desired pattern may be formed by photolithography using a photosensitive material having insulating properties.

The process of forming a new conductive layer on the insulating film is not particularly limited, and for example, a new conductive layer with a desired pattern may be formed by photolithography using a conductive photosensitive material.

In the method of manufacturing a laminate with a conductor pattern, it is also preferable to use a substrate having a plurality of conductive layers on both surfaces of the substrate, and to form circuits sequentially or simultaneously on the conductive layers formed on both surfaces of the substrate. With this structure, it is possible to form a laminate having a conductor pattern for a touch panel in which a first conductor pattern is formed on one surface of the base material and a second conductor pattern is formed on the other surface. In addition, it is also preferable to form a laminate having a conductor pattern for a touch panel with such a structure from both sides of the base material by roll-to-roll.

[Use of laminate with conductor pattern]

A laminate having a conductor pattern manufactured by the above manufacturing method can be applied to various devices. Examples of devices provided with a laminate having a conductor pattern manufactured by the above manufacturing method include display devices, printed wiring boards, semiconductor packages, and input devices, with touch panels being preferred, and capacitive touch devices. A panel is more preferable. Additionally, the input device can be applied to display devices such as organic EL display devices and liquid crystal display devices.

[Method for manufacturing laminate]

By using the above-mentioned transfer film, the photosensitive composition layer can be transferred to the transfer object.

Among them, the transfer film of the present invention is preferably used for manufacturing a touch panel.

Among them, the method for manufacturing the laminate of the present invention is:

A peeling process of peeling the protective film from the transfer film to expose the surface of the photosensitive composition layer;

The surface of the transfer film on the opposite side to the provisional support is brought into contact with a substrate having an electrically conductive portion and bonded to obtain a substrate with a photosensitive composition layer having the substrate, the conductive layer, the photosensitive composition layer, and the provisional support in this order. process,

An exposure process of pattern exposing the photosensitive composition layer,

Having a developing process to develop the exposed photosensitive composition layer to form a protective film pattern that protects the conductive layer,

It is preferable that the method for producing a laminate further includes a provisional support peeling step of peeling the provisional support from the substrate with the photosensitive composition layer between the bonding process and the exposure process, or between the exposure process and the development process.

Hereinafter, the procedure of the above process will be described in detail.

The peeling process, developing process, and temporary support peeling process in the manufacturing method of the laminate are the same as the peeling process, developing process, and temporary support peeling process in the manufacturing method of the laminate described above, and the suitable embodiments are also same.

[Bonding process]

In the bonding process, the surface on the side opposite to the provisional support of the transfer film is brought into contact with a substrate having an electrically conductive portion and bonded thereto, and the substrate, the conductive layer, the photosensitive composition layer, and the photosensitive composition layer having the provisional support are attached in this order. This is the process of obtaining a substrate.

The bonding method is the same as the bonding method in the method of manufacturing a laminate with a conductor pattern described above, and its suitable aspects are also the same.

The substrate having a conductive layer has a conductive layer on the substrate, and an arbitrary layer may be formed as needed. That is, a substrate with a conductive layer is a conductive substrate that has at least a substrate and a conductive layer disposed on the substrate.

Examples of the substrate include the same substrate as the substrate in the laminate having the conductor pattern, and the suitable aspects are also the same.

Examples of the conductive layer include the same conductive layer as that of the substrate in the laminate having the above-mentioned conductor pattern, and its suitable form is also the same.

As a substrate having a conductive layer, a substrate having at least one of a transparent electrode and a phosphor wiring is also preferable. The above substrate can be suitably used as a substrate for a touch panel.

A transparent electrode can function suitably as an electrode for a touch panel. The transparent electrode is preferably made of a metal oxide film such as ITO (indium tin oxide) and IZO (indium zinc oxide), a metal mesh, and a metal fine wire such as a metal nanowire.

Examples of fine metal wires include fine wires such as silver and copper. Among them, silver conductive materials such as silver mesh and silver nanowire are preferable.

As a material for phosphorus wiring, metal is preferable.

Examples of metals used as materials for phosphorus wiring include gold, silver, copper, molybdenum, aluminum, titanium, chromium, zinc, manganese, and alloys made of two or more of these metal elements. As a material for phosphorus wiring, copper, molybdenum, aluminum, or titanium is preferable, and copper is particularly preferable.

The electrode protective film for a touch panel formed using the photosensitive composition layer in the transfer film of the present invention is for the purpose of protecting electrodes, etc. (i.e., at least one of the touch panel electrode and the touch panel wiring), directly or otherwise. It is preferable to cover it with a layer interposed therebetween.

[Exposure process]

The exposure process is a process of pattern exposing the photosensitive composition layer.

By performing the exposure process and the development process described later, a protective film pattern that protects at least part of the conductive layer is formed on the conductive layer on the substrate.

In addition, here, “pattern exposure” refers to a form of exposure in a pattern, that is, a form of exposure in which an exposed part and a non-exposed part exist.

Regarding the method of the exposure process, the same method as that of the laminate having the above conductor pattern can be mentioned, and the suitable aspects are also the same.

[Post exposure process and post bake process]

The manufacturing method of the above-described laminate may include a process of exposing the pattern obtained by the development process (post-exposure process) and/or a process of heating (post-bake process).

When both the post-exposure process and the post-bake process are included, it is preferable to perform post-bake after post-exposure. The exposure amount of post exposure is preferably 100 to 5000 mJ/cm ² and more preferably 200 to 3000 mJ/cm ² . The post-bake temperature is preferably 80°C to 250°C, and more preferably 90°C to 160°C. The post-bake time is preferably 1 minute to 180 minutes, and more preferably 10 minutes to 60 minutes.

[Use of laminate]

The laminate manufactured by the laminate manufacturing method of the present invention can be applied to various devices. Examples of devices provided with the laminate include display devices, printed wiring boards, semiconductor packages, input devices, etc., and are preferably touch panels, and more preferably capacitive touch panels. Additionally, the input device can be applied to display devices such as organic electroluminescence display devices and liquid crystal display devices.

When the laminate is applied to a touch panel, the pattern formed from the photosensitive composition layer is preferably used as a protective film for touch panel electrodes or touch panel wiring. That is, the photosensitive composition layer contained in the transfer film is preferably used for forming an electrode protective film for a touch panel or wiring for a touch panel.

Example

The present invention will be described in more detail below based on examples.

Materials, usage amounts, ratios, processing details, processing procedures, etc. shown in the following examples can be appropriately changed without departing from the spirit of the present invention. Accordingly, the scope of the present invention should not be construed as limited by the examples shown below.

<Production of transfer film>

The transfer film used in the examples and comparative examples was produced according to the procedure shown below.

First, the composition used for producing the transfer film of each Example and Comparative Example will be described.

[Branched body]

As the branched support, the branched support A below was used.

· Branched support A: PET film with a thickness of 16 μm (16QS62, Toray Co., Ltd.)

[Composition for forming middle layer]

The following composition A for forming an intermediate layer was prepared.

·PVA205 (polyvinyl alcohol, Kuraray Co., Ltd., degree of saponification = 88%, degree of polymerization 550): 32.2 parts by mass

·Polyvinylpyrrolidone (manufactured by ISP Japan, K-30): 14.9 parts by mass

Distilled water: 524 parts by mass

Methanol: 429 parts by mass

[Composition for forming photosensitive composition layer]

The following composition A for forming a photosensitive resin was prepared.

Propylene glycol monomethyl ether acetate solution of styrene/methacrylic acid/methyl methacrylate = 52/29/19 (mass %) copolymer (solids concentration 30.0%, weight average molecular weight: 70000): 25 mass. wealth

・NK ester BPE-500 (manufactured by Shinnakamura Chemical Co., Ltd.): 3 parts by mass

・NK ester HD-N (manufactured by Shinnakamura Chemical Co., Ltd.): 2 parts by mass

・B-CIM (made by Kurogane Kasei): 1 part by mass

・SB-PI 701 (manufactured by Sanyo Boeki): 0.1 part by mass

・Ryuko Crystal Violet (manufactured by Tokyo Kasei Kogyo Co., Ltd.): 0.05 parts by mass

· Methyl ethyl ketone (manufactured by Sankyo Chemical Co., Ltd.): 40 parts by mass

Propylene glycol monomethyl ether acetate (manufactured by Showa Denko): 30 parts by mass

[Protective Film]

As a protective film, a protective film having the thickness and arithmetic mean roughness Ra1 and Ra2 shown in Table 1 below was prepared.

In addition, the arithmetic mean roughness Ra1 and Ra2 were measured using a fine shape measuring device (ET-350K, manufactured by Kosaka Kenkyusho Co., Ltd.), as described above, and three-dimensional analysis software (TDA-22, manufactured by Kosaka Co., Ltd.). The arithmetic mean illuminance Ra1 and Ra2 were obtained by analyzing with Kenkyusho (made by Kenkyu Sho).

In addition, the measurement conditions using the fine shape measuring device were as follows.

·Stylus pressure: 0.04mN

·Measure length: 0.5mm

·Transfer speed: 0.1mm/sec

·Line pitch: 5μm

· Number of lines: 40

·Height magnification: 50000 times

·Measurement direction: MD (Machine Direction) direction

[Production procedures for transfer film]

Representatively, the production of the transfer film used in Example 1 will be described.

The composition A for forming a photosensitive composition layer was applied to one surface of the temporary support A so that the film thickness after drying was 5 μm, and dried at 100° C. for 2 minutes to form the photosensitive composition layer A.

Next, it was bonded so that the surface of the photosensitive composition layer A and the surface of the protective film A on the side where the arithmetic mean roughness Ra1 was measured faced each other. For bonding, VAII-700 manufactured by Taisei Laminator Co., Ltd. was used, and the bonding conditions were a roller temperature of 100°C, a pressure of 0.08 MPa, and a conveyance speed of 3 m/min.

Regarding Example 4, before forming the photosensitive composition layer, the composition A for forming the intermediate layer was applied to one surface of the temporary support A so that the film thickness after drying was 2 μm, and the composition A was applied at 100° C. for 2 minutes. It was dried to form an intermediate layer A. Thereafter, a transfer film was produced in the same manner as in Example 1, except that the photosensitive composition layer A was formed on the surface of the intermediate layer A.

Regarding the transfer film used in other examples and comparative examples, the transfer film was produced in the same manner as in Example 1, except that the type of protective film was changed as shown in Table 1 below.

<Evaluation>

The following evaluation was performed on the produced transfer film.

[Bubble in transfer film]

For each of the produced transfer films, the area of a square with a side of 10 cm was inspected using an optical microscope from the protective film side, and the number of bubbles present in the transfer film was counted. Air bubbles existed at the interface between the photosensitive composition layer and the protective film. In addition, the magnification of the optical microscope was set to 10 times, and measurements were made in reflection mode.

The number of bubbles existing in the transfer film was evaluated based on the following standards. For practical purposes, the number of bubbles in the transfer film is preferably evaluated as C or higher.

·A: There are 0 bubbles in a square with a side of 10 cm.

·B: 1 to 5 bubbles in a square with a side of 10 cm

C: 6 to 10 bubbles in a square with a side of 10 cm

D: 11 or more bubbles in a square with a side of 10cm

[Defect testability]

Each of the produced transfer films was visually observed from the protective film side under a fluorescent lamp, and defects in the transfer film were inspected from reflection of light from the fluorescent lamp. If a defect was identified with the naked eye, the area was marked. The marked portion was observed for the presence or absence of foreign matter using an optical microscope.

The ratio of the number of parts where defects were confirmed with the naked eye to the number of parts where foreign substances were actually confirmed with an optical microscope was calculated and used as the defect detection rate (%), and defect inspection was evaluated according to the following criteria. For practical purposes, a rating of C or higher is preferable for defect testability. In addition, the higher the evaluation below, the easier it is to inspect defects with the naked eye.

·A: Defect detection rate exceeds 90% and below 100%

B: Defect detection rate is greater than 80% and less than 90%

·C: Defect detection rate exceeds 70% and below 80%

D: Defect detection rate is 70% or less

[Protective film windability]

The transfer film was peeled from the roll-shaped transfer film while winding up the protective film. The conditions during winding were room temperature, a winding speed of 4 m/min, a winding core made of plastic, and a diameter of 3 inches.

Under the above conditions, the windability of the protective film was evaluated based on the following criteria from the positional deviation of the winding cross section when continuously wound for 100 m. The winding cross-section refers to the cross-section of the roll formed at the end of the protective film along the longitudinal direction of the protective film in the roll on which the protective film is wound, and the positional deviation of the winding cross-section refers to protection from the position of the winding cross-section at the start of winding. This refers to the maximum positional deviation in the direction perpendicular to the longitudinal direction of the film (axial direction of the roll). In addition, it is thought that the positional deviation of the winding cross section is mainly caused by blocking that occurs on one side and the other side of the protective film when winding the protective film.

·A: Positional deviation of winding cross section is less than 3 mm

B: Positional deviation of the winding cross section is 3 mm or more and less than 6 mm

C: Positional deviation of the winding cross section is 6 mm or more and less than 10 mm

·D: Positional deviation of the winding cross section is 10 mm or more

[Pattern defect suppression]

A 0.5 mm thick glass substrate (a substrate with a conductive layer on the surface) with a 0.5 μm thick copper layer formed on the surface was prepared.

The protective film of the transfer film was peeled off to expose the photosensitive composition layer, and the substrate and the transfer film were laminated so that the copper layer of the substrate and the photosensitive composition layer were in close contact. Laminating was performed at a temperature of 100°C, a speed of 1 m/min, and a pressure of 1 MPa.

Next, exposure was performed with a high-pressure mercury lamp using a mask having a line and space pattern with lines and spaces of 10 μm. The exposure amount was such that the resist pattern after development reproduces the line and space pattern described above.

After exposure, shower development was performed for 30 seconds using a 1.0% by mass aqueous sodium carbonate solution (pH = 11.4) at 30°C as a developing solution. A flat nozzle was used as the shower nozzle, and the shower pressure was set to 1 MPa. Through the development process, a resist pattern of a line and space pattern with lines and spaces of 10 μm was formed.

The resist pattern formed by the above procedure was observed with an SEM from a direction perpendicular to the substrate to confirm the presence or absence of pattern defects (for example, missing part of the pattern). The observation magnification was 500 times. From the number of pattern defects confirmed by the above observation, pattern defect suppression was evaluated according to the following criteria.

·A: Number of pattern defects is 0 to 4

·B: Number of pattern defects is 5 to 9

C: Number of pattern defects is 10 to 19

D: The number of pattern defects is 20 or more.

[Resolution]

The transfer film and the substrate were laminated in the same manner as the above evaluation of pattern defect suppression properties.

Next, exposure was performed with a high-pressure mercury lamp using a mask having a line and space pattern of 3 to 10 μm (in units of 1 μm). The exposure amount was such that the portion corresponding to the 10 μm line and space pattern in the resist pattern after development reproduced the 10 μm line and space pattern.

After exposure, development was performed in the same manner as the above evaluation of pattern defect suppression properties, and the resist pattern was observed by SEM. Resolution was evaluated based on the width of the minimum line and space where the resist pattern was formed.

In addition, for Example 4, exposure was performed after peeling off the temporary support before exposure.

<Result>

Table 1 shows each composition of the above-produced transfer film and its evaluation results.

In Table 1, regarding the description in the column "Peeling of the provisional support during exposure," "A" indicates that the exposure was performed after the temporary support was peeled off before exposure, and "B" indicates that the provisional support was not peeled off during exposure. Indicates exposure.

[Table 1]

From the comparison of the examples and comparative examples, the arithmetic mean roughness Ra1 of the surface on the photosensitive composition layer side of the transfer film of the present invention, that is, the protective film, is the arithmetic average roughness Ra2 of the surface on the opposite side to the photosensitive composition layer of the protective film. It was confirmed that the smaller transfer film had excellent winding properties and pattern defect suppression properties of the protective film.

From a comparison between Example 3 and other examples, it was confirmed that pattern defect suppression was more excellent when the arithmetic mean roughness Ra1 was 0.050 μm or less.

From a comparison between Example 5 and other examples, it was confirmed that defect inspection properties were more excellent when the arithmetic mean roughness Ra2 was less than 0.150 μm.

From a comparison between Example 6 and other examples, it was confirmed that the bubble and pattern defect suppression properties of the transfer film were more excellent when the thickness of the protective film was 10 to 30 μm.

10, 20 transfer film
1, 11 limbs
2, 12 composition layers
3, 17 photosensitive composition layer
5 Refractive index adjustment layer
7, 19 protective film
13 Thermoplastic resin layer
15 middle layer

Claims (8)

A transfer film having a support, a photosensitive composition layer, and a protective film in this order,
The protective film includes polypropylene,
A transfer film wherein the arithmetic mean roughness Ra1 of the surface of the protective film on the photosensitive composition layer side is smaller than the arithmetic mean roughness Ra2 of the surface of the protective film on the side opposite to the photosensitive composition layer. In claim 1,
A transfer film wherein the arithmetic mean roughness Ra1 is 0.050 μm or less. In claim 1 or claim 2,
A transfer film wherein the arithmetic mean roughness Ra2 is greater than 0.050 μm. In claim 1 or claim 2,
A transfer film wherein the arithmetic mean roughness Ra2 is less than 0.150 μm. In claim 1 or claim 2,
A transfer film in which the thickness of the protective film is 10 to 30 μm. A laminate having a conductor pattern formed using the transfer film according to claim 1 or 2. A peeling process of peeling the protective film from the transfer film according to claim 1 or 2 to expose the surface of the photosensitive composition layer;
A bonding step of bonding the transfer film and the substrate having the conductive layer so that the exposed surface of the photosensitive composition layer is in contact with the conductive layer of the substrate having the conductive layer on the surface;
An exposure process of exposing the photosensitive composition layer,
A development process of performing a development treatment on the exposed photosensitive composition layer to form a resist pattern;
an etching process of performing an etching process on the conductive layer in a region where the resist pattern is not disposed, and a plating process of performing a plating process;
a resist pattern peeling process for peeling off the resist pattern;
In addition, in the case of having the plating process, the method of manufacturing a laminate with a conductor pattern includes a removal process of removing the conductive layer exposed by the resist pattern peeling process and forming a conductor pattern on the substrate. As,
A method for producing a laminate with a conductor pattern, further comprising a provisional support peeling step of peeling off the provisional support between the bonding step and the exposure step, or between the exposure step and the development step. A process of forming a photosensitive composition layer on a support,
A method for producing a transfer film comprising the step of bonding a protective film to a side of the photosensitive composition layer opposite to the support,
The protective film contains polypropylene,
A method for producing a transfer film, wherein the arithmetic average roughness Ra1 of the surface of the protective film on the photosensitive composition layer side is smaller than the arithmetic average roughness Ra2 of the surface of the protective film on the side opposite to the photosensitive composition layer.