CN115685672A

CN115685672A - Transfer film and method for manufacturing laminate having conductor pattern

Info

Publication number: CN115685672A
Application number: CN202210805407.6A
Authority: CN
Inventors: 儿玉邦彦; 松田知树
Original assignee: Fujifilm Corp
Current assignee: Fujifilm Corp
Priority date: 2021-07-30
Filing date: 2022-07-08
Publication date: 2023-02-03
Also published as: KR20230019012A; TW202307026A; JP2023020517A

Abstract

The invention provides a transfer film which has excellent resolution, can form a non-curled corrosion-resistant pattern and is easy to strip the corrosion-resistant pattern. A transfer film, comprising: a temporary support; and a photosensitive composition layer containing an alkali-soluble polymer, a polymerizable compound, and a polymerization initiator, wherein the alkali-soluble polymer contains a structural unit A having a carboxyl group and a structural unit B having an acid group that exhibits a pKa higher than the carboxyl group and lower than 14, and the acid value derived from the carboxyl group of the alkali-soluble polymer is 80mgKOH/g or more.

Description

Transfer film and method for manufacturing laminate having conductor pattern

Technical Field

The present invention relates to a transfer film and a method for manufacturing a laminate having a conductor pattern.

Background

A method of disposing a photosensitive composition layer on an arbitrary substrate using a transfer film, exposing the photosensitive composition layer through a mask, and then developing the photosensitive composition layer is widely used because the number of steps for obtaining a predetermined pattern is small.

For example, patent document 1 discloses a transfer film using a negative radiation-sensitive resin composition containing a polymer containing a structural unit represented by formula (1) below and a structural unit represented by formula (2) below, a compound having an ethylenically unsaturated double bond, and a radiation-sensitive radical polymerization initiator.

[ chemical formula 1]

Patent document 1: japanese patent laid-open No. 2007-293306

Recently, with the high integration of electronic devices, formation of finer conductor patterns is required, and miniaturization of resist patterns formed using a transfer film is also required.

The present inventors tried to form a fine resist pattern using a transfer film of the prior art as described in patent document 1, and as a result, they found that a fine resist pattern of a level required recently could not be formed, and that improvement in resolution was required.

Then, the cross-sectional shape of the obtained resist pattern was observed, and as a result, curling occurred. The curling of the resist pattern is a factor of a failure of the conductor pattern formed in the subsequent step, and therefore, it is also necessary to improve the curling.

Further, the present inventors have also found that it is difficult to peel off the resist pattern after the formation of the conductor pattern at the line width of the conductor pattern of the level recently required. It has been found that, particularly in the step of forming a conductor pattern by the semi-additive method, it is difficult to peel off the resist pattern after the plating treatment.

Disclosure of Invention

Accordingly, an object of the present invention is to provide a transfer film which can form a resist pattern having excellent resolution and no curling and which can easily peel off the resist pattern (particularly, can easily peel off the resist pattern after plating treatment in a semi-additive process).

Another object of the present invention is to provide a method for manufacturing a laminate having a conductor pattern.

The present inventors have conducted intensive studies to solve the above problems, and as a result, have completed the present invention. That is, the following configuration was found to solve the above problems.

[ 1] A transfer film comprising:

a temporary support; and

a photosensitive composition layer containing an alkali-soluble polymer, a polymerizable compound and a polymerization initiator,

the alkali-soluble polymer comprises a structural unit A having a carboxyl group and a structural unit B having an acid group exhibiting a pKa higher than that of the carboxyl group and lower than 14,

the acid value of the alkali-soluble polymer derived from the carboxyl group is 80mgKOH/g or more.

[ 2] the transfer film according to [ 1], wherein,

the pKa of the acid group is 7 to 12.

[ 3] the transfer film according to [ 1] or [ 2], wherein,

the structural unit B has 1 or more groups selected from the group consisting of a phenol group, an active methylene group, a sulfonamide group, an imide group and a hydroxyimide group.

[ 4] the transfer film according to any one of [ 1] to [ 3], wherein,

the structural unit B has 1 or more groups selected from the group represented by the formula (I) described later, the group represented by the formula (II) described later, and the group represented by the formula (III) described later.

[ 5] the transfer film according to any one of [ 1] to [ 4], wherein,

the content of the structural unit A is more than 12% by mass and 30% by mass or less with respect to all structural units of the alkali-soluble polymer,

the content of the structural unit B is 5 to 50% by mass based on the total structural units of the alkali-soluble polymer.

[ 6] the transfer film according to any one of [ 1] to [ 5], wherein,

the acid value derived from the acid group is 5 to 200mgKOH/g.

[ 7] A transfer film comprising:

a temporary support; and

a photosensitive composition layer containing an alkali-soluble polymer comprising a structural unit having a carboxyl group, a polymerizable compound, a polymerization initiator, and a compound having an acid group exhibiting a pKa higher than the above carboxyl group and lower than 14,

the content of the compound is 3 to 50% by mass based on the total mass of the photosensitive composition layer,

[ 8] the transfer film according to [ 7], wherein,

the pKa of the acid group is 7 to 12.

[ 9] the transfer film according to [ 7] or [ 8], wherein,

the compound has 1 or more groups selected from the group consisting of a phenol group, an active methylene group, a sulfonamide group, an imide group and a hydroxyimide group.

[ 10] the transfer film according to any one of [ 7] to [ 9], wherein,

the compound has 2 or more of the acid groups.

[ 11 ] the transfer film according to any one of [ 7] to [ 10],

the above-mentioned compound is a polymer containing a structural unit having the above-mentioned acid group.

The transfer film according to any one of [ 1] to [ 11 ], further comprising an intermediate layer between the temporary support and the photosensitive composition layer.

[ 13 ] the transfer film according to [ 12 ], wherein,

the intermediate layer contains a water-soluble resin.

[ 14] the transfer film according to [ 13 ], wherein,

the water-soluble resin includes at least one selected from the group consisting of a polyvinyl alcohol resin, a polyvinyl pyrrolidone resin, a cellulose resin, an acrylamide resin, a polyethylene oxide resin, gelatin, a vinyl ether resin, and a polyamide resin.

[ 15] A method for manufacturing a laminate having a conductor pattern, comprising:

a bonding step of bonding the transfer film to the substrate so that the photosensitive composition layer side of the transfer film described in any one of [ 1] to [ 14] is in contact with the conductive layer of the substrate having a conductive layer on the surface thereof;

an exposure step of exposing the photosensitive composition layer;

a resist pattern forming step of forming a resist pattern by performing a developing process on the exposed photosensitive composition layer;

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

a resist pattern stripping step of stripping the resist pattern,

the plating treatment step may further comprise a removing step of removing the conductive layer exposed in the resist pattern stripping step and forming a conductor pattern on the substrate,

a temporary support peeling step of peeling off the temporary support is further provided between the bonding step and the exposure step or between the exposure step and the development step.

[ 16 ] the method for producing a laminate having a conductor pattern according to [ 15], wherein,

the pH of the stripping liquid used in the resist pattern stripping step is 13 or more.

[ 17] the method for producing a laminate having a conductor pattern according to [ 15] or [ 16 ], wherein,

the pH of the developer used in the resist pattern forming step is less than 13.

[ 18] the method for producing a laminate having a conductor pattern according to any one of [ 15] to [ 17], wherein,

the exposure method in the exposure step is any one of mask exposure, direct imaging exposure, and projection exposure.

[ 19] the method for producing a laminate having a conductor pattern according to any one of [ 15] to [ 18], wherein,

the thickness of the temporary support is less than 16 μm.

[ 20 ] the method for producing a laminate having a conductor pattern according to any one of [ 15] to [ 19], wherein,

the step of peeling off the temporary support is provided between the bonding step and the exposure step,

the exposed surface exposed in the temporary support peeling step is brought into contact with a mask to expose the photosensitive composition layer.

Effects of the invention

According to the present invention, it is possible to provide a transfer film which can form a resist pattern having excellent resolution and no curling and which can easily peel off the resist pattern (particularly, can easily peel off the resist pattern after plating treatment in a semi-additive process).

Further, according to the present invention, a method for manufacturing a laminate having a conductor pattern can be provided.

Drawings

Fig. 1 is a schematic view showing an example of the structure of the transfer film of the present invention.

Detailed Description

The present invention will be described in detail below.

The following description of the constituent elements may be made in accordance with a representative embodiment of the present invention, but the present invention is not limited to such an embodiment.

The meanings of the respective descriptions in the present specification are shown below.

In the present specification, a numerical range expressed by "to" means a range in which numerical values before and after "to" are included as a lower limit value and an upper limit value.

In the present specification, in the numerical ranges described in the stepwise manner, the upper limit value or the lower limit value described in a certain numerical range may be replaced with the upper limit value or the lower limit value described in another stepwise manner. In addition, in the numerical ranges described in the present specification, the upper limit value or the lower limit value described in a certain numerical range may be replaced with the values shown in the examples.

In the present specification, the term "step" includes not only an independent step but also a step that can achieve the intended purpose of the step even when it cannot be clearly distinguished from other steps.

In the present specification, "transparent" means that the average transmittance of visible light having a wavelength of 400 to 700nm is 80% or more, preferably 90% or more.

In the present invention, the average transmittance of visible light is a value measured using a spectrophotometer, and can be measured using, for example, a spectrophotometer U-3310 manufactured by Hitachi, ltd.

In the present specification, unless otherwise specified, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are values in terms of polystyrene using a standard substance, which are measured by a Gel Permeation Chromatography (GPC) analyzer using TSKgel GMHxL, TSKgel G4000HxL, or TSKgel G2000HxL (both trade names manufactured by TOSOH CORPORATION) as a column, THF (tetrahydrofuran) as an eluent, a differential refractometer as a detector, and polystyrene as a standard substance.

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

In the present specification, unless otherwise specified, the content of the metal element is a value measured by an Inductively Coupled Plasma (ICP) spectroscopic analyzer.

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

In the present invention, the hue is a value measured by a colorimeter (CR-221, minolta Co., ltd.) unless otherwise specified.

In the present specification, "(meth) acrylic group" is a concept including both acrylic group and methacrylic group, and "(meth) acryloyloxy group" is a concept including both acryloyloxy group and methacryloyloxy group.

In the present specification, "alkali-soluble" means that the solubility of 100g of a1 mass% aqueous solution of sodium carbonate at 22 ℃ is 0.1g or more.

In the present specification, "water-soluble" means that the solubility of 100g of water having a pH of 7.0 at a liquid temperature of 22 ℃ is 0.1g or more. Thus, for example, a water-soluble resin refers to a resin that satisfies the solubility conditions described above.

In the present specification, "solid component" of the composition means a component forming a composition layer formed using the composition, and when the composition contains a solvent (an organic solvent, water, or the like), it means all components except the solvent. In addition, if the component is a component for forming the composition layer, the liquid component is also considered as a solid component.

< transfer film >

The transfer film of the present invention includes embodiment 1 and embodiment 2.

First, embodiment 1 will be explained below.

< embodiment 1 >

Embodiment 1 of the transfer film of the present invention includes: a temporary support; and a photosensitive composition layer containing an alkali-soluble polymer, a polymerizable compound, and a polymerization initiator, wherein the alkali-soluble polymer contains a structural unit A having a carboxyl group and a structural unit B having an acid group exhibiting a pKa higher than the carboxyl group and lower than 14, and the acid value derived from the carboxyl group is 80mgKOH/g or more.

Embodiment 1 of the transfer film of the present invention can form a resist pattern having excellent resolution and no curl, and can easily peel the resist pattern. The mechanism is not necessarily clear, but the present inventors speculate as follows.

In embodiment 1 of the transfer film of the present invention, a resist pattern having excellent resolution and no curl can be formed by setting the acid value of the alkali-soluble polymer derived from the carboxyl group to 80mgKOH/g or more. Further, when the alkali-soluble polymer contains the structural unit B, a resist pattern having no curling can be formed and the resist pattern can be easily peeled off. In particular, when the developing solution used for forming the resist pattern is different from the stripping solution used for stripping the resist pattern, the resist pattern having no curl is easily formed, and the resist pattern is easily stripped.

Hereinafter, the transfer film of the present invention is also referred to as "being more excellent in the effect of the present invention" when it satisfies at least one of the conditions that the resolution is more excellent, a resist pattern having less curling can be formed, and the resist pattern can be more easily peeled off.

Hereinafter, embodiment 1 of the transfer film of the present invention will be described.

[ Structure of transfer film ]

The transfer film may have other layers besides the temporary support and the photosensitive composition layer.

Examples of the other layer include an intermediate layer described later. The transfer film may have other members (e.g., a protective film) described later.

As an embodiment of the transfer film, for example, the following configuration (1) or (2) can be given, and the configuration (2) is preferable.

(1) "temporary support/photosensitive composition layer/protective film"

(2) "temporary support/intermediate layer/photosensitive composition layer/protective film"

The transfer film preferably has an intermediate layer.

The photosensitive composition layer in each of the above structures is preferably a negative photosensitive composition layer described later or a colored resin layer described later.

From the viewpoint of suppressing the generation of bubbles in the bonding step described later, the maximum width of the waviness of the transfer film is preferably 300 μm or less, more preferably 200 μm or less, and further preferably 60 μm or less. The lower limit of the maximum width of the corrugations is 0 μm or more, preferably 0.1 μm or more, and more preferably 1 μm or more.

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

First, the transfer film was cut into a size of 20cm long × 20cm wide in a direction perpendicular to the main surface to prepare a test sample. In addition, when the transfer film has a protective film, the protective film is peeled off. Next, the test sample was allowed to stand on a table having a smooth and horizontal surface so that the surface of the temporary support was opposed to the table. After standing, the surface of the test sample is scanned by a laser microscope (for example, VK-9700SP manufactured by KEYENCE CORPORATION) over a range of 10cm square from the center of the test sample to obtain a three-dimensional surface image, and the minimum concave height is subtracted from the maximum convex height observed in the obtained three-dimensional surface image. The above operation was performed on 10 test samples, and the arithmetic average value thereof was defined as "maximum width of moire of transfer film".

When another composition layer (for example, a photosensitive composition layer, an intermediate layer, or the like) is further provided on the surface of the photosensitive composition layer opposite to the temporary support, the total thickness of the other composition layer is preferably 0.1 to 30%, more preferably 0.1 to 20%, based on the total thickness of the photosensitive composition layer.

From the viewpoint of more excellent adhesion, the transmittance of light having a wavelength of 365nm of the photosensitive composition layer is preferably 10% or more, more preferably 30% or more, and further preferably 50% or more. The upper limit is preferably 99.9% or less, more preferably 99.0% or less.

An example of an embodiment of the transfer film will be described.

The transfer film 10 shown in fig. 1 includes a temporary support 11, a composition layer 17 including an intermediate layer 13 and a photosensitive composition layer 15, and a protective film 19 in this order.

The transfer film 10 shown in fig. 1 has the intermediate layer 13 and the protective film 19, but may not have the intermediate layer 13 and the protective film 19.

In fig. 1, each layer (for example, a photosensitive composition layer, an intermediate layer, and the like) other than the protective film 19, which can be disposed on the temporary support 11, is also referred to as a "composition layer".

Hereinafter, the transfer film will be described in detail with respect to each member and each component.

Further, the following description of the constituent elements may be made in accordance with a representative embodiment of the present invention, but the present invention is not limited to such an embodiment.

[ temporary support ]

The transfer film has a temporary support.

The temporary support is a member for supporting the photosensitive composition layer, and is finally removed by a peeling treatment.

The temporary 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. Further, as the temporary support, a film which is flexible and does not undergo significant deformation, shrinkage, or elongation under pressure or under pressure and heat, and a film which is free from deformation such as wrinkles or scratches is also preferable.

Examples of the film include a polyethylene terephthalate film (e.g., a biaxially stretched polyethylene terephthalate film), a polymethyl methacrylate film, a cellulose triacetate film, a polystyrene film, a polyimide film, and a polycarbonate film, and a polyethylene terephthalate film is preferable.

From the viewpoint of enabling pattern exposure via the temporary support, the temporary support preferably has high transparency, and the transmittance at 365nm is preferably 60% or more, more preferably 70% or more.

From the viewpoint of pattern formability during pattern exposure via the temporary support and transparency of the temporary support, the temporary support preferably has a low haze. Specifically, the value of the haze of the temporary support is preferably 2% or less, more preferably 0.5% or less, and further preferably 0.1% or less.

From the viewpoint of pattern formability during exposure through the temporary support pattern and transparency of the temporary support, the number of fine particles, foreign substances, and defects contained in the temporary support is preferably small. Fine particles and foreign matter having a diameter of 1 μm or more in the temporary supportAnd the number of defects is preferably 50/10 mm ² Hereinafter, more preferably 10/10 mm ² Hereinafter, more preferably 3/10 mm ² Hereinafter, particularly preferably 0 piece/10 mm ² 。

The thickness of the temporary support is preferably 5 μm or more, more preferably 6 μm or more. The upper limit is preferably 200 μm or less, more preferably 150 μm or less, further preferably 50 μm or less, particularly preferably 25 μm or less, and most preferably less than 16 μm from the viewpoint of easy handling and versatility.

The thickness of the temporary support was calculated as an average value of arbitrary 5 points measured by cross-sectional observation based on SEM (Scanning Electron Microscope).

The temporary support may have a layer containing fine particles (lubricant layer) on one surface or both surfaces of the temporary support from the viewpoint of handling properties.

The diameter of the fine particles contained in the lubricant layer is preferably 0.05 to 0.8 μm.

The thickness of the lubricant layer is preferably 0.05 to 1.0. Mu.m.

From the viewpoint of improving the adhesion between the temporary support and the photosensitive composition layer, the surface of the temporary support that is in contact with the photosensitive composition layer may be subjected to a surface modification treatment.

Examples of the surface modification treatment include treatments using UV irradiation, corona discharge, plasma, and the like.

The exposure amount in UV irradiation is preferably 10 to 2000mJ/cm ² More preferably 50 to 1000mJ/cm ² 。

If the exposure amount is within the above range, the lamp output and the illuminance are not particularly limited.

Examples of the light source for UV irradiation include a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a carbon arc lamp, a metal halide lamp, a xenon lamp, a chemical lamp, an electrodeless discharge lamp, and a Light Emitting Diode (LED) which emit light in a wavelength band of 150 to 450 nm.

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

Further, examples of the temporary support include paragraphs [0017] to [0018] of japanese patent application laid-open No. 2014-085643, paragraphs [0019] to [0026] of japanese patent application laid-open No. 2016-027363, paragraphs [0041] to [0057] of international publication No. 2012/081680, and paragraphs [0029] to [0040] of international publication No. 2018/179370, which are incorporated herein.

Examples of commercially available temporary supports include registered trademarks lumiror 16KS40 and lumiror 16FB40 (both of which are TORAY INDUSTRIES, inc.); cosmoshine a4100, cosmoshine a4300 and Cosmoshine a8300 (manufactured by Toyobo co.

[ photosensitive composition layer ]

The transfer film has a photosensitive composition layer.

The photosensitive composition layer is preferably a negative photosensitive composition layer. When the photosensitive composition layer is a negative photosensitive composition layer, the resist pattern formed corresponds to the cured film.

The photosensitive composition layer contains a resin, a polymerizable compound, and a polymerization initiator, and the resin contains an alkali-soluble polymer.

Such a photosensitive composition layer preferably contains a resin based on the total mass of the photosensitive composition layer: 10 to 90 mass percent; a polymerizable compound: 5 to 70 percent by mass; polymerization initiator: 0.01 to 20 mass%.

Hereinafter, the respective components will be described in order.

(resin)

When the photosensitive composition layer is a negative photosensitive composition layer, the resin contained in the photosensitive composition layer is also referred to as a polymer a in particular.

Polymer a comprises an alkali soluble polymer.

In embodiment 1, the polymer a may be composed of only the alkali-soluble polymer, or may be composed of the alkali-soluble polymer and other polymers, and the polymer a is preferably composed of only the alkali-soluble polymer. That is, the polymer a is preferably an alkali-soluble polymer.

As described above, in embodiment 1, the alkali-soluble polymer includes the structural unit a having a carboxyl group and the structural unit B having an acid group exhibiting a pKa higher than the carboxyl group and lower than 14, and the acid value derived from the carboxyl group of the alkali-soluble polymer is 80mgKOH/g or more.

From the viewpoint of further improving the effect of the present invention, the acid value derived from the carboxyl group is preferably from 80 to 250mgKOH/g, more preferably from 90 to 200mgKOH/g, and still more preferably from 100 to 180mgKOH/g.

Further, from the viewpoint of further improving the effect of the present invention, the acid value derived from an acid group having a pKa higher than that of the carboxyl group and lower than 14 is preferably 5 to 150mgKOH/g, more preferably 20 to 120mgKOH/g, and still more preferably 30 to 100mgKOH/g.

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

Hereinafter, the polymer a will be described in detail. First, the alkali-soluble polymer will be explained.

Structural unit A-

The alkali-soluble polymer contains a structural unit a having a carboxyl group.

The pKa of the carboxyl group of the structural unit A is not particularly limited, but is preferably 3 to 7, more preferably 4 to 6.

The alkali-soluble polymer is synthesized using at least a monomer having a carboxyl group in the molecule (monomer a) and a monomer having an acid group exhibiting a pKa higher than the carboxyl group and lower than 14 in the molecule (monomer B) described later.

Examples of the monomer A include (meth) acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, 4-vinylbenzoic acid, maleic acid, and maleic acid half ester. Among these, (meth) acrylic acid is preferable.

The content of the structural unit a in the alkali-soluble polymer is preferably 10 to 50% by mass, more preferably 10 to 40% by mass, and further preferably more than 12% by mass and 30% by mass or less with respect to all structural units of the alkali-soluble polymer.

From the viewpoint of easily setting the acid value derived from the carboxyl group of the alkali-soluble polymer to 80mgKOH/g or more, it is preferable that the content is set to more than 12% by mass. From the viewpoint of high resolution and curl shape of the resist pattern, and further from the viewpoint of chemical resistance of the resist pattern, the content is preferably 30% by mass or less.

Structural unit B-

The alkali-soluble polymer comprises a structural unit B having an acid group exhibiting a pKa higher than the carboxyl group and lower than 14. The pKa of the acid group contained in the structural unit B is not particularly limited as long as it is higher than the pKa of the carboxyl group and lower than 14, but is preferably 6 or more and lower than 14, more preferably 7 to 12, further preferably 8 to 12, and particularly preferably 9 to 12, from the viewpoint of further improving the effect of the present invention.

As the pKa, there can be referred to the values described in the Determination of Organic Structures by Physical Methods (authors: brown, H.C., mcDaniel, D.H., hafliger, O.A., nachod, F.C.; editions: braude, E.A., nachod, F.C.; academic Press, new York, 1955) or Dataforr Biochemical research (authors: dawson, R.M.C. et al; oxford, clarendon Press, 1959).

As for compounds not described in these documents, values calculated from a structural formula using software of ACD/pKa (manufactured by ACD/Labs) can be used.

Further, the pKa of a polymerizable monomer having a weak acid group used for synthesis of a polymer can also be measured by a neutralization titration method.

In view of further improving the effect of the present invention, the structural unit B preferably has 1 or more groups selected from a phenol group, an active methylene group, a sulfonamide group, an imide group, and a hydroxyimide group. In addition, these groups correspond to acid groups exhibiting a pKa higher than that of the carboxyl group and lower than 14.

And, the active methylene group means a methylene group (-CH) to which 2 electron withdrawing groups are bonded ₂ -)。

Preferred examples of the acid group in the structural unit B include groups having the following partial structures. At least 1 of the wavy line portions is bonded to the alkali-soluble polymer directly or via a linking group, and the rest is bonded to a hydrogen atom or an organic group.

[ chemical formula 2]

In the above partial structure, H shown in each structure dissociates to function as an acid group. The partial structure represents a structure having a phenol group, an active methylene group, an imide group, a hydroxyimide group, and a sulfonamide group in this order from the left.

Among them, the structural unit B preferably has 1 or more groups selected from the group represented by the following formula (I), the group represented by the following formula (II), and the group represented by the following formula (III), from the viewpoint of further improving the effects of the present invention.

[ chemical formula 3]

In the formula (I), R ₁ Represents a substituent having a valence of 1.

As R ₁ Examples of the substituent having a valence of 1 as represented herein include a halogen atom and an alkyl group having 1 to 10 carbon atoms which may have a substituent. The alkyl group which may have a substituent may be linear or branched. -CH constituting an alkyl group ₂ <xnotran> - -O-, -S-, -CO-, -COO- -OCO- . </xnotran> Wherein, as R ₁ An alkyl group having 1 to 3 carbon atoms is preferable.

In the formula (I), n ₁ Represents an integer of 1 or 2, n ₂ Represents an integer of 0 to 4. Wherein n is ₁ And n ₂ The sum of the amounts is 1 to 5.

n ₁ Preferably 1.n is ₂ An integer of 0 to 2 is preferable, and 0 is more preferable.

In the formula (II), R ₂ Represents a substituent having a valence of 1.

As R ₂ The 1-valent substituent may be an alkyl group having 1 to 10 carbon atoms which may have a substituent, a cycloalkyl group having 1 to 10 carbon atoms which may have a substituent, orPhenyl groups which may have a substituent, and combinations thereof. The alkyl group which may have a substituent may be linear or branched. -CH constituting alkyl and cycloalkyl groups ₂ <xnotran> - -O-, -S-, -CO-, -COO- -OCO- . </xnotran> Examples of the substituent that the alkyl group, the cycloalkyl group and the phenyl group may have include a hydroxyl group. Wherein R is ₂ An alkyl group having 1 to 3 carbon atoms is preferred.

In the formula (II), R ₃ Represents a hydrogen atom or a substituent having a valence of 1.

As R ₃ A substituent having a valence of 1, and R ₂ The 1-valent substituents are the same. Wherein R is ₃ An alkyl group having 1 to 3 carbon atoms or a hydrogen atom is preferable, and a hydrogen atom is more preferable.

In the formula (III), R ₄ Represents a substituent having a valence of 1.

As R ₃ A substituent having a valence of 1, and R ₁ The 1-valent substituents are the same. Wherein, as R ₃ An alkyl group having 1 to 3 carbon atoms is preferable.

In the formula (III), n ₃ Represents an integer of 1 or 2, n ₄ Represents an integer of 0 to 4. Wherein n is ₃ And n ₄ The sum of which is an integer of 1 to 5.

n ₃ Preferably 1.n is ₄ An integer of 0 to 2 is preferable, and 0 is more preferable.

Examples of the monomer (monomer B) having an acid group in the molecule, which exhibits a pKa higher than that of the carboxyl group and lower than that of 14, used for the synthesis of the alkali-soluble polymer include compounds having at least 1 polymerizable unsaturated group in the molecule and having the acid group.

More specifically, there may be mentioned (meth) acrylate derivatives, (meth) acrylamide derivatives and styrene derivatives having the weak acid group. Examples of the compound having an acid group include compounds having a phenol group such as catechol, hydroquinone, and resorcinol, and derivatives thereof; compounds having an active methylene group such as ester compounds of acetoacetic acid 1 molecule and ethylene glycol or propylene glycol 1 molecule; and compounds having a sulfonamide group such as 4-aminobenzenesulfonamide and 4-amino-n-propylbenzenesulfonamide.

As the monomer B, a compound having a phenol group such as p-vinylphenol; succinimide derivatives and imide-group-containing compounds such as maleimide; and compounds having a hydroxyimide group such as N-hydroxymaleimide.

The content of the structural unit B in the alkali-soluble polymer is preferably 3 to 60% by mass, more preferably 5 to 50% by mass, and further preferably 12 to 40% by mass, relative to all structural units of the alkali-soluble polymer.

By setting the content of the structural unit B in the alkali-soluble polymer within the above range, the resist pattern can be easily peeled off. In particular, the resist pattern can be easily peeled off after the plating treatment in the semi-additive method.

Structural units derived from monomers having aromatic hydrocarbon groups

In addition, from the viewpoint of suppressing deterioration in the line width and resolution when the focus position is shifted during exposure, the alkali-soluble polymer preferably contains a structural unit derived from a monomer having an aromatic hydrocarbon group. Examples of the aromatic hydrocarbon group include a substituted or unsubstituted phenyl group and a substituted or unsubstituted aralkyl group.

The content of the structural unit derived from a monomer having an aromatic hydrocarbon group in the alkali-soluble polymer is preferably 20% by mass or more, more preferably 30% by mass or more, with respect to all the structural units of the alkali-soluble polymer. 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 a plurality of alkali-soluble polymers are contained, it is preferable that the average value of the contents of the structural units derived from the monomer having an aromatic hydrocarbon group is within the above range.

Examples of the monomer having an aromatic hydrocarbon group include a monomer having an aralkyl group, styrene, and a polymerizable styrene derivative (for example, methylstyrene, vinyltoluene, tert-butoxystyrene, acetoxystyrene, a styrene dimer, a styrene trimer, and the like). Among them, monomers having an aralkyl group or styrene are preferable.

When the monomer having an aromatic hydrocarbon group is styrene, the content of the structural unit derived from styrene is preferably 10 to 70% by mass, more preferably 15 to 65% by mass, further preferably 20 to 60% by mass, and particularly preferably 25 to 55% by mass, based on all the structural units of the alkali-soluble polymer. When the photosensitive composition layer contains a plurality of alkali-soluble polymers, the content of the structural unit derived from the monomer having an aromatic hydrocarbon group is determined as a weight average value.

Examples of the aralkyl group include a phenylalkyl group which may have a substituent, and a benzyl group which may have a substituent is preferable.

Examples of the monomer containing a phenylalkyl group which may have a substituent include phenylethyl (meth) acrylate and the like.

Examples of the monomer containing a benzyl group which may have a substituent include (meth) acrylates having a benzyl group such as benzyl (meth) acrylate and chlorobenzyl (meth) acrylate; the vinyl monomer having a benzyl group such as vinylbenzyl chloride or vinylbenzyl alcohol is preferably a (meth) acrylate having a benzyl group, and more preferably benzyl (meth) acrylate.

When the monomer having an aromatic hydrocarbon group is benzyl (meth) acrylate, the content of the structural unit derived from benzyl (meth) acrylate is preferably 10 to 70% by mass, more preferably 15 to 65% by mass, further preferably 20 to 60% by mass, and particularly preferably 25 to 55% by mass, based on all the structural units of the alkali-soluble polymer.

-non-acidic structural units-

The alkali soluble polymer may comprise non-acidic structural units derived from monomers that are non-acidic and have at least 1 polymerizable unsaturated group in the molecule.

Examples of the monomer (non-acidic monomer) include (meth) acrylic esters such as methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, cyclohexyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate; vinyl alcohol esters such as vinyl acetate; and (meth) acrylonitrile, and the like. 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 derived from the non-acidic monomer in the alkali-soluble polymer is preferably 3 to 60% by mass, more preferably 5 to 50% by mass, and further preferably 7 to 30% by mass, based on all the structural units of the alkali-soluble polymer.

The alkali-soluble polymer may have any of a linear structure, a branched structure, and an alicyclic structure in a side chain.

In the present specification, "main chain" represents a relatively longest bonding chain in a molecule of a polymer compound constituting a resin, and "side chain" represents a group of atoms branched from the main chain.

By using a monomer containing a group having a branch structure in a side chain or a monomer containing a group having an alicyclic structure in a side chain, the branch structure or the alicyclic structure can be introduced into the side chain of the alkali-soluble polymer. The group having an alicyclic structure may be monocyclic or polycyclic.

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

Specific examples of the monomer containing a group having an alicyclic structure in a side chain include a monomer having a monocyclic aliphatic hydrocarbon group and a monomer having a polycyclic aliphatic hydrocarbon group. Further, a (meth) acrylate having an alicyclic hydrocarbon group having 5 to 20 carbon atoms can be mentioned. More specific examples include (bicyclo [2.2.1] heptyl-2) acrylate, (meth) acrylic acid-1-adamantyl ester, (meth) acrylic acid-2-adamantyl ester, (meth) acrylic acid-3-methyl-1-adamantyl ester, (meth) acrylic acid-3,5-dimethyl-1-adamantyl ester, (meth) acrylic acid-3-ethyl adamantyl ester, (meth) acrylic acid-3-methyl-5-ethyl-1-adamantyl ester, (meth) acrylic acid-3,5,8-triethyl-1-adamantyl ester, (meth) acrylic acid-3,5-dimethyl-8-ethyl-1-adamantyl ester, (meth) acrylic acid-2-methyl-2-adamantyl ester, (meth) acrylic acid-2-ethyl-2-adamantyl ester, (meth) acrylic acid-3-hydroxy-1-adamantyl ester, (meth) acrylic acid octahydro-4,7-endonexin) -5-yl ester, (meth) acrylic acid octahydro-36-methyl-hydroxy-1-menthyl ester, (meth) acrylic acid-3536 zxft-methyl-1-menthyl ester, (meth) acrylic acid-hydroxy-1-menthyl ester, (meth) acrylic acid-1-hydroxy-1-menthyl ester, 3,7,7-trimethyl-4-hydroxy-bicyclo [4.1.0] heptyl (meth) acrylate, (norbornyl (meth) acrylate, (isobornyl (meth) acrylate, fenchyl (meth) acrylate, 2,2,5-trimethylcyclohexyl (meth) acrylate, and the like. Among these (meth) acrylates, preferred is cyclohexyl (meth) acrylate, (norbornyl (meth) acrylate, isobornyl (meth) acrylate, 1-adamantyl (meth) acrylate, 2-adamantyl (meth) acrylate, fenchyl (meth) acrylate, 1-menthyl (meth) acrylate, or tricyclodecane (meth) acrylate, and more preferred is cyclohexyl (meth) acrylate, (norbornyl (meth) acrylate, isobornyl (meth) acrylate, 2-adamantyl (meth) acrylate, or tricyclodecane (meth) acrylate.

The alkali-soluble polymer may have a polymerizable group or may contain a structural unit having a polymerizable group.

The polymerizable group is preferably a radical polymerizable group, and more preferably an ethylenically unsaturated group. Also, when the alkali-soluble polymer has an ethylenically unsaturated group, the alkali-soluble polymer preferably contains a structural unit having an ethylenically unsaturated group in a side chain.

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

The structural unit having a polymerizable group is preferably a structural unit represented by the formula (P).

[ chemical formula 4]

In the formula (P), R ^P Represents a hydrogen atom or a methyl group. L is a radical of an alcohol ^P Represents a 2-valent linking group. P represents a polymerizable group.

R ^P Represents a hydrogen atom or a methyl group.

As R ^P Preferably a hydrogen atom.

L ^P Represents a 2-valent linking group.

As the above-mentioned linking group having a valence of 2, examples thereof include-CO-, -O-,; -S-, -SO ₂ -、-NR ^N A 2-valent hydrocarbon group, and a 2-valent group formed by combining these. R is ^N Represents a substituent.

Examples of the hydrocarbon group include an alkylene group, a cycloalkylene group, and an arylene group.

The alkylene group may be either linear or branched. The alkylene group preferably has 1 to 10 carbon atoms, more preferably 2 to 8 carbon atoms, and still more preferably 3 to 5 carbon atoms. The above alkylene group may have a hetero atom, and a methylene group in the above alkylene group may be substituted with a hetero atom. The hetero atom is preferably an oxygen atom, a sulfur atom or a nitrogen atom, and more preferably an oxygen atom.

The cycloalkylene group may be any of a monocyclic ring and a polycyclic ring. The carbon number of the cycloalkylene group is preferably 3 to 20, more preferably 5 to 10, and still more preferably 6 to 8.

The arylene group may be any of monocyclic and polycyclic. The arylene group preferably has 6 to 20, more preferably 6 to 15, and still more preferably 6 to 10 carbon atoms. As the above arylene group, phenylene group is preferable.

The cycloalkylene group and the arylene group may have a hetero atom as a ring member atom. The hetero atom is preferably an oxygen atom, a sulfur atom or a nitrogen atom, and more preferably an oxygen atom.

The above hydrocarbon group may have a substituent.

Examples of the substituent include a halogen atom (e.g., fluorine atom), a hydroxyl group, a nitro group, a cyano group, an alkyl group, an alkoxy group, an alkoxycarbonyl group, and an alkenyl group, and a hydroxyl group is preferable.

As L ^P An alkylene group which may have a hetero atom is preferable.

P represents a polymerizable group.

The polymerizable group is as described above.

Examples of the structural unit having a polymerizable group include the structural units described below, but are not limited thereto.

[ chemical formula 5]

In the above structural units, rx represents a hydrogen atom or a methyl group. In the above structural units, ry represents a hydrogen atom or a methyl group.

The alkali-soluble polymer may contain one kind of structural unit having a polymerizable group alone, or may contain two or more kinds.

When the alkali-soluble polymer contains a structural unit having a polymerizable group, the content of the structural unit having a polymerizable group is preferably 5 to 70% by mass, more preferably 10 to 50% by mass, and further preferably 20 to 40% by mass, relative to all the structural units of the alkali-soluble polymer, from the viewpoint that the effect of the present invention is more excellent.

From the viewpoint of further improving the effect of the present invention, the content of the structural unit having a polymerizable group in the alkali-soluble polymer is preferably 5 to 70 mol%, more preferably 10 to 60 mol%, and still more preferably 20 to 50 mol% based on all the structural units of the alkali-soluble polymer.

Examples of a method for introducing a polymerizable group into an alkali-soluble polymer include a method in which a compound such as an epoxy compound, a blocked isocyanate compound, an isocyanate compound, a vinyl sulfone compound, an aldehyde compound, a methylol compound, or a carboxylic anhydride is reacted with a functional group such as a hydroxyl group, a carboxyl group, a primary amino group, a secondary amino group, an acetoacetyl group (acetoacetyl group), or a sulfo group.

Preferable examples of the method for introducing a polymerizable group into the alkali-soluble polymer include the following methods: after a polymer having a carboxyl group is synthesized by a polymerization reaction, (meth) acrylic ester having an epoxy group such as glycidyl (meth) acrylate is reacted with a part of the carboxyl group of the obtained polymer by a polymer reaction to introduce a (meth) acryloyloxy group into the polymer. Another method includes the following steps: after a polymer having a hydroxyl group is synthesized by a polymerization reaction, (meth) acryloyloxy group is introduced into the polymer by reacting a (meth) acrylate having an isocyanate group with a part of the hydroxyl group of the obtained polymer by a high molecular reaction.

By this method, an alkali-soluble polymer having a (meth) acryloyloxy group in a side chain can be obtained.

The polymerization reaction is preferably carried out at a temperature of 70 to 100 ℃ and more preferably at a temperature of 80 to 90 ℃. As the polymerization initiator used in the above polymerization reaction, an azo-based initiator is preferred, and for example, V-601 (trade name) or V-65 (trade name) manufactured by FUJIFILM Wako Pure Chemical Corporation is more preferred. The polymerization reaction is preferably carried out at a temperature of 80 to 110 ℃. In the above-mentioned polymer reaction, a catalyst such as ammonium salt is preferably used.

The alkali-soluble polymer may be used alone or in combination of two or more.

When two or more kinds are used, it is preferable to use two kinds of alkali-soluble polymers containing a structural unit derived from a monomer having an aromatic hydrocarbon group in a mixture or use an alkali-soluble polymer containing a structural unit derived from a monomer having an aromatic hydrocarbon group in a mixture with an alkali-soluble polymer not containing a structural unit derived from a monomer having an aromatic hydrocarbon group in a mixture. In the latter case, the proportion of the alkali-soluble polymer containing a structural unit derived from a monomer having an aromatic hydrocarbon group is preferably 50% by mass or more, more preferably 70% by mass or more, further preferably 80% by mass or more, and particularly preferably 90% by mass or more, relative to the total mass of the alkali-soluble polymer.

The alkali-soluble polymer can be synthesized by polymerizing the above-mentioned single or plural monomers using a radical polymerization initiator such as a peroxide polymerization initiator (e.g., benzoyl peroxide) and an azo polymerization initiator (e.g., azobisisobutyronitrile).

The polymerization method is preferably performed by adding the monomer solution and the radical polymerization initiator solution dropwise under a nitrogen stream to a heated solvent (preferably acetone, methyl ethyl ketone, cyclohexanone, propylene glycol monomethyl ether acetate, and isopropyl alcohol) and heating and stirring the mixture. After the reaction is completed, a solvent may be further added to adjust the concentration to a desired level. As the synthesis method, bulk polymerization, suspension polymerization, or emulsion polymerization may be used in addition to solution polymerization.

The glass transition temperature Tg of the alkali-soluble polymer is preferably from 30 to 135 ℃. By using an alkali-soluble polymer having a Tg of 135 ℃ or less, deterioration in line width or resolution at the time of focus shift upon exposure can be suppressed. From this viewpoint, the Tg of the alkali-soluble polymer is more preferably 130 ℃ or lower, still more preferably 120 ℃ or lower, and particularly preferably 110 ℃ or lower. Also, from the viewpoint of improving the edge melting resistance, it is preferable to use an alkali-soluble polymer having a Tg of 30 ℃ or more. From this viewpoint, the Tg of the alkali-soluble polymer is more preferably 40 ℃ or higher, still more preferably 50 ℃ or higher, particularly preferably 60 ℃ or higher, and most preferably 70 ℃ or higher.

The weight average molecular weight of the alkali-soluble polymer is preferably 5,000 to 500,000. When the weight average molecular weight is 500,000 or less, it is preferable from the viewpoint of improving the resolution and the developability. The weight average molecular weight is more preferably 100,000 or less, and still more preferably 60,000 or less. On the other hand, a weight average molecular weight of 5,000 or more is preferable from the viewpoint of controlling the properties of the developed aggregates and the properties of the unexposed film such as edge meltability and chipping when the photosensitive resin laminate is used. The weight average molecular weight is more preferably 8000 or more, still more preferably 10000 or more, and particularly preferably 15000 or more. The edge meltability means how easily the photosensitive composition layer protrudes from the end face of the roll when the photosensitive resin laminate is wound into a roll. The swarf property is the ease with which swarf can be scattered when the unexposed film is cut with a cutter. If the chips adhere to the upper surface of the photosensitive resin laminate, they are transferred to a mask in a subsequent exposure step or the like, resulting in a defective product. The dispersion degree of the alkali-soluble polymer is preferably 1.0 to 6.0, more preferably 1.0 to 5.0, further preferably 1.0 to 4.0, particularly preferably 1.0 to 3.0. In the present invention, 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 invention, the weight average molecular weight and the number average molecular weight are values measured by gel permeation chromatography.

The content of the alkali-soluble polymer is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, still more preferably 30 to 70% by mass, and particularly preferably 40 to 60% by mass, based on the total mass of the photosensitive composition layer. From the viewpoint of controlling the development time, the content of the alkali-soluble polymer is preferably 90% by mass or less. On the other hand, from the viewpoint of improving the edge melting resistance, the content of the alkali-soluble polymer is preferably 10% by mass or more.

The photosensitive composition layer may contain other resins than the above.

Examples of the other resin include acrylic resins, styrene-acrylic copolymers, polyurethane resins, polyvinyl alcohols, polyvinyl formals, polyester resins, epoxy resins, polyacetal resins, polybenzoxazole resins, polysiloxane resins, polyethyleneimine, polyallylamine and polyalkylene glycols.

(polymerizable Compound)

The photosensitive composition layer contains a polymerizable compound having a polymerizable group. As the polymerizable compound, an ethylenically unsaturated compound is preferable.

In the present specification, the "polymerizable compound" refers to a compound different from the alkali-soluble polymer and polymerized by the action of a polymerization initiator described later.

The polymerizable group of the polymerizable compound may be a group participating in polymerization reaction, and examples thereof include groups having an ethylenically unsaturated group such as a vinyl group, an acryloyl group, a methacryloyl group, a styryl group, and a maleimide group; the group having a cationically polymerizable group such as an epoxy group or an oxetanyl group is preferably a group having an ethylenically unsaturated group, and more preferably an acryloyl group or a methacryloyl group.

Examples of the ethylenically unsaturated group of the ethylenically unsaturated compound include a vinyl group, an acryloyl group, a methacryloyl group, a styryl group, and a maleimide group. As the ethylenically unsaturated group, an acryloyl group or a methacryloyl group is preferable.

The polymerizable group of the polymerizable compound other than the ethylenically unsaturated compound is not particularly limited as long as it is a group participating in a polymerization reaction, and examples thereof include groups having a cationically polymerizable group such as an epoxy group and an oxetanyl group.

The ethylenically unsaturated compound will be described below.

The ethylenically unsaturated compound is preferably a compound having 2 or more ethylenically unsaturated groups in one molecule (polyfunctional ethylenically unsaturated compound) from the viewpoint of more excellent photosensitivity.

In addition, the number of ethylenically unsaturated groups contained in one molecule of the ethylenically unsaturated compound is preferably 6 or less, more preferably 3 or less, and further preferably 2 or less, from the viewpoint of further excellent resolution and peelability.

From the viewpoint of more excellent balance between the photosensitivity, the resolution, and the releasability of the photosensitive composition layer, the 2-or 3-functional ethylenically unsaturated compound having 2 or 3 ethylenically unsaturated groups in one molecule is preferably contained, and the 2-functional ethylenically unsaturated compound having 2 ethylenically unsaturated groups in one molecule is more preferably contained.

From the viewpoint of excellent peelability, the content of the 2-functional ethylenically unsaturated compound with respect to the total mass of the polymerizable compounds is preferably 20 mass% or more, more preferably more than 40 mass%, and further preferably 55 mass% or more. The upper limit is not particularly limited and may be 100 mass%. That is, the polymerizable compounds may be all 2-functional ethylenically unsaturated compounds.

The ethylenically unsaturated compound is preferably a (meth) acrylate compound having a (meth) acryloyl group as a polymerizable group.

Polymerizable compound B1-

The photosensitive composition layer also preferably contains, as a polymerizable compound, a polymerizable compound B1 having an aromatic ring and 2 ethylenically unsaturated groups.

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

Examples of the aromatic ring included in the polymerizable compound B1 include aromatic hydrocarbon rings such as benzene ring, naphthalene ring, and anthracene ring, aromatic heterocyclic rings such as thiophene ring, furan ring, pyrrole ring, imidazole ring, triazole ring, and pyridine ring, and condensed rings thereof, with aromatic hydrocarbon rings being preferred, and benzene rings being more preferred. The aromatic ring may have a substituent.

The polymerizable compound B1 may have only 1 aromatic ring, or may have 2 or more aromatic rings.

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

Examples of the bisphenol structure include a bisphenol a structure derived from bisphenol a (2,2-bis (4-hydroxyphenyl) propane), a bisphenol F structure derived from bisphenol F (2,2-bis (4-hydroxyphenyl) methane), and a bisphenol B structure derived from bisphenol B (2,2-bis (4-hydroxyphenyl) butane), and the bisphenol a structure is preferable.

Examples of the polymerizable compound B1 having a bisphenol structure include compounds having a bisphenol structure and 2 polymerizable groups (preferably (meth) acryloyl groups) bonded to both ends of the bisphenol structure.

The bisphenol structure may have 2 polymerizable groups bonded to both ends thereof directly or through 1 or more alkyleneoxy groups. The alkyleneoxy group added to both ends of the bisphenol structure is preferably an ethyleneoxy group or a propyleneoxy group, and more preferably an ethyleneoxy group. The number of addition of alkyleneoxy groups to the bisphenol structure is not particularly limited, but is preferably 4 to 16, more preferably 6 to 14 per 1 molecule.

The polymerizable compound B1 having a bisphenol structure is described in paragraphs [0072] to [0080] of Japanese patent application laid-open No. 2016-224162, the contents of which are incorporated herein by reference.

The polymerizable compound B1 is preferably a 2-functional ethylenically unsaturated compound having a bisphenol a structure, and more preferably 2,2-bis (4- ((meth) acryloyloxyalkyl) phenyl) propane.

Examples of 2,2-bis (4- ((meth) acryloyloxyalkylpolyalkoxy) phenyl) propane include 2,2-bis (4- (methacryloyloxydiethoxy) phenyl) propane (FA-324m, manufactured by hitachi Chemical Co., ltd., product), 2,2-bis (4- (methacryloyloxyethoxypropoxy) phenyl) propane, 2,2-bis (4- (methacryloyloxypentaethoxy) phenyl) propane (BPE-500, shift-Nakamura Chemical Co., manufactured by ltd., product), 2,2-bis (4- (methacryloyloxydodecaethoxytetrapropoxy) phenyl) propane (FA-3200 my, hitachi Chemical Co., ltd., product), 2,2-bis (4- (methacryloyloxypentadecyloxy) phenyl) propane (BPE-1300, n-3924-bis (4- (methacryloyloxydiethoxy) phenyl) propane (BPE-3534, manufactured by shin-200, bisphenol a-120, n-propylene glycol acrylate (naph-propylene glycol).

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

[ chemical formula 6]

In the general formula (B1), R ₁ And R ₂ Each independently represents 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 an integer of 1 to 39, and n1+ n3 is an integer of 2 to 40. n2 and n4 are each independently an integer of 0 to 29, and n2+ n4 is an integer of 0 to 30. The arrangement of the structural units- (A-O) -and- (B-O) -may be random, it may also be a block. Also, in the case of a block, either one of- (A-O) -and- (B-O) -may be on the biphenyl (bisphenyl) side.

In one aspect, n1+ n2+ n3+ n4 is preferably 2 to 20, more preferably 2 to 16, and further preferably 4 to 12. N2+ n4 is preferably 0 to 10, more preferably 0 to 4, further preferably 0 to 2, particularly preferably 0.

The polymerizable compound B1 may be used alone or in combination of two or more.

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

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

The polymerizable compound other than the polymerizable compound B1 is not particularly limited, and can be appropriately selected from known compounds. For example, there may be mentioned a compound having 1 ethylenically unsaturated group in one molecule (monofunctional ethylenically unsaturated compound), a 2-functional ethylenically unsaturated compound having no aromatic ring, and an ethylenically unsaturated compound having 3 or more functions.

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

Examples of the 2-functional ethylenically unsaturated compound having no aromatic ring include alkylene glycol di (meth) acrylate, polyalkylene glycol di (meth) acrylate, urethane di (meth) acrylate, and trimethylolpropane diacrylate.

Examples of the alkylene glycol di (meth) acrylate include tricyclodecane dimethanol diacrylate (A-DCP, manufactured by Shin-Nakamura Chemical Co., ltd.), tricyclodecane dimethanol dimethacrylate (DCP, manufactured by Shin-Nakamura Chemical Co., ltd.), 1,9-nonanediol diacrylate (A-NOD-N, manufactured by Shin-Nakamura Chemical Co., ltd.), 1,6-hexanediol diacrylate (A-HD-N, manufactured by Shin-Nakamura Chemical Co., ltd.), ltd.,), polyethylene glycol dimethacrylate (4G, 9G, 14G, 23G, etc., shin-Nakamura Chemical co., ltd., ltd.), ARONIX (registered trademark) M-220 (TOAGOSEI co., ltd.), ARONIX (registered trademark) M-240 (TOAGOSEI co., ltd., ltd, manufactured), ARONIX (registered trademark) M-270 (TOAGOSEI co., ltd, manufactured), ethylene glycol dimethacrylate, 1,10-decanediol diacrylate, and neopentyl glycol di (meth) acrylate.

Examples of the polyalkylene glycol di (meth) acrylate include polyethylene glycol di (meth) acrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate and polypropylene glycol di (meth) acrylate.

Examples of the urethane di (meth) acrylate include propylene oxide-modified urethane di (meth) acrylate and ethylene oxide-and propylene oxide-modified urethane di (meth) acrylate. Examples of commercially available products include 8UX-0 15A (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 the ethylenically unsaturated compound having 3 or more functions include dipentaerythritol (tri/tetra/penta/hexa) (meth) acrylate, pentaerythritol (tri/tetra) (meth) acrylate, trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, trimethylolethane tri (meth) acrylate, isocyanuric acid tri (meth) acrylate, glycerol tri (meth) acrylate, and alkylene oxide-modified products thereof.

In the above description, "(tri/tetra/penta/hexa) (meth) acrylate" is a concept including tri (meth) acrylate, tetra (meth) acrylate, penta (meth) acrylate and hexa (meth) acrylate, and "(tri/tetra) (meth) acrylate" is a concept including tri (meth) acrylate and tetra (meth) acrylate.

In one aspect, the photosensitive composition layer preferably contains the polymerizable compound B1 and an ethylenically unsaturated compound having 3 or more functions, and more preferably contains the polymerizable compound B1 and two or more ethylenically unsaturated compounds having 3 or more functions. In this case, the mass ratio of the polymerizable compound B1 to the 3 or more functional ethylenically unsaturated compound is preferably (total mass of the polymerizable compound B1: (total mass of the 3 or more functional ethylenically unsaturated compounds) =1:1 to 5:1, more preferably 1.2.

In one embodiment, the photosensitive composition layer preferably contains the polymerizable compound B1 and two or more 3-functional ethylenically unsaturated compounds.

Examples of the alkylene oxide-modified product of the 3-or more-functional ethylenically unsaturated compound include caprolactone-modified (meth) acrylate compounds (e.g., nippon Kayaku co., KAYARAD (registered trademark) DPCA-20 manufactured by ltd., a-9300-1CL manufactured by Shin-Nakamura Chemical co., ltd., etc.), ethoxylated trimethylolpropane trimethacrylate (e.g., TOMOE Engineering co., SR454, SR499, and SR502 manufactured by ltd.), alkylene oxide-modified (meth) acrylate compounds (e.g., nippon Kayaku co., KAYARAD RP-1040 manufactured by ltd., shin-Nakamura Chemical co., ATM-35 and ica-9300 manufactured by ltd., and eca-9300 manufactured by icd-allex ltd., ecryl (registered trademark) 135 manufactured by Nippon Kayaku co., ltd., and g.35 manufactured by Shin-Nakamura Chemical co., and g.35, and eag-3-Nakamura co., agy, and g.9-agoni (registered trademark, agony), and agony co., agony co., agy, agony (registered trademark).

As the polymerizable compound, a polymerizable compound having an acid group (such as a carboxyl group) can be used. The acid groups may form anhydride groups. Examples of the polymerizable compound having an acid group include ARONIX (registered trademark) TO-2349 (manufactured by TOAGOSEI co., ltd.), ARONIX (registered trademark) M-520 (manufactured by TOAGOSEI co., ltd.), and ARONIX (registered trademark) M-510 (manufactured by TOAGOSEI co., ltd.).

Examples of the polymerizable compound having an acid group include polymerizable compounds having an acid group described in paragraphs [0025] to [0030] of Japanese patent application laid-open No. 2004-239942.

One kind of the polymerizable compound may be used alone, or two or more kinds may be used.

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, based on the total mass of the photosensitive composition layer.

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

(polymerization initiator)

The photosensitive composition layer contains a polymerization initiator.

As the polymerization initiator, for example, a known polymerization initiator can be used depending on the form of the polymerization reaction. Specifically, a thermal polymerization initiator and a photopolymerization initiator can be mentioned.

The polymerization initiator may be any of a radical polymerization initiator and a cationic polymerization initiator.

The photosensitive composition layer preferably contains a photopolymerization initiator.

The photopolymerization initiator is a compound that initiates polymerization of the polymerizable compound upon receiving an active light such as ultraviolet light, visible light, and X-ray. The photopolymerization initiator is not particularly limited, and a known photopolymerization initiator can be used.

Examples of the photopolymerization initiator include a photo radical polymerization initiator and a photo cation polymerization initiator, and a photo radical polymerization initiator is preferable.

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

In addition, from the viewpoint of photosensitivity, visibility of exposed portions and unexposed portions, and resolution, the photosensitive composition layer preferably contains at least one selected from 2,4,5-triarylimidazole dimer and a derivative thereof as a photo radical polymerization initiator. In addition, 2,4,5-triarylimidazole dimer and its derivatives, 22,4,5-triarylimidazole structures may be the same or different.

Examples of 2,4,5-triarylimidazole dimer derivatives include 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (o-chlorophenyl) -4,5-bis (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.

Examples of the photo-radical polymerization initiator include 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. 2015-14783.

Examples of the photo-radical polymerization initiator include ethyl dimethylaminobenzoate (DBE, CAS No. 10287-53-3), benzoin methyl ether, (p, p '-dimethoxybenzyl) anise ester, TAZ-110 (trade name: midori Kagaku Co., ltd.), benzophenone, 4,4' -bis (diethylamino) benzophenone, TAZ-111 (trade name: midori Kagaku Co., ltd.), irgacure OXE01, OXE02, OXE03, OXE04 (BASF Co., ltd.), omnirad651 and 369 (trade name: IGM Resins B.V., ltd.), and 2,2 '-bis (2-chlorophenyl) -4,4',5,5 '-tetraphenyl-1,2' -biimidazole (Tokyo Co., ltd.).

Examples of commercially available products of the photo radical polymerization initiator include 1- [4- (phenylthio) phenyl ] -1,2-octanedione-2- (O-benzoyloxime) (trade name: IRGACURE (registered trademark) OXE-01, manufactured by BASF corporation), 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] ethanone-1- (O-acetyloxime) (trade name: IRGACURE OXE-02, manufactured by BASF corporation), IRGACURE OXE-03 (manufactured by BASF corporation), IRGACURE OXE-04 (manufactured by BASF corporation), 2- (dimethylamino) -2- [ (4-methylphenyl) methyl ] -1- [4- (4-morpholino) phenyl ] -1-butanone (trade name: omniarad 379EG, IGM Resins B.V.), 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one (trade name: omniarad 907, IGM Resins B.V.), 2-hydroxy-1- {4- [4- (2-hydroxy-2-methylpropionyl) benzyl ] phenyl } -2-methylpropan-1-one (trade name: omniarad 127, IGM Resins B.V.), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1 (trade name: omni) 369, manufactured by IGM Resins B.V.), 2-hydroxy-2-methyl-1-phenylpropan-1-one (trade name: omnirad 1173, igm Resins b.v.), 1-hydroxycyclohexyl phenyl ketone (trade name: omnirad 184, igm Resins b.v.), 2,2-dimethoxy-1,2-diphenylethan-1-one (trade name: omnirad651, igm Resins b.v., manufactured), 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (trade name: omnirad TPO H, manufactured by IGM Resins b.v.), bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide (trade name: omnirad 819, manufactured by igm Resins b.v.), a photopolymerization initiator of oxime ester type (trade name: lunar 6, dksh Japan k.k.), 2,2' -bis (2-chlorophenyl) -4,4',5,5' -tetraphenylbenzimidazole (2- (2-chlorophenyl) -4,5-diphenylimidazole dimer) (trade name: B-CIM, manufactured by hamford corporation) and 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer (trade name: BCTB, tokyo Chemical Industry co., ltd., manufactured), 1- [4- (phenylthio) phenyl ] -3-cyclopentylpropane-1,2-dione-2- (O-benzoyloxime) (trade name: TR-PBG-305, changzhou Tronly New Electronic Materials CO, ltd., manufactured), 1,2-propanedione, 3-cyclohexyl-1- [ 9-ethyl-6- (2-furylcarbonyl) -9H-carbazol-3-yl ] -,2- (O-acetyloxime) (trade name: TR-PBG-326, changzhou Tronly New Electronic Materials CO, ltd. Manufacture) and 3-cyclohexyl-1- (6- (2- (benzoyloxyimino) octanoyl) -9-ethyl-9H-carbazol-3-yl) -propane-1,2-dione-2- (O-benzoyl oxime) (trade name: TR-PBG-391, changzhou Tronly New Electronic Materials CO., LTD., manufactured).

The photo cation polymerization initiator (photo acid generator) is a compound that generates an acid upon receiving an activating light. The photo cation polymerization initiator is preferably a compound that generates an acid by reacting with an activating light having a wavelength of 300nm or more, preferably 300 to 450nm, but the chemical structure is not limited. The photo cation polymerization initiator that is not directly sensitive to the activation light having a wavelength of 300nm or more can be preferably used in combination with a sensitizer as long as it is a compound that generates an acid by being sensitive to the activation light having a wavelength of 300nm or more.

As the photo cationic polymerization initiator, a photo cationic polymerization initiator that generates an acid having a pKa of 4 or less is preferable, a photo cationic polymerization initiator that generates an acid having a pKa of 3 or less is more preferable, and a photo cationic polymerization initiator that generates an acid having a pKa of 2 or less is particularly preferable. The lower limit of pKa is not particularly limited, but is preferably at least-10.0.

Examples of the photo cation polymerization initiator include ionic photo cation polymerization initiators and nonionic photo cation polymerization initiators.

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

As the ionic photo-cationic polymerization initiator, the ionic photo-cationic polymerization initiators described in paragraphs [0114] to [0133] of Japanese patent application laid-open No. 2014-085643 can be used.

Examples of the nonionic photo cation polymerization initiator include trichloromethyl-s-triazines, diazomethane compounds, imidosulfonate compounds and oxime sulfonate compounds. As the trichloromethyl-s-triazines, diazomethane compounds and imidosulfonate compounds, compounds described in paragraphs [0083] to [0088] of jp 2011-221494 a can be used. Furthermore, as the oxime sulfonate compound, the compounds described in paragraphs [0084] to [0088] of International publication No. 2018/179640 can be used.

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

One kind of the polymerization initiator may be used alone, or two or more kinds may be used.

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

(pigments)

From the viewpoint of visibility of exposed portions and unexposed portions, pattern visibility after development, and resolution, the photosensitive composition layer preferably also contains a dye (also referred to as "dye N") having a maximum absorption wavelength of 450nm or more in a wavelength range of 400 to 780nm during color development and a maximum absorption wavelength that changes by an acid, an alkali, or a radical. When the pigment N is contained, although the detailed mechanism is not clear, the adhesion with an adjacent layer (for example, a water-soluble resin layer) is improved, and the resolution is further excellent.

In the present specification, the "change in the maximum absorption wavelength of a dye by an acid, an alkali, or a radical" may refer to any one of a method in which a dye in a developed state is decolorized by an acid, an alkali, or a radical, a method in which a dye in a decolorized state is developed by an acid, an alkali, or a radical, and a method in which a dye in a developed state is changed to a developed state of another color.

Specifically, the dye N may be a compound that develops color by changing from a decolored state by exposure, or may be a compound that develops color by changing from a colored state by exposure. In this case, the dye may be one in which an acid, a base, or a radical is generated in the photosensitive composition layer by exposure and acts to change the color development or the color removal state, or one in which the state (for example, pH) in the photosensitive composition layer is changed by an acid, a base, or a radical to change the color development or the color removal state. Further, the dye may be one which changes its color development or decoloration state by being directly stimulated by an acid, an alkali, or a radical without exposure.

Among them, the dye N is preferably a dye whose maximum absorption wavelength is changed by an acid or a radical, and more preferably a dye whose maximum absorption wavelength is changed by a radical, from the viewpoint of visibility and resolution of an exposed portion and a non-exposed portion.

When the photosensitive composition layer is a negative photosensitive composition layer, the negative photosensitive composition layer preferably contains a pigment whose maximum absorption wavelength is changed by a radical as both the pigment N and the photo radical polymerization initiator, from the viewpoint of visibility and resolution of an exposed portion and a non-exposed portion.

The dye N is preferably a dye that develops color by an acid, an alkali, or a radical, from the viewpoint of visibility of the exposed portion and the unexposed portion.

Examples of the color developing mechanism of the dye N include a method in which a radical reactive dye, an acid reactive dye, or a base reactive dye (for example, leuco dye) is developed by adding a photo radical polymerization initiator, a photo cation polymerization initiator (photo acid generator), or a photo base generator to a photosensitive composition layer, followed by exposure, and then by a radical, an acid, or a base generated by the photo radical polymerization initiator, the photo cation polymerization initiator, or the photo base generator.

From the viewpoint of visibility of the exposed portion and the non-exposed portion, the maximum absorption wavelength in the wavelength range of 400 to 780nm in color development of the dye N is preferably 550nm or more, more preferably 550 to 700nm, and still more preferably 550 to 650nm.

The dye N may have only the maximum absorption wavelength in the wavelength range of 400 to 780nm in 1 color development, or may have 2 or more. When the dye N has 2 or more maximum absorption wavelengths in the wavelength range of 400 to 780nm at the time of color development, the maximum absorption wavelength having the highest absorbance among the 2 or more maximum absorption wavelengths may be 450nm or more.

The maximum absorption wavelength of the pigment N is determined by using a spectrophotometer under an atmospheric environment: UV3100 (manufactured by Shimadzu Corporation) is obtained by measuring the transmission spectrum of a solution containing a dye N (liquid temperature 25 ℃) in the range of 400nm to 780nm and detecting a wavelength at which the intensity of light becomes extremely small (maximum absorption wavelength).

Examples of the dye that develops color or decolors by exposure include colorless compounds.

Examples of the coloring matter decolorized by exposure to light include a leuco compound, diarylmethane-based coloring matter, oxazine-based coloring matter, xanthene-based coloring matter, iminonaphthoquinone-based coloring matter, azomethine-based coloring matter, and anthraquinone-based coloring matter.

The dye N is preferably a colorless compound from the viewpoint of visibility of an exposed portion and a non-exposed portion.

Examples of the colorless compound include a colorless compound having a triarylmethane skeleton (triarylmethane-based colorant), a colorless compound having a spiropyran skeleton (spiropyran-based colorant), a colorless compound having a fluoran skeleton (fluoran-based colorant), a colorless compound having a diarylmethane skeleton (diarylmethane-based colorant), a colorless compound having a rhodamine lactam skeleton (rhodamine lactam-based colorant), a colorless compound having an indolylphthalein skeleton (indolylphthalein-based colorant), and a colorless compound having a leuco auramine skeleton (leuco auramine-based colorant).

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

The colorless compound preferably has a lactone ring, a sulfinyl lactone ring (sultone ring), or a sultone ring from the viewpoint of visibility of an exposed portion and a non-exposed portion. Thus, the lactone ring, sulfinyl lactone ring or sultone ring of the colorless compound can be reacted with a radical generated by the photo radical polymerization initiator or an acid generated by the photo cation polymerization initiator to change the colorless compound into a closed ring state and decolor the colorless compound, or the colorless compound can be changed into an open ring state and develop color. The colorless compound is preferably a compound having a lactone ring, a sulfinolactone ring, or a sultone ring and developing a color by radical or acid ring opening, and more preferably a compound having a lactone ring and developing a color by radical or acid ring opening.

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

Specific examples of the dye in the pigment N include brilliant green (brilliant green), ethyl violet, methyl green, crystal violet, basic fuchsin (basic fuchsin), methyl violet 2B, quinaldine red (quinaldine red), rose bengal (rose bengal), metanilghuane (metanilyl low), thymol sulfonphthalein (thymol sulfonphthalein), xylenol (xylenol) blue, methyl orange, p-methyl red, congo red, benzopurpurin (benzopurpurine) 4B, α -naphthyl red, nile blue (nile blue) 2B, nile blue a, methyl violet, malachite green (malachite green), parafuchsin (parafhucin), victoria pure blue (victoria pure blue) -naphthalene sulfonate, victoria pure blue h (hodaya), oil blue # co 603, manufactured by Chemical co, and Chemical co 603, and so on ltd. products), oil pink #312 (Orient Chemical Industries co., ltd. Products), oil red 5B (Orient Chemical Industries co., ltd. Products), oil scarlet (oil scarlet) #308 (Orient Chemical Industries co., ltd. Products), oil red OG (Orient Chemical Industries co., ltd. Products), oil red RR (Orient Chemical Industries co., ltd. Products), oil green #502 (Orient Chemical Industries co., ltd. Products), shi Bilong red (spilon red) BEH special (Hodogaya Chemical co., ltd. Products), m-cresol purple, cresol red, rhodamine B, rhodamine 6G, sulforhodamine B, auramine, 4-p-diethylaminophenylimino, 2-p-naphthylaminobenzoquinone-4-carboxyl-naphthoquinone-2-carboxyl-naphthoquinone-4-diethylaminobenzoquinone, 2-carboxystearylamino-4-p-N, N-bis (hydroxyethyl) amino-phenylimino-naphthoquinone, 1-phenyl-3-methyl-4-p-diethylaminophenylimino-5-pyrazolone and 1- β -naphthyl-4-p-diethylaminophenylimino-5-pyrazolone.

<xnotran> N , , p, p', p "- ( ), pergascript Blue SRB (Ciba-Geigy ), , , ,2- (N- -N- ) -6- (N- -N- ) ,2- -3- -6- (N- - ) , 5363 zxft 5363- ,3- (N, N- ) -5- -7- (N, N- ) ,3- (N- -N- ) -6- -7- ,3- (N, N- ) -6- -7- ,3- (N, N- ) -6- -7- ,3- (N, N- ) -6- -7- ,3- (N, N- ) -6- -7- ,3- (N, N- ) -7- (4- ) , </xnotran> 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-piperidinyl-6-methyl-7-anilinofluorane, 3-pyrrolidinyl-6-methyl-7-anilinofluorane, 3,3-bis (1-ethyl-2-methylindol-3-yl) phthalide (phthalide), 3,3-bis (1-N-butyl-2-methylindol-3-yl) phthalide, 3,3-bis (p-dimethylaminophenyl) -6-dimethylaminophenyl-6-dimethylaminophthalide, 3- (4-diethylamino-2-ethoxyphenyl) -3- (1-ethyl-2-methylindol-3-yl) phthalide, 3- (4-diethylamino-3 ' -diphenylamino) -3-ethyl-3 ' -diphenylindol-3-yl) phthalide, and 3- (4-ethyl-2-methyl-3 ' -diphenylindol-3-yl) phthalide, 9' - [9H ] xanthen-3-one.

The dye N is preferably a dye whose maximum absorption wavelength is changed by a radical, and more preferably a dye whose color is developed by a radical, from the viewpoints of visibility of an exposed portion and a non-exposed portion, pattern visibility after development, and resolution.

As the pigment N, leuco crystal violet, crystal violet lactone, brilliant green or victoria pure blue-naphthalene sulfonate is preferable.

One kind of the pigment N may be used alone, or two or more kinds thereof may be used.

The content of the dye N is preferably 0.1% by mass or more, more preferably 0.1 to 10% by mass, even more preferably 0.1 to 5% by mass, and particularly preferably 0.1 to 1% by mass, based on the total mass of the photosensitive composition layer, from the viewpoints of visibility of exposed portions and non-exposed portions, pattern visibility after development, and resolution.

The content of the pigment N is a content of the pigment when all the pigments N contained in the total mass of the photosensitive composition layer are in a colored state. Hereinafter, a method for quantifying the content of pigment N will be described by taking a pigment that develops color by a radical as an example.

A solution was prepared by dissolving 0.001g and 0.01g of a coloring matter in 100mL of methyl ethyl ketone. To each of the obtained solutions, a photoradical polymerization initiator (trade name, irgacure OXE01, manufactured by BASF Japan ltd.) was added, and 365nm light was irradiated, thereby generating radicals to bring all the pigments into a colored state. Then, the absorbance of each solution at a liquid temperature of 25 ℃ was measured using a spectrophotometer (UV 3100, manufactured by Shimadzu Corporation) under an atmospheric environment, and a calibration curve was prepared.

Next, the absorbance of the solution in which all the coloring matters were developed was measured by the same method as described above except that 3g of the photosensitive composition layer was dissolved in methyl ethyl ketone instead of the coloring matters. The content of the pigment contained in the photosensitive composition layer was calculated from the absorbance of the obtained solution containing the photosensitive composition layer based on the calibration curve.

The photosensitive composition layer 3g was the same as the photosensitive resin composition 3g in total solid content.

(thermally crosslinkable Compound)

When the photosensitive composition layer is a negative photosensitive composition layer, a thermally crosslinkable compound may be contained from the viewpoint of the strength of the obtained cured film and the adhesiveness of the obtained uncured film. In the present specification, a thermally crosslinkable compound having an ethylenically unsaturated group, which will be described later, is not treated as a polymerizable compound but as a thermally crosslinkable compound.

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

Since the blocked isocyanate compound reacts with a hydroxyl group and a carboxyl group, for example, when a resin and/or a polymerizable compound has at least one of a hydroxyl group and a carboxyl group, the hydrophilicity of the formed film is reduced, and the function tends to be enhanced when the film obtained by curing the negative photosensitive composition layer is used as a protective film.

The blocked isocyanate compound is a "compound having a structure in which an isocyanate group of an isocyanate is protected (so-called mask) with a blocking agent".

The dissociation temperature of the blocked isocyanate compound is not particularly limited, but is preferably 100 to 160 ℃, more preferably 130 to 150 ℃.

The dissociation temperature of the blocked isocyanate means "a temperature of an endothermic peak accompanying deprotection reaction of the blocked isocyanate when measured by DSC (Differential scanning calorimetry) analysis using a Differential scanning calorimeter".

As the differential scanning calorimeter, for example, a differential scanning calorimeter (model: DSC 6200) manufactured by Seiko Instruments Inc. can be preferably used. However, the differential scanning calorimeter is not limited thereto.

Examples of the blocking agent having a dissociation temperature of 100 to 160 ℃ include an active methylene compound [ malonic diester (dimethyl malonate, diethyl malonate, di-N-butyl malonate, di-2-ethylhexyl malonate, etc.) ]), an oxime compound (a compound having a structure represented by-C (= N-OH) -in the molecule, such as formaldoxime, acetaldoxime, acetoxime, methylethylketoxime, and cyclohexanone oxime).

Among these, the blocking agent having a dissociation temperature of 100 to 160 ℃ is preferably at least one selected from oxime compounds, for example, from the viewpoint of storage stability.

For example, the blocked isocyanate compound preferably has an isocyanurate structure from the viewpoints of improving the brittleness of the film, improving the adhesion to the transfer target, and the like.

The blocked isocyanate compound having an isocyanurate structure can be obtained, for example, by isocyanurating hexamethylene diisocyanate to protect it.

Among blocked isocyanate compounds having an isocyanurate structure, compounds having an oxime structure using an oxime compound as a blocking agent are preferable from the viewpoint that the dissociation temperature is more easily set in a preferable range and the development residue is easily reduced than those of compounds having no oxime structure.

The blocked isocyanate compound may have a polymerizable group.

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

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

Among these, the polymerizable group is preferably an ethylenically unsaturated group, more preferably a (meth) acryloyloxy group, and still more preferably an acryloyloxy group.

As the blocked isocyanate compound, commercially available products can be used.

Examples of commercially available products of the blocked isocyanate compound include Karenz (registered trademark) AOI-BM, karenz (registered trademark) MOI-BP, and the like (manufactured by SHOWA DENKO K., supra), and blocked Duranate series (for example, duranate (registered trademark) TPA-B80E, duranate (registered trademark) WT32-B75P, manufactured by Asahi Kasei Chemicals Corporation).

Further, as the blocked isocyanate compound, a compound having the following structure can also be used.

[ chemical formula 7]

The thermally crosslinkable compound may be used alone or in combination of two or more.

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.

(pigment)

The photosensitive composition layer may contain a pigment.

When the photosensitive composition layer contains a pigment, the photosensitive composition layer corresponds to the colored resin layer.

In recent years, a cover glass (cover glass) having a black frame-shaped light shielding layer formed on a peripheral edge portion of a back surface of a transparent glass substrate or the like is sometimes attached to a liquid crystal display window included in an electronic device in order to protect the liquid crystal display window. In order to form such a light shielding layer, a colored resin layer may be used.

The pigment may be appropriately selected depending on the desired hue, and examples thereof include a black pigment, a white pigment, and a color pigment other than black and white, and in the case of forming a black pattern, a black pigment is preferable.

Examples of the black pigment include known black pigments (e.g., organic pigments and inorganic pigments).

Among them, from the viewpoint of optical density, carbon black, titanium oxide, titanium carbide, iron oxide, or graphite is preferable as the black pigment, and carbon black is more preferable. As the carbon black, a surface-modified carbon black in which at least a part of the surface is coated with a resin is preferable from the viewpoint of surface resistance.

From the viewpoint of dispersion stability, the particle diameter (number average particle diameter) of the black pigment is preferably 0.001 to 0.1. Mu.m, more preferably 0.01 to 0.08. Mu.m.

The "particle diameter" refers to the diameter of a circle when the area of the pigment particle is determined from a photographic image of the pigment particle taken with an electron microscope and the circle having the same area as the area of the pigment particle is considered. The "number average particle diameter" refers to an average value obtained by obtaining the above particle diameter for any 100 particles and averaging the obtained 100 particle diameters.

Examples of the white pigment include inorganic pigments and white pigments described in paragraphs [0015] and [0114] of Japanese patent application laid-open No. 2005-007765.

As the inorganic pigment, titanium oxide, zinc oxide, lithopone, light calcium carbonate, white carbon, aluminum oxide, aluminum hydroxide, or barium sulfate is preferable, titanium oxide or zinc oxide is more preferable, titanium oxide is further preferable, rutile-type or anatase-type titanium oxide is particularly preferable, and rutile-type titanium oxide is most preferable.

The surface of the titanium oxide may be subjected to silica treatment, alumina treatment, titania treatment, zirconia treatment, or organic matter treatment, or two or more of these treatments may be performed. This suppresses the catalytic activity of titanium oxide, and improves the heat resistance and the light fading property.

From the viewpoint of reducing the thickness of the photosensitive composition layer after heating, at least one of the alumina treatment and the zirconia treatment is preferably performed as the surface treatment of the surface of the titanium oxide, and more preferably both of the alumina treatment and the zirconia treatment are performed.

When the photosensitive composition layer is a colored resin layer, the photosensitive composition layer preferably contains a color pigment other than a black pigment and a white pigment from the viewpoint of transferability.

The particle diameter (number average particle diameter) of the color pigment is preferably 0.1 μm or less, more preferably 0.08 μm or less, from the viewpoint of more excellent dispersibility. The lower limit is preferably 10nm or more.

Examples of the Color pigment include victoria pure blue BO (Color Index) (hereinafter, also known as "c.i.") 42595), auramine (c.i. 41000), fat black (fatbreak) HB (c.i. 26150), morronite yellow (monolithe yellow) GT (c.i. pigment yellow 12), permanent yellow (permanent yellow) GR (c.i. pigment yellow 17), permanent yellow HR (c.i. pigment yellow 83), permanent carmine (permanent carmine) FBB (c.i. pigment red 146), husksbam red (hostaperm red) ESB (c.i. pigment violet 19), permanent ruby red (permanent ruby) FBH (c.i. pigment red 11), baster pink (pasteil pink) bspela (subpura) (c.i. pigment red 81), montelukast blue (monstra blue) (c.i. pigment black 149), fate black pigment blue (c.i. pigment red 149), c.i. pigment black pigment blue (c.i. pigment red) 177, c.i. pigment red 15, c.i. pigment red (c.i. pigment red) fbi. pigment red 177, c.i. pigment red 15, c.7, c.i. pigment red 177, c.i. pigment red 15 pigment red and c.7 c.i. pigment red 15 pigment red (c.i. pigment red) 15, c.i. pigment red 122, c.i. pigment red 19.

One pigment may be used alone, or two or more pigments may be used.

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, further preferably more than 5% by mass and 35% by mass or less, and particularly preferably 10 to 35% by mass, based on the total mass of the photosensitive composition layer.

When the photosensitive composition layer contains a pigment other than a black pigment (for example, a white pigment, a color pigment, or the like), the content of the pigment other than the black pigment is preferably 30% by mass or less, more preferably 1 to 20% by mass, and further preferably 3 to 15% by mass, relative to the total mass of the black pigment.

When the photosensitive composition layer contains a black pigment, the black pigment (preferably, carbon black) is preferably introduced into the photosensitive composition in the form of a pigment dispersion.

The dispersion liquid may be prepared by adding a mixture obtained by mixing a black pigment and a pigment dispersant in advance to an organic solvent (or vehicle) and dispersing with a dispersing machine. The pigment dispersant may be selected according to the pigment and the solvent, and for example, a commercially available dispersant may be used.

The "vehicle" refers to a medium portion for dispersing the pigment when the pigment dispersion is prepared. The vehicle is in a liquid state and includes a binder component for holding the black pigment in a dispersed state and a solvent component (organic solvent) for dissolving and diluting the binder component.

Examples of the dispersing machine include known dispersing machines such as a kneader, a roll mill, an attritor, a super mill, a dissolver, a homomixer, and a sand mill.

Further, the fine grinding may be performed by mechanical grinding and utilizing a frictional force. Examples of the dispersing machine and the fine pulverization include a "pigment dictionary" (written by Nippon, first edition, shikoku, 2000, 438, 310).

(other additives)

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

Examples of the additives include radical polymerization inhibitors, antioxidants (e.g., phenidone), rust inhibitors (e.g., benzotriazoles and carboxybenzotriazoles), sensitizers, surfactants, plasticizers, heterocyclic compounds (e.g., triazole), pyridines (e.g., isonicotinamide), and purine bases (e.g., adenine).

Examples of the other additives include metal oxide particles, a chain transfer agent, an antioxidant, a dispersant, an acid amplifier, a development accelerator, conductive fibers, an ultraviolet absorber, a thickener, a crosslinking agent, an organic or inorganic anti-settling agent, and paragraphs [0165] to [0184] of jp 2014-085643 a, which are incorporated herein.

Each additive may be used alone or in combination of two or more.

The photosensitive composition layer may contain a radical polymerization inhibitor.

Examples of the radical polymerization inhibitor include thermal polymerization inhibitors described in paragraph [0018] of Japanese patent No. 4502784. Among them, phenothiazine, phenoxazine or 4-methoxyphenol is preferable. Examples of the other radical polymerization inhibitors include naphthylamine, cuprous chloride, nitrosophenylhydroxylamine aluminum salt, and diphenylnitrosamine. The nitrosophenylhydroxylamine aluminum salt is preferably used as a radical polymerization inhibitor in order not to impair the sensitivity of the photosensitive composition layer.

The content of the radical polymerization inhibitor is preferably 0.005 to 5.0% by mass, more preferably 0.01 to 3.0% by mass, and still more preferably 0.01 to 1.0% by mass, based on the total mass of the polymerizable compounds.

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.

Examples of the carboxybenzotriazole include 4-carboxy-1,2,3-benzotriazole, 5-carboxy-1,2,3-benzotriazole, N- (N, N-di-2-ethylhexyl) aminomethylene carboxybenzotriazole, N- (N, N-di-2-hydroxyethyl) aminomethylene carboxybenzotriazole and N- (N, N-di-2-ethylhexyl) aminoethylene carboxybenzotriazole. As the carboxybenzotriazole, for example, a commercially available product such as CBT-1 (johaku CHEMICAL co., ltd., trade name) can be used.

The total content of the benzotriazole and carboxybenzotriazole is preferably 0.01 to 3% by mass, more preferably 0.05 to 1% by mass, based on 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, the maintenance of sensitivity and the inhibition 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. Examples of the sensitizer include dialkylaminobenzophenone compounds, pyrazoline compounds, anthracene compounds, coumarin compounds, xanthenone (xanthone) compounds, thioxanthone (thioxanthone) compounds, acridone compounds, oxazole compounds, benzoxazole compounds, thiazole compounds, benzothiazole compounds, triazole compounds (for example, 1,2,4-triazole), stilbene compounds, triazine compounds, thiophene compounds, naphthalimide compounds, triarylamine compounds, and aminoacridine compounds.

One or more kinds of the sensitizer may be used alone.

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

Examples of the surfactant include surfactants described in paragraphs [0017] of Japanese patent No. 4502784 and paragraphs [0060] to [0071] of Japanese patent application No. 2009-237362.

The surfactant is preferably a nonionic surfactant, a fluorine surfactant, or a silicone surfactant.

As a commercially available product of the fluorine-based surfactant, examples thereof include MEGAFACE 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, MFS-578, MFS-579, MFS-586, MFS-587, R-41-LM, R-01, R-40-LM, RS-43, TF-DIC-1956, TF-90, R-94, ZRS-72-3425 (3421) or more, and more than 3421 Fluorad FC430, FC431, FC171 (manufactured by Sumitomo 3M Limited above), surflon S-382, SC-101, SC-103, SC-104, SC-105, SC-1068, SC-381, SC-383, S-393, KH-40 (manufactured by AGC Inc. above), polyFox PF636, PF656, PF6320, PF6520, PF7002 (manufactured by OMNOVA Solutions Inc. above), ftergent 710FL, 710FM, 610FM, 601 FM, AD 601ADH2, 602A, 215M, 245F, 251, 212M, 250, 209F, 222F, 208G, 710LA, FS, 730LM, 650AC, 681, 683 Corporation (manufactured by Neos Corporation) and the like.

Further, the fluorine-based surfactant can also preferably use an acrylic compound which has a molecular structure containing a functional group containing a fluorine atom, and in which a functional group portion containing a fluorine atom is cleaved when heat is applied, and the fluorine atom is volatilized. Examples of such fluorine-based surfactants include MEGAFACE DS series (chemical industry journal (2016, 2, 22 days), and sunrise industry news (2016, 2, 23 days)), such as MEGAFACE DS-21, manufactured by DIC Corporation.

Further, as the fluorine-based surfactant, 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 is also preferably used.

Further, as the fluorine-based surfactant, a terminal-capped polymer can also be used.

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

Further, as the fluorine-based surfactant, a fluorine-containing polymer having a group having an ethylenically unsaturated bond in a side chain can also be used. Examples thereof include MEGAFACE RS-101, RS-102, RS-718K, RS-72-K (manufactured by DIC Corporation).

From the viewpoint of improving environmental compatibility, preferred fluorine-based surfactants are surfactants derived from alternative materials to compounds having a linear perfluoroalkyl group having 7 or more carbon atoms, such as perfluorooctanoic acid (PFOA) and perfluorooctanesulfonic acid (PFOS).

Examples of the nonionic surfactant include glycerin, trimethylolpropane, trimethylolethane, and ethoxylates and propoxylates thereof (e.g., glycerin propoxylate, glycerin ethoxylate), 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, pluronic (registered trademark) L10, L31, L61, L62, 10R5, 17R2, 25R2 (manufactured by BASF), tetronic 304, 701, 704, 901, 904, 150R1 (manufactured by BASF), solsperse 20000 (manufactured by Lubrizol Japan company, inc.), NCW-101, NCW-1001, NCW-1002 (manufactured by jifilm Corporation, llc dump Corporation, pion D-6112, D-6112-8978, and Chemical Corporation, and Chemical co 1010, and Chemical co 104 manufactured by takeco 104, and Chemical co 104.

Examples of the silicone surfactant include linear polymers composed of siloxane bonds and modified siloxane polymers having organic groups introduced into side chains or terminals thereof.

Specific examples of Silicone surfactants include DOWNSIL 8032ADDITIVE, toray Silicone DC3PA, toray Silicone SH7PA, toray Silicone DC11PA, toray Silicone SH21PA, toray Silicone SH28PA, toray Silicone SH29PA, toray Silicone SH30PA, toray Silicone SH8400 (manufactured by Dow Corning Toray Silicone Co., ltd.), X-22-4952, X-22-4272, X-22-6266, KF-351-A, K52354L, KF-355 zxft 63-945, KF-640, KF-642, KF-44444444642, X-22-6191, X-22-4515, KF-6004, cheKP-BYb 341, KF-6001, KF-6002 TSTSTSTSTSTSTS44643 (manufactured by TSTSTSTSTSTSF 4427, etsu 44444460, and KF-44444444444460 (manufactured by Moformin KF-44323, KF-4440, KF-4444323, KF-444460, and/or more than or KF-351, BYX-351, KF, BYX-351, BYX-3236, TSF, and so as manufactured by.

One kind of surfactant may be used alone, or two or more kinds may be used in combination.

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 still more preferably 0.05 to 0.80% by mass, based on the total mass of the photosensitive composition layer.

From the viewpoint of improving reliability and laminatability, the content of water in the photosensitive composition layer is preferably 0.01 to 1.0 mass%, more preferably 0.05 to 0.5 mass%, based on the total mass of the photosensitive composition layer.

The layer thickness (film thickness) of the photosensitive composition layer is generally 0.1 to 300. Mu.m, preferably 0.2 to 100. Mu.m, more preferably 0.5 to 50 μm, still more preferably 0.5 to 15 μm, particularly preferably 0.5 to 10 μm, most preferably 0.5 to 8 μm. This improves the developability of the photosensitive composition layer, and can improve the resolution.

In one embodiment, the thickness is preferably 0.5 to 5 μm, more preferably 0.5 to 4 μm, and still more preferably 0.5 to 3 μm.

(impurities, etc.)

The photosensitive composition layer sometimes contains impurities.

Examples of the impurities include metal impurities or ions thereof, halide ions, residual organic solvents, residual monomers, and water.

Examples of the metal impurities include sodium, potassium, magnesium, calcium, iron, manganese, copper, aluminum, titanium, chromium, cobalt, nickel, zinc, tin, and ions thereof, and halide ions.

Among them, from the viewpoint of easy incorporation, sodium ions, potassium ions, and halide ions are preferably contained in the following amounts.

The metal impurities are compounds different from the particles (for example, metal oxide particles) that can be contained in the transfer film.

The content of the metal impurities is preferably 80 mass ppm or less, more preferably 10 mass ppm or less, and further preferably 2 mass ppm or less, with respect to the total mass of the photosensitive composition layer. The lower limit is preferably 1 mass ppb or more, more preferably 0.1 mass ppm or more, with respect to the total mass of the photosensitive composition layer.

Examples of the method for adjusting the content of the impurity include a method of selecting a raw material having a small content of the impurity as a raw material of the photosensitive composition layer, a method of preventing the impurity from being mixed in when the photosensitive composition layer is formed, and a method of cleaning and removing the impurity.

The content of the impurities can be quantified by a known method such as ICP emission spectrometry, atomic absorption spectrometry, or ion chromatography.

Examples of the residual organic solvent include benzene, formaldehyde, trichloroethylene, 1,3-butadiene, carbon tetrachloride, chloroform, N-dimethylformamide, N-dimethylacetamide, and hexane.

The content of the residual organic solvent is preferably 100 mass ppm or less, more preferably 20 mass ppm or less, and further preferably 4 mass ppm or less, with respect to the total mass of the photosensitive composition layer. The lower limit is preferably 10 ppb by mass or more, more preferably 100 ppb by mass or more, with respect to the total mass of the photosensitive composition layer.

As a method for adjusting the content of the residual organic solvent, a method for adjusting drying conditions in a transfer film production method described later can be given. The content of the residual organic solvent can be quantified by a known method such as gas chromatography.

[ intermediate layer ]

The transfer film may have an intermediate layer between the temporary support and the photosensitive composition layer.

Examples of the intermediate layer include a water-soluble resin layer and an oxygen barrier layer having an oxygen barrier function described as a "separation layer" in japanese patent laid-open No. 5-072724.

The intermediate layer is preferably an oxygen barrier layer, and more preferably an oxygen barrier layer which exhibits low oxygen permeability and is dispersed or dissolved in water or an aqueous alkaline solution (1 mass% aqueous solution of sodium carbonate at 22 ℃), from the viewpoint of improving productivity by improving sensitivity at the time of exposure and reducing the time load of the exposure machine.

Hereinafter, each component that the intermediate layer may contain will be described.

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

The water-soluble resin layer (intermediate layer) contains a resin.

The resin preferably contains a water-soluble resin as a part or all thereof.

Examples of the resin that can be used as the water-soluble resin include polyvinyl alcohol-based resins, polyvinyl pyrrolidone-based resins, cellulose-based resins, acrylamide-based resins, polyethylene oxide-based resins, gelatin, vinyl ether-based resins, polyamide resins, and copolymers thereof.

Further, as the water-soluble resin, a copolymer of (meth) acrylic acid/vinyl compound, or the like can also be used. As the copolymer of (meth) acrylic acid/vinyl compound, a copolymer of (meth) acrylic acid/(meth) allyl 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 (% by mole) is, for example, preferably 90/10 to 20/80, 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 still more preferably 10,000 or more. The upper limit value is preferably 200,000 or less, more preferably 100,000 or less, and still more preferably 50,000 or less.

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

One kind of the water-soluble resin may be used alone, or two or more kinds thereof may be used.

The content of the water-soluble resin is not particularly limited, but is preferably 50 mass% or more, more preferably 70 mass% or more, further preferably 80 mass% or more, and particularly preferably 90 mass% or more, with respect to the total mass of the water-soluble resin layer (intermediate layer), from the viewpoint of further improving the oxygen barrier property and the interlayer mixing suppression ability. The upper limit is not particularly limited, but is preferably 99.9% by mass or less, and more preferably 99.8% by mass or less.

The intermediate layer may contain other components in addition to the above-described water-soluble resin.

As the other component, a polyhydric alcohol, an alkylene oxide adduct of a polyhydric alcohol, a phenol derivative, or an amide compound is preferable, and a polyhydric alcohol, a phenol derivative, or an amide compound is more preferable.

Further, as other components, for example, a known surfactant can be cited.

Examples of the polyhydric alcohols include glycerin, diglycerin, and diethylene glycol.

The number of hydroxyl groups in the polyhydric alcohol is preferably 2 to 10.

Examples of the alkylene oxide adduct of a polyhydric alcohol include compounds obtained by adding an ethyleneoxy group, a propyleneoxy group, or the like to the polyhydric alcohol.

The average addition number of alkyleneoxy groups is preferably 1 to 100, more preferably 2 to 50, and still more preferably 2 to 20.

Examples of the phenol derivative include bisphenol a and bisphenol S.

Examples of the amide compound include N-methylpyrrolidone.

The intermediate layer preferably contains at least one selected from the group consisting of water-soluble cellulose derivatives, polyhydric alcohols, oxide adducts of polyhydric alcohols, polyether resins, phenol derivatives, and amide compounds.

The molecular weight of the other component is preferably less than 5,000, more preferably 4,000 or less, further preferably 3,000 or less, particularly preferably 2,000 or less, and most preferably 1,500 or less. The lower limit is preferably 60 or more.

One or more of the other components may be used alone.

The content of the other component is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and further preferably 1% by mass or more, based on the total mass of the intermediate layer. The upper limit is preferably less than 30% by mass, more preferably 10% by mass or less, and further preferably 5% by mass or less.

The intermediate layer may contain impurities.

Examples of the impurities include impurities contained in the photosensitive composition layer.

The thickness of the water-soluble resin layer (intermediate layer) is not particularly limited, but is preferably 0.1 to 5 μm, more preferably 0.5 to 3 μm. When the thickness of the water-soluble resin layer (intermediate layer) is within the above range, the interlayer mixing suppression capability is excellent without lowering the oxygen barrier property. In addition, the increase in the time for removing the water-soluble resin layer (intermediate layer) during development can be further suppressed.

[ protective film ]

The transfer film may have a protective film on the photosensitive composition layer.

As the protective film, a resin film having heat resistance and solvent resistance can be used, and examples thereof include polyolefin films such as polypropylene films and polyethylene films, polyester films such as polyethylene terephthalate films, polycarbonate films, and polystyrene films.

As the protective film, a resin film made of the same material as the temporary support may be used.

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

The thickness of the protective film is preferably 1 to 100. Mu.m, more preferably 5 to 50 μm, still more preferably 5 to 40 μm, and particularly preferably 15 to 30 μm.

The thickness of the protective film is preferably 1 μm or more from the viewpoint of excellent mechanical strength, and preferably 100 μm or less from the viewpoint of relative low cost.

In the protective film, the number of fish eyes (fishery) having a diameter of 80 μm or more contained in the protective film is preferably 5/m ² The following.

The term "fish eyes" refers to a phenomenon in which foreign matter, undissolved matter, oxidized and degraded matter, etc. of a material are taken into a film when the material is melted, kneaded, extruded, and the film is produced by a method such as biaxial stretching or casting.

The number of particles having a diameter of 3 μm or more contained in the protective film is preferably 30 particles/mm ² Hereinafter, more preferably 10 pieces/mm ² Hereinafter, more preferably 5 pieces/mm ² The following.

This can suppress defects caused by transfer of the unevenness caused by the particles contained in the protective film to the photosensitive composition layer or the conductive layer.

From the viewpoint of imparting windability, the arithmetic average roughness Ra of the surface of the protective film on the side opposite to the side in contact with the photosensitive composition layer is preferably 0.01 μm or more, more preferably 0.02 μm or more, and still more preferably 0.03 μm or more. On the other hand, it is preferably smaller than 0.50. Mu.m, more preferably 0.40 μm or smaller, and still more preferably 0.30 μm or smaller.

From the viewpoint of suppressing defects at the time of transfer, the surface roughness Ra of the surface of the protective film in contact with the photosensitive composition layer is preferably 0.01 μm or more, more preferably 0.02 μm or more, and still more preferably 0.03 μm or more. On the other hand, it is preferably less than 0.50. Mu.m, more preferably 0.40 μm or less, and further preferably 0.30 μm or less.

[ method for producing transfer film ]

The method for producing the transfer film is not particularly limited, and known methods can be used.

Examples of the method for producing the transfer film 10 include a method including the steps of: a step of applying the intermediate layer-forming composition to the surface of the temporary support 11 to form a coating film, and further drying the coating film to form the intermediate layer 13; and a step of applying a photosensitive composition to the surface of the intermediate layer 13 to form a coating film, and further drying the coating film to form the photosensitive composition layer 15.

When the transfer film 10 has the protective film 19, the protective film 19 may be pressure-bonded to the composition layer 17 of the transfer film 10 manufactured by the above-described manufacturing method.

As a method for producing the transfer film 10, it is preferable to produce the transfer film 10 including the temporary support 11, the intermediate layer 13, the photosensitive composition layer 15, and the protective film 19 by including a step of providing the protective film 19 so as to be in contact with a surface of the composition layer 17 on the side opposite to the temporary support 11 side.

After the transfer film 10 is manufactured by the above-described manufacturing method, the transfer film 10 can be wound to manufacture and store a roll-shaped transfer film. The transfer film 10 in the roll form can be supplied as it is to a step of bonding the substrate in a roll-to-roll manner, which will be described later.

The transfer film 10 may be produced by forming the composition layer 17 on the protective film 19.

(Water-soluble resin composition and method for Forming intermediate layer (Water-soluble resin layer))

The water-soluble resin composition preferably contains various components and solvents for forming the intermediate layer (water-soluble resin layer). In the water-soluble resin composition, the preferable range of the content of each component with respect to the total solid content of the composition is the same as the preferable range of the content of each component with respect to the total mass of the water-soluble resin layer.

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

Examples of the water-miscible organic solvent include alcohols having 1 to 3 carbon atoms, acetone, ethylene glycol and glycerol, preferably alcohols having 1 to 3 carbon atoms, and more preferably methanol or ethanol.

One solvent may be used alone, or two or more solvents 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 for 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-mentioned components, and examples thereof include known coating methods (slit coating, spin coating, curtain coating, inkjet coating, and the like).

(photosensitive composition and method for Forming photosensitive composition layer)

From the viewpoint of excellent productivity, it is preferable to form the photosensitive layer by a coating method using a photosensitive composition containing a component (for example, a binder polymer, a polymerizable compound, a polymerization initiator, and the like) constituting the photosensitive composition layer and a solvent.

Specifically, a method of forming a photosensitive composition layer by applying a photosensitive composition to an intermediate layer to form a coating film and drying the coating film at a predetermined temperature is preferable as a method of producing a transfer film.

The photosensitive composition preferably contains various components for forming the photosensitive composition layer and a solvent. In the photosensitive composition, the preferable range of the content of each component with respect to the total solid content of the composition is the same as the preferable range of the content of each component with respect to the total mass of the photosensitive composition layer.

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. Specific examples thereof include alkylene glycol ether solvents, alkylene glycol ether acetate solvents, alcohol solvents (methanol, ethanol, and the like), ketone solvents (acetone, methyl ethyl ketone, and the like), aromatic hydrocarbon solvents (toluene, and the like), aprotic polar solvents (N, N-dimethylformamide, and the like), cyclic ether solvents (tetrahydrofuran, and the like), ester solvents (N-propyl acetate, and the like), amide solvents, lactone solvents, and mixed solvents containing two or more of these solvents.

The solvent preferably contains at least one selected from the group consisting of an alkylene glycol ether solvent and an alkylene glycol ether acetate solvent. Among these, a mixed solvent containing at least one selected from the group consisting of an alkylene glycol ether solvent and an alkylene glycol ether acetate solvent and at least one selected from the group consisting of a ketone solvent and a cyclic ether solvent is more preferable, and a mixed solvent containing at least 3 of an alkylene glycol ether, an alkylene glycol ether acetate solvent, and a ketone solvent is further preferable.

Examples of the alkylene glycol ether solvent 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 the alkylene glycol ether acetate solvent include ethylene glycol monoalkyl ether acetate, propylene glycol monoalkyl ether acetate, diethylene glycol monoalkyl ether acetate, and dipropylene glycol monoalkyl ether acetate.

Examples of the ketone solvent include acetone, methyl ethyl ketone, methyl isobutyl ketone, 2-heptanone, and cyclohexanone.

As the solvent, a solvent described in paragraphs [0092] to [0094] of international publication nos. 2018/179640 and a solvent described in paragraph [0014] of japanese patent application laid-open No. 2018-177889 can be used, and these contents are incorporated in the present specification.

One solvent may be used alone, or two or more solvents may be used.

The content of the solvent is preferably 50 to 1,900 parts by mass, more preferably 100 to 1200 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 the method of applying the photosensitive composition include a printing method, a spray coating method, a roll coating method, a bar coating method, a curtain coating method, a spin coating method, and a die coating method (that is, a slit coating method).

As a method for drying the coating film of the photosensitive composition, heating drying and drying under reduced pressure are preferable.

The drying temperature is preferably 90 ℃ or higher, more preferably 100 ℃ or higher, and still more preferably 110 ℃ or higher. The upper limit is not particularly limited, but is preferably 130 ℃ or lower, more preferably 120 ℃ or lower.

The drying time is preferably 20 seconds or more, more preferably 40 seconds or more, and still more preferably 60 seconds or more. The upper limit value is not particularly limited, but is preferably 450 seconds or less, and more preferably 300 seconds or less. The drying temperature is preferably 80 ℃ or higher, more preferably 90 ℃ or higher. The upper limit thereof is preferably 130 ℃ or lower, more preferably 120 ℃ or lower. Drying can also be performed by continuously changing the temperature.

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

Further, the transfer film can be manufactured by bonding a protective film to the photosensitive composition layer.

The method for bonding the protective film to the photosensitive composition layer is not particularly limited, and known methods can be exemplified.

Examples of the device for bonding the protective film to the photosensitive composition layer include known laminating machines such as a vacuum laminating machine and an automatic cutting laminating machine.

The laminator is preferably provided with an optional heatable roller such as a rubber roller and can be pressurized and heated.

[ method for producing laminate having conductor Pattern ]

By using the transfer film, a laminate having a conductor pattern can be manufactured.

The method for producing the laminate having a conductor pattern is not particularly limited as long as it is a method for producing the laminate having a conductor pattern using the transfer film.

Among them, the method for producing a laminate having a conductor pattern according to the present invention is preferably a method for producing a laminate having a conductor pattern, the method including:

a bonding step of bonding the transfer film to the substrate so that the photosensitive composition layer side of the transfer film is in contact with the conductive layer of the substrate having the conductive layer on the surface thereof;

an exposure step of exposing the photosensitive composition layer;

a step of performing either an etching process for etching the conductive layer located in the region where the resist pattern is not disposed or a plating process for plating the conductive layer; and

a resist pattern stripping step of stripping the resist pattern,

when the plating process step is provided, a removing step of removing the conductive layer exposed in the resist pattern stripping step and forming a conductive pattern on the substrate,

a temporary support stripping step of stripping the temporary support is also provided between the bonding step and the exposure step or between the exposure step and the development step.

Hereinafter, specific steps of the method for manufacturing a laminate having a conductor pattern will be described.

(bonding step)

The bonding step is a step of bonding the surface of the transfer film on the opposite side to the temporary support with the substrate having the conductive layer in contact therewith to obtain a substrate with a photosensitive composition layer, which has the substrate, the conductive layer, the photosensitive composition layer, and the temporary support in this order.

In addition, when the transfer film has a structure having a protective film, the protective film is peeled off and then the bonding step is performed.

In the above bonding, it is preferable that the photosensitive composition layer side (the surface opposite to the temporary support side) of the transfer film is brought into contact with the conductive layer on the substrate and pressure-bonded.

The method of pressure bonding is not particularly limited, and a known transfer method and lamination method can be used. Among them, it is preferable to laminate the surface of the photosensitive composition layer on a substrate having a conductive portion and to apply pressure and heat by a roller or the like.

For bonding, a known laminator such as a vacuum laminator and an automatic cutting laminator can be used.

The lamination temperature is not particularly limited, and is preferably 70 to 130 ℃.

A substrate having a conductive layer on a surface thereof (a substrate with a conductive layer) includes a substrate and a conductive layer disposed on a surface of the substrate.

The substrate with a conductive layer may have any layer other than the conductive layer formed thereon as necessary. That is, the substrate with a conductive layer preferably has at least a substrate and a conductive layer disposed on a surface of the substrate.

Examples of the substrate include a resin substrate, a glass substrate, a ceramic substrate, and a semiconductor substrate, and the substrate described in paragraph [0140] of international publication No. 2018/155193 is preferable.

As a material of the resin substrate, polyethylene terephthalate, cycloolefin polymer, or polyimide is preferable.

The thickness of the resin substrate is preferably 5 to 200. Mu.m, more preferably 10 to 100. Mu.m.

The conductive layer is preferably at least one layer selected from a metal layer, a conductive metal oxide layer, a graphite layer, a carbon nanotube layer, and a conductive polymer layer, from the viewpoint of conductivity and thin line formability.

Further, only 1 conductive layer may be disposed on the substrate, or 2 or more conductive layers may be disposed on the substrate. When 2 or more conductive layers are arranged, conductive layers having different materials are preferable.

A preferred embodiment of the conductive layer is described in, for example, paragraph [0141] of international publication No. 2018/155193, the contents of which are incorporated herein.

The conductive layer is preferably a metal layer.

The metal layer is a layer containing a metal, and the metal is not particularly limited, and a known metal can be used. The metal layer is preferably a conductive layer.

Examples of the main component (so-called main metal) of the metal layer include copper, chromium, lead, nickel, gold, silver, tin, and zinc. The "main component" refers to the metal contained in the metal layer in the largest amount.

The method of forming the metal layer is not particularly limited, and examples thereof include a method of coating a dispersion in which metal fine particles are dispersed and sintering the coating film, and known methods such as a sputtering method and a vapor deposition method.

The thickness of the metal layer is not particularly limited, but is preferably 50nm or more, more preferably 100nm or more. The upper limit is preferably 2 μm or less.

1 or 2 or more metal layers may be disposed on the substrate.

When 2 or more metal layers are disposed, the 2 or more metal layers may be the same or different from each other, and preferably, metal layers of different materials are disposed.

The substrate having a conductive layer may be a substrate having at least one of a transparent electrode and a wiring. The substrate described above can be preferably used as a substrate for a touch panel.

The transparent electrode can preferably function as an electrode for a touch panel.

The transparent electrode is preferably formed of a metal oxide film such as ITO (indium tin oxide) or IZO (indium zinc oxide), and a thin metal wire such as a metal mesh or a metal nanowire.

Examples of the thin metal wires include silver, copper, and the like. Among them, silver conductive materials such as silver mesh and silver nanowire are preferable.

As a material for the wiring, metal is preferable.

Examples of the metal as a material of the interconnection include gold, silver, copper, molybdenum, aluminum, titanium, chromium, zinc, and manganese, and an alloy of two or more of these metal elements. As a material for the wiring, copper, molybdenum, aluminum, or titanium is preferable, and copper is particularly preferable.

(Exposure Process)

The exposure step is a step of exposing the photosensitive composition layer, and is preferably a step of performing pattern exposure.

The "pattern exposure" is a pattern-like exposure method, and refers to exposure in which an exposed portion and an unexposed portion are present.

The positional relationship between the exposed portion (exposed region) and the unexposed portion (unexposed region) in the pattern exposure can be appropriately adjusted. The exposure may be performed from the photosensitive composition layer side, or may be performed from the side (substrate side) opposite to the photosensitive composition layer side.

Examples of the exposure method in the exposure step include mask exposure, direct imaging exposure, and projection exposure, and mask exposure is preferable.

When a temporary support peeling step described later is performed between the bonding step and the exposure step, the exposure step is preferably an exposure step in which a surface of the laminate from which the temporary support obtained in the temporary support peeling step has been peeled, on the side opposite to the substrate side, is brought into contact with a light shield to perform pattern exposure. In other words, the exposure step of pattern-exposing the photosensitive composition layer by bringing the exposed surface of the laminate from which the temporary support has been peeled away into contact with the photomask is preferable. In addition, when the transfer film has a 3-layer structure of the temporary support, the intermediate layer, and the photosensitive composition layer, the surface of the intermediate layer corresponds to the exposed surface.

By adopting such an exposure process, a higher-definition resist pattern can be obtained, and finally a higher-definition conductor pattern can be obtained.

In particular, when a temporary support peeling step described later is performed between the bonding step and the exposure step, such an exposure step is preferably employed.

In the case where a temporary support peeling step described later is performed between the exposure step and the development step, the exposure step is preferably an exposure step in which the surface of the laminate of the substrate and the transfer film obtained in the bonding step, which is opposite to the side of the substrate having the transfer film, is brought into contact with a photomask to expose a pattern.

In the exposure step of performing pattern exposure, a curing reaction of the components contained in the photosensitive composition layer can be generated in an exposed region (region corresponding to the opening of the photomask) of the photosensitive composition layer. By performing a developing process after exposure, the non-exposed region of the photosensitive composition layer is removed to form a pattern.

The method of the present invention preferably includes a photomask removing step of removing the photomask used in the exposure step between the exposure step and the development step.

Examples of the photomask peeling step include a known peeling step.

The light source for pattern exposure may be selected and used as appropriate as long as it can irradiate light (for example, 365nm or 405 nm) in a wavelength region in which at least the photosensitive composition layer can be cured. Among them, the dominant wavelength of exposure light for pattern exposure is preferably 365nm. The dominant wavelength is a wavelength having the maximum intensity.

Examples of the light source include various lasers, light Emitting Diodes (LEDs), ultra-high pressure mercury lamps, and metal halide lamps.

The exposure amount is preferably 5 to 200mJ/cm ² More preferably 10 to 200mJ/cm ² 。

Preferable examples of the light source, the exposure amount, and the exposure method used for the exposure are described in paragraphs [0146] to [0147] of international publication No. 2018/155193, which are incorporated herein by reference.

By performing an exposure step and a development step described later, a resist pattern for protecting at least a part of the conductive layer can be formed on the conductive layer on the substrate.

(temporary support peeling step)

The temporary support peeling step is a step of peeling the temporary support from the substrate with the photosensitive composition layer between the bonding step and the exposure step or between the exposure step and a developing step 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.

(developing step)

The developing step is a step of developing the exposed photosensitive composition layer to form a resist pattern.

The photosensitive composition layer can be developed using a developer.

As the developer, an alkaline aqueous solution is preferable. Examples of the basic compound that can be contained in the basic aqueous solution include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, and choline (2-hydroxyethyltrimethylammonium hydroxide).

The liquid temperature of the developer in the development treatment is preferably 10 to 50 ℃, more preferably 15 to 40 ℃, and still more preferably 20 to 35 ℃.

The pH of the developer in the development treatment is preferably 9 or more, more preferably 10 or more, and further preferably 11 or more. The upper limit is preferably 14 or less, more preferably less than 13. The pH can be measured by a method in accordance with JIS Z8802-1984 using a known pH meter. The measurement temperature of pH was set to 25 ℃.

In the developer, the content of water is preferably 50% by mass or more and less than 100% by mass, and more preferably 90% by mass or more and less than 100% by mass, with respect to the total mass of the developer.

The content of the alkaline compound in the developer is preferably 0.01 to 20% by mass, more preferably 0.1 to 10% by mass, based on the total mass of the developer.

Examples of the development method include spin immersion development, shower development, spin development, and immersion development.

The developer preferably used in this specification includes, for example, the developer described in paragraph [0194] of international publication No. 2015/093271, and the developing method preferably used includes, for example, the developing method described in paragraph [0195] of international publication No. 2015/093271.

It is also preferable to perform a rinsing process for removing the developer remaining on the substrate with the conductive layer after the development and before the transfer to the next step. Water or the like can be used for the rinsing treatment.

After the development and/or rinsing process, a drying process may be performed to remove excess liquid from the substrate with the conductive layer.

The position and size of the resist pattern formed on the substrate with the conductive layer are not particularly limited, but a fine line shape is preferable.

Specifically, the line width of the resist pattern is preferably 20 μm or less, more preferably 15 μm or less, still more preferably 10 μm or less, and particularly preferably 5 μm or less. The lower limit is usually 1.0 μm or more.

(post-exposure step and post-baking step)

The method of the present invention may include a step of exposing the resist pattern obtained in the developing step (post-exposure step) and/or a step of heating the resist pattern (post-baking step).

When both the post-exposure step and the post-baking step are included, it is preferable to perform post-baking after the post-exposure. The exposure dose of the post-exposure is preferably 100 to 5000mJ/cm ² More preferably 200 to 3000mJ/cm ² . The temperature of the postbaking is preferably from 80 to 250 ℃ and more preferably from 90 to 160 ℃. The post-baking time is preferably 1 to 180 minutes, more preferably 10 to 60 minutes.

(etching Process)

The method for producing the laminate having the conductor pattern has an etching step or a plating step described later.

When the etching step is performed, the conductive layer is removed in the opening of the resist pattern, and the conductive layer has the same pattern shape as the resist pattern. Therefore, a laminate having a conductive pattern can be obtained by the etching step.

As a method of the etching treatment, known methods can be applied, and examples thereof include a method described in paragraphs [0209] to [0210] of japanese patent application laid-open publication No. 2017-120435, a method described in paragraphs [0048] to [0054] of japanese patent application laid-open publication No. 2010-152155, and a method of dry etching such as wet etching and plasma etching by immersing in an etching solution.

The etching solution used for wet etching may be an acidic or alkaline etching solution as appropriate depending on the object to be etched.

Examples of the acidic etching solution include an aqueous solution of an acidic component selected from hydrochloric acid, sulfuric acid, nitric acid, acetic acid, hydrofluoric acid, oxalic acid, and phosphoric acid alone, and a mixed aqueous solution of an acidic component and a salt selected from ferric chloride, ammonium fluoride, and potassium permanganate. The acidic component may be a combination of a plurality of acidic components.

Examples of the alkaline etching solution include an aqueous solution of an alkali component alone selected from sodium hydroxide, potassium hydroxide, ammonia, organic amines and salts of organic amines (e.g., tetramethylammonium hydroxide), and a mixed aqueous solution of an alkali component and a salt (e.g., potassium permanganate). The alkali component may be a combination of a plurality of alkali components.

The etching solution preferably does not dissolve the resist pattern.

The developing solution used in the developing step may also serve as an etching solution for the etching treatment. In this case, the developing step and the etching step may be performed simultaneously.

It is also preferable to perform a rinsing process for removing the etching solution remaining on the substrate with the conductive layer after the etching process and before the transfer to the next step. Water or the like can be used for the rinsing treatment.

After the etching process and/or rinsing process, a drying process may be performed to remove excess liquid from the substrate with the conductive layer.

(electroplating step)

The method for manufacturing the laminate having the conductor pattern includes the etching step or the plating step.

In addition, when the plating step is performed, a removal step described later is performed.

The electroplating process comprises the following steps; a plating layer is formed by plating on the conductive layer (the conductive layer exposed to the surface in the developing step) located in the region where the resist pattern is not arranged. When the plating step is performed, the conductive layer is preferably a metal layer.

Examples of the plating method include an electrolytic plating method and an electroless plating method, and the electrolytic plating method is preferable from the viewpoint of productivity.

When the plating step is performed, a plated layer having the same pattern shape as a region where the resist pattern is not arranged (an opening of the resist pattern) can be obtained on the substrate with the conductive layer.

Examples of the metal 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, the plating layer preferably contains copper or an alloy thereof from the viewpoint of more excellent conductivity of the conductive pattern. Further, from the viewpoint of more excellent conductivity of the conductive pattern, the plating layer preferably contains copper as a main component.

The thickness of the plating layer is preferably 0.1 μm or more, more preferably 1 μm or more. The upper limit is preferably 20 μm or less.

(protective layer Forming step)

It is also preferable to have a protective layer forming step between the plating step and a resist pattern stripping step described later.

The protective layer forming step is a step of forming a protective layer on the plating layer.

As a material of the protective layer, a material having resistance to a stripping liquid and/or an etching liquid in the resist pattern stripping step and/or the removal step is preferable. Examples thereof include metals such as nickel, chromium, tin, zinc, magnesium, gold, and silver, alloys thereof, and resins thereof, with nickel or chromium being preferred.

Examples of the method for forming the protective layer include an electroless plating method and a plating method, and the plating method is preferable.

The thickness of the protective layer is preferably 0.3 μm or more, more preferably 0.5 μm or more. The upper limit is preferably 3.0 μm or less, more preferably 2.0 μm or less.

(resist Pattern stripping Process)

In the method for producing a laminate having a conductor pattern, it is preferable to perform a step of stripping the remaining resist pattern (resist pattern stripping step).

The stripping step is not particularly limited and may be performed as needed, but is preferably performed after the etching step.

The method of removing the residual resist pattern is not particularly limited, and a method of removing by a chemical treatment may be mentioned, and a method of removing using a stripping liquid is preferred.

The removal may be performed by a known method such as spray coating, shower coating, spin coating, or the like using a stripping liquid.

Examples of the stripping solution include a solution obtained by dissolving an inorganic base component or an organic base component in water, dimethyl sulfoxide, N-methylpyrrolidone, or a mixed solution thereof. Examples of the inorganic alkali component include sodium hydroxide and potassium hydroxide. Examples of the organic base component include a primary amine compound, a secondary amine compound, a tertiary amine compound, and a quaternary ammonium salt compound. As the basic organic compound, tetramethylammonium hydroxide or an alkanolamine compound is preferable.

The stripping liquid also preferably does not dissolve the conductive layer.

As a method for removing the resist pattern, a method of immersing the substrate having the residual resist pattern in a stripping liquid while stirring at a liquid temperature of preferably 30 to 80 ℃, more preferably 50 to 80 ℃ for 1 to 30 minutes can be mentioned.

The pH of the stripping solution in the stripping treatment is preferably 11 or more, more preferably 12 or more, and still more preferably 13 or more. The upper limit is preferably 14 or less, more preferably 13.8 or less. The pH can be measured by a method in accordance with JIS Z8802-1984 using a known pH meter. The measurement temperature of pH was set to 25 ℃.

The liquid temperature of the stripping liquid when the stripping treatment is performed is preferably higher than the liquid temperature of the developing liquid when the developing treatment is performed. Specifically, the value obtained by subtracting the liquid temperature of the developing solution from the liquid temperature of the stripping solution (the liquid temperature of the stripping solution — the liquid temperature of the developing solution) is preferably 10 ℃ or higher, and more preferably 20 ℃ or higher. The upper limit is preferably 100 ℃ or lower, more preferably 80 ℃ or lower.

The pH of the stripping solution when the stripping treatment is performed is preferably higher than the pH of the developing solution when the developing treatment is performed. Specifically, the value obtained by subtracting the pH of the developing solution from the pH of the stripping solution (the pH of the stripping solution — the pH of the developing solution) is preferably 1 or more, and more preferably 1.5 or more. The upper limit is preferably 5 or less, more preferably 4 or less.

It is also preferable to perform a rinsing process for removing the stripping liquid remaining on the substrate after the resist pattern is stripped by the stripping liquid. Water or the like can be used for the rinsing treatment.

After the stripping and/or rinsing treatment of the resist pattern by the stripping liquid, a drying treatment for removing an excess liquid from the substrate may be performed.

(removal step)

In the method for manufacturing a laminate having a conductor pattern, the plating step is performed, and the removing step is performed.

The removing step is a step of removing the conductive layer exposed in the resist pattern stripping step to obtain a conductor pattern on the substrate.

In the removing step, etching treatment of the conductive layer located in the non-pattern-formed region (in other words, the region not protected by the plating layer) is performed using the plating layer formed in the plating step as an etching resist.

The method for removing a part of the conductive layer is not particularly limited, and a known etching solution is preferably used.

Examples of known etching solutions include ferric chloride solution, cupric chloride solution, ammonia-soda solution, sulfuric acid-hydrogen peroxide mixed solution, phosphoric acid-hydrogen peroxide mixed solution, and the like.

When the removing step is performed, the conductive layer exposed on the surface is removed from the substrate, and the plating layer (conductor pattern) having the pattern shape remains, whereby a laminated body having the conductor pattern can be obtained.

The upper limit of the line width of the conductor pattern to be formed 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 steps)

The method for producing the laminate having the conductor pattern may include any process (other process) other than the above-described process.

Examples of the step include, but are not limited to, the step of reducing the visible light reflectance described in paragraph [0172] of international publication No. 2019/022089, and the step of forming a new conductive layer on an insulating film described in paragraph [0172] of international publication No. 2019/022089.

A step of reducing the reflectance of visible rays

The method for manufacturing a laminate having a conductor pattern may include a step of performing a treatment for reducing the visible light reflectance of part or all of the plurality of conductive layers included in the base material.

As the treatment for reducing the visible light reflectance, an oxidation treatment may be mentioned. When the base material has a metal layer containing copper, the visible light reflectance of the metal layer can be reduced by oxidizing the copper to be copper oxide and blackening the metal layer.

The treatment for reducing the reflectance of visible light 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, and the contents of these publications are incorporated in the present specification.

A step of forming an insulating film, a step of forming a new conductive layer on the surface of the insulating film-

The method for producing a laminate having a conductor pattern preferably includes a step of forming an insulating film on the surface of the circuit wiring and a step of forming a new conductive layer on the surface of the insulating film.

Through the above steps, the second electrode pattern insulated from the first electrode pattern can be formed.

The step of forming the insulating film is not particularly limited, and a known method of forming a permanent film may be used. Further, an insulating film having a desired pattern may be formed by photolithography using an insulating photosensitive material.

The step of forming a new conductive layer on the insulating film is not particularly limited, and a new conductive layer having a desired pattern can be formed by photolithography using a photosensitive material having conductivity.

In the method for manufacturing a laminate having a conductor pattern, it is also preferable to use a substrate having a plurality of conductive layers on both surfaces of a base material, and to form a circuit in the conductive layers formed on both surfaces of the base material sequentially or simultaneously. With this configuration, it is possible to form a circuit wiring for a touch panel in which the first conductive pattern is formed on one surface of the base material and the second conductive pattern is formed on the other surface. Further, it is also preferable that the circuit wiring for a touch panel having such a configuration is formed from 2 surfaces of the base material in a roll-to-roll manner.

[ use of laminate having conductor Pattern ]

The method for manufacturing a laminate having a conductor pattern can be applied to the manufacture of conductive films such as touch panels, transparent heaters, transparent antennas, electromagnetic shielding materials, and light control films; manufacturing a printed circuit board and a semiconductor package; manufacturing a column and a pin for interconnection between semiconductor chips or packages; manufacturing a metal mask; and manufacturing Tape substrates such as COF (Chip on Film) and TAB (Tape Automated Bonding).

The touch panel may be a capacitance type touch panel. The method for manufacturing a laminate according to the present invention can be used for forming a conductive film or a peripheral circuit wiring in a touch panel. The touch panel can be applied to, for example, a display device such as an organic EL (electro-luminescence) display device or a liquid crystal display device.

< embodiment 2 >

Embodiment 2 of the transfer film of the present invention includes: a temporary support; and a photosensitive composition layer containing an alkali-soluble polymer containing a structural unit having a carboxyl group, a polymerizable compound, a polymerization initiator, and a compound having an acid group exhibiting a pKa higher than that of the carboxyl group and lower than 14 (hereinafter, also simply referred to as "compound B"), wherein the content of the compound B is 3 to 50% by mass relative to the total mass of the photosensitive composition layer, and the acid value of the alkali-soluble polymer derived from the carboxyl group is 80mgKOH/g or more.

Embodiment 2 of the transfer film of the present invention can form a resist pattern having excellent resolution and no curl, and can easily peel off the resist pattern, as in embodiment 1. The mechanism is not necessarily clear, but the present inventors speculate as follows.

In embodiment 2 of the transfer film of the present invention, a resist pattern having excellent resolution and no curl can be formed by the acid value derived from the carboxyl group being 80mgKOH/g or more. Further, by containing the compound B, a resist pattern having no curling can be formed and the resist pattern can be easily peeled off. In particular, when the developing solution used for forming the resist pattern is different from the stripping solution used for stripping the resist pattern, the resist pattern having no curl is easily formed, and the resist pattern is easily stripped.

Hereinafter, embodiment 2 of the transfer film of the present invention will be described.

The configuration of embodiment 2 of the transfer film other than the photosensitive composition layer is the same as embodiment 1, and the preferred embodiment is also the same, and therefore, the description thereof is omitted. Further, the method for manufacturing the transfer film and the method for manufacturing the laminate having the conductor pattern using the transfer film are also the same as those in embodiment 1, and therefore, the description thereof is omitted.

[ photosensitive composition layer ]

As in embodiment 1, the photosensitive composition layer of embodiment 2 is preferably a negative photosensitive composition layer.

The photosensitive composition layer of embodiment 2 includes a resin, a polymerizable compound, a polymerization initiator, and a compound B, and the resin contains an alkali-soluble polymer including a structural unit having a carboxyl group.

Such a photosensitive composition layer preferably contains a resin based on the total mass of the photosensitive composition layer: 10 to 90 mass percent; a polymerizable compound: 5 to 70 percent by mass; polymerization initiator: 0.01 to 20 mass%; compound B:3 to 50 mass%.

Hereinafter, the respective components will be described in order. The components other than the resin and the compound B are the same as those in embodiment 1, and therefore, the description thereof is omitted.

(Polymer A)

The polymer A contains an alkali-soluble polymer containing a structural unit having a carboxyl group.

As described above, in embodiment 2, the acid value of the alkali-soluble polymer derived from the carboxyl group is 80mgKOH/g or more.

The acid value derived from the above carboxyl group is preferably from 80 to 250mgKOH/g, more preferably from 90 to 200mgKOH/g, and still more preferably from 100 to 180mgKOH/g.

Structural units having carboxyl groups-

The alkali-soluble polymer contains a structural unit having a carboxyl group.

The structural unit having a carboxyl group is the same as the structural unit a described in embodiment 1, and therefore, description thereof is omitted.

Structural unit B-

The alkali-soluble polymer may include a structural unit B having an acid group exhibiting a pKa higher than that of a carboxyl group and a pKa lower than 14.

The structural unit B is the same as that described in embodiment 1, and therefore, description thereof is omitted.

Structural units derived from monomers having aromatic hydrocarbon groups

The alkali-soluble polymer preferably contains a structural unit derived from a monomer having an aromatic hydrocarbon group. The structural units derived from the monomer having an aromatic hydrocarbon group are the same as those described in embodiment 1, and therefore, the description thereof is omitted.

-non-acidic structural units-

The alkali-soluble polymer may comprise a non-acidic structural unit based on a monomer that is non-acidic and has at least 1 polymerizable unsaturated group in the molecule. The nonacidic structural units are the same as those described in embodiment 1, and therefore, description thereof is omitted.

The content of the alkali-soluble polymer is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, further preferably 30 to 70% by mass, and particularly preferably 40 to 60% by mass, based on the total mass of the negative photosensitive composition layer. From the viewpoint of controlling the development time, the content of the alkali-soluble polymer is preferably 90% by mass or less. On the other hand, from the viewpoint of improving the edge melting resistance, the content of the alkali-soluble polymer is preferably 10% by mass or more.

The photosensitive composition layer may contain other resins than the above.

(Compound B)

The photosensitive composition layer contains a compound (compound B) having an acid group exhibiting a pKa higher than that of the carboxyl group and a pKa lower than 14.

The pKa of the acid group contained in the compound B is not particularly limited as long as it is higher than the pKa of the carboxyl group and lower than 14, but is preferably 6 or more and lower than 14, more preferably 7 to 12, further preferably 8 to 12, and particularly preferably 9 to 12, from the viewpoint of further excellent effects of the present invention.

The compound B is not particularly limited as long as the pKa of the acid group of the compound B is higher than the pKa of the carboxyl group and lower than 14, but from the viewpoint of further improving the effect of the present invention, the compound B preferably has 1 or more groups selected from a phenol group, an active methylene group, a sulfonamide group, an imide group, and a hydroxyimide group, and more preferably has 1 or more groups selected from a phenol group, an active methylene group, and an imide group. In addition, the active methylene group means a methylene group (-CH) to which 2 electron withdrawing groups are bonded ₂ -)。

The number of the acid groups in the compound B may be 1 or more, but the number of the acid groups is preferably 2 or more from the viewpoint of further improving the effect of the present invention.

The compound B may be a polymer containing a structural unit having the acid group, and is preferably a polymer containing a structural unit having the acid group. When the compound B is a polymer, the compound B is preferably a polymer containing no structural unit having a carboxyl group.

Examples of the non-polymer compound B include compounds having a phenol group such as phenol, cresol, dibutylhydroxytoluene, and bisphenol; compounds having an active methylene group such as acetoacetates, oxaloacetates, and acetonedicarboxylates; sulfonamide group-containing compounds such as benzenesulfonamide, N-methylmethanesulfonamide and N-butyl-p-toluenesulfonamide, and imide group-containing compounds such as succinimide, glutarimide, phthalimide and pyrrolimide; and compounds having a hydroxyimide group such as N-hydroxysuccinimide and N-hydroxyphthalimide. Further, each compound may be a derivative of the above compound as long as it has each acid group.

The non-polymer compound B is preferably a compound having a plurality of phenol groups, active methylene groups, amide groups, sulfonamide groups, imide groups, and hydroxyimide groups in the molecule.

Examples of the non-polymer compound B include a polymer containing the structural unit B and a polymer synthesized using the non-polymer compound B.

Examples of the polymer containing the structural unit B include polyhydroxystyrene, novolak-type phenol resin, novolak-type cresol resin, novolak-type bisphenol resin, a polymer containing a structural unit derived from 4-hydroxyphenyl methacrylate, a polymer containing a structural unit derived from N- (4-hydroxyphenyl) (meth) acrylamide, a polymer containing a structural unit derived from ethylene glycol monoacetoacetate mono (meth) acrylate, and a polymer containing a structural unit derived from maleimide. Among them, polyhydroxystyrene, novolak-type phenol resin, novolak-type cresol resin, or a polymer containing a structural unit derived from ethylene glycol monoacetoacetate mono (meth) acrylate is preferable.

Further, from the viewpoint of further improving the effect of the present invention, the acid value of the compound B derived from the acid group is preferably 5 to 150mgKOH/g, more preferably 20 to 120mgKOH/g, and still more preferably 30 to 100mgKOH/g.

[ examples ]

Hereinafter, the present invention will be described in further detail with reference to examples.

The materials, the amounts used, the ratios, the contents of the processes, the steps of the processes, and the like described in the following examples can be appropriately modified without departing from the spirit of the present invention. The scope of the invention should therefore not be construed in a limiting sense by the examples presented below.

Unless otherwise specified, "part" and "%" are based on mass.

In the following examples, the weight average molecular weight of the resin was determined by polystyrene conversion based on Gel Permeation Chromatography (GPC). The acid value of the resin is a theoretical acid value derived from the structural unit ratio of the resin.

< transfer film >

Transfer films were produced using the compositions shown in table 2 of the latter stage.

First, each component used for manufacturing a transfer film will be described.

[ photosensitive composition ]

The photosensitive composition layer of the transfer film is formed using the photosensitive composition.

The materials shown in table 2 in the subsequent stage were mixed according to the formulation shown in table 2 to obtain photosensitive compositions used for the production of transfer films of examples and comparative examples.

Hereinafter, each component used for producing the photosensitive composition will be described.

(resin)

Synthesis of resin A1-1

10g of propylene glycol monomethyl ether and 10g of propylene glycol monomethyl ether acetate were charged into a flask under a nitrogen stream, and heated to 90 ℃ under a nitrogen stream. To this liquid, a solution prepared by dissolving 27.8g of styrene, 5.3g of methyl methacrylate, 12.3g of methacrylic acid and 8.0g of ethylene glycol monoacetylacetate monomethacrylate in 5g of propylene glycol monomethyl ether and 5g of propylene glycol monomethyl ether acetate and a solution prepared by dissolving 1.7g of a polymerization initiator V-601 (manufactured by FUJIFILM Wako Pure Chemical Corporation) in 5g of propylene glycol monomethyl ether and 5g of propylene glycol monomethyl ether acetate were simultaneously added dropwise over 2 hours. After the completion of the dropwise addition, 0.6g of V-601 was added 3 times per 1 hour. Then, it was further reacted for 3 hours. After the reaction, the reaction solution was diluted with propylene glycol monomethyl ether acetate to obtain a solution of resin A1-1 having a solid content of 30%.

The amount of residual monomer measured by gas chromatography was less than 0.1% by mass in any of the monomers relative to the solid content of the polymer.

Resins A1-3 to A1-8 and A2-1 to A2-2 were synthesized by the same method. The amount of residual monomer in each resin as determined by gas chromatography was less than 0.1% by mass relative to the polymer solids in either monomer.

Synthesis of resin A1-2

113.5g of propylene glycol monomethyl ether was charged into a flask, and heated to 90 ℃ under a nitrogen stream. To this liquid, a solution prepared by dissolving 16.6g of dicyclopentyl methacrylate, 16.6g of ethylene glycol monoacetoacetate monomethacrylate, 19.9g of methacrylic acid and 3.7g of a polymerization initiator V-601 (manufactured by FUJIFILM Wako Pure Chemical Corporation) in 17.1g of propylene glycol monomethyl ether was added dropwise over a period of 3 hours. After completion of the dropwise addition, 0.5g of V-601 was added 3 times per 1 hour. Then, it was further reacted for 3 hours. After the reaction, the reaction mixture was diluted with 30.2g of propylene glycol monomethyl ether acetate and 42.3g of propylene glycol monomethyl ether.

The diluted reaction solution was heated to 100 ℃ under an air stream, and 0.24g of tetraethylammonium bromide and 0.11g of p-methoxyphenol were added. To the liquid, 13.2G of glycidyl methacrylate (BLEMMER G manufactured by NOF CORPORATION) was added dropwise over a period of 20 minutes. After the reaction of the liquid at 100 ℃ for 7 hours, propylene glycol monomethyl ether acetate was diluted to obtain a solution of resin A1-2 having a solid content of 30%.

Resins A2-3 and A2-4 were synthesized in the same manner. The amount of residual monomer in each resin as determined by gas chromatography was less than 0.1% by mass relative to the polymer solids in either monomer.

The structure of each synthesized resin is shown below.

[ chemical formula 8]

Table 1 shows the weight average molecular weight and the dispersion degree of each of the synthesized resins, the pKa of an acid group showing a pKa higher than that of the carboxyl group and lower than 14 ("pKa of acid group" in the table), and the acid value derived from the carboxyl group and the acid value derived from the acid group of each of the resins.

[ Table 1]

(Compound having acid group showing pKa higher than that of carboxyl group and lower than pKa of 14 (Compound B))

PHS: poly (p-hydroxystyrene)

NVC: cresol novolac (m-/p-ratio 60/40)

AcAc: poly (ethylene glycol monoacetoacetate monomethacrylate)

(polymerizable Compound)

SR454: ethoxylated (3) trimethylolpropane trimethacrylate, TOMOE Engineering co., ltd

BPE-500: ethoxylated bisphenol A dimethacrylate, shin-Nakamura Chemical Co., ltd

BPE-100: ethoxylated bisphenol A dimethacrylate, shin-Nakamura Chemical Co., ltd

M-270: ARONIX M-270, polypropylene glycol diacrylate (n. Apprxeq.12), TOAGOSEI co., ltd

4G: NK Ester 4G, polyethylene glycol #200 dimethacrylate, shin-Nakamura Chemical Co., ltd

(photopolymerization initiator)

2- (o-chlorophenyl) -4,5-diphenylimidazole dimer

(sensitizer)

4,4' -bis (diethylamino) benzophenone

(polymerization inhibitor)

Phenothiazine (I)

(antioxidant)

Phenidone (Tabanzo)

(color-developing agent)

Colorless crystal violet: manufactured by Tokyo Chemical Industry Co., ltd

(Rust inhibitors)

CBT-1: carboxybenzotriazole, joohoku CHEMICAL co

(surfactant)

F552: MEGAFACE F-552 manufactured by DIC Corporation

(solvent)

MMPGAc: 1-methoxy-2-propyl acetate

MEK: methyl ethyl ketone

[ composition for Forming intermediate layer ]

The intermediate layer of the transfer film is formed using the intermediate layer-forming composition.

The materials shown in table 2 in the subsequent stage were mixed according to the formulation shown in table 2 to obtain the intermediate layer-forming composition used for the production of the transfer films of examples and comparative examples.

(resin)

PVA: polyvinyl alcohol, product name "KURARAAY POVAL PVA-205", manufactured by Kuraray Co., ltd

PVP: polyvinylpyrrolidone, product name "polyvinylpyrrolidone K-30", NIPPON shokubali co

HPMC: hydroxypropyl methylcellulose, product name "METOLOSE (registered trademark) 60SH-03", manufactured by Shin-Etsu Chemical Co., ltd

(surfactant)

F444: MEGAFACE F444, fluorosurfactant, DIC Corporation

(solvent)

Water

Methanol

[ production of transfer film ]

Transfer films for examples and comparative examples were produced, each of which was composed of a temporary support, an intermediate layer, and a photosensitive composition layer. The details are as follows.

First, an intermediate layer-forming composition was applied to the surface of a temporary support (a 16 μm thick polyethylene terephthalate film (lumiror (registered trademark) 169440, manufactured by toray industries, inc.) using a bar coater so that the thickness after drying became 1.0 μm. The coating film was dried at 90 ℃ using an oven to form an intermediate layer.

Next, a photosensitive composition was applied onto the surface of the formed intermediate layer using a bar coater so that the thickness after drying became 3.0 μm. The coating film was dried at 80 ℃ using an oven to form a photosensitive composition layer (negative photosensitive composition layer).

A polyethylene terephthalate (169440, produced by TORAY INDUSTRIES, INC.) having a thickness of 16 μm was pressure-bonded to the obtained photosensitive composition layer as a protective film, to prepare a transfer film used in each example or comparative example.

< evaluation >

The evaluation method of the evaluation items shown in table 2 in the subsequent paragraph will be described.

[ formation of resist Pattern ]

As the substrate having the conductive layer, a PET substrate with a copper layer in which a copper layer having a thickness of 500nm was formed on a PET film (polyethylene terephthalate film) having a thickness of 188 μm by a sputtering method was used.

The transfer film produced in the above procedure was cut into a 50cm square, and the protective film was peeled off, and the transfer film was laminated on the PET substrate with the copper layer under lamination conditions of a roll temperature of 90 ℃, a line pressure of 0.8MPa, and a line speed of 3.0m/min so that the photosensitive composition layer was in contact with the copper layer on the surface of the PET substrate, to obtain a laminate.

At this point, the laminate had a structure of "PET film-copper layer-photosensitive composition layer-intermediate layer-temporary support".

Next, the temporary support is peeled from the obtained laminate, and the intermediate layer is exposed on the surface of the laminate. A photomask having a line width of 1-10 [ mu ] m in 1 [ mu ] m steps and a line width of 1-1 [ mu ] m is brought into close contact with the exposed intermediate layer of the laminate.

The laminate was irradiated with light using a high-pressure mercury lamp exposure machine (MAP-1200L, japan Science Engineering Co., ltd., dominant wavelength: 365 nm) to expose the photosensitive composition layer. The exposure amount was set so that the resist pattern of the portion corresponding to the line-and-space shape of 5 μm of the photomask reproduced the exposure amount of the line-and-space shape of 5 μm after development.

Then, development was performed using a 1.0% sodium carbonate aqueous solution (pH = 11.4) at 28 ℃. Specifically, the developer was removed by performing a 30-second shower treatment with the developer and an air knife (AirKnife) treatment, and then, the developer was further subjected to an air knife treatment by performing a 30-second shower treatment with pure water.

This gave a laminate of a line-and-space shaped resist pattern having a line width of = 1:1.

The pattern formation stage 1 will be set up until now.

At this point, the laminate had a structure of "PET film-copper layer-resist pattern".

[ evaluation of resist resolution (minimum resolution line width) and resist pattern shape ]

After the 1 st pattern formation stage, the resist pattern was observed from above using a Scanning Electron Microscope (SEM). The minimum line width that can be formed without developing residue, pattern collapse, or the like is set as the minimum resolution line width.

Then, the cross-sectional shape of the resist pattern was observed with a Scanning Electron Microscope (SEM) to confirm the presence or absence of curling at the minimum resolution line width. The cross-sectional shape of the resist pattern was evaluated according to the following criteria.

(evaluation criteria for resist Pattern shape)

A: pattern shape without curling

B: slightly in the shape of a turned edge

C: edge curl shape

[ resist Pattern stripping Property ]

The laminate after the 1 st pattern formation stage was placed in a Copper sulfate plating bath (75 g/L Copper sulfate, 190g/L sulfuric acid, 50 ppm by mass chloride ion, manufactured by Meltex Inc. 'Copper Glyme PCM', 5 mL/L) at 1A/dm ² Copper plating treatment was performed under the conditions of (1).

After the above-described laminate after the copper plating treatment was washed with water and dried, it was immersed in a1 mass% potassium hydroxide aqueous solution (pH = 13.5) at 50 ℃, whereby the resist pattern was peeled off.

The resist pattern is stripped off until now.

The stripping was performed while changing the stripping time, and the time at which the resist was stripped at the 5 μm line and space pattern portion of the resist pattern was evaluated in the following manner. The shorter the time, the better the peelability.

(evaluation criteria for resist Pattern releasability)

A: less than 30 seconds

B:30 seconds or more and less than 60 seconds

C:60 seconds or more and less than 120 seconds

D: over 120 seconds

[ copper Wiring Pattern shape ]

The copper layer (seed layer) of the laminate after the resist pattern stripping step was removed with an aqueous solution containing 0.1 mass% sulfuric acid and 0.1 mass% hydrogen peroxide to obtain a copper wiring pattern. The cross-sectional shape of the copper wiring pattern was observed by a Scanning Electron Microscope (SEM).

Specifically, it was confirmed whether undercutting (undercut) occurred at the bottom of the copper pattern in the copper wiring pattern corresponding to the resist pattern of 5 μm line-to-space. The copper wiring pattern shape was evaluated according to the following evaluation criteria.

(evaluation criteria for copper Wiring Pattern shape)

A: pattern shape without undercut

B: slightly undercut shape

C: undercut shape

[ evaluation of straightness (LWR) of copper Wiring Pattern ]

A substrate on which a resist pattern was formed (a laminate having a resist pattern) was obtained by similarly performing the step 1 to the step 1 of pattern formation on the laminate after the step 1 of pattern formation obtained by the same method as described above.

A substrate on which a resist pattern was formed (a laminate having a resist pattern) was etched with a copper etching solution (Cu-02.

The line widths of the portions randomly selected from the copper wiring patterns of 5 μm lines and spaces were measured in 100 portions by SEM. The standard deviation (unit: nm) of the obtained Line Width was obtained, and the value of the standard deviation was defined as LWR (Line Width Roughness).

The obtained LWR values were classified by the following classification, and the linearity of the copper wiring pattern was evaluated.

The smaller the LWR, the smaller the line width variation, and thus is preferable.

(evaluation of linearity of copper Wiring Pattern)

A: LWR less than 150nm

B: LWR is more than 150nm and less than 200nm

C: LWR is more than 200nm and less than 300nm

D: LWR is above 300nm

< results >

Table 2 shows the recipes of the components of the transfer films of the examples and the comparative examples, and the evaluation results of the evaluation items.

In table 2, the components of the photosensitive composition and the intermediate layer-forming composition are as described above.

In table 2, the contents of the respective components are parts by mass.

In table 2, the mark "> 10" in the column of the minimum resolution line width indicates that the portion of the line and space pattern at 10 μm is also not resolved.

[ Table 2]

[ Table 3]

From the results of table 2, it was confirmed that the transfer film of the present invention exhibits the desired effects.

From the comparison of example 7 with examples 1,2,4 to 6 and 8 to 16, it was confirmed that the alkali-soluble polymer is more excellent in resolution when the pKa of the acid group showing a pKa higher than the carboxyl group and a pKa lower than 14 is 9 to 12.

From the comparison of example 3 with examples 1,2,4 to 6 and 8 to 16, it was confirmed that the alkali-soluble polymer is more excellent in resolution when the acid value derived from the carboxyl group is 100 to 180.

Transfer films were produced using the compositions and evaluated in the same manner as in examples 1 to 16, except that the polyester film (thickness: 6.9 μm) described in example 1 of jp 2000-309650 a was used as a temporary support, and as a result, the resist resolution, the resist pattern shape, the resist pattern peelability, and the LWR were good as in examples 1 to 16, respectively.

Description of the symbols

10-transfer film, 11-temporary support, 13-intermediate layer, 15-photosensitive composition layer, 17-composition layer, 19-protective film.

Claims

1. A transfer film, comprising:

a temporary support; and

the alkali-soluble polymer comprises a structural unit A having a carboxyl group and a structural unit B having an acid group exhibiting a pKa higher than the carboxyl group and lower than 14,

the alkali-soluble polymer has an acid value of 80mgKOH/g or more, which is derived from the carboxyl group.

2. The transfer film according to claim 1,

the pKa of the acid group is 7 to 12.

3. The transfer film according to claim 1 or 2,

the structural unit B has 1 or more groups selected from a phenol group, an active methylene group, a sulfonamide group, an imide group and a hydroxyimide group.

4. The transfer film according to claim 1 or 2,

the structural unit B has 1 or more groups selected from the group represented by the following formula (I), the group represented by the following formula (II) and the group represented by the following formula (III),

in the formula (I), R ₁ Represents a substituent having a valence of 1,

in the formula (I), n ₁ Represents an integer of 1 or 2, n ₂ Represents an integer of 0 to 4, wherein n ₁ And n ₂ The sum ofAn integer of 1 to 5, in which,

in the formula (II), R ₂ Represents a substituent having a valence of 1, R ₃ Represents a hydrogen atom or a substituent having a valence of 1,

in the formula (III), R ₄ Represents a substituent having a valence of 1,

in the formula (III), n ₃ Represents an integer of 1 or 2, n ₄ Represents an integer of 0 to 4, wherein n ₃ And n ₄ The sum of which is an integer of 1 to 5.

5. The transfer film according to claim 1 or 2,

the content of the structural unit B is 5 to 50% by mass relative to all structural units of the alkali-soluble polymer.

6. The transfer film according to claim 1 or 2,

the acid value derived from the acid group is 5mgKOH/g to 200mgKOH/g.

7. A transfer film, comprising:

a temporary support; and

a photosensitive composition layer containing an alkali-soluble polymer comprising a structural unit having a carboxyl group, a polymerizable compound, a polymerization initiator, and a compound having an acid group exhibiting a pKa higher than the carboxyl group and lower than 14,

the content of the compound is 3 to 50 mass% based on the total mass of the photosensitive composition layer,

8. The transfer film according to claim 7,

the pKa of the acid group is 7 to 12.

9. The transfer film according to claim 7 or 8,

the compound has 1 or more groups selected from a phenol group, an active methylene group, a sulfonamide group, an imide group, and a hydroxyimide group.

10. The transfer film according to claim 7 or 8,

the compound has 2 or more of the acid groups.

11. The transfer film according to claim 7 or 8,

the compound is a polymer comprising a structural unit having the acid group.

12. The transfer film according to claim 1,2, 7, or 8, further comprising an intermediate layer between the temporary support and the photosensitive composition layer.

13. The transfer film according to claim 12,

the intermediate layer includes a water-soluble resin.

14. The transfer film according to claim 13,

15. A method for manufacturing a laminate having a conductor pattern, comprising:

a bonding step of bonding the transfer film according to any one of claims 1 to 14 to a substrate having a conductive layer on a surface thereof so that the photosensitive composition layer side of the transfer film is in contact with the conductive layer of the substrate;

an exposure step of exposing the photosensitive composition layer;

a resist pattern stripping step of stripping the resist pattern,

16. The method for manufacturing a laminate having a conductor pattern according to claim 15,

17. The method for manufacturing a laminate having a conductor pattern according to claim 15 or 16,

18. The method for manufacturing a laminate having a conductor pattern according to claim 15 or 16,

19. The method for manufacturing a laminate having a conductor pattern according to claim 15 or 16,

the thickness of the temporary support is less than 16 μm.

20. The method of manufacturing a laminate having a conductor pattern according to claim 15 or 16, which comprises the step of peeling off the temporary support between the bonding step and the exposure step,