JP6756541B2 - Substrate manufacturing method - Google Patents

Description

The present invention comprises a color filter, a patterned metal layer formed directly on the color filter or via a transparent layer, and a coating resin layer covering the patterned metal layer on one main surface. It relates to the manufacturing method of the substrate provided above.

With the rapid spread of smartphones and tablet-type information and communication terminals, the touch panel market is growing rapidly.
In such a touch panel, electrodes or wiring made of metal may be formed in the display surface. For example, examples of such an electrode include a metal mesh electrode using Cu or Ag. However, when an electrode or wiring made of metal is formed on the display surface, there is a problem that the metal electrode or metal wiring is easily visible to the user of the touch panel, and the line width of the metal electrode or metal wiring is assumed to be human. Even if the metal is so thin that it cannot be visually recognized, there may be a problem that external light reflection occurs due to the high reflectance of the metal.

In order to solve such a problem, a method of providing a reflectance control means having a low reflectance on a metal thin film such as a metal electrode or a metal wiring has been proposed.
Specifically, a resin layer patterned by a photolithography method using a photosensitive resin composition is provided on a metal layer on a transparent support, and then exposed from an opening of the patterned resin layer. There is known a method of providing a reflectance control means (baked resin layer) that uniformly covers the surface of the etched metal layer by removing the metal layer to be etched by etching and then baking the resin layer (baked resin layer). See Patent Document 1).

Japanese Unexamined Patent Publication No. 2016-071242

From the viewpoint of expanding the choices of the touch panel manufacturing method and the touch panel structure, the coating resin layer (reflectance) is placed on the metal layer (metal wiring) not only on the transparent support but also on the substrate provided with the color filter. A method capable of forming a control means) is required.
Here, if the metal layer (metal wiring) can be arranged as it is on the substrate provided with the color filter, it becomes easier to control and manage the area where the metal layer (metal wiring) exists, and by extension, the aperture ratio of the pixel is lowered. It is expected that it will be difficult to invite.
As a result of studies by the present inventors on this point, if an appropriate photosensitive resin composition is not used for the substrate provided with the color filter, the coating resin layer (reflectivity control) formed on the metal layer (metal wiring) is not used. As for the means), it was found that there are cases where the metal wiring is insufficiently covered, and the pixel portion is covered by the excessive flow of the coating resin layer at the time of baking.

That is, if the processing is performed on a transparent support as described in Patent Document 1, the reflectance control means can be formed by baking at a uniform temperature. On the other hand, when processing is performed on a color filter, the coating resin layer (reflectance control) is caused by the non-uniformity of the amount of heat absorbed and the amount of heat reflected due to the difference in the material of the colored film such as black matrix and RGB. Means) are not heated uniformly.
For this reason, when the patterned metal layer provided on the substrate provided with the color filter is coated with the coating resin layer, there are places where the metal layer is insufficiently coated, or the coating resin layer is excessive at the time of baking. It is considered that the pixel portion where the metal layer is not formed is covered by the normal flow.

The present invention has been made in view of the above problems, and comprises a color filter, a patterned metal layer formed directly on the color filter or via a transparent layer, and a patterned metal layer. A method of manufacturing a substrate in which a coating resin layer (reflectivity control means) to be coated is provided on one main surface, and a patterned metal layer is uniformly formed by the coating resin layer on a substrate provided with a color filter. It is an object of the present invention to provide a method which is easy to cover and is difficult to cover a portion where a metal layer is not formed with a coating resin layer.

The present inventors have a color filter, a patterned metal layer formed directly on the color filter or via a transparent layer, and a coating resin layer for coating the patterned metal layer. When manufacturing a substrate to be provided on the main surface, a positive photosensitive resin composition containing a base resin component (A) having a degree of dispersion (weight average molecular weight Mw / number average molecular weight Mn) of 1 or more and 20 or less is used. It has been found that the above-mentioned problems can be solved by forming the coating resin layer in the above, and the present invention has been completed.

That is, in the present invention, one of the color filter, the patterned metal layer formed directly on the color filter or via the transparent layer, and the coating resin layer covering the patterned metal layer. It is a method of manufacturing a substrate provided on the main surface.
A positive photosensitive resin composition is applied onto a metal layer to be etched on a substrate to be processed, which comprises a color filter and a metal layer to be etched, which is formed directly on the color filter or via a transparent layer. And the process of forming the photosensitive layer,
An exposure process that exposes a position in the photosensitive layer other than the position where the patterned metal layer is formed.
A developing process in which the exposed photosensitive layer is developed to form a coating resin layer,
An etching process in which the coating resin layer is used as an etching mask and the metal layer to be etched exposed from the etching mask is removed by etching to form a patterned metal layer.
Including a post-baking process, which bake the coating resin layer,
The dispersity (weight average molecular weight Mw / number average molecular weight Mn) of the base resin component (A) contained in the positive photosensitive resin composition is 1 or more and 20 or less.
The present invention relates to a method in which the optical density of the coating resin layer in the manufactured substrate is 0.10 / μm or more.

According to the present invention, a color filter, a patterned metal layer formed directly or via a transparent layer on the color filter, and a coating resin layer (reflectivity control means) for coating the patterned metal layer. ) Is a method for manufacturing a substrate provided on one of the main surfaces, and the patterned metal layer can be easily uniformly covered by the coating resin layer on the substrate provided with the color filter, and the metal layer is formed. It is possible to provide a method in which the portion not covered with the coating resin layer is difficult to be coated.

It is a figure which shows the outline of the manufacturing method of a substrate schematically. It is a figure which shows an example of the use of the substrate manufactured in this Embodiment schematically.

Hereinafter, the present invention will be described based on a preferred embodiment. In addition, "~" in this specification represents the above (lower limit value) to the following (upper limit value) unless otherwise specified.

The present invention comprises a color filter, a patterned metal layer formed directly on the color filter or via a transparent layer, and a coating resin layer covering the patterned metal layer on one main surface. It relates to the manufacturing method of the substrate provided above.
The coating resin layer is formed so that the optical density after the post-baking step is 0.10 / μm or more. Therefore, in the touch panel provided with the substrate manufactured according to the method according to the present invention, the metal wiring is not easily visible to the user of the touch panel when the touch panel is used.

Specifically, the method for manufacturing the substrate of the present embodiment is described.
A positive photosensitive resin composition is applied onto a metal layer to be etched on a substrate to be processed, which comprises a color filter and a metal layer to be etched, which is formed directly on the color filter or via a transparent layer. And the process of forming the photosensitive layer,
An exposure process that exposes a position in the photosensitive layer other than the position where the patterned metal layer is formed.
A developing process in which the exposed photosensitive layer is developed to form a coating resin layer,
An etching process in which the coating resin layer is used as an etching mask and the metal layer to be etched exposed from the etching mask is removed by etching to form a patterned metal layer.
Includes a post-baking process, which involves baking the coating resin layer.

The positive photosensitive resin composition used in the photosensitive layer forming step contains a base resin composition (A) having a dispersity (weight average molecular weight Mw / number average molecular weight Mn) of 1 or more and 20 or less.
Therefore, when the substrate is manufactured, it is easy to uniformly cover the patterned metal layer with the coating resin layer, and it is difficult to cover the portion where the metal layer is not formed with the coating resin layer.

Hereinafter, each step included in the substrate manufacturing method will be described with reference to FIG. In the following description, the positive photosensitive resin composition is also referred to as a “positive composition”.

≪Photosensitive layer forming process≫
In the photosensitive layer forming step, as shown in FIGS. 1 (a) and 1 (b), the positive composition is applied onto the metal layer 11 to be etched on the substrate 10 to be processed including the metal layer 11 to be etched. The photosensitive layer 12 is formed.
Hereinafter, the substrate to be processed, the positive composition, and the coating method will be described.

<Substrate to be processed>
As the substrate 10 to be processed, a substrate having a color filter 13 and a metal layer 11 to be etched formed directly on the color filter 13 or via a transparent layer 14 is used.
In addition, FIG. 1A to FIG. 1E show an embodiment in which the substrate 10 to be processed provided with the transparent layer 14 is used. The configuration of the substrate 10 to be processed other than the metal layer 11 to be etched, the color filter 13, and the transparent layer 14 is not shown.

The material and manufacturing method of the color filter 13 in the substrate 10 to be processed are not particularly limited, and are appropriately selected from various conventionally known materials and various manufacturing methods. The color filter 13 usually includes a translucent colored film such as RGB (not shown in FIG. 1) in a region partitioned by a black matrix (not shown in FIG. 1).

The substrate 10 to be processed can be used without particular limitation as long as it is a substrate having a color filter 13 and a metal layer 11 to be etched formed directly on the color filter 13 or via a transparent layer 14. it can.

FIG. 2 shows a cross-sectional view of an example of the use of the substrate manufactured in this embodiment.
The substrate 1 shown in FIG. 2 is obtained by processing the substrate 10 to be processed, and has an array substrate 23, an insulating layer 22, a liquid crystal layer 20, a transparent resin layer 19, a color filter 13, a transparent layer 14, and a pattern. The metal layer 18 and the coating resin layer 17 are laminated in this order. Such a substrate is preferably used for an on-cell touch panel.
The color filter 13 includes a black matrix BM, a red colored film R, a green colored film G, and a blue colored film B.
Further, on the upper surface of the insulating layer 22, pixel electrodes 21 are formed at positions corresponding to the positions of the red colored film R, the green colored film G, and the blue colored film B of the color filter 13.
Further, the black matrix BM, the coating resin layer 17, and the patterned metal layer 18 are configured so as to overlap each other in the plan view of the substrate.
A liquid crystal display device is manufactured by combining such a substrate 1 with a member generally provided in a liquid crystal display device such as a backlight and appropriately wiring the substrate 1.

The substrate 1 shown in FIG. 2 is a liquid crystal cell after liquid crystal injection, and includes a liquid crystal layer 20 in its structure. In this case, due to the problem of heat resistance of the liquid crystal compound used, there may be a problem that the substrate 10 to be processed provided with the coating resin layer 17 cannot be baked at a high temperature in the post-baking step described later.
In consideration of such a point, in the present embodiment, it is preferable to carry out the baking temperature in the post-baking step described later at a low temperature such as 80 ° C. or higher and 150 ° C. or lower. Even under such temperature conditions, the coating resin layer 17 can be satisfactorily formed.

<Positive composition>
The positive composition contains a base resin component (A) having a degree of dispersion (weight average molecular weight Mw / number average molecular weight Mn) of 1 or more and 20 or less.
The base resin component (A) is a component that imparts properties such as film-forming property to the positive composition, and is formed by using the positive composition as it is or in a state of being chemically changed. Functions as a matrix material for membranes.

When the dispersibility of the base resin component (A) contained in the positive composition is 1 or more and 20 or less, the patterned metal layer 18 formed on the substrate 10 to be processed provided with the color filter 13 is formed. The coating resin layer 17 can be uniformly coated, and the portion where the metal layer 18 is not formed can be made difficult to be covered with the coating resin layer 17.
The degree of dispersion of the base resin component (A) is preferably 2 to 17, more preferably 3 to 15, and particularly preferably 4 to 12, because the effects according to the present invention can be particularly easily obtained.
Further, from the viewpoint of better flowability, it is also preferable that the dispersity of the base resin component (A) is more than 5 and 20 or less.
In this specification, the weight average molecular weight Mw and the number average molecular weight Mn can be defined as polystyrene-equivalent relative values in GPC (gel permeation chromatography) measurement.
When there are a plurality of types of resins constituting the base resin component (A) (for example, when a novolak resin (A1) and an alkali-soluble acrylic resin (A1-1) are used in combination), these plurality of types of resins are used. GPC (gel permeation chromatography) measurement may be performed in the state of combining the above, and the degree of dispersion may be determined from the obtained chart.

A suitable example of the positive composition used for forming the photosensitive layer 12 is a positive composition containing a novolak resin (A1) as a base resin component (A) and a quinonediazide group-containing compound (B1). , And a resin (A2) whose solubility in alkali is increased by the action of an acid as a base resin component (A), and a positive composition containing a compound (B2) that generates an acid by irradiation with active light or irradiation. And can be mentioned.

Hereinafter, the positive composition containing the novolak resin (A1) and the quinonediazide group-containing compound (B1) is also referred to as the first positive composition, and the resin (A2) whose solubility in alkali is increased by the action of an acid. , A positive composition containing a compound (B2) that generates an acid by irradiation with active light or irradiation is also referred to as a second positive composition.
Hereinafter, the first positive type composition and the second positive type composition will be described.

[First positive composition]
As described above, the first positive composition contains a novolak resin (A1) and a quinonediazide group-containing compound (B1). Hereinafter, essential or optional components of the first positive composition will be described.

(Novolak resin (A1))
As the novolak resin (A1), various novolak resins conventionally blended in the positive photosensitive resin composition can be used. The novolak resin (A1) is preferably one obtained by addition-condensing an aromatic compound having a phenolic hydroxyl group (hereinafter, simply referred to as "phenols") and aldehydes under an acid catalyst.

-Phenols Examples of phenols include phenols; cresols such as o-cresol, m-cresol, and p-cresol; 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-. Xylenols such as xylenol, 3,4-xylenol, 3,5-xylenol; ethylphenols such as o-ethylphenol, m-ethylphenol, p-ethylphenol; 2-isopropylphenol, 3-isopropylphenol, 4- Alkylphenols such as isopropylphenol, o-butylphenol, m-butylphenol, p-butylphenol, and p-tert-butylphenol; trialkylphenols such as 2,3,5-trimethylphenol and 3,4,5-trimethylphenol; Multivalent phenols such as resorcinol, catechol, hydroquinone, hydroquinone monomethyl ether, pyrogallol, and fluoroglycinol; alkyl polyhydric phenols such as alkylresorcin, alkylcatechol, and alkylhydroquinone (all alkyl groups have 1 or more carbon atoms and 4). ); Α-naphthol; β-naphthol; hydroxydiphenyl; and bisphenol A and the like. These phenols may be used alone or in combination of two or more.

Among these phenols, m-cresol and p-cresol are preferable, and it is more preferable to use m-cresol and p-cresol in combination. In this case, various characteristics such as sensitivity as a positive composition and heat resistance of the coated resin layer 17 to be formed can be adjusted by adjusting the blending ratio of both. The blending ratio of m-cresol and p-cresol is not particularly limited, but the mass ratio of m-cresol / p-cresol is preferably 3/7 or more and 8/2 or less. When the ratio of m-cresol is 3/7 or more, the sensitivity as a positive composition can be improved, and when it is 8/2 or less, the heat resistance of the coating resin layer 17 can be improved.

-Aldehydes Examples of aldehydes include formaldehyde, paraformaldehyde, furfural, benzaldehyde, nitrobenzaldehyde, acetaldehyde and the like. These aldehydes may be used alone or in combination of two or more.

-Acid catalyst Examples of the acid catalyst include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, and phosphorous acid; organic acids such as formic acid, oxalic acid, acetic acid, diethylsulfuric acid, and p-toluenesulfonic acid; and acetic acid. Examples include metal salts such as zinc. These acid catalysts may be used alone or in combination of two or more.

-Molecular weight The polystyrene-equivalent weight average molecular weight (Mw; hereinafter, also simply referred to as "weight average molecular weight") of the novolak resin (A1) is the dispersibility (weight) of the base resin component (A) containing the novolak resin (A1). The average molecular weight Mw / number average molecular weight Mn) is not particularly limited as long as it is 1 or more and 20 or less.
The dispersity of the novolak resin (A1) is also preferably 1 or more and 20 or less, more preferably 2 to 17, particularly preferably 3 to 15, and even more preferably 4 to 12, as in the case of the base resin component (A) described above.
From the viewpoint of developability, resolution and the like of the first positive composition, the weight average molecular weight of the novolak resin (A1) is preferably 1000 or more, more preferably 2000 or more, further preferably 3000 or more, and 50,000 or less. Is preferable, 40,000 or less is more preferable, 30,000 or less is further preferable, and 20,000 or less is even more preferable.

As the novolak resin (A1), at least two types having different polystyrene-equivalent weight average molecular weights can be used in combination. By using a combination of large and small ones having different weight average molecular weights, it is possible to impart multifaceted excellent properties such as developability, resolution, and film forming property to the positive composition.
The combination of the novolak resin (A1) and the resins having different weight average molecular weights is not particularly limited, but is a resin on the low weight average molecular weight side having a weight average molecular weight of 1000 to 10000 and a weight average molecular weight of 5000 to 50000. A combination with a resin on the high weight average molecular weight side is preferable, and a combination of a resin on the low weight average molecular weight side having a weight average molecular weight of 2000 to 8000 and a resin on the high weight average molecular weight side having a weight average molecular weight of 8000 to 40,000. Is more preferable, and a combination of a resin on the low weight average molecular weight side having a weight average molecular weight of 3000 to 7000 and a resin on the high weight average molecular weight side having a weight average molecular weight of 1000 to 20000 is even more preferable.

When resins having different weight average molecular weights are used in combination as the novolak resin (A1), the content of each is not particularly limited, but the content of the resin on the low weight average molecular weight side in the total amount of the novolak resin (A1) is 5. It is preferably mass% or more, more preferably 10% by mass or more, further preferably 15% by mass or more, while preferably 50% by mass or less, more preferably 40% by mass or less.

The content of the novolak resin (A1) in the total solid content of the first positive composition is preferably 40% by mass or more, more preferably 45% by mass or more, further preferably 50% by mass or more, and preferably 90% by mass or less. , 85% by mass or less is more preferable. By setting the content within the above range, it is possible to exhibit positivity with respect to the metal component while appropriately binding the other components contained in the first positive composition, and as a result, the adhesion to the patterned metal layer 18 can be exhibited. It is possible to form the coating resin layer 17 having excellent properties.

The first positive composition may contain a resin other than the novolak resin (A1) as the base resin component (A). The type of other resin is not particularly limited as long as the photolithography characteristics such as sensitivity and resolution of the positive composition are not excessively impaired.
Preferable examples of other resins include alkali-soluble acrylic resins (A1-1). The alkali-soluble acrylic resin (A1-1) acts as a plasticizer in the coated resin layer 17 and suppresses the occurrence of cracks in the coated resin layer 17.
As the alkali-soluble acrylic resin (A1-1), those blended in the positive composition as a plasticizer are generally used as long as the dispersity of the base resin component (A) is within a predetermined range. be able to.

More specifically, the alkali-soluble acrylic resin (A1-1) has a constitutional unit based on a polymerizable compound having an ether bond of 30 mol% or more and 90 mol% or less, and a constitution based on a polymerizable compound having a carboxy group. Examples thereof include resins containing a unit of 2 mol% or more and 50 mol% or less.

Examples of the polymerizable compound having an ether bond include 2-methoxyethyl (meth) acrylate, methoxytriethylene glycol (meth) acrylate, 3-methoxybutyl (meth) acrylate, ethylcarbitol (meth) acrylate, and phenoxypolyethylene glycol (meth). ) Radical polymerizable compounds such as acrylates, methoxypolypropylene glycol (meth) acrylates, and (meth) acrylic acid derivatives having ether and ester bonds such as tetrahydrofurfuryl (meth) acrylates. Among these, 2-methoxyethyl acrylate and methoxytriethylene glycol acrylate are preferably used. These compounds may be used alone or in combination of two or more.

Polymerizable compounds having a carboxy group include monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid; dicarboxylic acids such as maleic acid, fumaric acid, and itaconic acid; and 2-methacryloyloxyethyl succinic acid, 2-. Examples thereof include radically polymerizable compounds such as methacrylic acid derivatives having a carboxy group and an ester bond such as methacryloyloxyethyl maleic acid, 2-methacryloyloxyethyl phthalic acid, and 2-methacryloyloxyethyl hexahydrophthalic acid. Among these, it is preferable to use acrylic acid and methacrylic acid. These compounds may be used alone or in combination of two or more.

The content of the unit derived from the polymerizable compound having an ether bond in the alkali-soluble acrylic resin (A1-1) is preferably 30 to 90 mol%, more preferably 40 to 80 mol%. By blending an alkali-soluble acrylic resin (A1-1) containing a unit derived from a polymerizable compound having an ether bond in an amount within such a range as a plasticizer into the first positive type composition, the coating resin layer 17 is formed. It is easy to form a homogeneous coating resin layer 17 while suppressing the occurrence of cracks.

The content of the structural unit based on the polymerizable compound having a carboxy group in the alkali-soluble acrylic resin (A1-1) component is preferably 2 to 50 mol%, more preferably 5 to 40 mol%. By blending an alkali-soluble acrylic resin (A1-1) containing a structural unit based on a polymerizable compound having a carboxy group in an amount within such a range as a plasticizer into the first positive type composition, the first positive type is used. The developability of the composition can be improved.

The polystyrene-equivalent weight average molecular weight of the alkali-soluble acrylic resin (A1-1) is not particularly limited as long as the dispersity of the base resin component (A) is 1 or more and 20 or less. The polystyrene-equivalent weight average molecular weight of the alkali-soluble acrylic resin (A1-1) is preferably 1000 to 800,000, more preferably 30,000 to 500,000.

The alkali-soluble acrylic resin (A1-1) may contain a structural unit based on another radically polymerizable compound for the purpose of appropriately controlling the physical and chemical properties. Here, the "other radically polymerizable compound" means a radically polymerizable compound other than the above-mentioned polymerizable compound.

Other such radically polymerizable compounds include (meth) acrylic acid alkyl esters such as methyl (meth) acrylate, ethyl (meth) acrylate, and butyl (meth) acrylate; 2-hydroxyethyl (meth) acrylate, And (meth) acrylic acid hydroxyalkyl esters such as 2-hydroxypropyl (meth) acrylate; (meth) acrylic acid aryl esters such as phenyl (meth) acrylate and benzyl (meth) acrylate; diethyl maleate, and fumal. Dicarboxylic acid diesters such as dibutyl acid; vinyl group-containing aromatic compounds such as styrene and α-methylstyrene; vinyl group-containing aliphatic compounds such as vinyl acetate; conjugated diolefins such as butadiene and isoprene; acrylonitrile and methacrylo A nitrile group-containing polymerizable compound such as nitrile; a chlorine-containing polymerizable compound such as vinyl chloride and vinylidene chloride; and an amide bond-containing polymerizable compound such as acrylamide and methacrylicamide can be used. These compounds may be used alone or in combination of two or more. Among these compounds, it is particularly preferable to use n-butyl acrylate, benzyl methacrylate, methyl methacrylate and the like. The content of the structural unit based on the other radically polymerizable compound in the alkali-soluble acrylic resin (A1-1) is preferably less than 50% by mass, more preferably less than 40% by mass.

Examples of the polymerization solvent used for synthesizing the alkali-soluble acrylic resin component include alcohols such as ethanol and diethylene glycol; alkyl ethers of polyhydric alcohols such as ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, and diethylene glycol ethyl methyl ether; Alkyl ether acetates of polyhydric alcohols such as ethylene glycol ethyl ether acetate and propylene glycol methyl ether acetate; aromatic hydrocarbons such as toluene and xylene; ketones such as acetone and methyl isobutyl ketone; and ethyl acetate and butyl acetate Etc. and the like can be used. Among these polymerizable solvents, it is particularly preferable to use alkyl ethers of polyhydric alcohols and alkyl ether acetates of polyhydric alcohols.

As the polymerization catalyst used in synthesizing the alkali-soluble acrylic resin (A1-1), a usual radical polymerization initiator can be used, for example, an azo compound such as 2,2'-azobisisobutyronitrile; and benzoyl. Peroxide and organic peroxides such as di-tert-butyl peroxide can be used.

When the alkali-soluble acrylic resin (A1-1) is contained in the first positive composition, the blending amount is preferably 30 parts by mass or less, preferably 20 parts by mass or less, based on 100 parts by mass of the novolak resin (A1). More preferred.

(Chinone diazide group-containing compound (B1))
The first positive composition contains a quinonediazide group-containing compound (B1). The quinone diazide group-containing compound (B1) can be appropriately selected from compounds having a quinone diazide group that have been conventionally blended in various positive-type compositions.
Suitable specific examples of the quinone diazide group-containing compound (B1) include 2,3,4-trihydroxybenzophenone, 2,4,4'-trihydroxybenzophenone, 2,4,6-trihydroxybenzophenone, 2,3. 6-Trihydroxybenzophenone, 2,3,4-trihydroxy-2'-methylbenzophenone, 2,3,4,4'-tetrahydroxybenzophenone, 2,2', 4,4'-tetrahydroxybenzophenone, 2, 3', 4,4', 6-pentahydroxybenzophenone, 2,2', 3,4,4'-pentahydroxybenzophenone, 2,2', 3,4,5-pentahydroxybenzophenone, 2,3', Polyhydroxybenzophenones such as 4,4', 5', 6-hexahydroxybenzophenone, 2,3,3', and 4,4', 5'-hexahydroxybenzophenone; bis (2,4-dihydroxyphenyl) methane , Bis (2,3,4-trihydroxyphenyl) methane, 2- (4-hydroxyphenyl) -2- (4'-hydroxyphenyl) propane, 2- (2,4-dihydroxyphenyl) -2- (2) ', 4'-dihydroxyphenyl) propane, 2- (2,3,4-trihydroxyphenyl) -2- (2', 3', 4'-trihydroxyphenyl) propane, 4,4'-{1- [4- [2- (4-Hydroxyphenyl) -2-propyl] phenyl] ethylidene} bisphenol and 3,3'-dimethyl- {1- [4- [2- (3-methyl-4-hydroxyphenyl)) -2-propyl] phenyl] ethylidene} bisphenol and other bis [(poly) hydroxyphenyl] alkanes; tris (4-hydroxyphenyl) methane, bis (4-hydroxy-3,5-dimethylphenyl) -4-hydroxyphenyl Methan, bis (4-hydroxy-2,5-dimethylphenyl) -4-hydroxyphenylmethane, bis (4-hydroxy-3,5-dimethylphenyl) -2-hydroxyphenylmethane, bis (4-hydroxy-2, 5-Dimethylphenyl) -2-hydroxyphenylmethane, bis (4-hydroxy-2,5-dimethylphenyl) -3,4-dihydroxyphenylmethane, and bis (4-hydroxy-3,5-dimethylphenyl) -3 , 4-Dihydroxyphenylmethane and other tris (hydroxyphenyl) methanes or methyl substituents thereof; bis (3-cyclohexyl-4-hydroxyf) Enyl) -3-hydroxyphenylmethane, bis (3-cyclohexyl-4-hydroxyphenyl) -2-hydroxyphenylmethane, bis (3-cyclohexyl-4-hydroxyphenyl) -4-hydroxyphenylmethane, bis (5-cyclohexyl) -4-Hydroxy-2-methylphenyl) -2-hydroxyphenylmethane, bis (5-cyclohexyl-4-hydroxy-2-methylphenyl) -3-hydroxyphenylmethane, bis (5-cyclohexyl-4-hydroxy-2) -Methylphenyl) -4-hydroxyphenylmethane, bis (3-cyclohexyl-2-hydroxyphenyl) -3-hydroxyphenylmethane, bis (5-cyclohexyl-4-hydroxy-3-methylphenyl) -4-hydroxyphenylmethane , Bis (5-cyclohexyl-4-hydroxy-3-methylphenyl) -3-hydroxyphenylmethane, bis (5-cyclohexyl-4-hydroxy-3-methylphenyl) -2-hydroxyphenylmethane, bis (3-cyclohexyl) -2-Hydroxyphenyl) -4-hydroxyphenylmethane, bis (3-cyclohexyl-2-hydroxyphenyl) -2-hydroxyphenylmethane, bis (5-cyclohexyl-2-hydroxy-4-methylphenyl) -2-hydroxy Bis (cyclohexylhydroxyphenyl) (hydroxyphenyl) methanes such as phenylmethane and bis (5-cyclohexyl-2-hydroxy-4-methylphenyl) -4-hydroxyphenylmethane or methyl substituents thereof; phenol, p-methoxy Hydroxy groups or amino groups such as phenol, dimethylphenol, hydroquinone, naphthol, pyrocatechol, pyrogallol, pyrogallol monomethyl ether, pyrogallol-1,3-dimethyl ether, gallic acid, aniline, p-aminodiphenylamine, and 4,4'-diaminobenzophenone. Complete ester compound and partial ester compound of quinonediazide group-containing sulfonic acid and homopolymer of novolak, pyrogallol-acetone resin, and p-hydroxystyrene homopolymer or a monomer capable of copolymerizing with the homopolymer. , Amidate, partial amidate and the like. These quinone diazide group-containing compounds (B1) may be used alone or in combination of two or more.

The quinone diazide group-containing sulfonic acid used as the quinone diazide group-containing compound (B1) is not particularly limited, and is, for example, naphthoquinone-1,2-diazide-5-sulfonic acid, naphthoquinone-1,2-diazide-4-. Naphthoquinone diazide sulfonic acid such as sulfonic acid; orthoanthraquinone diazido sulfonic acid and the like can be mentioned, and naphthoquinone diazido sulfonic acid is preferable. The above ester compound of quinonediazide group-containing sulfonic acid, preferably naphthoquinonediazide sulfonic acid, dissolves well in a solvent usually used when a positive composition is used as a solution, and has good compatibility with novolak resin (A1). Is. When these compounds are blended with the first positive type composition as a quinonediazide group-containing compound (B1), it is easy to obtain a highly sensitive first positive type composition.

The method for producing the above ester compound as the quinonediazide group-containing compound (B1) is not particularly limited, and for example, a quinonediazide group-containing sulfonic acid is added as a sulfonyl chloride such as naphthoquinone-1,2-diazide-sulfonyl chloride. Then, in a solvent such as dioxane, a method of condensing in the presence of an alkali such as triethanolamine, alkali carbonate, alkali hydrogencarbonate and the like to complete esterification or partial esterification can be mentioned.

The content of the quinonediazide group-containing compound (B1) is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, based on 100 parts by mass of the novolak resin (A1) from the viewpoint of the sensitivity of the first positive composition. It is preferably 100 parts by mass or less, more preferably 50 parts by mass or less, and even more preferably 30 parts by mass or less.

(Crosslinking agent)
The first positive composition may contain a cross-linking agent. The cross-linking agent can be appropriately selected from the compounds capable of cross-linking the novolak resin (A1). For example, a melamine compound; an amine-based cross-linking agent such as hexamethylenetetramine or a urea derivative; an epoxy compound may be used. Can be done. When the first positive composition contains such a cross-linking agent, it is possible to form a coating resin layer 17 having excellent water resistance, heat resistance, and solvent resistance.

As the melamine compound, a compound having a chemical structure that can be derived from melamine and acting as a cross-linking agent for the novolak resin (A1) can be used, and is represented by, for example, the following formula (I). Compounds can be used.

（式中、Ｒ^１〜Ｒ^６はそれぞれ独立に水素原子又は−ＣＨ_２−Ｏ−Ｒ^７で表される基を示し、Ｒ^７は水素原子又は炭素原子数１〜１０のアルキル基であり、Ｒ^１〜Ｒ^６の少なくとも１つは−ＣＨ_２−Ｏ−Ｒ^７で表される基である。）

(In the formula, R ^{1 to} R ⁶ each independently represent a hydrogen atom or a group represented by -CH _2- O-R ⁷ , and R ⁷ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. At least one of R ^{1 to} R ⁶ is a group represented by -CH _2- O-R ^7. )

The formula _(I), the group represented by -CH 2 ^{-O-R 7,} of the R 1 to R ^6, it is preferably present at least two.
Examples of the alkyl group represented by R ⁷ include alkyl groups having 1 to 6 carbon atoms such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, t-butyl group and n-hexyl group. More preferred.

Examples of the melamine compound represented by the above formula (I) include hexamethylol melamine, hexabutyrol melamine, partially methylolated melamine and alkylated products thereof; tetramethylolbenzoguanamine and partially methylolated benzoguanamine, and alkylated thereof; Can be mentioned.

As the epoxy compound, a compound having an epoxy group and acting as a cross-linking agent for the novolak resin (A1) can be used. As the epoxy compound, a polyfunctional epoxy compound having two or more epoxy groups in one molecule is preferable. In addition, in this specification, among the silane coupling agents described later, those having an epoxy group in the structure are not considered to be epoxy compounds used as a cross-linking agent.

As the epoxy compound, phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, polyfunctional alicyclic epoxy resin, aliphatic polyglycidyl ether and the like are preferable.

The above-mentioned cross-linking agent may be used alone or in combination of two or more.
The content of the cross-linking agent can be 3 parts by mass or more, 10 parts by mass or more, and 15 parts by mass or more with respect to 100 parts by mass of the novolak resin (A1). Further, the content of the cross-linking agent can be 40 parts by mass or less, 30 parts by mass or less, and 25 parts by mass or less with respect to 100 parts by mass of the novolak resin (A1). .. When the content of the cross-linking agent is not less than the above lower limit value, the resin is likely to be sufficiently cross-linked, and when it is not more than the above upper limit value, the storage stability of the first positive composition tends to be good.

(Silane coupling agent)
The first positive composition may contain a silane coupling agent.
Since the silane coupling agent can react with the phenolic hydroxyl group of the novolak resin (A1) via the alkoxy group and / or the reactive group bonded to the silicon atom, it acts as a cross-linking agent and is the first positive type. The coated resin layer 17 formed by using the composition can be brought into close contact with each other, and the water resistance, solvent resistance, heat resistance, etc. of the coated resin layer 17 can be improved, and the coated resin layer 17 is patterned. The adhesion with the metal layer 18 can be improved.

Examples of the silane coupling agent include methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, and n-butyltrimethoxysilane. Monoalkyltrialkoxysilanes such as n-butyltriethoxysilane; dialkyldialkoxysilanes such as dimethyldimethoxysilane and dimethyldiethoxysilane; monophenyltrialkoxysilanes such as phenyltrimethoxysilane and phenyltriethoxysilane; diphenyldimethoxysilane, Diphenyldialkoxysilanes such as diphenyldiethoxysilane; monovinyltrialkoxysilanes such as vinyltrimethoxysilane and vinyltriethoxysilane; 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropyl (Meta) acryloxyalkyl monoalkyldialkoxysilanes such as methyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane; (meth) acryloxyalkyltrialkoxysilanes such as 3-acryloxypropyltrimethoxysilane; 3-amino Amino group-containing tri such as propyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane Alkoxysilane; Non-lipid ring-type epoxy group-containing alkyltrialkoxysilane such as 3-glycidoxypropyltrimethoxysilane and 3-glycidoxypropyltriethoxysilane; Non-fat such as 3-glycidoxypropylmethyldiethoxysilane Cyclic epoxy group-containing alkyl monoalkyldialkoxysilane; alicyclic epoxy group-containing alkyl such as 2- (3,4-epylcyclohexyl) ethyltrimethoxysilane, 2- (3,4-epylcyclohexyl) ethyltriethoxysilane Trialkoxysilane; alicyclic epoxy group-containing alkylmonoalkyldialkoxysilane such as 2- (3,4-epylcyclohexyl) ethylmethyldiethoxysilane; [(3-ethyl-3-oxetanyl) methoxy] propyltrimethoxysilane , [(3-Ethyl-3-oxetanyl) methoxy] oxetanyl group-containing alkyltrialkoxysilane such as propyltriethoxysilane; Mercaptoalkyltrialkoxysilanes such as 3-mercaptopropyltrimethoxysilane; mercaptoalkylmonoalkyldialkoxysilanes such as 3-mercaptopropylmethyldimethoxysilane; ureidoalkyltrialkoxysilanes such as 3-ureidopropyltriethoxysilane; 3-isocyanate Isocyanate alkyltrialkoxysilanes such as propyltriethoxysilane; alkyltrialkoxysilanes containing acid anhydride groups such as 3-trimethoxysilylpropyl succinate; Nt-butyl-3- (3-trimethoxysilylpropyl) An imide group-containing alkyl trialkoxysilane such as imide succinate; and the like. The silane coupling agent may be used alone or in combination of two or more.

Among the silane coupling agents, a silane coupling agent having a reactive group is preferable.
As the silane coupling agent having a reactive group, a silane coupling agent having a vinyl group, an amino group, an epoxy group or an oxetanyl group is preferable. A silane coupling agent having an epoxy group is more preferable from the viewpoint of having high compatibility with the developing solution, reducing the residue (undissolved residue), and particularly forming the coating resin layer 17 having excellent adhesion to the metal.

As the silane coupling agent having an epoxy group, either a silane coupling agent having a non-alicyclic epoxy group or a silane coupling agent having an alicyclic epoxy group can be preferably used.

The content of the silane coupling agent can be 0.1 part by mass or more, 0.5 part by mass or more, and 1 part by mass or more with respect to 100 parts by mass of the novolak resin (A1). can do. Further, the content of the silane coupling agent can be 10 parts by mass or less, 7 parts by mass or less, and 5 parts by mass or less with respect to 100 parts by mass of the novolak resin (A1). It can be 3 parts by mass or less.
When the content of the silane coupling agent is at least the above lower limit value, it is easy to form the coating resin layer 17 having excellent adhesion to the patterned metal layer 18.
When the content of the silane coupling agent is not more than the above upper limit value, it is easy to suppress the generation of residues during development due to the condensation reaction between the silane coupling agents during storage.

(Colorant)
The optical density of the coating resin layer 17 formed by the method of the present embodiment is 0.10 / μm or more. From the viewpoint of achieving such an optical density, the first positive composition typically contains a colorant for the purpose of adjusting the optical density.
The colorant is not particularly limited, but for example, a compound classified as Pigment in the Color Index (CI; The Society of Dyers and Colorists), specifically, as follows. It is preferable to use one having a color index (CI) number.

Examples of preferably usable yellow pigments include C.I. I. Pigment Yellow 1 (hereinafter, "CI Pigment Yellow" is the same and only the number is described), 3, 11, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53. , 55, 60, 61, 65, 71, 73, 74, 81, 83, 86, 93, 95, 97, 98, 99, 100, 101, 104, 106, 108, 109, 110, 113, 114, 116 , 117, 119, 120, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 166, 167, 168, 175, 180. , And 185.

Examples of preferably usable orange pigments include C.I. I. Pigment Orange 1 (hereinafter, "CI Pigment Orange" is the same and only the number is described), 5, 13, 14, 16, 17, 24, 34, 36, 38, 40, 43, 46. , 49, 51, 55, 59, 61, 63, 64, 71, and 73.

Examples of suitably usable purple pigments include C.I. I. Pigment Violet 1 (hereinafter, "CI Pigment Violet" is the same and only the number is described), 19, 23, 29, 30, 32, 36, 37, 38, 39, 40, and 50. Can be mentioned.

Examples of preferably usable red pigments include C.I. I. Pigment Red 1 (hereinafter, "CI Pigment Red" is the same and only the number is described.) 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 40, 41, 42, 48: 1, 48: 2, 48: 3, 48: 4, 49: 1, 49: 2, 50: 1, 52: 1, 53: 1, 57, 57: 1, 57: 2, 58: 2, 58: 4, 60: 1, 63: 1, 63: 2, 64: 1, 81: 1, 83, 88, 90: 1, 97, 101, 102, 104, 105, 106, 108, 112, 113, 114, 122, 123, 144, 146, 149, 150, 151, 155, 166, 168, 170, 171, 172, 174, 175, 176, 177, 178, 179, 180, 185, 187, 188, 190, 192, 193, 194, 202, 206, 207, 208, 209, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, 242, 243, 245, 254, 255, 264, and 265.

Examples of preferably usable blue pigments include C.I. I. Pigment Blue 1 (hereinafter, "CI Pigment Blue" is the same and only the number is described), 2, 15, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64 , And 66.

Examples of pigments of the above other hues that can be suitably used include C.I. I. Pigment Green 7, C.I. I. Pigment Green 36, C.I. I. Pigment Green 37 and other green pigments, C.I. I. Pigment Brown 23, C.I. I. Pigment Brown 25, C.I. I. Pigment Brown 26, C.I. I. Pigment Brown 28 and other brown pigments, C.I. I. Pigment Black 1, C.I. I. Examples thereof include black pigments such as Pigment Black 7.

In addition, the first positive composition may contain a light-shielding agent as a colorant. When the colorant is a light-shielding agent, it is preferable to use a black pigment or a purple pigment as the light-shielding agent. Examples of black pigments and purple pigments include carbon blacks, perylene pigments, lactam pigments, titanium blacks, copper, iron, manganese, cobalt, chromium, nickel, zinc, calcium, silver and other metal oxides and composite oxides. , Metal sulfides, metal sulfates, metal carbonates, and other pigments, regardless of whether they are organic or inorganic.

As the carbon black, known carbon blacks such as channel black, furnace black, thermal black, and lamp black can be used. Moreover, you may use resin-coated carbon black.

As the carbon black, carbon black that has been subjected to a treatment for introducing an acidic group is also preferable. The acidic group introduced into carbon black is a functional group that exhibits acidity as defined by Bronsted. Specific examples of the acidic group include a carboxy group, a sulfonic acid group, a phosphoric acid group and the like. The acidic group introduced into the carbon black may form a salt. The cation forming a salt with the acidic group is not particularly limited as long as the object of the present invention is not impaired. Examples of the cation include various metal ions, cations of nitrogen-containing compounds, ammonium ions and the like, and alkali metal ions such as sodium ion, potassium ion and lithium ion, and ammonium ions are preferable.

The carbon black that has been subjected to the treatment for introducing the acidic group described above has one or more functional groups selected from the group consisting of a carboxylic acid group, a carboxylic acid base, a sulfonic acid group, and a sulfonic acid base. Carbon black is preferred.

The method for introducing an acidic group into carbon black is not particularly limited. Examples of the method for introducing an acidic group include the following methods.
1) A method of introducing a sulfonic acid group into carbon black by a direct substitution method using concentrated sulfuric acid, fuming sulfuric acid, chlorosulfonic acid or the like, or an indirect substitution method using sulfite, hydrogen sulfite or the like.
2) A method of diazo-coupling an organic compound having an amino group and an acidic group with carbon black.
3) A method in which an organic compound having a halogen atom and an acidic group and carbon black having a hydroxyl group are reacted by Williamson's etherification method.
4) A method of reacting an organic compound having a halocarbonyl group and an acidic group protected by a protecting group with carbon black having a hydroxyl group.
5) A method of deprotecting carbon black after carrying out a Friedel-Crafts reaction using an organic compound having a halocarbonyl group and an acidic group protected by a protecting group.

Among these methods, method 2) is preferable because the introduction treatment of acidic groups is easy and safe. As the organic compound having an amino group and an acidic group used in the method 2), a compound in which an amino group and an acidic group are bonded to an aromatic group is preferable. Examples of such compounds include aminobenzenesulfonic acids such as sulfanilic acid and aminobenzoic acids such as 4-aminobenzoic acid.

The number of moles of acidic groups introduced into carbon black is not particularly limited as long as the object of the present invention is not impaired. The number of moles of acidic groups introduced into carbon black is preferably 1 to 200 mmol, more preferably 5 to 100 mmol, based on 100 g of carbon black.

The carbon black into which the acidic group has been introduced may be coated with a resin.
When a photosensitive resin composition containing carbon black coated with a resin is used, it is easy to form a light-shielding coating resin layer 17 having excellent light-shielding properties and low surface reflectance.
Examples of resins that can be used for coating carbon black include thermosetting resins such as phenol resin, melamine resin, xylene resin, diallyl phthalate resin, glyptal resin, epoxy resin, and alkylbenzene resin, and polystyrene, polycarbonate, polyethylene terephthalate, and poly. Examples thereof include thermoplastic resins such as butylene terephthalate, modified polyphenylene oxide, polysulphon, polyparaphenylene terephthalamide, polyamideimide, polyimide, polyaminobismaleimide, polyether sulfopolyphenylensulphon, polyarylate, and polyether ether ketone. The coating amount of the resin on the carbon black is preferably 1 to 30% by mass with respect to the total of the mass of the carbon black and the mass of the resin.

Further, a perylene-based pigment is also preferable as the light-shielding agent. Specific examples of the perylene-based pigment include a perylene-based pigment represented by the following formula (e-1), a perylene-based pigment represented by the following formula (e-2), and a perylene-based pigment represented by the following formula (e-3). Perylene-based pigments can be mentioned. In the commercially available products, product names K0084 and K0083 manufactured by BASF, Pigment Black 21, 30, 31, 32, 33, 34 and the like can be preferably used as the perylene-based pigment.

式（ｅ−１）中、Ｒ^ｅ１及びＲ^ｅ２は、それぞれ独立に炭素原子数１〜３のアルキレン基を表し、Ｒ^ｅ３及びＲ^ｅ４は、それぞれ独立に、水素原子、水酸基、メトキシ基、又はアセチル基を表す。

In the formula (e-1), R ^e1 and R ^e2 each independently represent an alkylene group having 1 to 3 carbon atoms, and R ^e3 and R ^e4 independently represent a hydrogen atom, a hydroxyl group, a methoxy group, or a hydrogen atom, respectively. Represents an acetyl group.

式（ｅ−２）中、Ｒ^ｅ５及びＲ^ｅ６は、それぞれ独立に、炭素原子数１〜７のアルキレン基を表す。

In the formula (e-2), R ^e5 and R ^e6 independently represent an alkylene group having 1 to 7 carbon atoms.

式（ｅ−３）中、Ｒ^ｅ７及びＲ^ｅ８は、それぞれ独立に、水素原子、炭素原子数１〜２２のアルキル基であり、Ｎ，Ｏ、Ｓ、又はＰのヘテロ原子を含んでいてもよい。Ｒ^ｅ７及びＲ^ｅ８がアルキル基である場合、当該アルキル基は、直鎖状であっても、分岐鎖状であってもよい。

In formula (e-3), R ^e7 and R ^e8 are independently alkyl groups having a hydrogen atom and 1 to 22 carbon atoms, and may contain heteroatoms of N, O, S, or P, respectively. Good. When R ^e7 and R ^e8 are alkyl groups, the alkyl groups may be linear or branched.

The compound represented by the above formula (e-1), the compound represented by the formula (e-2), and the compound represented by the formula (e-3) are, for example, JP-A-62-1753. , No. 63-26784 can be synthesized by using the method described in Japanese Patent Publication No. 63-26784. That is, a heating reaction is carried out in water or an organic solvent using perylene-3,5,9,10-tetracarboxylic acid or its dianhydride or amines as raw materials. Then, the desired product can be obtained by reprecipitating the obtained crude product in sulfuric acid or recrystallizing it in water, an organic solvent or a mixed solvent thereof.

In order to satisfactorily disperse the perylene-based pigment in the first positive-type composition, the average particle size of the perylene-based pigment is preferably 10 to 1000 nm.

Further, as the light shielding agent, a lactam pigment may be included. Examples of the lactam pigment include compounds represented by the following formula (e-4).

In formula (e-4), X ^e shows a double bond and is independently E-form or Z-form as geometric isomers, and ^Re9 is independently hydrogen atom, methyl group, nitro group, and methoxy. ^{Represents a} group, a bromine atom, a chlorine atom, a fluorine atom, a carboxy group, or a sulfo group, ^{Re 10} independently represents a hydrogen atom, a methyl group, or a phenyl group, and ^{Re 11} independently represents a hydrogen atom. , Methyl group, or hydrogen atom.
The compound represented by the formula (e-4) can be used alone or in combination of two or more.
R ^e9 is preferably bonded to the 6-position of the dihydroindron ring because the compound represented by the formula (e-4) can be easily produced, and ^Re11 is bonded to the 4-position of the dihydroindron ring. It is preferable to do so. From the same ^viewpoint, R ^{e9, R e10,} and ^{R e11} are preferably hydrogen atom.
The compound represented by the formula (e-4) has an EE form, a ZZ form, and an EZ form as geometric isomers, but may be a single compound of any one of these, or these geometric isomers. May be a mixture of.
The compound represented by the formula (e-4) can be produced, for example, by the methods described in International Publication No. 2000/24736 and International Publication No. 2010/081624.

In order to disperse the lactam pigment well in the first positive composition, the average particle size of the lactam pigment is preferably 10 to 1000 nm.

Further, fine particles containing silver-tin (AgSn) alloy as a main component (hereinafter, referred to as "AgSn alloy fine particles") are also preferably used as a light-shielding agent. The AgSn alloy fine particles may be mainly composed of the AgSn alloy, and may contain, for example, Ni, Pd, Au, etc. as other metal components.
The average particle size of the AgSn alloy fine particles is preferably 1 to 300 nm.

When the AgSn alloy is represented by the chemical formula AgxSn, the range of x in which a chemically stable AgSn alloy can be obtained is 1 ≦ x ≦ 10, and the range of x in which both chemical stability and blackness can be obtained at the same time is. 3 ≦ x ≦ 4.
Here, when the mass ratio of Ag in the AgSn alloy is obtained in the range of x above,
When x = 1, Ag / AgSn = 0.4762
When x = 3, 3.Ag / Ag3Sn = 0.7317
When x = 4, 4. Ag / Ag4Sn = 0.7843
When x = 10, 10 · Ag / Ag10Sn = 0.9008
Will be.
Therefore, this AgSn alloy becomes chemically stable when it contains 47.6 to 90% by mass of Ag, and is effective with respect to the amount of Ag when it contains 73.17 to 78.43% by weight of Ag. Chemical stability and blackness can be obtained.

The AgSn alloy fine particles can be produced by using a usual fine particle synthesis method. Examples of the fine particle synthesis method include a gas phase reaction method, a spray pyrolysis method, an atomizing method, a liquid phase reaction method, a freeze-drying method, and a hydrothermal synthesis method.

The AgSn alloy fine particles have high insulating properties, but the surface may be covered with an insulating film in order to further improve the insulating properties. As a material for such an insulating film, a metal oxide or an organic polymer compound is suitable.
As the metal oxide, insulating metal oxides such as silicon oxide (silica), aluminum oxide (alumina), zirconium oxide (zirconia), yttrium oxide (itria), titanium oxide (titania) and the like are preferably used. Be done.
Further, as the organic polymer compound, a resin having an insulating property, for example, a polyimide, a polyether, a polyacrylate, a polyamine compound or the like is preferably used.

The thickness of the insulating film is preferably 1 to 100 nm, more preferably 5 to 50 nm in order to sufficiently enhance the insulating property on the surface of the AgSn alloy fine particles.
The insulating film can be easily formed by a surface modification technique or a surface coating technique. In particular, it is preferable to use an alkoxide such as tetraethoxysilane or aluminum triethoxyde because an insulating film having a uniform film thickness can be formed at a relatively low temperature.

As the light-shielding agent, the above-mentioned perylene-based pigment, lactam-based pigment, and AgSn alloy fine particles may be used alone, or these may be used in combination.
In addition, the light-shielding agent may contain a pigment having a hue such as red, blue, green, or yellow in addition to the above-mentioned black pigment or purple pigment for the purpose of adjusting the color tone. The pigments having other hues of the black pigment and the purple pigment can be appropriately selected from known pigments. For example, as the pigments having other hues of black pigments and purple pigments, the above-mentioned various pigments can be used. The amount of the pigment having a hue other than the black pigment and the purple pigment is preferably 15% by mass or less, more preferably 10% by mass or less, based on the total mass of the light-shielding agent.

Further dispersants may be used to uniformly disperse the colorant in the first positive composition. As such a dispersant, it is preferable to use a polyethyleneimine-based, urethane resin-based, or acrylic resin-based polymer dispersant. In particular, when carbon black is used as the colorant, it is preferable to use an acrylic resin-based dispersant as the dispersant.
Depending on the type of dispersant, the manufacturing conditions of the display device, and the conditions of use, the volatile components caused by the dispersant may adversely affect the display device. Therefore, the colorant is dispersed without using the dispersant. It is also preferable to be done.

Further, the inorganic pigment and the organic pigment may be used alone or in combination of two or more, but when they are used in combination, the amount of the organic pigment is 10 to 80 parts by mass with respect to 100 parts by mass of the total amount of the inorganic pigment and the organic pigment. It is preferable to use it in the range of 20 to 40 parts by mass, and it is more preferable to use it in the range of 20 to 40 parts by mass.

In the first positive composition, a dye can be used as the colorant in addition to the pigment. This dye may be appropriately selected from known materials.
Examples of dyes applicable to the first positive type composition include azo dyes, metal complex salt azo dyes, anthraquinone dyes, triphenylmethane dyes, xanthene dyes, cyanine dyes, naphthoquinone dyes, quinoneimine dyes, methine dyes, and phthalocyanine dyes. And so on.
Further, these dyes can be dispersed in an organic solvent or the like by rake (chlorination) and used as a colorant.
In addition to these dyes, for example, JP-A-2013-225132, JP-A-2014-178477, JP-A-2013-137543, JP-A-2011-38085, JP-A-2014-197206, etc. The dyes and the like described can also be preferably used.
These dyes can also be used in combination with the above-mentioned pigments (for example, perylene-based pigments, lactam-based pigments, AgSn alloy fine particles, etc.).

The amount of the colorant used in the first positive composition is not particularly limited as long as the optical density of the coating resin layer 17 after the post-baking step is 0.10 / μm or more.
The amount of the colorant used in this first positive composition is, for example, preferably 1 part by mass or more, more preferably 3 parts by mass or more, and 5 parts by mass or more with respect to 100 parts by mass of the novolak resin (A1). Further, 60 parts by mass or less is preferable, 50 parts by mass or less is more preferable, 45 parts by mass or less is further preferable, and 40 parts by mass or less is even more preferable.
Further, the optical density of the coating resin layer 17 is more preferably 0.20 to 2.0 / μm, and further preferably 0.30 to 1.0 / μm.

The colorant is preferably a dispersion liquid dispersed in the presence or absence of the dispersant at an appropriate concentration, and then added to the first positive composition.

(Other ingredients)
The first positive composition may contain various additives such as a sensitizer, an adhesion improver, a surfactant, and a plasticizer as long as the object of the present invention is not impaired.

-Sensitizer The sensitizer is not particularly limited, and can be arbitrarily selected from the sensitizers usually used in the positive composition. Examples of the sensitizer include compounds having a phenolic hydroxyl group having a molecular weight of 1000 or less.

-Adhesion improver The adhesion improver can be appropriately selected from materials capable of improving the adhesion between the coating resin layer 17 and the patterned metal layer 18. For example, a hydroxyalkyl nitrogen-containing heterocyclic compound such as 2-hydroxyethylpyridine can be used as the adhesion improver.

-Surfactant The first positive composition may contain a surfactant in order to improve coatability, defoaming property, leveling property and the like. Examples of surfactants include BM-1000, BM-1100 (manufactured by BM Chemie), Megafuck F142D, Megafuck F172, Megafuck F173, Megafuck F183 (manufactured by Dainippon Ink and Chemicals), and Florard FC-135. , Florard FC-170C, Florard FC-430, Florard FC-431 (manufactured by Sumitomo 3M), Surfron S-112, Surfron S-113, Surfron S-131, Surfron S-141, Surfron S-145 (manufactured by Asahi Glass Co., Ltd.) ), SH-28PA, SH-190, SH-193, SZ-6032, SF-8428 (manufactured by Toray Silicone), BYK-310, BYK-330 (manufactured by Big Chemie Japan), etc. Silicon-based or fluorine-based surfactants can be used.

The content of the surfactant is preferably 0.05 parts by mass or more and 5 parts by mass or less with respect to 100 parts by mass of the novolak resin (A1).

<Solvent>
The first positive photosensitive resin composition is preferably used in the form of a solution by dissolving each of the above components in an appropriate solvent. Such solvents include ethylene glycol alkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether; diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, and Diethylene glycol dialkyl ethers such as diethylene glycol dibutyl ether; ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate; propylene such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and propylene glycol monopropyl ether acetate. Glycolalkyl ether acetates; ketones such as acetone, methyl ethyl ketone, cyclohexanone, and methylamyl ketone; aromatic hydrocarbons such as toluene and xylene; cyclic ethers such as dioxane; and methyl 2-hydroxypropionate, 2- Ethyl hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl oxyacetate, methyl 2-hydroxy-3-methylbutanoate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, Examples thereof include esters such as ethyl formate, ethyl acetate, butyl acetate, methyl acetoacetate, and ethyl acetoacetate. These solvents may be used alone or in combination of two or more.

The content of the solvent in the first positive composition is appropriately adjusted in consideration of the viscosity and coatability of the first positive composition. Specifically, the solvent is used so that the solid content concentration of the first positive composition is preferably 5 to 50% by mass, more preferably 10 to 30% by mass.

<Method for preparing the first positive composition>
The first positive composition can be prepared by blending each of the above components in a predetermined ratio, and then mixing and stirring by a usual method. Further, if necessary, it may be further filtered using a mesh, a membrane filter or the like.

[Second positive composition]
As described above, the second positive composition contains a resin (A2) whose solubility in alkali is increased by the action of an acid, and a compound (B2) which generates an acid by irradiation with active light or radiation.
Hereinafter, the resin (A2) whose solubility in alkali is increased by the action of an acid is also referred to as “resin (A2)”. Further, the compound (B2) that generates an acid by irradiation with active light or radiation is also referred to as an "acid generator (B2)".
Hereinafter, essential or optional components contained in the second positive composition will be described.

(Resin (A2))
The second positive composition contains a resin (A2) whose solubility in alkali is increased by the action of an acid as a base resin component (A). The resin (A2) is not particularly limited, and any resin whose solubility in alkali is increased by the action of an acid can be used.
The degree of dispersion of the resin (A2) is preferably 1 or more and 20 or less, more preferably 2 to 17, particularly preferably 3 to 15, and even more preferably 4 to 12, similar to the above-mentioned base resin component (A).
Among the resins (A2), a novolak resin (A2-1) having an acid dissociative dissolution inhibitory group (hereinafter, also simply referred to as novolak resin (A2-1)) and a polyhydroxystyrene resin having an acid dissociative dissolution inhibitory group. At least one resin selected from the group consisting of (A2-2) (hereinafter, also simply referred to as polyhydroxystyrene resin (A2-2)) and acrylic resin (A2-3) having a specific structural unit described later. Is preferably contained.

・ Novolac resin (A2-1)
As the novolak resin (A2-1), a resin containing a structural unit represented by the following formula (a1) can be used.

In the above formula (a1), R ^1a represents an acid dissociative dissolution inhibitory group, and R ^2a and R ^3a independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, respectively.

Examples of the acid dissociative dissolution inhibitor group represented by R ^1a include a group represented by the following formulas (a2) and (a3), a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms. , Vinyloxyethyl group, tetrahydropyranyl group, tetrafuranyl group, or trialkylsilyl group is preferable.

In the above formulas (a2) and (a3), ^R4a and ^R5a each independently represent a hydrogen atom or a linear or branched alkyl group having 1 to 6 carbon atoms, and ^R6a is a carbon atom. The number 1 to 10 represents a linear, branched, or cyclic alkyl group, R ^7a represents a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms, and o is 0 or. Represents 1.

Examples of the linear or branched alkyl group include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group and the like. .. Examples of the cyclic alkyl group include a cyclopentyl group and a cyclohexyl group.

Here, as the acid dissociative dissolution inhibitory group represented by the above formula (a2), specifically, a methoxyethyl group, an ethoxyethyl group, an n-propoxyethyl group, an isopropoxyethyl group, an n-butoxyethyl group, Examples thereof include isobutoxyethyl group, tert-butoxyethyl group, cyclohexyloxyethyl group, methoxypropyl group, ethoxypropyl group, 1-methoxy-1-methyl-ethyl group, 1-ethoxy-1-methylethyl group and the like. Specific examples of the acid dissociative dissolution inhibitory group represented by the above formula (a3) include a tert-butoxycarbonyl group and a tert-butoxycarbonylmethyl group. Examples of the trialkylsilyl group include those having 1 to 6 carbon atoms in each alkyl group such as a trimethylsilyl group and a tri-tert-butyldimethylsilyl group.

-Polyhydroxystyrene resin (A2-2)
As the polyhydroxystyrene resin (A2-2), a resin containing a structural unit represented by the following formula (a4) can be used.

In the above formula (a4), R ^8a represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R ^9a represents an acid dissociative dissolution inhibitory group.

The alkyl group having 1 to 6 carbon atoms is, for example, a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms. Examples of the linear or branched alkyl group include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group and the like. Examples of the cyclic alkyl group include a cyclopentyl group and a cyclohexyl group.

As the acid dissociative dissolution inhibitor group represented by R ^9a , the same acid dissociative dissolution inhibitor group as those exemplified in the above formulas (a2) and (a3) can be used.

Further, the polyhydroxystyrene resin (A2-2) can contain other polymerizable compounds as a constituent unit for the purpose of appropriately controlling the physical and chemical properties. Examples of such a polymerizable compound include known radical polymerizable compounds and anionic polymerizable compounds. Examples of such polymerizable compounds include monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid; dicarboxylic acids such as maleic acid, fumaric acid, and itaconic acid; 2-methacryloyloxyethyl succinic acid, 2-. Methacrylic acid derivatives having carboxy groups and ester bonds such as methacryloyloxyethyl maleic acid, 2-methacryloyloxyethylphthalic acid, 2-methacryloyloxyethyl hexahydrophthalic acid; methyl (meth) acrylate, ethyl (meth) acrylate, butyl (Meta) acrylic acid alkyl esters such as (meth) acrylate; (meth) acrylic acid hydroxyalkyl esters such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate; phenyl (meth) acrylate, (Meta) acrylic acid aryl esters such as benzyl (meth) acrylate; Dicarboxylic acid diesters such as diethyl maleate and dibutyl fumarate; styrene, α-methylstyrene, chlorostyrene, chloromethylstyrene, vinyltoluene, hydroxystyrene, Vinyl group-containing aromatic compounds such as α-methylhydroxystyrene and α-ethylhydroxystyrene; Vinyl group-containing aliphatic compounds such as vinyl acetate; Conjugate diolefins such as butadiene and isoprene; Acrylonitrile, methacrylonitrile and the like Examples thereof include nitrile group-containing polymerizable compounds; chlorine-containing polymerizable compounds such as vinyl chloride and vinylidene chloride; and amide bond-containing polymerizable compounds such as acrylamide and methacrylicamide.

・ Acrylic resin (A2-3)
As the acrylic resin (A2-3), a resin containing the structural units represented by the following formulas (a5), (a6-1), (a6-2), and (a7) in an appropriate combination can be used. ..

In the above formulas (a5), (a6-1), (a6-2), and (a7), R ^10a and R ^{14a to} R ^19a are independently linear hydrogen atoms and 1 to 6 carbon atoms, respectively. Represents a linear or branched alkyl group, a fluorine atom, or a linear or branched fluorinated alkyl group having 1 to 6 carbon atoms, and R ^{11a to} R ^13a independently have 1 to 6 carbon atoms. Represents a linear or branched alkyl group, a linear or branched fluorinated alkyl group having 1 to 6 carbon atoms, or an aliphatic cyclic group having 5 to 20 carbon atoms, R ^12a and R ^13a. , taken together, together with the carbon atom to which both are attached may form a hydrocarbon ring carbon atoms 5 to 20, Y ^a is optionally substituted aliphatic cyclic group Alternatively, it represents an alkyl group, p represents an integer of 0 to 4, and q represents 0 or 1.

Examples of the linear or branched alkyl group include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group and the like. Can be mentioned. Further, the fluorinated alkyl group is one in which a part or all of the hydrogen atom of the alkyl group is substituted with a fluorine atom.
Specific examples of the aliphatic cyclic group include a group obtained by removing one or more hydrogen atoms from a polycycloalkane such as a monocycloalkane, a bicycloalkane, a tricycloalkane, or a tetracycloalkane. Specifically, a group obtained by removing one hydrogen atom from monocycloalkanes such as cyclopentane, cyclohexane, cycloheptane, and cyclooctane, and polycycloalkanes such as adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane. Can be mentioned. In particular, a group obtained by removing one hydrogen atom from cyclohexane or adamantane (which may further have a substituent) is preferable.

When the R ^12a and R ^13a do not bond with each other to form a hydrocarbon ring, the carbon atoms of the R ^11a , R ^12a , and R ^13a are high in contrast and have good resolution, depth of focus, and the like. It is preferably a linear or branched alkyl group of number 2-4. The R ^15a , R ^16a , R ^18a , and R ^19a are preferably hydrogen atoms or methyl groups.

The R ^12a and R ^13a may form an aliphatic cyclic group having 5 to 20 carbon atoms together with the carbon atom to which both are bonded. Specific examples of such an aliphatic cyclic group include a group obtained by removing one or more hydrogen atoms from a polycycloalkane such as a monocycloalkane, a bicycloalkane, a tricycloalkane, or a tetracycloalkane. Specifically, one or more hydrogen atoms were removed from monocycloalkanes such as cyclopentane, cyclohexane, cycloheptane, and cyclooctane, and polycycloalkanes such as adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane. The group is mentioned. In particular, a group obtained by removing one or more hydrogen atoms from cyclohexane or adamantane (which may further have a substituent) is preferable.

Further, when the aliphatic cyclic group formed by R ^12a and R ^13a has a substituent on its ring skeleton, examples of the substituent include a hydroxyl group, a carboxy group, a cyano group, and an oxygen atom (= O). ) And other polar groups, and linear or branched alkyl groups having 1 to 4 carbon atoms can be mentioned. As the polar group, an oxygen atom (= O) is particularly preferable.

Said Y ^a is an aliphatic cyclic group or an alkyl group, and monocycloalkane, bicycloalkane, tricycloalkane, or the like groups obtained by removing one or more hydrogen atoms from polycycloalkanes such as tetramethylammonium cycloalkane .. Specifically, one or more hydrogen atoms were removed from monocycloalkanes such as cyclopentane, cyclohexane, cycloheptane, and cyclooctane, and polycycloalkanes such as adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane. The basis etc. can be mentioned. In particular, a group obtained by removing one or more hydrogen atoms from adamantane (which may further have a substituent) is preferable.

Furthermore, the alicyclic group of the abovementioned Y ^a is, the case of having a substituent on the ring skeleton, examples of the substituent, a hydroxyl group, a carboxyl group, a cyano group, an oxygen atom (= O) polar groups such as Examples thereof include a linear or branched alkyl group having 1 to 4 carbon atoms. As the polar group, an oxygen atom (= O) is particularly preferable.

Also, if Y ^a is an alkyl group, having 1 to 20 carbon atoms, it is preferred that preferably a linear or branched alkyl group having 6 to 15. Such an alkyl group is particularly preferably an alkoxyalkyl group, and examples of such an alkoxyalkyl group include a 1-methoxyethyl group, a 1-ethoxyethyl group, a 1-n-propoxyethyl group, and a 1-isopropoxy. Ethyl group, 1-n-butoxyethyl group, 1-isobutoxyethyl group, 1-tert-butoxyethyl group, 1-methoxypropyl group, 1-ethoxypropyl group, 1-methoxy-1-methyl-ethyl group, 1 Examples thereof include -ethoxy-1-methylethyl group.

As a preferable specific example of the structural unit represented by the above formula (a5), those represented by the following formulas (a5-1) to (a5-33) can be mentioned.

In the above formulas (a5-1) to (a5-33), R ^20a represents a hydrogen atom or a methyl group.

As a preferable specific example of the structural unit represented by the above formula (a6-1), those represented by the following formulas (a6-1-1) to (a6-1-25) can be mentioned.

In the above formulas (a6-1-1) to (a6-1-25), R ^20a represents a hydrogen atom or a methyl group.

As a preferable specific example of the structural unit represented by the above formula (a6-2), the carbonyl group represented by the above formulas (a6-1-1) to (a6-1-25) is a phenylene group (preferably p). -The unit changed to (phenylene group) can be mentioned.

As a preferable specific example of the structural unit represented by the above formula (a7), those represented by the following formulas (a7-1) to (a7-15) can be mentioned.

In the above formulas (a7-1) to (a7-15), R ^20a represents a hydrogen atom or a methyl group.

Further, the acrylic resin (A2-3) is made from a copolymer containing a structural unit derived from a polymerizable compound having an ether bond with respect to the structural units represented by the above formulas (a5) to (a7). Resin may be used.

Examples of the polymerizable compound having an ether bond include a radically polymerizable compound such as a (meth) acrylic acid derivative having an ether bond and an ester bond, and specific examples thereof include 2-methoxyethyl (meth) acrylate. , 2-Esterethyl (meth) acrylate, methoxytriethylene glycol (meth) acrylate, 3-methoxybutyl (meth) acrylate, ethylcarbitol (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) Examples thereof include acrylate, methoxypolypropylene glycol (meth) acrylate, and tetrahydrofurfuryl (meth) acrylate. The polymerizable compound having an ether bond is preferably 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, or methoxytriethylene glycol (meth) acrylate. These polymerizable compounds may be used alone or in combination of two or more.

Further, the acrylic resin (A2-3) can contain other polymerizable compounds as a constituent unit for the purpose of appropriately controlling the physical and chemical properties. Examples of such a polymerizable compound include known radical polymerizable compounds and anionic polymerizable compounds.

Examples of such polymerizable compounds include monocarboxylic acids such as acrylic acid, methacrylic acid and crotonic acid; dicarboxylic acids such as maleic acid, fumaric acid and itaconic acid; 2-methacryloyloxyethyl succinic acid and 2-methacryloyloxy. Methacrylate derivatives having carboxy groups and ester bonds such as ethylmaleic acid, 2-methacryloyloxyethylphthalic acid, 2-methacryloyloxyethyl hexahydrophthalic acid; methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) (Meta) acrylic acid alkyl esters such as acrylate and cyclohexyl (meth) acrylate; (meth) acrylic acid hydroxyalkyl esters such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate; phenyl ( (Meta) acrylic acid aryl esters such as meta) acrylates and benzyl (meth) acrylates; dicarboxylic acid diesters such as diethyl maleate and dibutyl fumarate; styrene, α-methylstyrene, chlorostyrene, chloromethylstyrene, vinyltoluene , Hydroxystyrene, α-methylhydroxystyrene, α-ethylhydroxystyrene and other vinyl group-containing aromatic compounds; vinyl group-containing aliphatic compounds such as vinyl acetate; conjugated diolefins such as butadiene and isoprene; acrylonitrile, methacryl Binitrile group-containing polymerizable compounds such as bnitrile; chlorine-containing polymerizable compounds such as vinyl chloride and vinylidene chloride; amide bond-containing polymerizable compounds such as acrylamide and methacrylicamide; and the like can be mentioned.

Further, as the polymerizable compound, a compound having an epoxy group and / or an oxetanyl group is also preferable. The 3-membered cyclic ether group is also called an epoxy group, and the 4-membered cyclic ether group is also called an oxetanyl group.
A compound having an epoxy group and / or an oxetanyl group may have at least one epoxy group or an oxetanyl group in one molecule, and has one or more epoxy groups and one or more oxetanyl groups or two or more epoxys. It may have a group or two or more oxetanyl groups. A compound having a total of 1 to 3 epoxy groups and / or oxetanyl groups is preferable, a compound having a total of 1 or 2 epoxy groups and / or oxetanyl groups is more preferable, and a compound having 1 epoxy group or oxetanyl group is further preferable. ..

Specific examples of the polymerizable compound having an epoxy group include glycidyl acrylate, glycidyl methacrylate, glycidyl α-ethyl acrylate, glycidyl α-n-propyl acrylate, glycidyl α-n-butyl acrylate, and acrylic acid. -3,4-epoxybutyl, -3,4-epoxybutyl methacrylate, -3,4-epoxycyclohexylmethyl acrylate, -3,4-epoxycyclohexylmethylmethacrylate, -3,4-ethylacrylic acid-3,4- Epoxycyclohexylmethyl, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, compounds containing an alicyclic epoxy skeleton described in paragraphs 0031 to 0035 of JP-A-2005-46991, etc. Can be mentioned.
Specific examples of the polymerizable compound having an oxetanyl group include (meth) acrylic acid esters having an oxetanyl group described in paragraphs 0011 to 0016 of JP-A-2001-330953.
Specific examples of the polymerizable compound having an epoxy group and / or an oxetanyl group are preferably a monomer containing a methacrylic acid ester structure and a monomer containing an acrylic acid ester structure.

Among these, glycidyl methacrylate, 3,4-epoxycyclohexylmethyl acrylate, 3,4-epoxycyclohexylmethyl methacrylate, methyl acrylate (3-ethyloxetane-3-yl) methyl, and methacrylic acid are preferable. (3-Ethyloxetane-3-yl) methyl is mentioned. These polymerizable compounds having an epoxy group and / or an oxetanyl group can be used alone or in combination of two or more.

Further, examples of the polymerizable compound include (meth) acrylic acid esters having an acid non-dissociable aliphatic polycyclic group, vinyl group-containing aromatic compounds and the like. As the acid non-dissociative aliphatic polycyclic group, a tricyclodecanyl group, an adamantyl group, a tetracyclododecanyl group, an isobornyl group, a norbornyl group and the like are particularly preferable in terms of industrial availability. These aliphatic polycyclic groups may have a linear or branched alkyl group having 1 to 5 carbon atoms as a substituent.

Specific examples of the (meth) acrylic acid esters having an acid-non-dissociative aliphatic polycyclic group include those having the structures of the following formulas (a8-1) to (a8-5). it can.

In the above formulas (a8-1) to (a8-5), R ^21a represents a hydrogen atom or a methyl group.

Among the above resins (A2), it is preferable to use an acrylic resin (A2-3). Among such acrylic resins (A2-3), the structural unit represented by the above formula (a5), the structural unit derived from (meth) acrylic acid, and the structural unit derived from (meth) acrylic acid alkyl esters are derived. It is preferable that the copolymer has a constituent unit and a constituent unit derived from (meth) acrylic acid aryl esters.

As such a copolymer, for example, a copolymer represented by the following formula (a9) is preferable.

In the above formula (a9), R ^22a represents a hydrogen atom or a methyl group, R ^23a represents a linear or branched alkyl group having 2 to 4 carbon atoms, and X ^a represents a bonded alkyl group. Represents a hydrocarbon ring having 5 to 20 carbon atoms formed together with the carbon atoms, and R ^24a is a linear or branched alkyl group having 1 to 6 carbon atoms or an alkoxy having 1 to 6 carbon atoms. Represents an alkyl group, where R ^25a represents an aryl group having 6 to 12 carbon atoms.

Further, in the copolymer represented by the above formula (a9), s, t, u and v represent the molar ratio of each constituent unit, s is 8 to 45 mol%, and t is 10 to 65 mol. %, U is 3 to 25 mol%, and v is 6 to 25 mol%.

The polystyrene-equivalent weight average molecular weight of the resin (A2) is preferably 4000 to 60,000, more preferably 6,000 to 40,000, and even more preferably 8,000 to 30,000. By setting such a weight average molecular weight, the adhesion to the patterned metal layer 18 is good, the mechanical strength is excellent, and the coating resin layer 17 in which cracks are less likely to occur can be easily formed.

The polystyrene-equivalent weight average molecular weight of the resin (A2) is not particularly limited as long as the dispersity (weight average molecular weight Mw / number average molecular weight Mn) of the base resin component (A) is 1 or more and 20 or less.
The dispersity of the resin (A2) is preferably 1.05 to 18, more preferably 1.2 to 12, and particularly preferably 1.5 to 6.
When the second positive composition has an alkali-soluble resin (A2-4) described later, the degree of dispersion of this resin (A2) is GPC in a state where the alkali-soluble resin (A2-4) is combined. (Gel permeation chromatography) measurements can be made and derived from the resulting chart.

The content of the resin (A2) is preferably 60 to 98% by mass, more preferably 70 to 95% by mass, based on the total solid content of the second positive composition.

(Alkali-soluble resin (A2-4))
The second positive composition may further contain an alkali-soluble resin (A2-4) as the base resin component (A) for the purpose of improving the crack resistance of the coating resin layer 17.
Here, the alkali-soluble resin (A2-4) refers to a resin having a functional group (for example, a phenolic hydroxyl group, a carboxy group, a sulfonic acid group, etc.) having alkali solubility in the molecule.
The alkali-soluble resin (A2-4) is at least one resin selected from the group consisting of novolak resin (A2-4a), polyhydroxystyrene resin (A2-4b), and acrylic resin (A2-4c). Is preferable.

-Novolak resin (A2-4a)
Similar to the above-mentioned novolak resin (A1), the novolak resin (A2-4a) is prepared by adding, for example, an aromatic compound having a phenolic hydroxyl group (hereinafter, simply referred to as “phenols”) and aldehydes under an acid catalyst. Obtained by condensation.

Examples of the phenols include phenol, o-cresol, m-cresol, p-cresol, o-ethylphenol, m-ethylphenol, p-ethylphenol, o-butylphenol, m-butylphenol, p-butylphenol, 2 , 3-Xylenol, 2,4-Xylenol, 2,5-Xylenol, 2,6-Xylenol, 3,4-Xylenol, 3,5-Xylenol, 2,3,5-trimethylphenol, 3,4,5- Examples thereof include trimethylphenol, p-phenylphenol, resorcinol, hydroquinone, hydroquinone monomethyl ether, pyrogallol, fluoroxylenol, hydroxydiphenyl, bisphenol A, gallic acid, gallic acid ester, α-naphthol, β-naphthol and the like.
Examples of the aldehydes include formaldehyde, furfural, benzaldehyde, nitrobenzaldehyde, acetaldehyde and the like.
The catalyst for the addition condensation reaction is not particularly limited, but for example, hydrochloric acid, nitric acid, sulfuric acid, formic acid, oxalic acid, acetic acid and the like are used as the acid catalyst.

-Polyhydroxystyrene resin (A2-4b)
Examples of the hydroxystyrene compound constituting the polyhydroxystyrene resin (A2-4b) include p-hydroxystyrene, α-methylhydroxystyrene, α-ethylhydroxystyrene and the like.
Further, the polyhydroxystyrene resin (A2-4b) is preferably a copolymer with the styrene resin. Examples of the styrene-based compound constituting such a styrene resin include styrene, chlorostyrene, chloromethylstyrene, vinyltoluene, α-methylstyrene and the like.

・ Acrylic resin (A2-4c)
As the acrylic resin (A2-4c), a resin containing a structural unit derived from a polymerizable compound having an ether bond and a structural unit derived from a polymerizable compound having a carboxy group is preferable.

Examples of the polymerizable compound having an ether bond include 2-methoxyethyl (meth) acrylate, methoxytriethylene glycol (meth) acrylate, 3-methoxybutyl (meth) acrylate, ethylcarbitol (meth) acrylate, and phenoxypolyethylene glycol ( Examples thereof include (meth) acrylic acid derivatives having ether bonds and ester bonds such as meth) acrylates, methoxypolypropylene glycol (meth) acrylates, and tetrahydrofurfuryl (meth) acrylates. The polymerizable compound having an ether bond is preferably 2-methoxyethyl acrylate or methoxytriethylene glycol acrylate. These polymerizable compounds may be used alone or in combination of two or more.

Examples of the polymerizable compound having a carboxy group include monocarboxylic acids such as acrylic acid, methacrylic acid and crotonic acid; dicarboxylic acids such as maleic acid, fumaric acid and itaconic acid; 2-methacryloyloxyethyl succinic acid and 2-methacryloyloxy. Examples of compounds having a carboxy group and an ester bond such as ethylmaleic acid, 2-methacryloyloxyethylphthalic acid, 2-methacryloyloxyethyl hexahydrophthalic acid; and the like can be exemplified. The polymerizable compound having a carboxy group is preferably acrylic acid or methacrylic acid. These polymerizable compounds may be used alone or in combination of two or more.

The content of the alkali-soluble resin (A2-4) can be 0 to 50 parts by mass when the total of the resin (A2) and the alkali-soluble resin (A2-4) is 100 parts by mass. , 0 to 30 parts by mass.

<Acid generator (B2)>
The acid generator (B2) is a compound that generates an acid by irradiation with active light or radiation, and is not particularly limited as long as it is a compound that directly or indirectly generates an acid by light. As the acid generator (B2), the acid generators of the first to fifth aspects described below are preferable. Hereinafter, the preferred acid generator (B2) preferably used in the second positive composition will be described as the first to fifth aspects.

As a first aspect of the acid generator (B2), a compound represented by the following formula (b1) can be mentioned.

In the above formula (b1), X ^1b represents a sulfur atom or an iodine atom having a valence of g, and g is 1 or 2. h represents the number of repeating units of the structure in parentheses. R ^1b is an organic group bonded to X ^1b , and is an aryl group having 6 to 30 carbon atoms, a heterocyclic group having 4 to 30 carbon atoms, an alkyl group having 1 to 30 carbon atoms, and a carbon atom number. 2-30 alkenyl group, or an alkynyl group having a carbon number of 2 to ^{30, R 1b} is alkyl, hydroxy, alkoxy, alkylcarbonyl, arylcarbonyl, alkoxycarbonyl, aryloxycarbonyl, arylthiocarbonyl, acyloxy, arylthio , Alkylthio, aryl, heterocyclic, aryloxy, alkylsulfinyl, arylsulfinyl, alkylsulfonyl, arylsulfonyl, alkyleneoxy, amino, cyano, nitro groups, and at least one selected from the group consisting of halogens. You may. The number of R ^1b is g + h (g-1) + 1, and R ^1b may be the same or different from each other. Also, directly with each other two or more ^{R 1b,} or _{-O -, - S -, -} SO -, - SO 2 -, - NH -, - NR 2b -, - CO -, - COO -, - CONH- , An alkylene group having 1 to 3 carbon atoms or a phenylene group may be bonded to form a ring structure containing X ^1b . R ^2b is an alkyl group having 1 to 5 carbon atoms or an aryl group having 6 to 10 carbon atoms.

X ^2b has a structure represented by the following formula (b2).

In the above formula (b2), X ^4b represents an alkylene group having 1 to 8 carbon atoms, an arylene group having 6 to 20 carbon atoms, or a divalent group of a heterocyclic compound having 8 to 20 carbon atoms. ^4b is at least one selected from the group consisting of alkyl having 1 to 8 carbon atoms, alkoxy having 1 to 8 carbon atoms, aryl, hydroxy, cyano, and nitro groups having 6 to 10 carbon atoms, and halogen. It may be replaced. X ^5b is _{-O -, - S -, -} SO -, - SO 2 -, - NH -, - NR 2b -, - CO -, - COO -, - CONH-, alkylene group having 1 to 3 carbon atoms , Or a phenylene group. h represents the number of repeating units of the structure in parentheses. The h + 1 X ^4b and the h X ^5b may be the same or different, respectively. R ^2b is the same as the above definition.

X ^3b- is a counterion of onium, a sulfonate anion represented by the following formula (b9), a nitrogen-containing anion represented by the following formulas (b13) and (b14), and represented by the following formula (b17). Fluorophosphate anion or borate anion represented by the following formula (b18) can be mentioned.

In the above formula (b9), R ^20b is a group represented by the following formulas (b10), (b11), and (b12).

In the above equation (b10), x represents an integer of 1 to 4. Further, in the above formula (b11), R ^21b is a hydrogen atom, a hydroxyl group, a linear or branched alkyl group having 1 to 6 carbon atoms, or a linear or branched alkyl group having 1 to 6 carbon atoms. It represents an alkoxy group, and y represents an integer of 1 to 3. Among these, trifluoromethanesulfonate and perfluorobutane sulfonate are preferable from the viewpoint of safety.

In the above formulas (b13) and (b14), X ^b represents a linear or branched alkylene group in which at least one hydrogen atom is substituted with a fluorine atom, and the number of carbon atoms of the alkylene group is 2 to 6. The number of carbon atoms is preferably 3 to 5, and most preferably 3 carbon atoms. Further, Y ^b and Z ^b each independently represent a linear or branched alkyl group in which at least one hydrogen atom is substituted with a fluorine atom, and the number of carbon atoms of the alkyl group is 1 to 10. It is preferably 1 to 7, more preferably 1 to 3.

The smaller the number of carbon atoms of the alkylene group of X ^b or the number of carbon atoms of the alkyl group of Y ^b and Z ^b , the better the solubility in an organic solvent, which is preferable.

Further, in the alkylene group of X ^b or the alkyl group of Y ^b and Z ^b , the larger the number of hydrogen atoms substituted with fluorine atoms, the stronger the acid strength, which is preferable. The ratio of fluorine atoms in the alkylene group or alkyl group, that is, the fluorination rate is preferably 70 to 100%, more preferably 90 to 100%, and most preferably all hydrogen atoms are substituted with fluorine atoms. It is a perfluoroalkylene group or a perfluoroalkyl group.

In the above formula (b17), R ^3b represents an alkyl group in which 80% or more of hydrogen atoms are substituted with fluorine atoms. j indicates the number thereof, and is an integer of 0 to 5. The j R ^3bs may be the same or different.

In the above formula (b18), R ^{4b to} R ^7b independently represent a fluorine atom or a phenyl group, and some or all of the hydrogen atoms of the phenyl group are selected from the group consisting of a fluorine atom and a trifluoromethyl group. It may be replaced with at least one of these.

Examples of the onium ion in the compound represented by the above formula (b1) include triphenylsulfonium, tri-p-tolylsulfonium, 4- (phenylthio) phenyldiphenylsulfonium, and bis [4- (diphenylsulfonio) phenyl] sulfide. Bis [4- {bis [4- (2-hydroxyethoxy) phenyl] sulfonio} phenyl] sulfide, bis {4- [bis (4-fluorophenyl) sulfonio] phenyl} sulfide, 4- (4-benzoyl-2-) Chlorophenylthio) phenylbis (4-fluorophenyl) sulfonium, 7-isopropyl-9-oxo-10-thia-9,10-dihydroanthracene-2-yldi-p-tolylsulfonium, 7-isopropyl-9-oxo-10 −Thia-9,10-dihydroanthracen-2-yldiphenylsulfonium, 2-[(diphenyl) sulfonio] thioxanthone, 4- [4- (4-tert-butylbenzoyl) phenylthio] phenyldi-p-tolylsulfonium, 4- (4-benzoylphenylthio) phenyldiphenylsulfonium, diphenylphenacil sulfonium, 4-hydroxyphenylmethylbenzylsulfonium, 2-naphthylmethyl (1-ethoxycarbonyl) ethylsulfonium, 4-hydroxyphenylmethylphenacilsulfonium, phenyl [4- (4-biphenylthio) phenyl] 4-biphenylsulfonium, phenyl [4- (4-biphenylthio) phenyl] 3-biphenylsulfonium, [4- (4-acetophenylthio) phenyl] diphenylsulfonium, octadecylmethylphenacylsulfonium , Diphenyliodonium, di-p-tolyliodonium, bis (4-dodecylphenyl) iodonium, bis (4-methoxyphenyl) iodonium, (4-octyloxyphenyl) phenyliodonium, bis (4-decyloxy) phenyliodonium, 4- Examples thereof include (2-hydroxytetradecyloxy) phenylphenyl iodonium, 4-isopropylphenyl (p-tolyl) iodonium, 4-isobutylphenyl (p-tolyl) iodonium, and the like.

Among the onium ions in the compound represented by the above formula (b1), preferred onium ions include sulfonium ions represented by the following formula (b19).

In the above formula (b19), R ^8b is independently derived from hydrogen atom, alkyl, hydroxy, alkoxy, alkylcarbonyl, alkylcarbonyloxy, alkyloxycarbonyl, halogen atom, aryl, arylcarbonyl, which may have a substituent. Represents a group selected from the group. X ^2b represents the same meaning as ^{X 2b} in the formula (b1).

Specific examples of the sulfonium ion represented by the above formula (b19) include 4- (phenylthio) phenyldiphenylsulfonium, 4- (4-benzoyl-2-chlorophenylthio) phenylbis (4-fluorophenyl) sulfonium, 4-. (4-Benzoylphenylthio) phenyldiphenylsulfonium, phenyl [4- (4-biphenylthio) phenyl] 4-biphenylsulfonium, phenyl [4- (4-biphenylthio) phenyl] 3-biphenylsulfonium, [4- (4) Examples thereof include −acetophenylthio) phenyl] diphenylsulfonium and diphenyl [4- (p-terphenylthio) phenyl] diphenylsulfonium.

In the fluorophosphate anion represented by the above formula (b17), R ^3b represents an alkyl group substituted with a fluorine atom, and the preferable number of carbon atoms is 1 to 8, and the more preferable number of carbon atoms is 1 to 4. Specific examples of the alkyl group include linear alkyl groups such as methyl, ethyl, propyl, butyl, pentyl and octyl; branched alkyl groups such as isopropyl, isobutyl, sec-butyl and tert-butyl; and further cyclopropyl, cyclobutyl and cyclopentyl. , Cycloalkyl group such as sikuhexyl, and the ratio of the hydrogen atom of the alkyl group substituted with the fluorine atom is usually 80% or more, preferably 90% or more, and more preferably 100%.

Particularly preferable R ^3b is a linear or branched perfluoroalkyl group having 1 to 4 carbon atoms and a fluorine atom substitution rate of 100%, and specific examples thereof include CF ₃ and CF ₃ CF _{2. , (CF 3) 2 CF,} CF 3 CF 2 CF 2, CF 3 CF 2 CF 2 CF 2, (CF 3) 2 CFCF 2, CF 3 CF 2 (CF 3) CF, include _{(CF 3)} 3 C Be done. The number j of R ^3b is an integer of 0 to 5, preferably 1 to 4, and particularly preferably 2 or 3.

Specific examples of preferable fluorophosphate anions include [PF ₆ ] ⁻ , [(CF ₃ CF ₂ ) ₂ PF ₄ ] ⁻ , [(CF ₃ CF ₂ ) ₃ PF ₃ ] ⁻ , [((CF ₃ ) ₂ ). CF) ₂ PF ₄ ] ^- , [((CF ₃ ) ₂ CF) ₃ PF ₃ ] ^- , [(CF ₃ CF ₂ CF ₂ ) ₂ PF ₄ ] ^- , [(CF ₃ CF ₂ CF ₂ ) ₃ PF ₃ ] ^- , [((CF ₃ ) ₂ CFCF ₂ ) ₂ PF ₄ ] ^- , [((CF ₃ ) ₂ CFCF ₂ ) ₃ PF ₃ ] ^- , [(CF ₃ CF ₂ CF ₂ CF ₂ ) ₂ PF ₄ ] ^-, or _{[(CF 3 CF 2 CF 2} ) 3 PF 3] - , and the like.

Preferred specific examples of the borate anion represented by the above formula (b18) include tetrafluoroborate (BF ₄ ) ⁻ , tetrakis (pentafluorophenyl) borate ([B (C ₆ F ₅ ) ₄ ] ⁻ ), and tetrakis [ (Trifluoromethyl) phenyl] borate ([B (C ₆ H ₄ CF ₃ ) ₄ ] ^- ), difluorobis (pentafluorophenyl) borate ([(C ₆ F ₅ ) ₂ BF ₂ ] ^- ), trifluoro ( Examples thereof include pentafluorophenyl) borate ([(C ₆ F ₅ ) BF ₃ ] ⁻ ) and tetrakis (difluorophenyl) borate ([B (C ₆ H ₃ F ₂ ) ₄ ] ⁻ ). Of these, tetrakis (pentafluorophenyl) borate ([B (C ₆ F ₅ ) ₄ ] ⁻ ) is particularly preferable.

The second aspect of the acid generator (B2) is 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2. -(2-Frill) ethenyl] -s-triazine, 2,4-bis (trichloromethyl) -6- [2- (5-methyl-2-furyl) ethenyl] -s-triazine, 2,4-bis ( Trichloromethyl) -6- [2- (5-ethyl-2-furyl) ethenyl] -s-triazine, 2,4-bis (trichloromethyl) -6- [2- (5-propyl-2-furyl) ethenyl ] -S-Triazine, 2,4-bis (trichloromethyl) -6- [2- (3,5-dimethoxyphenyl) ethenyl] -s-triazine, 2,4-bis (trichloromethyl) -6- [2 -(3,5-diethoxyphenyl) ethenyl] -s-triazine, 2,4-bis (trichloromethyl) -6- [2- (3,5-dipropoxyphenyl) ethenyl] -s-triazine, 2, 4-bis (trichloromethyl) -6- [2- (3-methoxy-5-ethoxyphenyl) ethenyl] -s-triazine, 2,4-bis (trichloromethyl) -6- [2- (3-methoxy-) 5-propoxyphenyl) ethenyl] -s-triazine, 2,4-bis (trichloromethyl) -6- [2- (3,4-methylenedioxyphenyl) ethenyl] -s-triazine, 2,4-bis ( Trichloromethyl) -6- (3,4-methylenedioxyphenyl) -s-triazine, 2,4-bis-trichloromethyl-6- (3-bromo-4-methoxy) phenyl-s-triazine, 2,4 -Bis-trichloromethyl-6- (2-bromo-4-methoxy) phenyl-s-triazine, 2,4-bis-trichloromethyl-6- (2-bromo-4-methoxy) styrylphenyl-s-triazine, 2,4-Bis-trichloromethyl-6- (3-bromo-4-methoxy) styrylphenyl-s-triazine, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -1,3 5-Triazine, 2- (4-methoxynaphthyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- [2- (2-furyl) ethenyl] -4,6-bis ( Trichloromethyl) -1,3,5-triazine, 2- [2- (5-methyl-2-furyl) ethenyl] -4,6-bis (trichloromethyl) -1,3,5-triazine, 2-[ 2- (3,5 -Dimethoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- [2- (3,4-dimethoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (3,4-methylenedioxyphenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, tris (1,3-dibromopropyl)- Halogen-containing triazine compounds such as 1,3,5-triazine and tris (2,3-dibromopropyl) -1,3,5-triazine, and tris (2,3-dibromopropyl) isocyanurate and the like (b3) ), A halogen-containing triazine compound represented by) can be mentioned.

In the above formula (b3), R ^9b , R ^10b , and R ^11b each independently represent an alkyl halide group.

Further, as a third aspect of the acid generator (B2), α- (p-toluenesulfonyloxyimino) -phenylacetonitrile, α- (benzenesulfonyloxyimino) -2,4-dichlorophenylacetonitrile, α- (benzene) Contains sulfonyloxyimino) -2,6-dichlorophenylacetonitrile, α- (2-chlorobenzenesulfonyloxyimino) -4-methoxyphenylacetonitrile, α- (ethylsulfonyloxyimino) -1-cyclopentenyl acetonitrile, and oxime sulfonate groups Examples thereof include compounds represented by the following formula (b4).

In the above formula (b4), R ^12b represents a monovalent, divalent or trivalent organic group, and R ^13b is a substituted or unsubstituted saturated hydrocarbon group, unsaturated hydrocarbon group, or aromatic group. It represents a compound group, and n represents the number of repeating units of the structure in parentheses.

In the above formula (b4), the aromatic compound group indicates a group of a compound exhibiting physical and chemical properties peculiar to an aromatic compound, for example, an aryl group such as a phenyl group or a naphthyl group, or a frill group. , Heteroaryl groups such as thienyl group can be mentioned. These may have one or more suitable substituents such as a halogen atom, an alkyl group, an alkoxy group, a nitro group and the like on the ring. Further, R ^13b is particularly preferably an alkyl group having 1 to 6 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group and a butyl group. In particular, a compound in which R ^12b is an aromatic compound group and R ^13b is an alkyl group having 1 to 4 carbon atoms is preferable.

As the acid generator represented by the above formula (b4), when n = 1, R ^12b is any of a phenyl group, a methyl phenyl group, and a methoxy phenyl group, and R ^{13 b} is a compound having a methyl group, specifically. Specifically, α- (methylsulfonyloxyimino) -1-phenyl acetonitrile, α- (methylsulfonyloxyimino) -1- (p-methylphenyl) acetonitrile, α- (methylsulfonyloxyimino) -1- (p-) Examples thereof include methoxyphenyl) acetonitrile, [2- (propylsulfonyloxyimino) -2,3-dihydroxythiophene-3-iriden] (o-tolyl) acetonitrile and the like. When n = 2, the acid generator represented by the above formula (b4) specifically includes an acid generator represented by the following formula.

Further, as a fourth aspect of the acid generator (B2), an onium salt having a naphthalene ring in the cation portion can be mentioned. By "having a naphthalene ring", it means having a structure derived from naphthalene, and it means that the structure of at least two rings and their aromaticity are maintained. This naphthalene ring may have a substituent such as a linear or branched alkyl group having 1 to 6 carbon atoms, a hydroxyl group, or a linear or branched alkoxy group having 1 to 6 carbon atoms. .. The structure derived from the naphthalene ring may be a monovalent group (one free valence) or a divalent group (two free valences) or more, but it may be a monovalent group. Desirable (however, at this time, the free valence shall be counted except for the portion bonded to the above substituent). The number of naphthalene rings is preferably 1 to 3.

The structure represented by the following formula (b5) is preferable as the cation portion of the onium salt having a naphthalene ring in the cation portion.

In the above formula (b5), at least one of R ^14b , R ^15b , and R ^16b represents a group represented by the following formula (b6), and the rest are linear or branched with 1 to 6 carbon atoms. It represents an alkyl group, a phenyl group which may have a substituent, a hydroxyl group, or a linear or branched alkoxy group having 1 to 6 carbon atoms. Alternatively, one of R ^14b , R ^15b , and R ^16b is a group represented by the following formula (b6), and the remaining two are independently linear or branched with 1 to 6 carbon atoms. It is an alkylene group, and these ends may be bonded to form a cyclic group.

In the above formula (b6), R ^17b and R ^18b are independently hydroxyl groups, linear or branched alkoxy groups having 1 to 6 carbon atoms, or linear or branched groups having 1 to 6 carbon atoms, respectively. Represents the alkyl group of, and R ^19b represents a linear or branched alkylene group having 1 to 6 carbon atoms which may have a single bond or a substituent. l and m each independently represent an integer of 0 to 2, and l + m is 3 or less. However, when there are a plurality of R ^17b , they may be the same or different from each other. Further, when a plurality of R ^18b are present, they may be the same or different from each other.

Of the above R ^14b , R ^15b , and R ^16b , the number of groups represented by the above formula (b6) is preferably one from the viewpoint of compound stability, and the rest are straight lines having 1 to 6 carbon atoms. It is a shaped or branched alkylene group, and these ends may be bonded to form a cyclic. In this case, the two alkylene groups form a 3- to 9-membered ring including a sulfur atom. The number of atoms (including sulfur atoms) constituting the ring is preferably 5 to 6.

Examples of the substituent that the alkylene group may have include an oxygen atom (in this case, a carbonyl group is formed together with a carbon atom constituting the alkylene group), a hydroxyl group and the like.

The substituents that the phenyl group may have include a hydroxyl group, a linear or branched alkoxy group having 1 to 6 carbon atoms, and a linear or branched alkyl having 1 to 6 carbon atoms. Group etc. can be mentioned.

Suitable examples of these cation portions include those represented by the following formulas (b7) and (b8), and a structure represented by the following formula (b8) is particularly preferable.

The cation portion may be an iodonium salt or a sulfonium salt, but a sulfonium salt is preferable from the viewpoint of acid generation efficiency and the like.

Therefore, an anion capable of forming a sulfonium salt is desirable as an anion portion of an onium salt having a naphthalene ring in the cation portion.

The anion portion of such an acid generator is a fluoroalkyl sulfonic acid ion or an aryl sulfonic acid ion in which a part or all of hydrogen atoms are fluorinated.

The alkyl group in the fluoroalkyl sulfonic acid ion may be linear, branched or cyclic with 1 to 20 carbon atoms, and is preferably 1 to 10 carbon atoms from the viewpoint of the bulkiness of the generated acid and its diffusion distance. .. In particular, branched or annular ones are preferable because they have a short diffusion distance. Moreover, since it can be synthesized at low cost, a methyl group, an ethyl group, a propyl group, a butyl group, an octyl group and the like can be mentioned as preferable ones.

Examples of the aryl group in the aryl sulfonic acid ion include an aryl group having 6 to 20 carbon atoms, an alkyl group, a phenyl group which may or may not be substituted with a halogen atom, and a naphthyl group. In particular, an aryl group having 6 to 10 carbon atoms is preferable because it can be synthesized at low cost. Specific examples of preferred ones include a phenyl group, a toluenesulfonyl group, an ethylphenyl group, a naphthyl group, a methylnaphthyl group and the like.

In the above fluoroalkyl sulfonic acid ion or aryl sulfonic acid ion, the fluorination rate when a part or all of hydrogen atoms is fluorinated is preferably 10 to 100%, more preferably 50 to 100%. In particular, it is preferable to replace all hydrogen atoms with fluorine atoms because the strength of the acid becomes stronger. Specific examples of such substances include trifluoromethanesulfonate, perfluorobutane sulfonate, perfluorooctane sulfonate, and perfluorobenzene sulfonate.

Among these, preferable anion portions include anions represented by the above-mentioned formula (b9) and anions represented by the above-mentioned formulas (b13) and (b14).

Preferred as an onium salt having a naphthalene ring in such a cation portion include compounds represented by the following formulas (b15) and (b16).

Further, as a fifth aspect of the acid generator (B2), bis (p-toluenesulfonyl) diazomethane, bis (1,1-dimethylethylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (2,4-) Dimethylphenylsulfonyl) Bissulfonyldiazomethanes such as diazomethane; p-toluenesulfonic acid 2-nitrobenzyl, p-toluenesulfonic acid 2,6-dinitrobenzyl, nitrobenzyltosylate, dinitrobenzyltosylate, nitrobenzylsulfonate, nitro Nitrobenzyl derivatives such as benzylcarbonate and dinitrobenzylcarbonate; pyrogalloltrimesylate, pyrogalloltritosylate, benzyltosylate, benzylsulfonate, N-methylsulfonyloxysuccinimide, N-trichloromethylsulfonyloxysuccinimide, N-phenylsulfonyl Sulfonic acid esters such as oxymaleimide and N-methylsulfonyloxyphthalimide; trifluoromethanesulfonic acid esters such as N-hydroxyphthalimide and N-hydroxynaphthalimide; diphenyliodonium hexafluorophosphate, (4-methoxyphenyl) phenyliodonium Trifluoromethanesulphonate, bis (p-tert-butylphenyl) iodonium trifluoromethanesulphonate, triphenylsulfonium hexafluorophosphate, (4-methoxyphenyl) diphenylsulfonium trifluoromethanesulphonate, (p-tert-butylphenyl) diphenyl Onium salts such as sulfonium trifluoromethanesulfonate; benzointosylates such as benzointosilate and α-methylbenzointosylate; other diphenyliodonium salts, triphenylsulfonium salts, phenyldiazonium salts, benzylcarbonate and the like can be mentioned.

This acid generator (B2) may be used alone or in combination of two or more. The content of the acid generator (B2) is preferably 0.1 to 10% by mass, preferably 0.5 to 5% by mass, based on the total solid content of the second positive composition. Is more preferable. By setting the amount of the acid generator (B2) to be used in the above range, it is easy to prepare a positive composition having good sensitivity, a uniform solution, and excellent storage stability.

(Acid diffusion control agent (C))
The second positive composition may further contain an acid diffusion control agent (C) in order to improve the shape of the coating resin layer 17 and the retention stability of the photosensitive layer. As the acid diffusion control agent (C), a nitrogen-containing compound is preferable, and if necessary, an organic carboxylic acid, or an oxo acid of phosphorus or a derivative thereof can be contained.

Examples of nitrogen-containing compounds include trimethylamine, diethylamine, triethylamine, di-n-propylamine, tri-n-propylamine, tri-n-pentylamine, tribenzylamine, diethanolamine, triethanolamine, n-hexylamine and n-. Heptylamine, n-octylamine, n-nonylamine, ethylenediamine, N, N, N', N'-tetramethylethylenediamine, tetramethylenediamine, hexamethylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diamino Diphenyl ether, 4,4'-diaminobenzophenone, 4,4'-diaminodiphenylamine, formamide, N-methylformamide, N, N-dimethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, propionamide, benzamide , Pyrrolidone, N-methylpyrrolidone, Methylurea, 1,1-dimethylurea, 1,3-dimethylurea, 1,1,3,3-tetramethylurea, 1,3-diphenylurea, imidazole, benzimidazole, 4 -Methylimidazole, 8-oxyquinolin, aclysine, purine, pyrrolidine, piperidine, 2,4,6-tri (2-pyridyl) -S-triazine, morpholine, 4-methylmorpholin, piperazine, 1,4-dimethylpiperazin, 1,4-diazabicyclo [2.2.2] octane, pyridine and the like can be mentioned. These may be used alone or in combination of two or more.

The acid diffusion control agent (C) is usually used in the range of 0 to 5 parts by mass with respect to 100 parts by mass of the total mass of the resin (A2) and the alkali-soluble resin (A2-4), and is 0 to 3 parts by mass. It is particularly preferable that it is used in a range of parts.

Of the organic carboxylic acid, or the oxo acid of phosphorus or a derivative thereof, the organic carboxylic acid is specifically malonic acid, citric acid, malic acid, succinic acid, benzoic acid, salicylic acid and the like, and particularly salicylic acid. Is preferable.

Phosphonic oxo acids or derivatives thereof include phosphoric acids such as phosphoric acid, di-n-butyl ester of phosphoric acid, diphenyl ester of phosphoric acid and derivatives such as esters thereof; phosphonic acid, dimethyl phosphonic acid ester, phosphonic acid- Phosphonates such as di-n-butyl ester, phenylphosphonic acid, phosphonic acid diphenyl ester, phosphonic acid dibenzyl ester and derivatives such as their esters; such as phosphinic acids such as phosphinic acid and phenylphosphinic acid and their esters. Derivatives; etc. Of these, phosphonic acid is particularly preferable. These may be used alone or in combination of two or more.

The organic carboxylic acid, or the oxo acid of phosphorus or a derivative thereof is usually used in the range of 0 to 5 parts by mass with respect to 100 parts by mass of the total mass of the resin (A2) and the alkali-soluble resin (A2-4), and is 0. It is particularly preferable to use it in the range of ~ 3 parts by mass.

Further, in order to form and stabilize the salt, it is preferable to use an organic carboxylic acid, or an oxo acid of phosphorus or a derivative thereof in an amount equivalent to that of the above nitrogen-containing compound.

(Colorant)
The optical density of the coating resin layer 17 after the post-baking step, which is formed according to the method of the present embodiment, is 0.10 / μm or more. For this reason, the second positive composition, like the first positive composition, typically contains a colorant for the purpose of adjusting the optical density.
In the second positive type composition, as the colorant, the same colorant as that described for the first positive type composition can be used.
The amount of the colorant used in this second positive composition is preferably 1 part by mass or more with respect to 100 parts by mass of the total mass of the resin (A2) and the alkali-soluble resin (A2-4), for example. 3 parts by mass or more is more preferable, 5 parts by mass or more is further preferable, 60 parts by mass or less is preferable, 50 parts by mass or less is more preferable, 45 parts by mass or less is further preferable, and 40 parts by mass or less is further preferable.
Further, the optical density of the coating resin layer 17 is more preferably 0.20 to 2.0 / μm, and further preferably 0.30 to 1.0 / μm.

(solvent)
The second positive composition is preferably used in the form of a solution in which each of the above components is dissolved in an appropriate solvent. The type of solvent is not particularly limited as long as it does not impair the object of the present invention, and can be appropriately selected from the organic solvents conventionally used in positive photosensitive resin compositions.

Specific examples of the solvent include ketones such as acetone, methyl ethyl ketone, cyclohexanone, methyl isoamyl ketone, and 2-heptanone; ethylene glycol, ethylene glycol monoacetate, diethylene glycol, diethylene glycol monoacetate, propylene glycol, propylene glycol monoacetate, and dipropylene glycol. , Monomethyl ether of dipropylene glycol monoacetate, monoethyl ether, monopropyl ether, monobutyl ether, monophenyl ether and other polyvalent alcohols and derivatives thereof; cyclic ethers such as dioxane; ethyl formate, methyl lactate, ethyl lactate , Methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, methyl acetoacetate, ethyl acetoacetate, ethyl pyruvate, ethyl ethoxyacetate, methyl methoxypropionate, ethyl ethoxypropionate, methyl 2-hydroxypropionate, 2-hydroxy Ethers such as ethyl propionate, ethyl 2-hydroxy-2-methylpropionate, methyl 2-hydroxy-3-methylbutanoate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate; toluene, xylene and the like Aromatic hydrocarbons; etc. can be mentioned. These may be used alone or in combination of two or more.

The amount of the solvent used is not particularly limited as long as it does not impair the object of the present invention. The amount of the solvent used is preferably such that the solid content concentration of the second positive composition is 10 to 40% by mass, and more preferably 12 to 30% by mass.

(Other ingredients)
The second positive composition may further contain a polyvinyl resin in order to improve the plasticity. Specific examples of the polyvinyl resin include polyvinyl chloride, polystyrene, polyhydroxystyrene, polyvinyl acetate, polyvinyl benzoic acid, polyvinyl methyl ether, polyvinyl ethyl ether, polyvinyl alcohol, polyvinylpyrrolidone, polyvinyl phenol, and copolymers thereof. Can be mentioned. The polyvinyl resin is preferably polyvinyl methyl ether because of its low glass transition point.

In addition, the second positive composition may further contain an adhesion improver in order to improve the adhesion between the coating resin layer 17 and the patterned metal layer 18. As the adhesion improver, the same one as shown in the item of the first positive composition can be used.

In addition, the second positive composition may further contain a surfactant in order to improve coatability, defoaming property, leveling property and the like. Specific examples of surfactants include BM-1000 and BM-1100 (all manufactured by BM Chemie), Megafuck F142D, Megafuck F172, Megafuck F173, and Megafuck F183 (all manufactured by Dainippon Ink and Chemicals). ), Florard FC-135, Florard FC-170C, Florard FC-430, Florard FC-431 (all manufactured by Sumitomo 3M), Surfron S-112, Surfron S-113, Surfron S-131, Surfron S-141, Commercially available fluorine-based surfactants such as Surflon S-145 (all manufactured by Asahi Glass Co., Ltd.), SH-28PA, SH-190, SH-193, SZ-6032, SF-8428 (all manufactured by Toray Silicone Co., Ltd.) are listed. However, it is not limited to these.

In addition, the second positive composition may further contain an acid, an acid anhydride, or a high boiling point solvent in order to finely adjust the solubility in a developing solution.

Specific examples of acids and acid anhydrides include monocarboxylic acids such as acetic acid, propionic acid, n-butyric acid, isobutyric acid, n-valeric acid, isovaleric acid, benzoic acid and cinnamic acid; lactic acid, 2-hydroxybutyric acid, Hydroxymonocarboxylics such as 3-hydroxybutyric acid, salicylic acid, m-hydroxybenzoic acid, p-hydroxybenzoic acid, 2-hydroxysuccinic acid, 3-hydroxysuccinic acid, 4-hydroxysuccinic acid, 5-hydroxyisophthalic acid, silingic acid Acids; oxalic acid, succinic acid, glutaric acid, adipic acid, maleic acid, itaconic acid, hexahydrophthalic acid, phthalic acid, isophthalic acid, terephthalic acid, 1,2-cyclohexanedicarboxylic acid, 1,2,4-cyclohexanetricarboxylic acid Polyvalent carboxylic acids such as acid, butanetetracarboxylic acid, trimellitic acid, pyromellitic acid, cyclopentanetetracarboxylic acid, butanetetracarboxylic acid, 1,2,5,8-naphthalenetetracarboxylic acid; itaconic anhydride, anhydrous Succinic acid, citraconic anhydride, dodecenyl succinic anhydride, tricarbanyl anhydride, maleic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hymic anhydride, 1,2,3,4-butanetetracarboxylic anhydride, Cyclopentanetetracarboxylic dianhydride, phthalic anhydride, pyromellitic anhydride, trimellitic anhydride, benzophenonetetracarboxylic anhydride, ethylene glycol bis anhydride trimeritate, glycerintris anhydride trimeritate and other acid anhydrides; it can.

Specific examples of the high boiling point solvent include N-methylformamide, N, N-dimethylformamide, N-methylformamide, N-methylacetamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, and benzyl. Ethyl ether, dihexyl ether, acetyl acetone, isophorone, caproic acid, capric acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate , Propylene carbonate, phenylcellosolveacetate and the like.

In addition, the second positive composition may further contain a sensitizer in order to improve the sensitivity.

(Method for preparing the second positive composition)
The second positive composition is prepared by mixing and stirring each of the above components by a usual method. Examples of the device that can be used when mixing and stirring each of the above components include a dissolver, a homogenizer, and a three-roll mill. After uniformly mixing each of the above components, the obtained mixture may be further filtered using a mesh, a membrane filter or the like.

<Application method>
The positive composition described above is applied onto the metal layer 11 to be etched to form the photosensitive layer 12. The film thickness of the photosensitive layer 12 is not particularly limited, but is preferably 0.1 to 10 μm.
As a method for applying the positive composition, a spin coating method, a slit coating method, a roll coating method, a screen printing method, an applicator method and the like can be adopted. It is preferable to prebake the photosensitive layer 12. The prebaking conditions vary depending on the type of each component in the photosensitive layer, the blending ratio, the coating film thickness, and the like, but are usually 70 to 150 ° C., preferably 80 to 140 ° C. for about 2 to 60 minutes.

The substrate 10 to be processed provided with the photosensitive layer 12 formed as described above is then subjected to an exposure step.

≪Exposure process≫
In the exposure step, as shown in FIG. 1C, exposure is performed at a position in the photosensitive layer 12 other than the position where the patterned metal layer 18 is formed.
The photosensitive layer 12 is formed by using the positive composition as described above. In the photosensitive layer 12 made of the positive composition, the exposed portion is solubilized in the alkaline developer. Therefore, the exposure causes solubilization of the photosensitive layer 12 at positions other than the position where the patterned metal layer 18 is formed.

In the exposure step, the photosensitive layer 12 formed as described above is regioselectively irradiated with the exposure light 16 via the photomask 15 having a predetermined pattern.
As the exposure light 16, active light or radiation, for example, ultraviolet light or visible light having a wavelength of 300 to 500 nm is used.

As the radiation source, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a metal halide lamp, an argon gas laser, or the like can be used. Further, the radiation includes microwaves, infrared rays, visible rays, ultraviolet rays, X-rays, γ-rays, electron beams, proton beams, neutron beams, ion rays and the like. The irradiation amount varies depending on the composition of the positive composition, the film thickness of the photosensitive layer 12, and the like, but is 100 to 10,000 mJ / cm ² when an ultrahigh pressure mercury lamp is used, for example.

≪Development process≫
The photosensitive layer 12 exposed in a regioselective manner as shown in FIG. 1 (c) is developed in the developing step, so that the photosensitive layer 12 is patterned as shown in FIG. 1 (d). A coating resin layer 17 is formed. At this time, an alkaline aqueous solution is used as the developing solution.

Examples of the developing solution include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, n-propylamine, diethylamine, di-n-propylamine, triethylamine, methyldiethylamine, and the like. Dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, pyrrole, piperidine, 1,8-diazabicyclo [5,4,0] -7-undecene, 1,5-diazabicyclo [4,3 0] An aqueous solution of an alkali such as -5-nonane can be used. Further, an aqueous solution obtained by adding an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a known surfactant to the above alkaline aqueous solution can also be used as a developing solution.

The developing time varies depending on the composition of the positive composition, the film thickness of the photosensitive layer 12, and the like, but is usually 1 to 30 minutes. The developing method may be any of a liquid filling method, a dipping method, a paddle method, a spray developing method and the like.

After development, it is washed with running water for 30 to 90 seconds and dried using an air gun, an oven or the like. In this way, the coated resin layer 17, which is the patterned photosensitive layer 12, is formed on the metal layer 11 to be etched.

≪Etching process≫
In the etching step, as shown in FIGS. 1D and 1E, the coating resin layer 17 formed in the developing step is used as an etching mask to etch the metal layer 11 to be etched exposed from the etching mask. To form a patterned metal layer 18.
The etching method is not particularly limited, and is appropriately selected depending on the material of the metal layer 11 to be etched. The etching method may be wet etching or dry etching, and wet etching is preferable because of low cost.

≪Post-baking process≫
In the post-baking step, the coating resin layer 17 formed as shown in FIG. 1 (e) is baked. Baking may be performed between the developing process and the etching process, or may be performed after the etching process.
By baking the coated resin layer 17, the coating resin layer 17 is cured or the coated resin layer 17 is brought into close contact with each other. As a result, the water resistance, heat resistance, solvent resistance, etc. of the coating resin layer 17 are improved.
Further, in the above-mentioned etching step, under-etching occurs in which the etching excessively progresses in the lower part of the end portion of the coating resin layer 17, and the width of the top (coating resin layer 17 side) of the patterned metal layer 18 is the bottom (the coating resin layer 17 side). It may be narrower than the width of the transparent layer 14 side).
In this case, it is preferable to carry out the post-baking step after the etching step. This is because the coating resin layer 17 is softened by heating in the post-baking step, and the coating resin layer 17 is deformed along the surface shape of the patterned metal layer 18. As a result, the coating resin layer 17 that adheres to almost the entire surface of the patterned metal layer 18 is formed, so that the patterned metal layer 18 is not easily visible to the user of the touch panel.

Baking is performed using, for example, a heating device such as a hot plate or an oven. The temperature of the bake is not particularly limited, and is appropriately determined in consideration of the heat resistance of the material constituting the substrate 10 to be processed. The bake temperature is, for example, preferably 80 to 400 ° C, more preferably 150 to 300 ° C.
When the substrate 10 to be processed includes a liquid crystal cell including a liquid crystal layer 20, the baking temperature is preferably 80 to 150 ° C.
The bake time is preferably 15 to 60 minutes, more preferably 30 minutes or less.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the scope of the present invention is not limited to these Examples. In addition, Examples 1 and 3 shall be read as Reference Examples 1 and 3, respectively.

[Example 1]
The solid content concentration of 100 parts by mass of the novolak resin, 13 parts by mass of the sensitizer, 22.6 parts by mass of the quinonediazide group-containing compound, and 27% by mass with respect to the total solid content mass is 20% by mass. As described above, the mixture was uniformly dissolved and dispersed in propylene glycol monomethyl ether acetate to obtain a positive composition.
The positive composition contains 1% by mass of 2-hydroxyethylpyridine based on the total solid content and 0.4% by mass of the silicon-based surfactant based on the total solid content (BYK-310, Big Chemie Co., Ltd.). Made) was included.

As the novolak resin, a cresol-type novolak resin having a weight average molecular weight of 4700 and a dispersity of 4.5 was used.
As the sensitizer, a phenol resin (trade name: TrisP-PA-MF, manufactured by Honshu Chemical Industry Co., Ltd.) was used.
As the quinone diazide group-containing compound, a compound obtained by esterifying 2,3,4,4'-tetrahydroxybenzophenone and naphthoquinone-1,2-diazide-5-sulfonic acid was used.
As the pigment, a red pigment manufactured by Mikuni Color Co., Ltd. having a total solid content of 14.9% by mass and a blue pigment manufactured by Mikuni Color Co., Ltd. having a total solid content of 12.1% by mass were used.

The obtained positive composition is applied onto the metal layer to be etched of the substrate to be etched, which includes a color filter and a metal layer to be etched (Al layer), using a spin coater, and then prebaked at 90 ° C. for 60 seconds. , A photosensitive layer having a film thickness of 1.5 μm was formed.
The obtained photosensitive layer was exposed using an exposure apparatus (MPA-600FA, 365 mW, 100 mJ / cm ² , manufactured by Canon Inc.) through a photomask having a width of 3 μm at L / S = 1: 1.
Next, development was carried out using an aqueous solution of tetramethylammonium hydroxide (TMAH) having a concentration of 2.38% by mass as a developing solution to form a coated resin layer patterned in a predetermined shape.
The formed coating resin layer was used as an etching mask, and etching was performed using an Al etchant mixed acid (phosphoric acid, nitric acid, acetic acid) to form a patterned metal layer. The surface of the patterned metal layer was coated with a coating resin layer.
The etched substrate was post-baked at 120 ° C. for 5 minutes to obtain a substrate having a patterned metal layer and a coating resin layer.

As the substrate to be processed, the following ones were used on a trial basis.
That is, first, a black matrix having a line width of 5 μm and an RGB pattern are provided on one surface of the glass substrate, and an aluminum layer having a thickness of 0.2 μm is sputtered on the surface of the other surface of the glass substrate. As a substrate to be processed.

The optical density of the formed coating resin layer was 0.60 / μm.
Further, when the shape of the formed coating resin layer was observed under a microscope, the pixels were not coated with the coating resin layer, the film thickness of the coating resin layer was almost uniform, and the exposed metal layer was patterned. Not observed.

[Example 2]
A positive composition was prepared in the same manner as in Example 1 except that the novolak resin was changed to a cresol-type novolak resin having a weight average molecular weight of 4700 and a dispersity of 10.0, and the same as in Example 1. A patterned metal layer and a coating resin layer were formed on the substrate.
The optical density of the formed coating resin layer was 0.60 / μm.
Further, when the shape of the formed coating resin layer was observed under a microscope, the pixels were not coated with the coating resin layer, the film thickness of the coating resin layer was almost uniform, and the exposed metal layer was patterned. Not observed.

[Example 3]
100 parts by mass of acrylic resin, 3 parts by mass of photoacid generator, and 5 parts by mass of colorant are dissolved and dispersed in propylene glycol monomethyl ether acetate so as to have a solid content concentration of 12% by mass to form a positive composition. I got something.

As acrylic resin, 40 mol% of 1-ethoxyethyl ether of p-hydroxystyrene, 35 mol% of methyl methacrylate (3-ethyloxetane-3-yl), 15 mol% of methyl methacrylate, and 20 mol% of 2-hydroxyethyl methacrylate. A mol% copolymer was used. The weight average molecular weight of the acrylic resin was 12400, and the dispersity was 4.5.
As the photoacid generator, a triarylsulfonium salt (trade name: DTS-105, manufactured by Midori Kagaku Co., Ltd.) was used.
As the colorant, 13.1 parts by mass of carbon black, 0.65 parts by mass of the dispersant in 79.53 parts by mass of propylene glycol monomethyl ether, and polymers (benzyl methacrylate (72 mol%) and methacrylic acid (28 mol%)). %) And a random copolymer with an important average molecular weight of 37,000) and dispersed black pigments were used.

Using the obtained positive composition, a patterned metal layer and a coating resin layer were formed on the substrate in the same manner as in Example 1.
The optical density of the formed coating resin layer was 0.60 / μm.
Further, when the shape of the formed coating resin layer was observed under a microscope, the pixels were not coated with the coating resin layer, the film thickness of the coating resin layer was almost uniform, and the exposed metal layer was patterned. Not observed.

[Comparative Example 1]
A positive composition was prepared in the same manner as in Example 1 except that the novolak resin was changed to a cresol-type novolak resin having a weight average molecular weight of 4700 and a dispersity of 30.0, and the same as in Example 1. A patterned metal layer and a coating resin layer were formed on the substrate.
The optical density of the formed coating resin layer was 0.60 / μm.
However, when the shape of the formed coating resin layer was observed under a microscope, the coating resin layer flowed excessively at the time of post-baking, and the parts covered by the coating resin layer on the pixels were scattered or patterned. The exposure of the metal layer was observed.

1 Substrate 10 Substrate to be processed 11 Metal layer to be etched 12 Photosensitive layer 13 Color filter 14 Transparent layer 15 Photomask 16 Exposure light 17 Coating resin layer 18 Patterned metal layer 19 Transparent resin layer 20 Liquid crystal layer 21 Pixel electrode 22 Insulation layer 23 Array substrate BM Black matrix R, G, B Red (R) colored film, green (G) colored film, blue (B) colored film

Claims (4)

A color filter, a patterned metal layer formed directly on the color filter or via a transparent layer, and a coating resin layer covering the patterned metal layer are placed on one of the main surfaces. It is a method of manufacturing a substrate to be provided.
A positive photosensitive resin composition is applied onto the metal layer to be etched on a substrate to be processed, which comprises the color filter and a metal layer to be etched, which is formed directly or via a transparent layer on the color filter. The photosensitive layer forming step of forming the photosensitive layer and
An exposure step of exposing a position in the photosensitive layer other than the position where the patterned metal layer is formed.
A developing step of developing the exposed photosensitive layer to form the coating resin layer,
An etching step in which the coating resin layer is used as an etching mask and the metal layer to be etched exposed from the etching mask is removed by etching to form the patterned metal layer.
Including a post-baking step of baking the coated resin layer.
The dispersity (weight average molecular weight Mw / number average molecular weight Mn) of the base resin component (A) contained in the positive photosensitive resin composition is more than 5 and 20 or less.
A method in which the optical density of the coating resin layer in the manufactured substrate is 0.10 / μm or more. The production method according to claim 1, wherein the positive photosensitive resin composition contains a novolak resin (A1) as a base resin component (A) and a quinonediazide group-containing compound (B1). The positive photosensitive resin composition is a resin (A2) whose solubility in alkali is increased by the action of an acid as a base resin component (A), and a compound (B2) that further generates an acid by irradiation with active light or irradiation. ), The manufacturing method according to claim 1. The manufacturing method according to any one of claims 1 to 3, wherein the substrate to be processed includes a liquid crystal cell, and the baking temperature in the post-baking step is 80 ° C. or higher and 150 ° C. or lower.

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