TWI735597B - Manufacturing method of substrate - Google Patents

Abstract

A method for manufacturing a substrate is provided. The substrate is provided with a color filter on one main surface, a patterned metal layer formed directly on the color filter or through a transparent layer, and a patterned coating The substrate of the metal layer coated with a resin layer (reflectance control means), through the above method, on a substrate with a color filter, it is easy to coat the patterned metal layer uniformly by the coating resin layer, and it is not formed The part of the metal layer is not easily covered by the coating resin layer.

When manufacturing a substrate with a color filter on one main surface, a patterned metal layer formed directly on the color filter or through a transparent layer, and a resin layer coated with the patterned metal layer A positive photosensitive resin composition containing a matrix 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 to form the coating resin layer.

Description

Substrate manufacturing method

The present invention relates to a method for manufacturing a substrate. The substrate is provided on one main surface with a color filter and a patterned metal layer formed directly on the color filter or through a transparent layer. Coating resin layer covering the patterned metal layer.

With the rapid spread of smart phones or tablet-type information communication terminals, the touch panel market is developing rapidly.

In the touch panel, electrodes or wires made of metal are sometimes formed in the display surface. For example, as such an electrode, a metal mesh electrode using Cu or Ag can be mentioned. However, when electrodes or wires made of metal are formed in the display surface, there is a problem that users who touch the panel can easily visually recognize the metal electrodes or metal wires, even if the line width of the metal electrodes or metal wires is changed. Even if it is so fine that the human eye cannot visually recognize it, the following problem will still occur: the reflection of external light occurs due to the high reflectivity of the metal.

In order to solve the above-mentioned problems, a method of providing a reflectance control means with a low reflectance on a metal thin film such as a metal electrode or a metal wiring has been proposed.

Specifically, the following method is known: a photosensitive resin composition is used, a patterned resin layer is provided on a metal layer on a transparent support by photolithography, and then the patterned resin layer is removed by etching. The metal layer exposed at the opening of the resin layer is removed, and then the resin layer is baked, thereby providing a reflectance control means (baked resin layer) that uniformly coats the surface of the etched metal layer (See Patent Document 1.).

[Prior Technical Literature] [Patent Literature]

[Patent Document 1] JP 2016-071242 A

From the viewpoint of expanding the selection of the manufacturing method of the touch panel or the selection of the structure of the touch panel, it is required not only on the transparent support, but also on the metal layer (metal wiring) on the substrate with the color filter. A method of coating a resin layer (reflectance control means).

Here, in the case where the metal layer (metal wiring) can be directly arranged on the substrate with the color filter, it is expected that the area where the metal layer (metal wiring) exists will be easy to control and manage, and it will not be easy to cause The opening ratio of the picture element drops.

The inventors of the present application have conducted studies on this point and found that if an appropriate photosensitive resin composition is not used for a substrate with a color filter, the coating resin layer (reflective layer) formed on the metal layer (metal wiring) In terms of rate control means), the following situations may occur: insufficient coverage of the metal wiring occurs; or, due to excessive flow of the coating resin layer during baking, the picture element portion is covered.

That is, if processing is performed on a transparent support as described in Patent Document 1, it can be baked at a uniform temperature to form a reflectance control means. In contrast, in the case of processing on a color filter, the non-uniformity of the heat absorbed due to the difference in the material of the black matrix or the coloring film of RGB, etc., makes the coating resin layer (reflectivity control Means) Cannot be heated uniformly.

Therefore, it is considered that when a patterned metal layer provided on a substrate with a color filter is coated with a coating resin layer, insufficient coverage of the metal layer will occur, or it may be caused by the coating resin during baking. Excessive flow of the layer covers the picture element part where the metal layer is not formed.

The present invention was made in view of the above-mentioned problems, and its object is to provide a method of manufacturing a substrate having a color filter on one main surface, and a color filter formed directly or via a transparent layer. The patterned metal layer, and the substrate of the coating resin layer (reflectance control means) coating the patterned metal layer, through the method, on the substrate with the color filter, the coating resin layer can easily The patterned metal layer is uniformly covered, and the portion where the metal layer is not formed is not easily covered by the covering resin layer.

The inventor of the present application found that when manufacturing a color filter on one main surface, and a patterned metal layer formed directly on the color filter or formed through a transparent layer, and a patterned metal layer covering When the substrate is coated with a resin layer, the coating resin layer is formed by using a positive photosensitive resin composition containing a matrix resin component (A) with a dispersion (weight average molecular weight Mw/number average molecular weight Mn) of 1 or more and 20 or less, The above-mentioned problems can be solved, and the present invention has been completed.

That is, the present invention relates to a method of manufacturing a substrate, the substrate having on one main surface: a color filter, and a patterned metal layer formed directly on the color filter or formed through a transparent layer, and A coating resin layer covering a patterned metal layer, the method includes the following steps: a photosensitive layer forming step, provided with a color filter, and an etched metal formed directly on the color filter or via a transparent layer In the processed substrate of the layer, the positive photosensitive resin composition is coated on the metal layer to be etched, the photosensitive layer is formed, and the exposure step is to expose a position other than the position where the patterned metal layer is formed in the photosensitive layer, In the developing step, the exposed photosensitive layer is developed to form a coating resin layer, and the etching step uses the coating resin layer as an etching mask to remove the etched metal layer exposed from the etching mask by etching to form a patterned metal The layer, and the post-baking step, the coating resin layer is baked, and the dispersion degree (weight average molecular weight Mw/number average molecular weight Mn) of the matrix resin component (A) contained in the positive photosensitive resin composition is 1 or more 20 Hereinafter, in the manufactured substrate, the optical density of the coating resin layer is 0.10/μm or more.

Through the present invention, a method for manufacturing a substrate can be provided, the substrate is provided with a color filter on one main surface, and a patterned metal layer formed directly on the color filter or formed through a transparent layer, and A substrate coated with a coating resin layer (reflectance control means) of a patterned metal layer is easy to uniformly coat the patterned metal layer on a substrate with a color filter by the method described above In addition, the portion where the metal layer is not formed is not easily covered by the coating resin layer.

1‧‧‧Substrate

10‧‧‧Processed substrate

11‧‧‧Etched metal layer

12‧‧‧Photosensitive layer

13‧‧‧Color filter

14‧‧‧Transparent layer

15‧‧‧Photomask

16‧‧‧Exposure light

17‧‧‧Coated resin layer

18‧‧‧Patterned metal layer

19‧‧‧Transparent resin layer

20‧‧‧Liquid crystal layer

21‧‧‧Pattern electrode

22‧‧‧Insulation layer

23‧‧‧Array substrate

B‧‧‧Blue colored film

BM‧‧‧Black matrix

G‧‧‧Green colored film

R‧‧‧Red tinted film

[Fig. 1] is a diagram schematically showing the outline of a method of manufacturing a substrate.

[Fig. 2] Fig. 2 is a diagram schematically showing an example of the use of the substrate manufactured in this embodiment.

[Best form for implementing the present invention]

Hereinafter, the present invention will be described based on preferred embodiments. However, unless otherwise specified, "~" in this manual means from above (lower limit) to below (upper limit).

The present invention relates to a method for manufacturing a substrate having a color filter on one main surface, a patterned metal layer formed directly on the color filter or through a transparent layer, and a coating The patterned metal layer is covered with a resin layer.

The coating resin layer is formed so that the optical density after the baking step is 0.10/μm or more. Therefore, for a touch panel provided with a substrate manufactured according to the method of the present invention, when the touch panel is used, the metal wiring is not easy to be visually recognized by the user of the touch panel.

The manufacturing method of the substrate of the present embodiment specifically includes the following steps: a photosensitive layer forming step in a substrate to be processed including a color filter and an etched metal layer formed directly on the color filter or formed through a transparent layer , The positive photosensitive resin composition is coated on the etched metal layer, the photosensitive layer is formed, the exposure step, the photosensitive layer is exposed to a position other than the position where the patterned metal layer is formed, and the development step will be exposed The photosensitive layer is developed to form a coating resin layer. The etching step uses the coating resin layer as an etching mask to remove the etched metal layer exposed from the etching mask by etching to form a patterned metal layer, and post-baking Step, baking the coating resin layer.

Furthermore, the positive photosensitive resin composition used in the photosensitive layer formation step contains a matrix 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.

Therefore, when the substrate is manufactured, it is easy to uniformly coat the patterned metal layer by the coating resin layer, and the portion where the metal layer is not formed is not easily covered by the coating resin layer.

Hereinafter, each step included in the method of manufacturing the substrate will be described with reference to FIG. 1. In the following description, the positive photosensitive resin composition is also referred to as "positive composition".

≪Steps of forming photosensitive layer≫

In the photosensitive layer forming step, as shown in Figures 1(a) and 1(b), the processed substrate 10 provided with the metal layer 11 to be etched is coated with a positive composition on the metal to be etched. The photosensitive layer 12 is thus formed on the layer 11.

Hereinafter, the substrate to be processed, the positive type composition, and the coating method will be described.

<Substrate to be processed>

As the substrate 10 to be processed, a substrate provided with a color filter 13 and an etched metal layer 11 formed directly on the color filter 13 or via a transparent layer 14 can be used.

1(a) to 1(e) show an aspect in which the substrate 10 to be processed including the transparent layer 14 is used. Illustration of the structure 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 omitted.

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

However, for the substrate 10 to be processed, as long as it is provided with a color filter 13, and a substrate with the etched metal layer 11 formed directly on the color filter 13 or via the transparent layer 14, there is no particular limitation. To use.

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 a substrate obtained by processing a substrate 10 to be processed. An array substrate 23, an insulating layer 22, a liquid crystal layer 20, a transparent resin layer 19, a color filter 13, and a transparent layer 14 are sequentially laminated. , Patterned metal layer 18, coating resin layer 17. The substrate can be suitably 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.

In addition, on the insulating layer 22, picture element 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.

In addition, the black matrix BM, the coating resin layer 17, and the patterned metal layer 18 are configured to overlap when the substrate is viewed from above.

A liquid crystal display device can be manufactured by combining the substrate 1 with components normally provided in a liquid crystal display device, such as a backlight, and wiring them appropriately.

Furthermore, the substrate 1 shown in FIG. 2 is a liquid crystal cell after liquid crystal is injected, and the structure includes a liquid crystal layer 20. In this case, due to the heat resistance of the liquid crystal compound used, there may be a problem that the processed substrate 10 provided with the coating resin layer 17 cannot be baked at a high temperature in the post-baking step described later.

In consideration of the above-mentioned circumstances, in this embodiment, it is preferable to implement the baking temperature in the post-baking step described later at a low temperature such as 80°C or more and 150°C or less. Even under such temperature conditions, the coating resin layer 17 can be formed satisfactorily.

<Positive type composition>

The positive composition contains a matrix 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 matrix resin component (A) is a component that imparts characteristics such as film-forming properties to the positive-type composition, and functions as a matrix material of a film formed using the positive-type composition directly or in a state of being chemically changed.

By setting the dispersion degree of the matrix resin component (A) contained in the positive type composition to 1 or more and 20 or less, the pattern formed on the processed substrate 10 provided with the color filter 13 can be integrated by the coating resin layer 17 The modified metal layer 18 is uniformly covered, and it is possible to make it difficult for the part where the metal layer 18 is not formed to be covered by the covering resin layer 17.

In terms of particularly easily obtaining the effects of the present invention, the dispersion degree of the matrix resin component (A) is preferably 2-17, more preferably 3-15, and particularly preferably 4-12.

In addition, from the viewpoint of better fluidity, the degree of dispersion of the matrix 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 relative values in terms of polystyrene in GPC (gel permeation chromatography) measurement.

In addition, when there are multiple resins constituting the matrix resin component (A) (for example, when a novolak resin (A1) and an alkali-soluble acrylic resin (A1-1) are used in combination, etc.), these multiple resins can be combined GPC (Gel Permeation Chromatography) measurement was performed in the state of, and the degree of dispersion was determined from the obtained graph.

As a preferable example of the positive type composition for forming the photosensitive layer 12, there may be mentioned: a novolak resin (A1) containing as the matrix resin component (A), and a further containing a quinonediazide group The positive composition of the compound (B1) and the resin (A2) that contains the matrix resin component (A) that increases the solubility in alkali through the action of acid, and further generates acid by irradiation of active light or radiation The positive composition of the compound (B2).

Hereinafter, the positive type composition containing the novolak resin (A1) and the quinonediazide group-containing compound (B1) will also be referred to as the first positive type composition, and will also include the increase in alkali through the action of acid The positive composition of the soluble resin (A2) and the compound (B2) that generates acid by irradiation with active light or radiation is referred to as the second positive composition.

Hereinafter, the first positive type composition and the second positive type composition will be described.

〔The first positive type composition〕

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

(Novolac resin (A1))

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

‧Phenols

Examples of phenols include: phenol; cresols such as o-cresol, m-cresol, and p-cresol; 2,3-xylenol, 2,4-xylenol, 2,5-diphenol Xylenol, 2,6-xylenol, 3,4-xylenol, 3,5-xylenol, etc.; ethyl phenol, m-ethylphenol, p-ethylphenol, etc. Alkylphenols; 2-isopropylphenol, 3-isopropylphenol, 4-isopropylphenol, o-butylphenol, m-butylphenol, p-butylphenol, and p-tert-butylphenol, etc. Phenols; 2,3,5-trimethylphenol, and 3,4,5-trimethylphenol and other trialkylphenols; resorcinol, catechol, hydroquinone, p-benzene Diphenol monomethyl ether, pyrogallol, and phloroglucinol and other polyphenols; alkyl resorcinol, alkyl catechol, and alkyl hydroquinone and other alkyl polyphenols (Any alkyl group has a carbon number of 1 or more and 4 or less.); α-naphthol; β-naphthol; hydroxybiphenyl; and bisphenol A, etc. These phenols may be used alone or in combination of two or more kinds.

Among these phenols, meta-cresol and p-cresol are preferred, and meta-cresol and p-cresol are more preferably used in combination. In this case, by adjusting the blending ratio of the two, various characteristics such as sensitivity as a positive composition and heat resistance of the coating resin layer 17 formed can be adjusted. The blending ratio of m-cresol and p-cresol is not particularly limited, and 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, and acetaldehyde. These aldehydes can be used alone, or two or more of them can be used in combination.

‧Acid catalyst

Examples of acid catalysts 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, diethyl sulfate, and p-toluenesulfonic acid; and metals such as zinc acetate. Salt, etc. These acid catalysts may be used alone or in combination of two or more kinds.

‧Molecular weight

The weight average molecular weight (Mw; hereafter, also referred to as "weight average molecular weight") of the novolak resin (A1) in terms of polystyrene, as long as it contains the base resin component (A) of the novolak resin (A1) The degree of dispersion (weight average molecular weight Mw/number average molecular weight Mn) of 1 or more and 20 or less is not particularly limited.

The degree of dispersion of the novolak resin (A1) is also the same as the aforementioned matrix resin component (A), preferably from 1 to 20, more preferably from 2 to 17, particularly preferably from 3 to 15, and even more preferably from 4 to 12.

From the viewpoints of the developability and resolution of the first positive composition, the weight average molecular weight of the novolak resin (A1) is preferably 1,000 or more, more preferably 2,000 or more, and still more preferably 3,000 or more. It is preferably 50,000 or less, more preferably 40,000 or less, still more preferably 30,000 or less, and still more preferably 20,000 or less.

As the novolak resin (A1), at least two types of novolak resins having different weight average molecular weights in terms of polystyrene can be used in combination. By using a combination of novolak resins of different sizes and molecular weights with different weight average molecular weights, it is possible to impart various excellent properties such as developability, resolution, and film forming properties to the positive composition.

Regarding the novolak resin (A1), there are no particular restrictions on the combination of resins with different weight average molecular weights. Preferably, resins on the low weight average molecular weight side with a weight average molecular weight of 1,000 to 10,000, and resins with a weight average molecular weight of 5,000 to 50,000 are preferred. The combination of the weight average molecular weight side resin, more preferably the weight average molecular weight of 2000 to 8000 low weight average molecular weight side resin, and the weight average molecular weight of 8000 to 40,000 high weight average molecular weight side resin combination, more preferably weight A combination of a low weight average molecular weight side resin with an average molecular weight of 3,000 to 7,000 and a high weight average molecular weight side resin with a weight average molecular weight of 10,000 to 20,000.

As the novolak resin (A1), when resins with different weight average molecular weights are used in combination, the content of each is not particularly limited. The content of the resin on the low weight average molecular weight side in the total amount of the novolak resin (A1) is preferably 5 mass% or more, more preferably 10 mass% or more, further preferably 15 mass% or more, on the other hand, it is preferably 50 mass% or less, more preferably 40 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, still more preferably 50% by mass or more, and more preferably 90% by mass % Or less, more preferably 85% by mass or less. By setting the content of the novolak resin (A1) within the above range, it is possible to appropriately bond the other components contained in the first positive type composition while exhibiting lyophilicity with respect to the metal component. As a result, it can be formed with The coating resin layer 17 is also excellent in adhesion of the patterned metal layer 18.

The first positive composition may contain other resins than the novolak resin (A1) as the matrix resin component (A). The types of other resins are not particularly limited, as long as they do not excessively impair the lithographic characteristics such as the sensitivity and resolution of the positive type composition.

As a preferable example of other resin, alkali-soluble acrylic resin (A1-1) is mentioned. The alkali-soluble acrylic resin (A1-1) functions as a plasticizer in the coating resin layer 17 and suppresses the generation of cracks in the coating resin layer 17.

As the alkali-soluble acrylic resin (A1-1), as long as the degree of dispersion of the matrix resin component (A) is within a predetermined range, an alkali-soluble acrylic resin usually blended into a positive composition as a plasticizer can be used.

As the alkali-soluble acrylic resin (A1-1), more specifically, a structural unit based on a polymerizable compound having an ether bond containing 30 mol% or more and 90 mol% or less, and 2 mol% or more and 50 mol% Mole% or less resin based on the structural unit of the polymerizable compound having a carboxyl group.

Examples of the polymerizable compound having an ether bond include 2-methoxyethyl (meth)acrylate, methoxytriethylene glycol (meth)acrylate, and 3-methoxybutyl (meth)acrylate. Ester, ethyl carbitol (meth)acrylate, phenoxy polyethylene glycol (meth)acrylate, methoxy polypropylene glycol (meth)acrylate, and tetrahydrofurfuryl (meth)acrylate Radical polymerizable compounds such as (meth)acrylic acid derivatives having ether bonds and ester bonds such as esters. Among these, 2-methoxyethyl acrylate and methoxytriethylene glycol acrylate are preferably used. These compounds may be used alone, or two or more of them may be mixed and used.

Examples of the polymerizable compound having a carboxyl 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-methyl succinic acid 2-methacryloxyethyl maleate, 2-methacryloxyethyl maleate, 2-methacryloxyethyl phthalate, and 2-methyl hexahydrophthalate Radical polymerizable compounds such as methacrylic acid derivatives having a carboxyl group and an ester bond such as allyloxyethyl. Among these, acrylic acid and methacrylic acid are preferably used. These compounds may be used alone, or two or more of them may be mixed and used.

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 units derived from a polymerizable compound having an ether bond in an amount within the above range as a plasticizer into the first positive composition, it is easy to suppress the coating While cracks are generated in the resin layer 17, a uniform coating resin layer 17 is formed.

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

The weight average molecular weight in terms of polystyrene of the alkali-soluble acrylic resin (A1-1) is not particularly limited as long as the degree of dispersion of the matrix resin component (A) is 1 or more and 20 or less. The weight average molecular weight of the alkali-soluble acrylic resin (A1-1) in terms of polystyrene is preferably 10,000 to 800,000, more preferably 30,000 to 500,000.

For the purpose of appropriately controlling the physical/chemical properties, the alkali-soluble acrylic resin (A1-1) may also contain structural units based on other radically polymerizable compounds. The term "other radically polymerizable compound" as used herein refers to a radically polymerizable compound other than the aforementioned polymerizable compound.

As such other radically polymerizable compounds, alkyl (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, and butyl (meth)acrylate can be used; Hydroxyalkyl (meth)acrylates such as 2-hydroxyethyl meth)acrylate and 2-hydroxypropyl (meth)acrylate; phenyl (meth)acrylate and benzyl (meth)acrylate (Meth)acrylic acid aryl esters such as; diethyl maleate, and dibutyl fumarate and other dicarboxylic acid diesters; styrene, and α-methylstyrene, etc. containing vinyl Aromatic compounds; aliphatic compounds containing vinyl groups such as vinyl acetate; conjugated dienes such as butadiene and isoprene; polymerizable compounds containing nitrile groups such as acrylonitrile and methacrylonitrile; chlorine Polymeric compounds containing chlorine such as ethylene and vinylidene chloride; and polymerizable compounds containing amide bonds such as acrylamide and methacrylamide. These compounds may be used alone, or two or more of them may be mixed and used. Among these compounds, n-butyl acrylate, benzyl methacrylate, and methyl methacrylate are particularly preferred. The content of the structural unit based on other radical polymerizable compounds in the alkali-soluble acrylic resin (A1-1) is preferably less than 50% by mass, and more preferably less than 40% by mass.

As the polymerization solvent used in the synthesis of the alkali-soluble acrylic resin component, for example, alcohols such as ethanol and diethylene glycol; ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, and diethylene diethylene glycol can be used. Alkyl ethers of polyhydric alcohols such as ethyl methyl ether; alkyl ether acetates of polyhydric alcohols such as ethylene glycol ethyl ether acetate and propylene glycol methyl ether acetate; toluene and xylene And other aromatic hydrocarbons; ketones such as acetone and methyl isobutyl ketone; and esters such as ethyl acetate and butyl acetate. Among these polymerizable solvents, alkyl ethers of polyhydric alcohols and alkyl ether acetates of polyhydric alcohols are particularly preferably used.

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

Regarding the first positive composition, the blending amount in the case of containing the alkali-soluble acrylic resin (A1-1) is preferably 30 parts by mass or less with respect to 100 parts by mass of the novolak resin (A1), and more Preferably it is 20 parts by mass or less.

(Compounds containing quinonediazide group (B1))

The first positive composition contains a quinonediazide group-containing compound (B1). As the quinonediazide group-containing compound (B1), it can be appropriately selected from compounds having a quinonediazide group that have been blended in various positive compositions in the past.

As a preferable specific example of the compound (B1) containing a quinonediazide group, a complete esterification product, a partial esterification product, an amidate, or a quinonediazide group-containing sulfonic acid formed by the following substances Partial amides, etc., the substances are: 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 Benzophenone, 2,2',3,4,5-pentahydroxybenzophenone, 2,3',4,4',5',6-hexahydroxybenzophenone, 2,3,3' ,4,4',5'-hexahydroxybenzophenone and other polyhydroxybenzophenones; 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'-dihydroxybenzene Yl)propane, 2-(2,3,4-trihydroxyphenyl)-2-(2',3',4'-trihydroxyphenyl)propane, 4,4'-{1-[4-〔 2-(4-Hydroxyphenyl)-2-propyl]phenyl]ethylene}bisphenol, and 3,3'-dimethyl-{1-[4-〔2-(3-methyl- Bis[(poly)hydroxyphenyl]alkanes such as 4-hydroxyphenyl)-2-propyl]phenyl]ethylene}bisphenol; tris(4-hydroxyphenyl)methane, bis(4-hydroxy) -3,5-Dimethylphenyl)-4-hydroxyphenylmethane, 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, etc. (hydroxyl Phenyl) methanes or their methyl substituents; bis(3-cyclohexyl-4-hydroxyphenyl)-3-hydroxyphenylmethane, bis(3-cyclohexyl-4-hydroxyphenyl)-2-hydroxy Phenylmethane, 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-hydroxybenzene Methyl methane, 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-methyl) Phenyl)-2-hydroxyphenylmethane, bis(3-cyclohexyl-2-hydroxyphenyl)-4-hydroxyphenylmethane, bis(3-cyclohexyl-2-hydroxyphenyl)-2-hydroxy Phenylmethane, bis(5-cyclohexyl-2-hydroxy-4-methylphenyl)-2-hydroxyphenylmethane, and bis(5-cyclohexyl-2-hydroxy-4-methylphenyl)- Bis(cyclohexylhydroxyphenyl)(hydroxyphenyl)methanes such as 4-hydroxyphenylmethane or its methyl substituents; phenol, p-methoxyphenol, dimethylphenol, hydroquinone, naphthol , Catechol, pyrogallol, pyrogallol monomethyl ether, pyrogallol-1,3-dimethyl ether, gallic acid, aniline, N-phenyl-p-phenylenediamine ( p-aminodiphenylamine), and 4,4'-diaminobenzophenone and other compounds having hydroxyl or amino groups; and homopolymers of novolac, pyrogallol-acetone resin, and p-hydroxystyrene or Copolymers of p-hydroxystyrene and copolymerizable monomers, etc. These quinonediazide group-containing compounds (B1) may be used alone or in combination of two or more kinds.

The above-mentioned quinonediazide group-containing sulfonic acid that can be used as the quinonediazide group-containing compound (B1) is not particularly limited. For example, naphthoquinone-1,2-diazide-5- Naphthoquinone-1,2-diazido-5-sulfonicacid (naphthoquinone-1,2-diazido-5-sulfonicacid), naphthoquinone-1,2-diazido-4-sulfonic acid, etc. naphthoquinone diazide sulfonic acid; o-anthraquinone diazide Sulfonic acid, etc., preferably naphthoquinone diazide sulfonic acid. The sulfonic acid containing a quinonediazide group, preferably the above esterified product of naphthoquinonediazide sulfonic acid, can be sufficiently dissolved in the solvent usually used when the positive composition is used in the form of a solution, and is combined with the novolak resin ( A1) has good compatibility. If these compounds are blended into the first positive composition as a quinonediazide group-containing compound (B1), it is easy to obtain a highly sensitive first positive composition.

There are no particular limitations on the method for producing the above-mentioned esterified compound (B1) containing a quinonediazide group. For example, the following method may be mentioned: for example, naphthoquinone-1,2-diazidosulfonyl chloride Add sulfonic acid containing quinonediazide in the form of other sulfonic acid chlorides, in solvents such as dioxane, in the presence of bases such as triethanolamine, alkali metal carbonates, and alkali metal bicarbonates Then, it is condensed to carry out complete esterification or partial esterification.

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

(Crosslinking agent)

The first positive composition may contain a crosslinking agent. The crosslinking agent can be appropriately selected from compounds capable of crosslinking the novolak resin (A1). For example, melamine compounds; amine-based crosslinking agents such as hexamethylenetetramine and urea derivatives; epoxy compounds can be used. By including such a crosslinking agent in the first positive type composition, the coating resin layer 17 having excellent water resistance, heat resistance, and solvent resistance can be formed.

As the melamine compound, a compound having a chemical structure derived from melamine that acts as a crosslinking agent and acts on the novolak resin (A1), for example, a compound represented by the following formula (I) can be used.

(式中，R¹~R⁶各自獨立地以表示氫原子或以-CH₂-O-R⁷表示的基，R⁷為氫原子或碳數為1~10的烷基，R¹~R⁶中的至少1個為-CH₂-O-R⁷表示的基。)

(In the formula, R ¹ to R ⁶ each independently represent a hydrogen atom or a group represented _{by -CH 2} -OR ^{7 , R 7} is a hydrogen atom or an alkyl group having 1 to 10 carbons, and R ¹ to R ⁶ At least one of is a group represented by _{-CH 2} -OR ^7.)

In the above formula (I), it is preferable that two or more groups represented by _{-CH 2} -OR ^{7 are present in R 1} to R ^6.

The alkyl group represented by R ⁷ is more preferably an alkyl group having 1 to 6 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, and n-hexyl.

Examples of the melamine compound represented by the above formula (I) include: hexamethylol melamine, hexahydroxybutyl melamine, partially methylolated melamine, and alkyl compounds thereof; tetramethylol benzoguanamine And some methylolated benzoguanamines and these alkylates; etc.

As the epoxy compound, a compound having an epoxy group that acts as a crosslinking agent with the novolak resin (A1) can be used. As an epoxy compound, the polyfunctional epoxy compound which has 2 or more epoxy groups in 1 molecule is preferable. In addition, in this specification, the silane coupling agent which has an epoxy group in its structure among the silane coupling agents mentioned later does not belong to the epoxy compound used as a crosslinking agent.

As the epoxy compound, phenol novolak type epoxy resin, cresol novolak type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, polyfunctional alicyclic epoxy resin, Aliphatic polyglycidyl ether, etc.

The above-mentioned crosslinking agent may be used alone or in combination of two or more kinds.

The content of the crosslinking agent may be 3 parts by mass or more, 10 parts by mass or more, or 15 parts by mass or more with respect to 100 parts by mass of the novolak resin (A1). In addition, with respect to 100 parts by mass of the novolak resin (A1), the content of the crosslinking agent may be 40 parts by mass or less, may be 30 parts by mass or less, or may be 25 parts by mass or less. When the content of the crosslinking agent is more than the above lower limit value, the crosslinking of the resin tends to be sufficient, and when the content is below the above upper limit value, the storage stability of the first positive composition tends to become good.

(Silane coupling agent)

The first positive composition may contain a silane coupling agent.

The silane coupling agent can react with the phenolic hydroxyl group of the novolak resin (A1) via the alkoxy group and/or reactive group bonded to the silicon atom, so it can function as a crosslinking agent, making it useful The coating resin layer 17 formed of the first positive composition is compacted, thereby not only improving the water resistance, solvent resistance, heat resistance, etc. of the coating resin layer 17, but also improving the coating resin layer 17 and the patterned metal Adhesion of layer 18.

As the silane coupling agent, for example, methyl trimethoxy silane, methyl triethoxy silane, ethyl trimethoxy silane, ethyl triethoxy silane, n-propyl trimethoxy silane, n-propyl trimethoxy silane, Monoalkyl trialkoxy silanes such as propyl triethoxy silane, n-butyl trimethoxy silane, n-butyl triethoxy silane; dimethyl dimethoxy silane, dimethyl diethoxy Dialkyl dialkoxysilanes such as silyl silane; monophenyl trialkoxy silanes such as phenyl trimethoxy silane and phenyl triethoxy silane; diphenyl dimethoxy silane, diphenyl Diphenyldialkoxysilane such as diethoxysilane; monovinyltrialkoxysilane such as vinyltrimethoxysilane and vinyltriethoxysilane; 3-methacryloxypropane Trimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyl (Meth) propylene oxyalkyl monoalkyl dialkoxy silane such as methyl diethoxy silane; (meth) propylene oxy silane such as 3-propylene oxy propyl trimethoxy silane Alkyl trialkoxysilane; 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl Trialkoxysilanes containing amino groups such as butylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, etc.; 3-glycidoxypropyl trimethoxysilane Alkyl trialkoxysilanes containing non-alicyclic epoxy groups such as 3-glycidoxy propyl triethoxy silane; 3-glycidoxy propyl methyl diethoxy Non-alicyclic epoxy-containing alkyl monoalkyl dialkoxy silanes such as base silanes; 2-(3,4-epoxycyclohexyl) ethyl trimethoxy silane, 2-(3,4- (Epoxycyclohexyl) ethyl triethoxy silane and other alicyclic epoxy-containing alkyl trialkoxy silanes; 2-(3,4-epoxycyclohexyl) ethyl methyl diethoxy Alkyl monoalkyldialkoxysilanes containing alicyclic epoxy groups such as silanes; [(3-ethyl-3-oxetanyl)methoxy]propyltrimethoxysilane, [( 3-Ethyl-3-oxetanyl) methoxy] propyl triethoxysilane and other oxetanyl-containing alkyl trialkoxysilanes; 3-mercaptopropyl trimethoxysilane Such as mercaptoalkyl trialkoxy silane; 3-mercaptopropyl methyl dimethoxy silane and other mercapto alkyl monoalkyl dialkoxy silane; 3-ureidopropyl triethoxy silane, etc. Ureayl alkyl trialkoxy silane; 3-isocyanate propyl triethoxy silane and other isocyanate alkyl trialkoxy silane; 3-trimethoxy silyl propyl succinic anhydride, etc. containing anhydride group Alkyl trialkoxysilanes; N-tert-butyl-3-(3-trimethoxysilylpropyl) succinimidyl group-containing alkyltrialkoxysilanes, etc.; etc. . The silane coupling agent may be used alone or in combination of two or more kinds.

Among the silane coupling agents, a silane coupling agent having a reactive group is preferred.

The silane coupling agent having a reactive group is preferably a silane coupling agent having a vinyl group, an amino group, an epoxy group, or an oxetanyl group. From the viewpoint of high compatibility with the developing solution to reduce residues (undissolved and remaining), and in particular to form a coating resin layer 17 with excellent adhesion to metals, silane coupling with epoxy groups is more preferable Agent.

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

The content of the silane coupling agent may be 0.1 parts by mass or more, 0.5 parts by mass or more, or 1 part by mass or more with respect to 100 parts by mass of the novolak resin (A1). In addition, relative to 100 parts by mass of the novolak resin (A1), the content of the silane coupling agent may be 10 parts by mass or less, 7 parts by mass or less, 5 parts by mass or less, or 3 parts by mass or less.

When the content of the silane coupling agent is greater than or equal to the above lower limit, 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 below the above upper limit, 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 this embodiment is 0.10/μm or more. From the viewpoint of achieving such an optical density, the first positive composition typically contains a coloring agent for adjusting the optical density.

The coloring agent is not particularly limited. For example, it is preferable to use a compound classified as a pigment in the dye index (CI; issued by The Society of Dyers and Colourists). Specifically, it is preferable to use a compound with a dye index (CI) as described below. ) Number of substances.

Examples of yellow pigments that can be suitably used include CI Pigment Yellow 1 (hereinafter, also "CI Pigment Yellow", and only the numbers are 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 orange pigments that can be suitably used include CI Pigment Orange 1 (hereinafter, also "CI Pigment Orange", and only the numbers are 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 purple pigments that can be suitably used include CI Pigment Violet 1 (hereinafter, also "CI Pigment Violet", with only the number described), 19, 23, 29, 30, 32, 36, 37, 38, 39, 40, and 50.

Examples of red pigments that can be suitably used include CI Pigment Red 1 (hereinafter, also "CI Pigment Red", 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 blue pigments that can be suitably used include CI Pigment Blue 1 (hereinafter, also "CI Pigment Blue", and only the numbers are described), 2, 15, 15: 3, 15: 4, 15: 6 , 16, 22, 60, 64, and 66.

Examples of pigments of hue other than the above that can be suitably used include green pigments such as CI Pigment Green 7, CI Pigment Green 36, CI Pigment Green 37, CI Pigment Brown 23, CI Pigment Brown 25, and CI Pigment Brown 26. Brown pigments such as CI Pigment Brown 28, CI Pigment Black 1, CI Pigment Black 7 and other black pigments.

In addition, the first positive composition may contain a light-shielding agent as a coloring agent. 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 or purple pigments include metal oxides such as carbon black, perylene-based pigments, internal amide-based pigments, titanium black, copper, iron, manganese, cobalt, chromium, nickel, zinc, calcium, and silver. , Complex oxides, metal sulfides, metal sulfates or metal carbonates and other pigments, whether organic or inorganic.

As the carbon black, known carbon blacks such as channel black, furnace black, thermal black, and lamp black can be used. In addition, resin-coated carbon black can also be used.

As the carbon black, carbon black subjected to the treatment of introducing acidic groups is also preferable. The acidic group introduced into the carbon black is a functional group showing acidity based on the definition of Bronsted. As a specific example of an acidic group, a carboxyl group, a sulfonic acid group, a phosphoric acid group, etc. are mentioned. The acidic group introduced into the carbon black can form a salt. The cation forming a salt with an acidic group is not particularly limited within a range that does not interfere with the purpose of the present invention. Examples of the cation include various metal ions, cations of nitrogen-containing compounds, ammonium ions, etc., and alkali metal ions such as sodium ions, potassium ions, and lithium ions, and ammonium ions are preferred.

Among the carbon blacks that have been subjected to the treatment of introducing acidic groups described above, there are carbons having one or more functional groups selected from the group consisting of carboxylic acid groups, carboxylate groups, sulfonic acid groups, and sulfonate groups Black is better.

The method of introducing acidic groups into carbon black is not particularly limited. As a method of introducing an acidic group, for example, the following methods can be cited.

Method 1): Introduce sulfonic acid groups into carbon black via direct substitution method (where concentrated sulfuric acid, oleum, chlorosulfonic acid, etc.) or indirect substitution method (where sulfite, bisulfite, etc. are used).

Method 2): Diazo coupling an organic compound with an amine group and an acidic group and carbon black.

Method 3): The organic compound having a halogen atom and an acidic group is reacted with a carbon black having a hydroxyl group by the Williamson etherification method.

Method 4): Reacting an organic compound having a halogenated carbonyl group and an acidic group protected by a protective group with a carbon black having a hydroxyl group.

Method 5): Use an organic compound with a halogenated carbonyl group and an acidic group protected by a protecting group to perform Friedel-Crafts reaction on carbon black, and then perform deprotection.

Among these methods, the method 2) is preferred in terms of easy and safe treatment of introducing acidic groups. As the organic compound having an amine group and an acidic group used in the method 2), a compound having an amine group and an acidic group bonded to an aromatic group is preferred. Examples of such compounds include aminobenzenesulfonic acid such as p-aminobenzenesulfonic acid or aminobenzoic acid such as 4-aminobenzoic acid.

The number of moles of acidic groups introduced into carbon black is not particularly limited within a range that does not interfere with the purpose of the present invention. The number of moles of acidic groups introduced into the carbon black is preferably 1 to 200 mmol, and more preferably 5 to 100 mmol, relative to 100 g of carbon black.

Carbon black into which acidic groups have been introduced can be coated with resin.

When a photosensitive resin composition containing resin-coated carbon black 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 to coat carbon black include: phenolic resins, melamine resins, xylene resins, diallylphthalate resins, glyptal resins, epoxy resins, and alkane resins. Thermosetting resin such as base benzene resin; polystyrene, polycarbonate, polyethylene terephthalate, polybutylene terephthalate, modified polyphenylene ether, polypene, poly(p-phenylene) Dimethyl p-phenylenediamine, polyamide imide, polyimide, polyamino bismaleimide, polyether phenylene, polyarylate, polyether ether ketone, etc. Plastic resin. The coating amount of the resin on the carbon black is preferably 1 to 30% by mass relative to the total of the mass of the carbon black and the mass of the resin.

In addition, as a light-shielding agent, perylene-based pigments are also preferred. Specific examples of perylene pigments include perylene pigments represented by the following formula (e-1), perylene pigments represented by the following formula (e-2), and perylene pigments represented by the following formula (e-3) Perylene pigments. Among commercially available products, product names K0084, K0086, and pigment black 21, 30, 31, 32, 33, and 34 manufactured by BASF Corporation can be preferably used as perylene pigments.

In 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 each independently represent a hydrogen atom, a hydroxyl group, a methoxy group, or an acetyl group .

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

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

The compound represented by the above-mentioned formula (e-1), the compound represented by the formula (e-2), and the compound represented by the formula (e-3) can be used, for example, in Japanese Patent Laid-Open No. 62-1753 and Japanese Patent Publication It was synthesized by the method described in Bulletin 63-26784. That is, using perylene-3,5,9,10-tetracarboxylic acid or its dianhydride and amines as raw materials, the heating reaction is carried out in water or an organic solvent. Then, the obtained crude product is reprecipitated in sulfuric acid, or recrystallized in water, an organic solvent, or a mixed solvent of these, thereby obtaining the target product.

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

In addition, as a light-shielding agent, internal amide-based pigments may also be included. As an internal amine type pigment, the compound represented by following formula (e-4) is mentioned, for example.

In formula (e-4), X ^e represents a double bond. As geometric isomers, each is independently an E form or a Z form, and R ^e9 each independently represents a hydrogen atom, a methyl group, a nitro group, a methoxy group, and a bromine. Atom, a chlorine atom, a fluorine atom, a carboxyl group, or a sulfonic acid group, R ^e10 each independently represents a hydrogen atom, a methyl group, or a phenyl group, and R ^e11 each independently represents a hydrogen atom, a methyl group, or a chlorine atom.

The compound represented by formula (e-4) can be used individually or in combination of 2 or more types.

From the viewpoint of easy production of the compound represented by the formula (e-4), R ^{e9 is} preferably bonded to the 6 position of the indolinone ring, and R ^{e11 is} preferably bonded to the 4 position of the indolinone ring. From the same viewpoint, R ^e9 , R ^e10 , and R ^{e11 are} preferably hydrogen atoms.

For the compound represented by the formula (e-4), as geometric isomers, there are EE form, ZZ form, and EZ form. It may be a single compound of any one of these, or may be such geometric isomers. mixture.

The compound represented by the formula (e-4) can be produced, for example, by the method described in International Publication No. 2000/24736 and International Publication No. 2010/081624.

In order to disperse the internal amine-based pigment in the first positive type composition well, the average particle diameter of the internal amine-based pigment is preferably 10 to 1000 nm.

In addition, fine particles mainly composed of silver tin (AgSn) alloy (hereinafter referred to as "AgSn alloy fine particles") are also preferably used as a light-shielding agent. For the AgSn alloy fine particles, as long as the AgSn alloy is the main component, as other metal components, for example, Ni, Pd, Au, etc. may be contained.

The average particle size of the AgSn alloy particles is preferably 1 to 300 nm.

x

10，可同時得到化學穩定性與黑度的x的範圍為3

x

4。 When the AgSn alloy is represented by the chemical formula AgxSn, a chemically stable AgSn alloy can be obtained. The range of x is 1

x

10. The range of x that can obtain both chemical stability and blackness is 3

x

4.

Here, the mass ratio of Ag in the AgSn alloy in the range of x is calculated, and the result is:

In the case of 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.

Therefore, for this AgSn alloy, when it contains 47.6 to 90% by weight of Ag, it is chemically stable, and when it contains 73.17 to 78.43% by weight of Ag, it can effectively obtain chemical stability corresponding to the amount of Ag. Sex and darkness.

The AgSn alloy fine particles can be produced using a normal 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, a hydrothermal synthesis method, and the like.

Although the AgSn alloy particles are highly insulating materials, in order to further improve the insulating properties, the surface may be covered with an insulating film. As the material of such an insulating film, a metal oxide or an organic polymer compound is preferable.

As the metal oxide, metal oxides with insulating properties can be suitably used, such as silicon oxide (silica), aluminum oxide (alumina, aluminum oxide), zirconia (zirconia, zirconium dioxide), and yttrium oxide ( yttria, yttrium trioxide), titanium oxide (titania, titanium dioxide), etc.

In addition, as the organic polymer compound, resins having insulating properties, such as polyimide, polyether, polyacrylate, polyamine compound, etc., can be suitably used.

As for the thickness of the insulating film, in order to sufficiently improve the insulating properties on the surface of the AgSn alloy particles, the thickness is preferably from 1 to 100 nm, and more preferably from 5 to 50 nm.

The insulating film can be easily formed through surface modification technology or surface coating technology. In particular, when alkoxides such as tetraethoxysilane and aluminum oxide (Aluminum Ethoxide) are used, an insulating film with uniform film thickness can be formed at a relatively low temperature, which is preferable.

As the light-shielding agent, the above-mentioned perylene-based pigments, internal amine-based pigments, and AgSn alloy fine particles may be used alone, or they may be used in combination.

In addition, for the purpose of adjusting the color tone, etc., the light-shielding agent may include not only the above-mentioned black pigment or purple pigment, but also color pigments of red, blue, green, and yellow. Colorants of hues other than black pigments and purple pigments can be appropriately selected from known pigments. For example, as a coloring matter other than a black pigment or a purple pigment, the various pigments mentioned above can be used. Regarding the usage amount of the coloring matter of a hue other than the black pigment or the purple pigment, relative to the total mass of the sunscreen, it is preferably 15% by mass or less, and more preferably 10% by mass or less.

In order to uniformly disperse the above-mentioned colorant in the first positive composition, a dispersant may be further used. As such a dispersing agent, polyethyleneimine-based, polyurethane resin-based, and acrylic resin-based polymer dispersing agents are preferably used. In particular, when carbon black is used as a colorant, it is preferable to use an acrylic resin-based dispersant as the dispersant.

However, depending on the type of dispersant or the manufacturing conditions and use conditions of the display device, the volatile components generated by the dispersant may have an adverse effect on the display device. Therefore, the colorant should be treated without the use of a dispersant. Dispersion treatment is also preferable.

In addition, an inorganic pigment and an organic pigment can be used individually or in combination of 2 or more types, respectively. When used in combination, the organic pigment is preferably used in the range of 10 to 80 parts by mass, and more preferably in the range of 20 to 40 parts by mass relative to 100 parts by mass of the total amount of the inorganic pigment and organic pigment.

In addition, in the first positive type composition, in addition to pigments, dyes may also be used as colorants. The dye can be appropriately selected from known materials.

Examples of dyes applicable to the first positive type composition include azo dyes, metal complex azo dyes, anthraquinone dyes, triphenylmethane dyes, xanthene dyes, Cyanine dyes, naphthoquinone dyes, quinoneimine dyes, methine dyes, phthalocyanine dyes, etc.

In addition, these dyes can be used as a colorant by dispersing them in an organic solvent or the like by being laked (salted).

In addition to these dyes, for example, Japanese Patent Application Publication No. 2013-225132, Japanese Patent Application Publication No. 2014-178477, Japanese Patent Application Publication No. 2013-137543, Japanese Patent Application Publication No. 2011-38085, Japan Dyes and the like described in Japanese Patent Laid-Open No. 2014-197206 etc.

These dyes may be further used in combination with the aforementioned pigments (for example, perylene-based pigments, internal amide-based pigments, AgSn alloy particles, etc.).

The amount of the coloring agent 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.

Regarding the usage amount of the coloring agent in the first positive composition, for example, relative to 100 parts by mass of the novolak resin (A1), it is preferably 1 part by mass or more, more preferably 3 parts by mass or more, and more It is preferably 5 parts by mass or more, more preferably 60 parts by mass or less, more preferably 50 parts by mass or less, still more preferably 45 parts by mass or less, and still more preferably 40 parts by mass or less.

In addition, the optical density of the coating resin layer 17 is more preferably 0.20 to 2.0/μm, and still more preferably 0.30 to 1.0/μm.

The coloring agent is preferably dispersed at an appropriate concentration in the presence or absence of a dispersant to prepare a dispersion, 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 within a range that does not interfere with the purpose of the present invention.

‧Sensitizer

The sensitizer is not particularly limited, and can be arbitrarily selected from sensitizers generally used in positive-type compositions. As a sensitizer, the compound etc. which have a phenolic hydroxyl group with a molecular weight of 1000 or less are mentioned, for example.

‧Adhesion improver

As the adhesion improver, it is possible to appropriately select from materials capable of improving the adhesion between the coating resin layer 1 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

In order to improve coating properties, defoaming properties, leveling properties, etc., the first positive composition may contain a surfactant. As the surfactant, for example, BM-1000, BM-1100 (manufactured by BM Chemie), Megafac F142D, Megafac F172, Megafac F173, Megafac F183 (manufactured by Dainippon Ink Chemical Industry Co., Ltd.), Fluorad FC-135, Fluorad FC-170C, Fluorad FC-430, Fluorad FC-431 (manufactured by Sumitomo 3M Ltd.), Surflon S-112, Surflon S-113, Surflon S-131, Surflon S-141, Surflon 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 BYK Chemie Japan), etc. Or fluorine-based surfactants.

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>

For the first positive photosensitive resin composition, it is preferable to dissolve the above-mentioned components in an appropriate solvent and use it as a solution. Examples of such solvents include glycol alkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether. Class; Diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, and diethylene glycol dibutyl ether; Methyl cellosolve acetate (methyl cellosolve acetate), ethyl cellosolve acetate and other glycol alkyl ether acetates; propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether ethyl Acid esters, propylene glycol alkyl ether acetates such as propylene glycol monopropyl ether acetate; ketones such as acetone, methyl ethyl ketone, cyclohexanone, and methyl amyl ketone; toluene and xylene, etc. Aromatic hydrocarbons; cyclic ethers such as dioxane; and methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl Ethyl oxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutyrate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, ethyl formate , Ethyl acetate, butyl acetate, methyl acetyl acetate, and ethyl acetyl acetate, etc. These solvents may be used alone, or two or more of them may be mixed and used.

The content of the solvent in the first positive type composition can be appropriately adjusted in consideration of the viscosity or coatability of the first positive type composition. Specifically, the solvent can be used such that the solid content concentration of the first positive composition becomes preferably 5-50% by mass, more preferably 10-30% by mass.

<Preparation method of the first positive type composition>

The first positive composition can be prepared by blending the above-mentioned components in a predetermined ratio, then mixing and stirring by a usual method. In addition, if necessary, a screen, a membrane filter, etc. can be further used for filtration.

〔The second positive type composition〕

As described above, the second positive composition includes a resin (A2) that increases the solubility in an alkali through the action of an acid, and a compound (B2) that generates an acid through irradiation with active rays or radiation.

Hereinafter, the resin (A2) that increases the solubility in alkali through the action of acid is also referred to as "resin (A2)". In addition, the compound (B2) that generates an acid by irradiation with active light or radiation is also referred to as "acid generator (B2)".

Hereinafter, the essential components or optional components contained in the second positive composition will be described.

(Resin (A2))

The second positive composition includes a resin (A2) that increases the solubility in alkali through the action of an acid as the matrix resin component (A). The resin (A2) is not particularly limited, and any resin that increases the solubility in alkali through the action of an acid can be used.

Regarding the degree of dispersion of the resin (A2), similar to the aforementioned matrix resin component (A), it is preferably 1 or more and 20 or less, more preferably 2 to 17, particularly preferably 3 to 15, and still more preferably 4 ~12.

The resin (A2) preferably contains a novolak resin (A2-1) (hereinafter, also referred to simply as novolak resin (A2-1)) having an acid dissociable dissolution inhibiting group, and an acid dissociable dissolution inhibiting group Polyhydroxystyrene resin (A2-2) (hereinafter also referred to as polyhydroxystyrene resin (A2-2)) and acrylic resin (A2-3) having specific structural units described later At least one resin.

‧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 dissociable dissolution inhibiting group, and R ^2a and R ^3a each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

The acid dissociable dissolution inhibiting group represented by R ^1a is preferably a group represented by the following formula (a2), (a3), a linear, branched, or cyclic alkane having 1 to 6 carbon atoms Group, vinyloxyethyl, tetrahydropyranyl, tetrafuranyl, or trialkylsilyl.

In the above formulas (a2) and (a3), R ^4a and R ^5a each independently represent a hydrogen atom or a linear or branched alkyl group having 1 to 6 carbon atoms, and R ^6a represents a carbon number of 1~ 10 is 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 represents 0 or 1.

Examples of the linear or branched alkyl group include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, isopentyl, and neopentyl. Base and so on. Moreover, as said cyclic alkyl group, a cyclopentyl group, a cyclohexyl group, etc. are mentioned.

Here, as the acid dissociable dissolution inhibiting group represented by the above formula (a2), specifically, methoxyethyl, ethoxyethyl, n-propoxyethyl, isopropoxyethyl Group, n-butoxyethyl, isobutoxyethyl, tert-butoxyethyl, cyclohexoxyethyl, methoxypropyl, ethoxypropyl, 1-methoxy-1- Methyl-ethyl, 1-ethoxy-1-methylethyl, etc. In addition, specific examples of the acid dissociable dissolution inhibiting group represented by the above formula (a3) include a tert-butoxycarbonyl group, a tert-butoxycarbonylmethyl group, and the like. In addition, examples of the above-mentioned trialkylsilyl groups include trialkylsilyl groups having 1 to 6 carbon atoms in each of the alkyl groups such as trimethylsilyl group and 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 dissociable dissolution inhibiting 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 linear or branched alkyl groups include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, isopentyl, and neopentyl. Etc., as the cyclic alkyl group, cyclopentyl, cyclohexyl and the like can be mentioned.

As the acid dissociable dissolution inhibiting group represented by the above-mentioned R ^9a , the same acid dissociable dissolution inhibiting group as the acid dissociable dissolution inhibiting group exemplified in the above formulas (a2) and (a3) can be used.

In addition, in order to appropriately control physical properties and chemical properties, the polyhydroxystyrene resin (A2-2) may contain other polymerizable compounds as constituent units. Examples of such polymerizable compounds include known radical polymerizable compounds or anionic polymerizable compounds. In addition, 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; and succinic acid 2- Methacryloxyethyl, 2-methacryloxyethyl maleate, 2-methacryloxyethyl phthalate, 2-methyl hexahydrophthalate Methacrylic acid derivatives with carboxyl groups and ester bonds such as oxyethyl acrylate; methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, etc. (Meth)acrylic acid alkyl esters; (meth)acrylic acid 2-hydroxyethyl ester, (meth)acrylic acid 2-hydroxypropyl ester, etc.; (meth)acrylic acid hydroxyalkyl esters; (meth)acrylic acid phenyl ester, (Meth) aryl (meth)acrylate esters such as benzyl acrylate; dicarboxylic acid diesters such as diethyl maleate and dibutyl fumarate; styrene, α-methylstyrene Vinyl-containing aromatic compounds such as chlorostyrene, chloromethylstyrene, vinyl toluene, hydroxystyrene, α-methylhydroxystyrene, α-ethylhydroxystyrene, etc.; among others Aliphatic compounds containing vinyl groups; conjugated dienes such as butadiene and isoprene; polymerizable compounds containing nitrile groups such as acrylonitrile and methacrylonitrile; vinyl chloride and vinylidene chloride Polymeric compounds containing chlorine such as acrylamide and methacrylamide; polymerizable compounds containing amide bond such as acrylamide and methacrylamide; etc.

‧Acrylic resin (A2-3)

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

In the above formulas (a5), (a6-1), (a6-2), and (a7), R ^10a and R ^14a to R ^19a each independently represent a hydrogen atom and a straight chain with carbon number of 1 to 6 Or a branched alkyl group, a fluorine atom, or a linear or branched fluoroalkyl group ^{with a carbon number of 1 to 6, R 11a} to R ^13a each independently represent a straight chain with a carbon number of 1 to 6 Or branched alkyl, linear or branched fluoroalkyl with 1 to 6 carbons, or aliphatic cyclic group with 5 to 20 carbons, R ^12a and R ^13a can be mutually Bonded to form a hydrocarbon ring with a carbon number of 5-20 together with the carbon atoms to which the two are bonded, Y ^a represents an aliphatic cyclic group or alkyl group that may have a substituent, p represents an integer from 0 to 4, q Represents 0 or 1.

Still, examples of the above-mentioned linear or branched alkyl groups include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, isopentyl, Neopentyl and so on. In addition, the fluorinated alkyl group refers to a group obtained by substituting a part or all of the hydrogen atoms of the above-mentioned alkyl group with fluorine atoms.

Specific examples of the aliphatic cyclic group include groups obtained by removing one or more hydrogen atoms from polycyclic alkanes such as monocycloalkanes, bicycloalkanes, tricycloalkanes, and tetracycloalkanes. Specifically, examples include monocycloalkanes such as cyclopentane, cyclohexane, cycloheptane, and cyclooctane, or adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane. A group obtained by removing one hydrogen atom from a polycyclic alkane. In particular, a group obtained by removing one hydrogen atom from cyclohexane and adamantane (which may further have a substituent) is preferred.

In the case where R ^12a and R ^{13a are} not bonded to each other to form a hydrocarbon ring, R ^11a , R ^12a , and R ^{13a are} preferably carbon in terms of high contrast and good resolution and focal depth range. A linear or branched alkyl group having a number of 2 to 4. As the above-mentioned R ^15a , R ^16a , R ^18a , and R ^19a , a hydrogen atom or a methyl group is preferable.

The above-mentioned R ^12a and R ^13a may form an aliphatic cyclic group having 5 to 20 carbons together with the carbon atom to which the two are bonded. Specific examples of such aliphatic cyclic groups include groups obtained by removing one or more hydrogen atoms from polycyclic alkanes such as monocycloalkanes, bicycloalkanes, tricycloalkanes, and tetracycloalkanes. Specifically, examples include monocycloalkanes such as cyclopentane, cyclohexane, cycloheptane, and cyclooctane, or adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane. A group obtained by removing more than one hydrogen atom from a polycyclic alkane. Particularly preferred is a group obtained by removing one or more hydrogen atoms from cyclohexane and adamantane (which may further have a substituent).

In addition, 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 carboxyl group, a cyano group, an oxygen atom (=O), etc. The polar group or a linear or branched alkyl group with 1 to 4 carbon atoms. As the polar group, an oxygen atom (=O) is particularly preferred.

The above-mentioned Y ^a is an aliphatic cyclic group or an alkyl group, and examples thereof include groups obtained by removing one or more hydrogen atoms from polycyclic alkanes such as monocycloalkanes, bicycloalkanes, tricycloalkanes, and tetracycloalkanes. Specifically, examples include monocycloalkanes such as cyclopentane, cyclohexane, cycloheptane, and cyclooctane, or adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane. The group obtained by removing more than one hydrogen atom from the polycyclic alkanes. Particularly preferred is a group obtained by removing one or more hydrogen atoms from adamantane (which may further have a substituent).

In addition, when the ^{aliphatic cyclic group of Y a} has a substituent on its ring skeleton, examples of the substituent include a polar group such as a hydroxyl group, a carboxyl group, a cyano group, and an oxygen atom (=O), or carbon A linear or branched alkyl group having a number of 1 to 4. As the polar group, an oxygen atom (=O) is particularly preferred.

In addition, when Y ^a is an alkyl group, a linear or branched alkyl group having 1 to 20 carbon atoms (preferably 6 to 15) is preferred. Such alkyl groups are particularly preferably alkoxyalkyl groups. Examples of such alkoxyalkyl groups include 1-methoxyethyl, 1-ethoxyethyl, and 1-n-propoxy. Ethyl, 1-isopropoxyethyl, 1-n-butoxyethyl, 1-isobutoxyethyl, 1-tert-butoxyethyl, 1-methoxypropyl, 1-ethyl Oxypropyl, 1-methoxy-1-methyl-ethyl, 1-ethoxy-1-methylethyl and the like.

Preferred specific examples of the structural unit represented by the above formula (a5) include structural units represented by the following formulas (a5-1) to (a5-33).

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 said formula (a6-1), the structural unit represented by the following formula (a6-1-1)-(a6-1-25) is 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 shown in the above formula (a6-1-1) to (a6-1-25) can be changed to sub A unit derived from phenyl (preferably p-phenylene).

As a preferable specific example of the structural unit represented by the said formula (a7), the structural unit represented by the following formula (a7-1)-(a7-15) is mentioned.

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

In addition, the acrylic resin (A2-3) may be a resin composed of a copolymer that further contains a structural unit derived from a polymerizable compound having an ether bond in addition to the structural units represented by the above formulas (a5) to (a7) .

As the above-mentioned polymerizable compound having an ether bond, radical polymerizable compounds such as (meth)acrylic acid derivatives having an ether bond and an ester bond may be mentioned. As a specific example, 2-methyl (meth)acrylic acid may be mentioned. Ethoxyethyl, 2-ethoxyethyl (meth)acrylate, methoxytriethylene glycol (meth)acrylate, 3-methoxybutyl (meth)acrylate, ethyl carbitol (Meth) acrylate, phenoxy polyethylene glycol (meth) acrylate, methoxy polyethylene glycol (meth) acrylate, methoxy polypropylene glycol (meth) acrylate, (methyl) ) Tetrahydrofurfuryl acrylate, etc. In addition, the above-mentioned polymerizable compound having an ether bond is preferably 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, and methoxytriethylene glycol (meth) Acrylate. These polymerizable compounds may be used alone or in combination of two or more kinds.

In addition, acrylic resin (A2-3) may contain other polymerizable compounds as constituent units in order to appropriately control physical properties and chemical properties. Examples of such polymerizable compounds include known radical polymerizable compounds or 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-methyl succinic acid Acrylonyloxyethyl, 2-methacryloxyethyl maleate, 2-methacryloxyethyl phthalate, 2-methacrylic acid hexahydrophthalate Methacrylic acid derivatives with carboxyl group and ester bond such as acetoxyethyl; methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, (meth)acrylic acid Alkyl (meth)acrylates such as cyclohexyl ester; hydroxyalkyl (meth)acrylates such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate; (Meth)acrylic acid aryl esters such as phenyl meth)acrylate and benzyl (meth)acrylate; dicarboxylic acid diesters such as diethyl maleate and dibutyl fumarate; styrene , Α-methylstyrene, chlorostyrene, chloromethylstyrene, vinyl toluene, hydroxystyrene, α-methylhydroxystyrene, α-ethylhydroxystyrene and other aromatic compounds containing vinyl groups Classes; aliphatic compounds containing vinyl groups such as vinyl acetate; conjugated dienes such as butadiene and isoprene; polymerizable compounds containing nitrile groups such as acrylonitrile and methacrylonitrile; Polymeric compounds containing chlorine such as vinyl chloride and vinylidene chloride; polymerizable compounds containing amide bonds such as acrylamide and methacrylamide; etc.

In addition, as the polymerizable compound, a compound having an epoxy group and/or oxetanyl group is also preferable. The three-membered ring cyclic ether group is also called epoxy group, and the four-membered ring cyclic ether group is also called oxetanyl group.

The compound having an epoxy group and/or oxetanyl group only needs to have at least one epoxy group or oxetanyl group in one molecule, and may have one or more epoxy groups and one or more oxygen groups. Etanyl, 2 or more epoxy groups, or 2 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 a total of 1 or 2 epoxy groups and/or oxetanyl groups is more preferable. One epoxy or oxetanyl compound.

As specific examples of the polymerizable compound having an epoxy group, for example, glycidyl acrylate, glycidyl methacrylate, α-glycidyl acrylate, α-n-propyl glycidyl acrylate, α -N-butyl glycidyl acrylate,-3,4-epoxybutyl acrylate,-3,4-epoxybutyl methacrylate,-3,4-epoxycyclohexylmethyl acrylate, methacrylic acid- 3,4-epoxycyclohexyl methyl ester, α-ethyl acrylate-3,4-epoxycyclohexyl methyl ester, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-ethylene Benzyl glycidyl ether, a compound containing an alicyclic epoxy skeleton described in paragraphs 0031 to 0035 of JP 2005-49691 A, etc.

As a specific example of the polymerizable compound having an oxetanyl group, for example, the (meth)acrylate having an oxetanyl group described in paragraphs 0011 to 0016 of JP 2001-330953 A can be cited. .

As a specific example of the polymerizable compound having an epoxy group and/or oxetanyl group, a monomer containing a methacrylate structure and a monomer containing an acrylate structure are preferred.

Among the preferred compounds, glycidyl methacrylate, 3,4-epoxycyclohexylmethyl acrylate, 3,4-epoxycyclohexylmethyl methacrylate, acrylic acid (3-ethyloxy Etidine-3-yl) methyl ester, and (3-ethyloxetan-3-yl) methyl methacrylate. These polymerizable compounds having epoxy groups and/or oxetanyl groups may be used alone or in combination of two or more kinds.

In addition, examples of the polymerizable compound include (meth)acrylates having an acid non-dissociable aliphatic polycyclic group, vinyl group-containing aromatic compounds, and the like. As the acid non-dissociable aliphatic polycyclic group, tricyclodecyl, adamantyl, tetracyclododecyl, isobornyl, norbornyl, etc. are particularly preferred from the viewpoint of easy 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 (meth)acrylates having an acid-non-dissociable aliphatic polycyclic group include compounds having structures of the following formulas (a8-1) to (a8-5).

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

Among the above-mentioned resins (A2), acrylic resins (A2-3) are preferably used. Such acrylic resin (A2-3) has a structural unit represented by the above formula (a5), a structural unit derived from (meth)acrylic acid, and a structural unit derived from alkyl (meth)acrylates, Copolymers with structural units derived from aryl (meth)acrylates are preferred.

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

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 a} carbon number of 2 to 4, and X a represents a carbon atom to which it is bonded. A hydrocarbon ring with 5 to 20 ^{carbon atoms, R 24a} represents a linear or branched alkyl group with 1 to 6 carbon atoms, or an alkoxyalkyl group with 1 to 6 ^{carbon atoms, and R 25a} represents a carbon number 6~12 aryl groups.

In addition, 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%, t is 10 to 65 mol%, and u is 3-25 mol%, v is 6-25 mol%.

The weight average molecular weight in terms of polystyrene of the resin (A2) is preferably 4,000 to 60,000, more preferably 6,000 to 40,000, and still more preferably 8,000 to 30,000. By having such a weight average molecular weight, it is easy to form the coating resin layer 17 that has good adhesion to the patterned metal layer 18, excellent mechanical strength, and is hard to crack.

Regarding the weight average molecular weight of the resin (A2) in terms of polystyrene, as long as the dispersion degree of the matrix resin component (A) (weight average molecular weight Mw/number average molecular weight Mn) is 1 or more and 20 or less, there is no particular limitation. .

Furthermore, the dispersion degree of the resin (A2) is preferably 1.05-18, more preferably 1.2-12, and particularly preferably 1.5-6.

In addition, when the second positive composition has an alkali-soluble resin (A2-4) described later, the dispersion of the resin (A2) can be carried out in a state in which the alkali-soluble resin (A2-4) is combined. GPC (Gel Permeation Chromatography) measurement is exported from the obtained graph.

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

(Alkali-soluble resin (A2-4))

For the purpose of improving the crack resistance of the coating resin layer 17, the second positive composition may further include an alkali-soluble resin (A2-4) as the matrix resin component (A).

Here, the alkali-soluble resin (A2-4) refers to a resin having an alkali-soluble functional group (for example, a phenolic hydroxyl group, a carboxyl group, a sulfonic acid group, etc.) in the molecule.

The alkali-soluble resin (A2-4) is preferably at least selected from the group consisting of novolac resin (A2-4a), polyhydroxystyrene resin (A2-4b), and acrylic resin (A2-4c) 1 kind of resin.

‧Novolac resin (A2-4a)

Regarding the novolak resin (A2-4a), similar to the aforementioned novolak resin (A1), for example, an aromatic compound having a phenolic hydroxyl group (hereinafter, abbreviated as "phenol") can be used in the presence of an acid catalyst. ) Is obtained by addition condensation with aldehydes.

As the above-mentioned phenols, for example, phenol, o-cresol, m-cresol, p-cresol, o-ethylphenol, m-ethylphenol, p-ethylphenol, o-butylphenol, m-butylphenol, p-cresol Butylphenol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5-dimethylphenol Phenol, 2,3,5-trimethylphenol, 3,4,5-trimethylphenol, p-phenylphenol, resorcinol, hydroquinone, hydroquinone monomethyl ether, biphenyl Triphenol, phloroglucinol, hydroxybiphenyl, bisphenol A, gallic acid, gallic acid ester, α-naphthol, β-naphthol, etc.

As said aldehydes, formaldehyde, furfural, benzaldehyde, nitrobenzaldehyde, acetaldehyde, etc. are mentioned, for example.

The catalyst in the addition condensation reaction is not particularly limited. For example, among the acid catalysts, hydrochloric acid, nitric acid, sulfuric acid, formic acid, oxalic acid, acetic acid, etc. can be used.

‧Polyhydroxystyrene resin (A2-4b)

Examples of the hydroxystyrene-based compound constituting the polyhydroxystyrene resin (A2-4b) include p-hydroxystyrene, α-methylhydroxystyrene, α-ethylhydroxystyrene, and the like.

In addition, the polyhydroxystyrene resin (A2-4b) is preferably a copolymer with a styrene resin. As the styrene-based compound constituting such a styrene resin, styrene, chlorostyrene, chloromethylstyrene, vinyl toluene, α-methylstyrene, etc. may be mentioned.

‧Acrylic resin (A2-4c)

The acrylic resin (A2-4c) is preferably 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 carboxyl group.

Examples of the above-mentioned polymerizable compound having an ether bond include 2-methoxyethyl (meth)acrylate, methoxytriethylene glycol (meth)acrylate, and 3-methoxy (meth)acrylate. Butyl ester, ethyl carbitol (meth)acrylate, phenoxy polyethylene glycol (meth)acrylate, methoxy polypropylene glycol (meth)acrylate, tetrahydrofurfuryl (meth)acrylate (Meth)acrylic acid derivatives having ether bonds and ester bonds such as esters. The polymerizable compound having an ether bond is preferably 2-methoxyethyl acrylate and methoxytriethylene glycol acrylate. These polymerizable compounds may be used alone or in combination of two or more kinds.

Examples of the polymerizable compound having a carboxyl 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-methyl succinic acid Acrylonyloxyethyl, 2-methacryloxyethyl maleate, 2-methacryloxyethyl phthalate, 2-methacrylic acid hexahydrophthalate Compounds having a carboxyl group and an ester bond such as acyloxyethyl; etc. The above-mentioned polymerizable compound having a carboxyl group is preferably acrylic acid or methacrylic acid. These polymerizable compounds may be used alone or in combination of two or more kinds.

Regarding the content of the alkali-soluble resin (A2-4), when the total of the above-mentioned resin (A2) and the alkali-soluble resin (A2-4) is taken as 100 parts by mass, it can be 0-50 parts by mass. In addition, You may make it 0-30 mass parts.

<Acid Generator (B2)>

The acid generator (B2) is a compound that generates an acid through irradiation with active light or radiation, and it is not particularly limited as long as it directly or indirectly generates an acid through the action of light. As an acid generator (B2), the acid generator of the 1st-5th aspect demonstrated below is preferable. Hereinafter, preferred examples of acid generators (B2) that can be suitably used in the second positive type composition will be described in the first to fifth aspects.

As a 1st aspect in an acid generator (B2), the compound represented by following formula (b1) is 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 , representing an aryl group with 6 to 30 carbons, a heterocyclic group with 4 to 30 carbons, an alkyl group with 1 to 30 carbons, and 2 to 30 carbons. R ^1b can be selected from the group consisting of alkyl, hydroxy, alkoxy, alkylcarbonyl, arylcarbonyl, alkoxycarbonyl, aryloxycarbonyl, or alkynyl with 2-30 carbons. Arylthiocarbonyl, acyloxy, arylthio, alkylthio, aryl, heterocycle, aryloxy, alkylsulfinyl, arylsulfinyl, alkylsulfinyl , Arylsulfonyl group, alkyleneoxy group, amine group, cyano group, nitro group, and halogen group consisting of at least one kind of substitution. The number of R ^1b is g+h(g-1)+1, and R ^1b may be the same or different from each other. In addition, two or more R ^1b may be directly bonded to each other, or via -O-, -S-, -SO-, -SO ₂ -, -NH-, -NR ^2b -, -CO-, -COO- , -CONH-, an alkylene group having 1 to 3 carbon atoms, or a phenylene group are bonded to form a ring structure ^{containing X 1b.} R ^2b is an alkyl group having 1 to 5 carbons or an aryl group having 6 to 10 carbons.

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

In the above formula (b2), X ^4b represents a divalent group of an alkylene group having 1 to 8 carbons, an arylene group having 6 to 20 carbons, or a heterocyclic compound having 8 to 20 carbons, and X ^4b can be selected from alkyl groups having 1 to 8 carbons, alkoxy groups having 1 to 8 carbons, aryl groups having 6 to 10 carbons, hydroxyl, cyano, nitro groups, and halogens. At least one substitution in the group. X ^5b represents -O-, -S-, -SO-, -SO ₂ -, -NH-, -NR ^2b -, -CO-, -COO-, -CONH-, alkylene with carbon number 1~3 Group, or phenylene. 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. R ^2b is the same as defined above.

X ^3b- is an onium counter ion (counter ion), such as the sulfonate anion represented by the following formula (b9), the nitrogen-containing anion represented by the following formula (b13) and (b14), and the following formula (b17) The fluorophosphate anion represented by) or the borate anion represented by the following formula (b18).

[Formula _{^{17] R 20b SO 3 - (}} b9)

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

In the above formula (b10), x represents an integer of 1 to 4. In addition, in the above formula (b11), R ^21b represents a hydrogen atom, a hydroxyl group, a linear or branched alkyl group with a carbon number of 1 to 6, or a linear or branched chain with a carbon number of 1 to 6 In the alkoxy group, y represents an integer of 1 to 3. Among these, from the viewpoint of safety, trifluoromethanesulfonate and perfluorobutanesulfonate are preferred.

In the above formulas (b13) and (b14), X ^b represents a linear or branched alkylene group obtained by substituting at least one hydrogen atom with a fluorine atom, and the carbon number of the alkylene group is 2-6, Preferably it is 3~5, and the optimal carbon number is 3. In addition, Y ^b and Z ^b each independently represent a linear or branched alkyl group obtained by substituting at least one hydrogen atom with a fluorine atom, and the carbon number of the alkyl group is 1-10, preferably 1~ 7, more preferably 1~3.

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

In addition, ^{in the alkylene group of X b} or the alkyl group of Y ^b and Z ^b , the greater the number of hydrogen atoms substituted by fluorine atoms, the stronger the strength of the acid, which is preferable. The ratio of fluorine atoms in the alkylene or alkyl group, that is, the fluorination rate is preferably 70-100%, more preferably 90-100%, and most preferably a perfluorinated compound obtained by substituting all hydrogen atoms with fluorine atoms Alkylene or perfluoroalkyl.

[化20][(R ^3b ) _j PF _6-j ] ^- (b17)

In the above formula (b17), R ^3b represents an alkyl group obtained by substituting fluorine atoms for 80% or more of hydrogen atoms. j represents its number and is an integer from 0 to 5. The j pieces of R ^3b may be the same or different.

In the above formula (b18), R ^4b to R ^7b each independently represent a fluorine atom or a phenyl group, and some or all of the hydrogen atoms of the phenyl group may be selected from at least the group consisting of fluorine atoms and trifluoromethyl 1 kind of substitution.

Examples of the onium ion in the compound represented by the above formula (b1) include triphenyl arunnium, tri-p-tolyl arunnium, 4-(phenylthio) phenyl diphenyl arunnium, bis[4-(two Phenylsulfonyl)phenyl]sulfide, bis[4-{bis[4-(2-hydroxyethoxy)phenyl]sulfonio}phenyl]sulfide, bis{4-[bis( 4-fluorophenyl) sulfonyl) phenyl) sulfide, 4-(4-benzyl-2-chlorophenylsulfanyl) phenyl bis(4-fluorophenyl) sulfide, 7-isopropyl -9-oxo-10-thia-9,10-dihydroanthracene-2-yldi-p-tolyl arunnium, 7-isopropyl-9-oxo-10-thia-9,10-dihydro Anthracene-2-yl diphenyl arunnium, 2-[(diphenyl) arunnyl] thioxanthone, 4-[4-(4-tert-butylbenzyl) phenylthio] phenyl two pairs Tolyl sulfonium, 4-(4-benzyl phenylsulfanyl) phenyl diphenyl sulfonium, diphenyl benzyl sulfonium, 4-hydroxyphenylmethyl benzyl sulfonium, 2-naphthyl Methyl (1-ethoxycarbonyl) ethyl alumite, 4-hydroxyphenylmethyl benzylmethyl alumite, phenyl [4-(4-biphenylsulfanyl) phenyl] 4-biphenyl Aluminium, phenyl [4-(4-biphenylthio)phenyl] 3-biphenyl sulfonium, [4-(4-acetylphenylthio) phenyl] diphenyl sulfonium, octadecane Benzylmethylbenzamide, diphenyliodonium, di-p-tolyliodonium, bis(4-dodecylphenyl)iodonium, bis(4-methoxyphenyl)iodonium, (4-octyloxyphenyl) phenyl iodonium, bis (4-decyloxy) phenyl iodonium, 4-(2-hydroxytetradecyloxy) phenyl phenyl iodonium, 4 -Isopropylphenyl (p-tolyl) iodonium, or 4-isobutylphenyl (p-tolyl) iodonium, etc.

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

In the above formula (b19), R ^8b each independently represents a hydrogen atom, an alkyl group, a hydroxyl group, an alkoxy group, an alkylcarbonyl group, an alkylcarbonyloxy group, an alkyloxycarbonyl group, a halogen atom, and may have a substituent The group in the group consisting of aryl and arylcarbonyl. X ^2b has the same meaning as ^{X 2b} in the above formula (b1).

As specific examples of the sulfonium ion represented by the above formula (b19), 4-(phenylthio)phenyl diphenyl sulfonium, 4-(4-benzyl-2-chlorophenylsulfanyl) ) Phenyl bis(4-fluorophenyl) sulfonium, 4-(4-benzylphenylsulfanyl) phenyl diphenyl sulfonium, phenyl [4-(4-biphenylsulfanyl) phenyl ]4-Biphenyl sulfanium, phenyl [4-(4-biphenylsulfanyl) phenyl] 3-biphenyl sulfanium, [4-(4-acetylphenylsulfanyl) phenyl] diphenyl Amenium, diphenyl [4-(p-terphenylthio) phenyl] diphenyl amenium.

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

Particularly preferred R ^3b is a linear or branched perfluoroalkyl group having a carbon number of 1 to 4 and a fluorine atom substitution rate of 100%. Specific examples include CF ₃ , 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, (CF ₃ ) ₃ C. The number j of R ^{3b is} an integer of 0-5, preferably 1-4, 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 ] ^- .

As preferred specific examples of the borate anion represented by the above formula (b18), tetrafluoroborate (BF ₄ ) ^- , tetrakis(pentafluorophenyl) borate ([B(C ₆ F ₅ ) ₄ ] ^- ), tetrakis[(trifluoromethyl)phenyl]borate ([B(C ₆ H ₄ CF ₃ ) ₄ ] ^- ), difluorobis(pentafluorophenyl)borate ([(C ₆ F ₅ ) ₂ BF ₂ ] ^- ), trifluoro(pentafluorophenyl) borate ([(C ₆ F ₅ )BF ₃ ] ^- ), tetrakis(difluorophenyl) borate ([B(C ₆ H ₃ F ₂ ) ₄ ] ^- ) and so on. Among these, tetrakis(pentafluorophenyl)borate ([B(C ₆ F ₅ ) ₄ ] ^- ) is particularly preferred.

As the second aspect of the acid generator (B2), 2,4-bis(trichloromethyl)-6-piperonyl-1,3,5-triazine, 2,4-bis(trichloromethyl) Methyl)-6-[2-(2-furyl)vinyl]s-triazine, 2,4-bis(trichloromethyl)-6-[2-(5-methyl-2-furyl) Vinyl]s-triazine, 2,4-bis(trichloromethyl)-6-[2-(5-ethyl-2-furyl)vinyl]s-triazine, 2,4-bis(trichloro Methyl)-6-[2-(5-propyl-2-furyl)vinyl]s-triazine, 2,4-bis(trichloromethyl)-6-[2-(3,5-di Methoxyphenyl) vinyl]s-triazine, 2,4-bis(trichloromethyl)-6-[2-(3,5-diethoxyphenyl) vinyl]s-triazine, 2 ,4-bis(trichloromethyl)-6-[2-(3,5-dipropoxyphenyl)vinyl]s-triazine, 2,4-bis(trichloromethyl)-6-[ 2-(3-Methoxy-5-ethoxyphenyl)vinyl]s-triazine, 2,4-bis(trichloromethyl)-6-[2-(3-methoxy-5- Propoxyphenyl)vinyl]s-triazine, 2,4-bis(trichloromethyl)-6-[2-(3,4-methylenedioxyphenyl)vinyl]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-triazine Chloromethyl-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-methoxyphenyl) Naphthyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-[2-(2-furyl)vinyl]-4,6-bis(trichloromethyl) )-1,3,5-triazine, 2-[2-(5-methyl-2-furyl)vinyl]-4,6-bis(trichloromethyl)-1,3,5-tri Oxazine, 2-[2-(3,5-dimethoxyphenyl)vinyl]-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-[2-( 3,4-Dimethoxyphenyl)vinyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(3,4-methylenedioxybenzene) Yl)-4,6-bis(trichloromethyl)-1,3,5-triazine, tris(1,3-dibromopropyl)-1,3,5-triazine, tris(2,3 -Dibromopropyl)-1,3,5-triazine and other halogen-containing triazine compounds, and tris(2,3-dibromopropyl)isocyanurate, etc., represented by the following formula (b3) Triazine compounds containing halogens.

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

In addition, as the third aspect of the acid generator (B2), α-(p-toluenesulfonyloxyimino)-phenylacetonitrile, α-(benzenesulfonyloxyimino)-2, 4-Dichlorophenylacetonitrile, α-(benzenesulfonyloxyimino)-2,6-dichlorophenylacetonitrile, α-(2-chlorobenzenesulfonyloxyimino)-4-methoxy Phenylacetonitrile, α-(ethylsulfonyloxyimino)-1-cyclopentenylacetonitrile, and a compound represented by the following formula (b4) containing an oxime sulfonate group.

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

In the above formula (b4), the so-called aromatic compound group means a group of a compound showing physical/chemical properties peculiar to an aromatic compound. Examples include aryl groups such as phenyl and naphthyl, furyl, and thienyl. The heteroaryl. These may have one or more appropriate substituents on the ring, such as halogen atoms, alkyl groups, alkoxy groups, nitro groups, and the like. In addition, 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. The ^{compound in which R 12b} is an aromatic compound group and R ^13b is an alkyl group having 1 to 4 carbon atoms is particularly preferable.

As the acid generator represented by the above formula (b4), when n=1, R ^12b is any one of a phenyl group, a methylphenyl group, and a methoxyphenyl group, and R ^13b is a methyl group. Compounds, specifically α-(methylsulfonyloxyimino)-1-phenylacetonitrile, α-(methylsulfonyloxyimino)-1-(p-methylphenyl)acetonitrile, α-( Methylsulfonyloxyimino)-1-(p-methoxyphenyl)acetonitrile, (2-(propylsulfonyloxyimino)-2,3-dihydroxythiophen-3-ylidene (ylidene) )] (o-tolyl)acetonitrile and the like. When n=2, as the acid generator represented by the above formula (b4), specific examples include acid generators represented by the following formula.

In addition, as a fourth aspect of the acid generator (B2), an onium salt having a naphthalene ring in the cation part is exemplified. The "having a naphthalene ring" means having a structure derived from naphthalene, and a structure having at least two rings, and the aromaticity is maintained. The naphthalene ring may have substituents such as a linear or branched alkyl group having 1 to 6 carbons, a hydroxyl group, and a linear or branched alkoxy group having 1 to 6 carbons. The structure derived from the naphthalene ring may be a monovalent group (free atomic valence is 1), or a bivalent (free atomic valence of 2) or higher group, preferably a monovalent group (wherein, in this case, it will be Except the part where the substituents are bonded, the free atomic valence is counted). The number of naphthalene rings is preferably 1-3.

As such a cation part of an onium salt having a naphthalene ring in the cation part, a structure represented by the following formula (b5) is preferred.

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 represent linear or branched alkane having 1 to 6 carbon atoms Group, optionally substituted phenyl group, hydroxyl group, or a linear or branched alkoxy group having 1 to 6 carbon atoms. Alternatively, it may also be the case where 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 with carbon numbers of 1 to 6 Or a branched alkylene group, and these ends are bonded to form a ring.

In the above formula (b6), R ^17b and R ^18b each independently represent a hydroxyl group, a linear or branched alkoxy group having 1 to 6 carbons, or a linear or branched linear or branched carbon number of 1 to 6 In the chain alkyl group, R ^19b represents a single bond or an optionally substituted linear or branched alkylene group having 1 to 6 carbon atoms. 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 as or different from each other. In addition, ^{when there are a plurality of R 18b} , these may be the same as or different from each other.

From the viewpoint of the stability of the compound, ^{the number of groups represented by the above formula (b6) in the above R 14b} , R ^15b , and R ^16b is preferably 1, and the rest are linear or linear with carbon numbers of 1 to 6 For branched alkylene groups, these ends may be bonded to form a ring. In this case, the two alkylene groups (including the sulfur atom) constitute a 3- to 9-membered ring. The number of atoms (including sulfur atoms) constituting the ring is preferably 5-6.

In addition, examples of the substituent that the above-mentioned alkylene group may have include an oxygen atom (in this case, it forms a carbonyl group together with the carbon atom constituting the alkylene group), a hydroxyl group, and the like.

In addition, examples of substituents that the phenyl group may have include a hydroxyl group, a linear or branched alkoxy group having 1 to 6 carbons, and a linear or branched linear or branched group having 1 to 6 carbons. Alkyl and so on.

As for the structure suitable as these cation parts, the structure represented by following formula (b7), (b8), etc. are mentioned, The structure represented by following formula (b8) is especially preferable.

As such a cation part, it may be an iodonium salt or a sulfonium salt. From the viewpoint of acid production efficiency, etc., it is more compressed than a sulfonium salt.

Therefore, with regard to the structure suitable for the anion portion of the onium salt having a naphthalene ring in the cation portion, an anion capable of forming a sulfonium salt is preferable.

The anion part of such an acid generator is a fluoroalkylsulfonate ion or an arylsulfonate ion obtained by substituting a part or all of hydrogen atoms with fluorine.

The alkyl group in the fluoroalkyl sulfonate ion can be linear with 1-20 carbon atoms, branched, or cyclic. Considering the volume of the acid generated and its diffusion distance, it is more The best carbon number is 1~10. In particular, when a branched or cyclic alkyl group is used, the diffusion distance is short, which is preferable. In addition, from the viewpoint of low-cost synthesis, methyl, ethyl, propyl, butyl, octyl, etc. can be cited as preferred examples.

The aryl group in the arylsulfonate ion is an aryl group having 6 to 20 carbon atoms, and examples thereof include a phenyl group and a naphthyl group substituted or unsubstituted with an alkyl group or a halogen atom. In particular, from the viewpoint of being able to be synthesized inexpensively, an aryl group having 6 to 10 carbon atoms is preferred. Preferred specific examples include phenyl, tosyl, ethylphenyl, naphthyl, methylnaphthyl and the like.

In the above-mentioned fluoroalkylsulfonate ion or arylsulfonate ion, the fluorination rate when part or all of the hydrogen atoms are replaced by fluorine is preferably 10-100%, more preferably 50-100%, especially , The product obtained by replacing all hydrogen atoms with fluorine atoms can increase the strength of the acid, so it is preferred. Specific examples of such ions include trifluoromethanesulfonate, perfluorobutanesulfonate, perfluorooctanesulfonate, and perfluorobenzenesulfonate.

Among these, the anion represented by the aforementioned formula (b9) and the anions represented by the aforementioned formulas (b13) and (b14) are exemplified as a preferable anion part.

As a compound preferably used as such an onium salt having a naphthalene ring in the cation part, compounds represented by the following formulas (b15) and (b16) can be cited.

In addition, as the fifth aspect of the acid generator (B2), bis(p-toluenesulfonyl)diazomethane, bis(1,1-dimethylethylsulfonyl)diazomethane, Bis(cyclohexylsulfonyl)diazomethane, bis(2,4-dimethylphenylsulfonyl)diazomethane and other bissulfonyldiazomethanes; 2-nitrobenzyl p-toluenesulfonic acid Esters, 2,6-dinitrobenzyl p-toluenesulfonate, nitrobenzyl tosylate, dinitrobenzyl tosylate, nitrobenzyl sulfonate, nitrobenzyl carbonate , Dinitrobenzyl carbonate and other nitrobenzyl ester derivatives; pyrogallol trimesylate (pyrogallol trimesylate), pyrogallol tritosylate, benzyl tosylate, benzyl sulfonate Base ester, N-methylsulfonyloxysuccinimide, N-trichloromethylsulfonyloxysuccinimide, N-phenylsulfonyloxymaleimide, N-methanesulfonate Sulfonic acid esters such as oxophthalimide; trifluoromethanesulfonate esters such as N-hydroxyphthalimide and N-hydroxynaphthalimide; diphenyl iodide Onium hexafluorophosphate, (4-methoxyphenyl) phenyl iodonium trifluoromethanesulfonate, bis(p-tert-butylphenyl) iodonium trifluoromethanesulfonate, triphenyl sulfonium hexafluoro Phosphate, (4-methoxyphenyl) diphenyl sulfonium trifluoromethanesulfonate, (p-tert-butylphenyl) diphenyl sulfonium trifluoromethanesulfonate and other onium salts; benzoin toluene Benzoin tosylate such as sulfonate and α-methylbenzoin tosylate; other diphenyl iodonium salts, triphenyl sulfonium salts, phenyl diazonium salts, benzyl carbonates Wait.

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

(Acid diffusion control agent (C))

In order to improve the shape of the coating resin layer 17 or the storage stability after application of the photosensitive layer, the second positive composition may further contain an acid diffusion control agent (C). The acid diffusion control agent (C) is preferably a nitrogen-containing compound, and if necessary, it may further contain an organic carboxylic acid, or an oxo acid of phosphorus or a derivative thereof.

Examples of nitrogen-containing compounds include trimethylamine, diethylamine, triethylamine, di-n-propylamine, tri-n-propylamine, tri-n-pentylamine, tribenzylamine, diethanolamine, tris Ethanolamine, n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, ethylenediamine, N,N,N',N'-tetramethylethylenediamine, tetramethylenediamine, six Methylene diamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 4,4'-diaminobenzophenone, 4,4'- Diaminodiphenylamine, formamide, N-methylformamide, N,N-dimethylformamide, acetamide, N-methylacetamide, N,N-dimethyl Acetamide, acetamide, benzamide, pyrrolidone, N-methylpyrrolidone, methylurea, 1,1-dimethylurea, 1,3-dimethylurea, 1,1,3,3 -Tetramethylurea, 1,3-diphenylurea, imidazole, benzimidazole, 4-methylimidazole, 8-hydroxyquinoline, acridine, purine, pyrrolidine, pyridine, 2,4,6- Tris(2-pyridyl)-S-triazine, morpholine, 4-methylmorpholine, piperazine, 1,4-dimethyl piperazine, 1,4-diazabicyclo[2.2.2]octane Alkane, pyridine, etc. These can be used alone or in combination of two or more kinds.

For the acid diffusion control agent (C), relative to 100 parts by mass of the total mass of the resin (A2) and the alkali-soluble resin (A2-4), it is usually used in the range of 0 to 5 parts by mass, particularly preferably Use in the range of 0 to 3 parts by mass.

Among organic carboxylic acids, or phosphorus-containing oxyacids or their derivatives, as organic carboxylic acids, specifically, malonic acid, citric acid, malic acid, succinic acid, benzoic acid, salicylic acid, etc. are preferred. Good salicylic acid.

Examples of phosphorus oxyacids or derivatives thereof include: phosphoric acid, di-n-butyl phosphate, diphenyl phosphate and other derivatives such as phosphoric acid and esters; phosphonic acid, dimethyl phosphonate, Phosphonic acids such as di-n-butyl phosphonate, phenylphosphonic acid, diphenyl phosphonate, dibenzyl phosphonate and derivatives of their esters; phosphinic acid such as phosphinic acid and phenylphosphinic acid And these esters and other derivatives; etc. Among these, phosphonic acid is particularly preferred. These can be used alone or in combination of two or more kinds.

For organic carboxylic acid or phosphorus oxo acid or its derivatives, it is usually used in the range of 0 to 5 parts by mass relative to 100 parts by mass of the total mass of resin (A2) and alkali-soluble resin (A2-4) , Especially preferably used in the range of 0 to 3 parts by mass.

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

(Colorant)

The optical density of the coating resin layer 17 after the post-baking step is formed according to the method of this embodiment is 0.10/μm or more. Therefore, the second positive type composition typically contains a coloring agent for adjusting the optical density, similarly to the first positive type composition.

In the second positive type composition, as the coloring agent, the same coloring agent as described for the first positive type composition can be used.

Regarding the usage amount of the coloring agent in the second positive type composition, for example, it is preferably 1 part by mass relative to 100 parts by mass of the total mass of the above-mentioned resin (A2) and the above-mentioned alkali-soluble resin (A2-4) Above, more preferably 3 parts by mass or more, still more preferably 5 parts by mass or more, more preferably 60 parts by mass or less, more preferably 50 parts by mass or less, still more preferably 45 parts by mass or less, and still more preferably It is 40 parts by mass or less.

In addition, the optical density of the coating resin layer 17 is more preferably 0.20 to 2.0/μm, and still more preferably 0.30 to 1.0/μm.

(Solvent)

For the second positive composition, it is preferable to dissolve the above-mentioned components in an appropriate solvent and use it in the form of a solution. The type of solvent is not particularly limited as long as it does not interfere with the purpose of the present invention, and it can be appropriately selected and used from organic solvents conventionally used in positive photosensitive resin compositions.

Specific examples of solvents include: ketones such as acetone, methyl ethyl ketone, cyclohexanone, methyl isoamyl ketone, 2-heptanone, etc.; ethylene glycol, ethylene glycol monoacetate, two Monomethyl ether, monoethyl ether, monopropyl ether, monobutyl ether of ethylene glycol, diethylene glycol monoacetate, propylene glycol, propylene glycol monoacetate, dipropylene glycol, and dipropylene glycol monoacetate , Monophenyl ether and other polyols and their derivatives; dioxane and other cyclic ethers; ethyl formate, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, Methyl pyruvate, methyl acetylacetate, ethyl acetylacetate, ethyl pyruvate, ethyl ethoxyacetate, methyl methoxypropionate, ethyl ethoxypropionate, 2-hydroxypropionic acid Methyl ester, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, methyl 2-hydroxy-3-methylbutanoate, 3-methoxybutyl acetate, 3-methyl acetate Benzyl-3-methoxybutyl ester and other esters; toluene, xylene and other aromatic hydrocarbons; etc. These may be used alone, or two or more kinds may be mixed and used.

The amount of the solvent used is not particularly limited within a range that does not hinder the purpose of the present invention. The amount of solvent used is preferably an amount such that the solid content concentration of the second positive type composition becomes 10-40% by mass, and more preferably an amount such that the solid content concentration of the second positive type composition becomes 12-30% by mass .

(Other ingredients)

In order to improve plasticity, the second positive composition may further contain a polyvinyl-based resin. Specific examples of polyvinyl resins include polyvinyl chloride, polystyrene, polyhydroxystyrene, polyvinyl acetate, polyvinyl benzoic acid, polyvinyl methyl ether, and polyvinyl ethyl ether. , Polyvinyl alcohol, polyvinylpyrrolidone, polyvinylphenol, and their copolymers. From the viewpoint of low glass transition temperature, the polyvinyl-based resin is preferably polyvinyl methyl ether.

In addition, in order to improve the adhesion between the coating resin layer 17 and the patterned metal layer 18, the second positive composition may further contain an adhesion improver. As this adhesion improver, the same thing as the adhesion improver shown in the item of the 1st positive type composition can be used.

In addition, in order to improve coating properties, defoaming properties, leveling properties, etc., the second positive composition may further contain a surfactant. Specific examples of surfactants include BM-1000, BM-1100 (all made by BM Chemie), Megafac F142D, Megafac F172, Megafac F173, Megafac F183 (all made by Dainippon Ink Chemical Co., Ltd.), FluoradFC -135, Fluorad FC-170C, FluoradFC-430, Fluorad FC-431 (all manufactured by Sumitomo 3M Ltd.), Surflon S-112, Surflon S-113, Surflon S-131, Surflon S-141, Surflon S-145 (All manufactured by Asahi Glass), SH-28PA, SH-190, SH-193, SZ-6032, SF-8428 (all manufactured by Toray Silicone) and other commercially available fluorine-based surfactants, but not limited to these .

In addition, in order to fine-tune the solubility in the developer, the second positive composition may further contain an acid, an acid anhydride, or a high boiling point solvent.

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 , 3-hydroxybutyric acid, salicylic acid, meta-hydroxybenzoic acid, p-hydroxybenzoic acid, 2-hydroxycinnamic acid, 3-hydroxycinnamic acid, 4-hydroxycinnamic acid, 5-hydroxyisophthalic acid, syringic acid, etc. Hydroxymonocarboxylic 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, butanetetracarboxylic acid, trimellitic acid, pyromellitic acid, cyclopentanetetracarboxylic acid, butanetetracarboxylic acid, 1,2, 5,8-Naphthalenetetracarboxylic acid and other polycarboxylic acids; itaconic anhydride, succinic anhydride, citraconic anhydride, dodecenyl succinic anhydride, tricarboxylic acid anhydride, maleic anhydride, hexahydrophthalic anhydride, methyl tetracarboxylic acid Hydrogen phthalic anhydride, himicanhydride, 1,2,3,4-butane tetracarboxylic anhydride, cyclopentane tetracarboxylic dianhydride, phthalic anhydride, pyromellitic dianhydride, trimellitic anhydride , Benzophenone tetracarboxylic acid anhydride, ethylene glycol bistrimellitic acid anhydride, glycerol trimellitic acid anhydride and other acid anhydrides; etc.

In addition, as specific examples of high boiling point solvents, N-methylformamide, N,N-dimethylformamide, N-methylformaniline, N-methylacetamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfide, benzyl ethyl ether, dihexyl ether, acetonyl acetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, phenyl cellosolve acetic acid Ester etc.

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

(Preparation method of the second positive type composition)

The second positive composition is prepared by mixing and stirring the above-mentioned components by a normal method. As an apparatus which can be used when mixing and stirring the said each component, a dissolver (dissolver), a homogenizer, a three-roll mill, etc. are mentioned. After the above-mentioned components are uniformly mixed, the obtained mixture can be further filtered using a mesh, a membrane filter, and the like.

<Coating method>

The positive composition described above is applied on the metal layer 11 to be etched to form the photosensitive layer 12. The thickness of the photosensitive layer 12 is not particularly limited, but is preferably 0.1 to 10 μm.

As the coating method of the positive type composition, a spin coating method, a slit coating method, a roll coating method, a screen printing method, an applicator method, etc. can be used. Preferably, the photosensitive layer 12 is pre-baked. The pre-baking conditions vary according to the types of components in the photosensitive layer, blending ratios, coating film thickness, etc., usually at 70 to 150°C, preferably 80 to 140°C, for about 2 to 60 minutes.

Next, the substrate 10 to be processed having the photosensitive layer 12 formed as described above is subjected to an exposure step.

≪Exposure steps≫

In the exposure step, as shown in FIG. 1(c), a position other than the position where the patterned metal layer 18 is formed in the photosensitive layer 12 is exposed.

As described above, the photosensitive layer 12 is formed using a positive type composition. For the photosensitive layer 12 composed of a positive type composition, the exposed portion becomes soluble in the alkaline developer. Therefore, by exposing, a position other than the position where the patterned metal layer 18 is formed in the photosensitive layer 12 becomes soluble in the developing solution.

In the exposure step, the photosensitive layer 12 formed as described above is selectively irradiated with exposure light 16 via a photomask 15 of a predetermined pattern.

As the exposure light 16, active light or radiation can be used, for example, ultraviolet or visible light with a wavelength of 300 to 500 nm.

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

≪Development procedure≫

The photosensitive layer 12 that has been selectively exposed to positions as shown in FIG. 1(c) is developed in the developing step, thereby forming a patterned photosensitive layer as shown in FIG. 1(d) 12的covered resin layer 17. At this time, as the developer, an alkaline aqueous solution can be used.

As the developer, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, di-n-propylamine, Triethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, pyrrole, piperidine, 1,8-diazabicyclo[5, 4,0]-7-undecene, 1,5-diazabicyclo[4,3,0]-5-nonane and other alkali aqueous solutions. In addition, an aqueous solution obtained by adding an appropriate amount of a water-soluble organic solvent such as methanol and ethanol, and a known surfactant to the aqueous solution of the alkalis can also be used as a developer.

The development time also varies depending on the composition of the positive type composition, the film thickness of the photosensitive layer 12, and the like, but it is usually 1 to 30 minutes. The developing method can be any method among the liquid method, the dipping method, the puddle method, the spray developing method, and the like.

After development, wash with running water for 30 to 90 seconds, and dry with an air gun or oven. By operating as described above, the coating resin layer 17 as the patterned photosensitive layer 12 is formed on the etched metal layer 11.

≪Etching step≫

In the etching step, as shown in FIG. 1(d) and FIG. 1(e), the coating resin layer 17 formed in the development step is used as an etching mask, and the etched metal exposed from the etching mask is etched. The layer 11 is removed, and a patterned metal layer 18 is formed.

The etching method is not particularly limited, and can be appropriately selected according to the material of the metal layer 11 to be etched. The etching method may be wet etching or dry etching, and wet etching is preferred due to its low cost.

≪Post-baking steps≫

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 development step and the etching step, or may be performed after the etching step.

By baking the coating resin layer 17, the curing of the coating resin layer 17 progresses, and the coating resin layer 17 is made compact. As a result, the water resistance, heat resistance, solvent resistance, etc. of the coating resin layer 17 are improved.

In addition, in the aforementioned etching step, the following situation may occur: under etch in which the lower part of the end portion of the coating resin layer 17 is excessively etched, the top of the patterned metal layer 18 (the coating resin layer) The width of the 17 side) becomes narrower than the width of the bottom (the transparent layer 14 side).

In this case, it is preferable to perform the post-baking step after the etching step. The reason is that the coating resin layer 17 is softened by the heating in the post-baking step, and the coating resin layer 17 is deformed according to the surface shape of the patterned metal layer 18. As a result, the coating resin layer 17 is formed in close contact with substantially the entire surface of the patterned metal layer 18, and therefore, the patterned metal layer 18 is not easily visually recognized by a user who touches the panel.

Baking can be performed using a heating device such as a hot plate or an oven, for example. The baking temperature is not particularly limited, and can be appropriately determined in consideration of the heat resistance of the material constituting the substrate 10 to be processed, and the like. The baking temperature is preferably 80 to 400°C, more preferably 150 to 300°C, for example.

However, when the substrate 10 to be processed includes a liquid crystal cell including the liquid crystal layer 20, the baking temperature is preferably 80 to 150°C.

The baking time is preferably 15-60 minutes, more preferably 30 minutes or less.

[Example]

Hereinafter, examples are shown to further specifically explain the present invention, but the scope of the present invention is not limited by these examples.

[Example 1]

100 parts by mass of novolak resin, 13 parts by mass of sensitizer, 22.6 parts by mass of quinonediazide group-containing compound, and 27% by mass of the pigment relative to the total solid content were uniformly dissolved and dispersed in the propylene glycol monomer. In methyl ether acetate, the solid content concentration was set to 20% by mass to obtain a positive composition.

Moreover, the positive composition contains 1% by mass of 2-hydroxyethylpyridine relative to the total solid content, and 0.4% by mass relative to the total solid content of a silicon-based surfactant (BYK-310 , BYK Chemie Corporation).

As the novolak resin, a cresol-type novolak resin having a weight average molecular weight of 4,700 and a degree of dispersion 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 a compound containing a quinonediazide group, it is obtained by esterifying 2,3,4,4'-tetrahydroxybenzophenone and naphthoquinone-1,2-diazide-5-sulfonic acid. compound of.

As the pigment, a red pigment manufactured by Mikuni Color Co., Ltd. at 14.9% by mass relative to the total solid content and a blue pigment manufactured by Mikuni Color Co., Ltd. at 12.1% by mass relative to the total solid content were used.

Use a spin coater to coat the obtained positive composition on the etched metal layer of the processed substrate with the color filter and the etched metal layer (Al layer), and then pre-baked at 90°C for 60 seconds. A photosensitive layer with a thickness of 1.5 μm is formed.

A photomask with a spacing of L/S=1:1 and a width of 3 μm was used to expose ^{the obtained photosensitive layer using an exposure device (MPA-600FA, 365 mW, 100 mJ/cm 2} , manufactured by Canon).

Next, a tetramethylammonium hydroxide (TMAH) aqueous solution with a concentration of 2.38% by mass was used as a developing solution for development to form a coating resin layer patterned into a predetermined shape.

Using the formed coating resin layer as an etching mask, etching is performed using an Al mixed acid etchant (phosphoric acid/nitric acid/acetic acid) to form a patterned metal layer. The surface of the patterned metal layer is covered 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.

Still, as the substrate to be processed, the following substrates to be processed were experimentally used.

That is, first, a pattern of black matrix and RGB with a line width of 5 μm is set on one surface of the glass substrate, and an aluminum layer with a thickness of 0.2 μm is sputtered on the other surface of the glass substrate to form a processed substrate. .

The optical density of the formed coating resin layer was 0.60/μm.

In addition, the shape of the formed coating resin layer was observed with a microscope. As a result, the upper part of the picture element was not covered by the coating resin layer, and the thickness of the coating resin layer was approximately uniform, and the patterned metal layer was not observed to be exposed.

[Example 2]

Except that the novolak resin was changed to a cresol novolak resin with a weight average molecular weight of 4700 and a degree of dispersion of 10.0, the same procedure as in Example 1 was carried out to prepare a positive composition, and the same as in Example 1 The operation forms a patterned metal layer and a coating resin layer on the substrate.

The optical density of the formed coating resin layer was 0.60/μm.

In addition, the shape of the formed coating resin layer was observed with a microscope. As a result, the upper part of the picture element was not covered by the coating resin layer, and the thickness of the coating resin layer was approximately uniform, and the patterned metal layer was not observed to be exposed.

[Example 3]

100 parts by mass of acrylic resin, 3 parts by mass of photoacid generator, and 5 parts by mass of coloring agent were dissolved and dispersed in propylene glycol monomethyl ether acetate so that the solid content concentration was 12% by mass to obtain a positive composition.

As the acrylic resin, 40 mol% of 1-ethoxyethyl ether of p-hydroxystyrene, 35 mol% of methacrylic acid (3-ethyloxetane-3-yl) methyl ester, and methyl group were used. A copolymer of 15 mol% of methyl acrylate and 20 mol% of 2-hydroxyethyl methacrylate. The weight average molecular weight of the acrylic resin is 12,400, and the dispersion degree is 4.5.

As the photoacid generator, triaryl sulfonium salt (trade name: DTS-105, manufactured by Midori Kagaku Co., Ltd.) was used.

As the coloring agent, the following black pigment was used: 0.65 parts by mass of a dispersant and a polymer (a random copolymer of benzyl methacrylate (72 mol%) and methacrylic acid (28 mol%)) were used, by weight The average molecular weight is 37,000), and a black pigment obtained by dispersing 13.1 parts by mass of carbon black in 79.53 parts by mass of propylene glycol monomethyl ether.

Using the obtained positive composition, in the same manner 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.

In addition, the shape of the formed coating resin layer was observed with a microscope. As a result, the upper part of the picture element was not covered by the coating resin layer, and the thickness of the coating resin layer was approximately uniform, and the patterned metal layer was not observed to be exposed.

[Comparative Example 1]

The novolak resin was changed to a cresol type novolak resin with a weight average molecular weight of 4700 and a degree of dispersion of 30.0, except that it was the same as Example 1 to prepare a positive composition, and the same as Example 1 The operation forms a patterned metal layer and a coating resin layer on the substrate.

The optical density of the formed coating resin layer was 0.60/μm.

However, as a result of observing the shape of the coating resin layer formed with a microscope, the coating resin layer flows excessively during post-baking, and the parts covered by the coating resin layer above the picture element are seen everywhere, and the warp is observed. The patterned metal layer is exposed.

10‧‧‧Processed substrate

11‧‧‧Etched metal layer

12‧‧‧Photosensitive layer

13‧‧‧Color filter

14‧‧‧Transparent layer

15‧‧‧Photomask

16‧‧‧Exposure light

17‧‧‧Coated resin layer

18‧‧‧Patterned metal layer

Claims (4)

A method of manufacturing a substrate, the substrate is provided on one main surface with: a color filter, and a patterned metal layer formed directly on the color filter or formed through a transparent layer, and covering the patterned metal layer The method includes the following steps: forming a photosensitive layer, including the color filter and the etched metal layer formed directly on the color filter or formed through a transparent layer In the substrate to be processed, a positive photosensitive resin composition is coated on the metal layer to be etched to form a photosensitive layer, and an exposure step is performed to expose a position other than the position where the patterned metal layer is formed in the photosensitive layer A developing step, developing the exposed photosensitive layer to form the coating resin layer, and an etching step, using the coating resin layer as an etching mask, and removing the etched metal layer exposed from the etching mask by etching, The patterned metal layer is formed, and the post-baking step is to bake the coating resin layer. The degree of dispersion of the matrix resin component (A) contained in the positive photosensitive resin composition (weight average molecular weight Mw/ The number average molecular weight Mn) is more than 5 and 20 or less, and in the manufactured substrate, the optical density of the coating resin layer is 0.10/μm or more. The manufacturing method according to claim 1, wherein the positive photosensitive resin composition includes a novolak resin (A1) as a matrix resin component (A), and a compound (B1) further containing a quinonediazide group. The manufacturing method according to claim 1, wherein the positive photosensitive resin composition includes as the matrix resin component (A) a resin (A2) that increases solubility in alkali by the action of an acid and a resin (A2) that is activated by the action of an acid. The acid compound (B2) is generated by irradiation of light or radiation. The manufacturing method according to any one of claims 1 to 3, wherein the substrate to be processed includes liquid crystal cells, and the baking temperature in the post-baking step is 80° C. or more and 150° C. or less.

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