JP2020079408A - Resin composition, photosensitive resin composition, method for producing resist pattern, and touch panel member - Google Patents

Abstract

To provide a resin composition capable of forming a resin film excellent in adhesiveness to a metal material, especially a metal material containing molybdenum.SOLUTION: The resin composition contains a polymer (A), a compound (B) represented by formula (b1), and a crosslinking agent (D) having a functional group (d) capable of reacting with a functional group (b) of the compound (B). Ar is an aromatic ring selected from a monocyclic aromatic ring and a condensed polycyclic aromatic ring; Ris a group having an ethylenically unsaturated double bond, a group having a cationic reactive group, a carboxyl group, a group having a carboxylic acid anhydride group, or a hydroxyl group, and at least one selected from an ethylenically unsaturated double bond, a cationic reactive group, a carboxyl group, a carboxylic acid anhydride group, and a hydroxyl group is described as the functional group (b); Ris a direct bond or a divalent group; Ris a halogen atom or a C1-20 hydrocarbon group; -OH is bonded to the aromatic ring; and a is an integer of 1 or more, b is an integer of 0 or more, and c is an integer of 2 or more.SELECTED DRAWING: None

Description

  The present invention relates to a resin composition, a photosensitive resin composition, a method for producing a resist pattern, and a touch panel member.

  The touch panel member is a component of an input device that allows an operator to touch a display screen with a finger, a pen, or the like to detect a contact position and input data. Since the touch panel member allows intuitive input, it is used for various electronic devices such as mobile phones, personal digital assistants, and car navigation system devices.

  Although there are various types of touch panel members, in recent years, a capacitance type touch panel that detects a touch position of an operator by utilizing a change in capacitance has become widespread. In the capacitive touch panel member, an indium-tin complex oxide (ITO) thin film having excellent transparency is used for the surface electrode. However, the specific resistance of ITO is 10 times higher than that of metal alone. Therefore, there is known a method of using a highly conductive metal material such as a three-layer structure of molybdenum film/aluminum film/molybdenum film instead of ITO as the surface electrode. Further, since the surface electrode is formed in the display area, it is necessary to improve the visibility of the touch panel member. For example, there is known a method of improving the visibility of a touch panel member by using a metal material containing molybdenum for a surface electrode (see Patent Documents 1 and 2).

International Publication No. 2009/108758 JP, 2013-020347, A

According to the study by the present inventor, it became clear that there is a problem in that the adhesiveness between a metal material, particularly a metal material containing molybdenum, and a resin film for protecting the metal material is low.
The present invention relates to a resin composition and a photosensitive resin composition capable of forming a resin film having excellent adhesion to a metal material, particularly a metal material containing molybdenum, and a method for producing a resist pattern using the photosensitive resin composition. And a touch panel member in which the molybdenum-containing metal member is protected by the resist pattern.

  The present inventors have diligently studied to solve the above problems. As a result, they have found that the above problems can be solved by the following constitutions, and have completed the present invention. That is, the present invention relates to the following [1] to [13], for example.

  [1] A resin composition containing the compound (B) represented by the formula (b1) and a polymer (A) having a functional group (a) capable of reacting with the following functional group (b) of the compound (B).

［式（ｂ１）中、Ａｒは、単環芳香族環および縮合多環芳香族環から選ばれる芳香族環であり；Ｒ^B1は、エチレン性不飽和二重結合を有する基、カチオン反応性基を有する基、カルボキシル基、カルボン酸無水物基を有する基、または水酸基であり、ここでエチレン性不飽和二重結合、カチオン反応性基、カルボキシル基、カルボン酸無水物基および水酸基から選ばれる少なくとも１種を「官能基（ｂ）」と記載し；Ｒ^B2は、前記芳香族環に結合する基であり、直接結合または２価の基であり；Ｒ^B3は、前記芳香族環に結合する基であり、ハロゲン原子または炭素数１〜２０の炭化水素基であり；−ＯＨは、前記芳香族環に結合しており；ａは１以上の整数であり；ｂは０以上の整数であり；ｃは２以上の整数である。］

[In the formula (b1), Ar is an aromatic ring selected from a monocyclic aromatic ring and a condensed polycyclic aromatic ring; R ^B1 is a group having an ethylenically unsaturated double bond, a cation-reactive group. A group having a, a carboxyl group, a group having a carboxylic acid anhydride group, or a hydroxyl group, wherein at least an ethylenically unsaturated double bond, a cation reactive group, a carboxyl group, a carboxylic acid anhydride group and a hydroxyl group are selected. One is described as "functional group (b)"; R ^B2 is a group bonded to the aromatic ring, is a direct bond or a divalent group, and R ^B3 is bonded to the aromatic ring. A group, a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms; -OH is bonded to the aromatic ring; a is an integer of 1 or more; b is an integer of 0 or more. C is an integer of 2 or more. ]

  [2] The functional group (a) contained in the polymer (A) is at least one selected from a cation reactive group, a carboxyl group, a carboxylic acid anhydride group, a hydroxyl group and an ethylenically unsaturated double bond, The resin composition according to the above [1], which is a group capable of reacting with the functional group (b) of the compound (B).

  [3] The resin composition according to [1] or [2], further containing at least one photoreactive compound (C) selected from a photopolymerization initiator and a photocation generator.

  [4] The resin composition according to the above [3], wherein the photoreactive compound (C) is a photopolymerization initiator.

  [5] Further, an unsaturated compound (D1) having at least one ethylenically unsaturated double bond in one molecule, and a cation reactive compound (D2) having at least one cation reactive group in one molecule. The resin composition according to the above [3] or [4], which contains at least one cross-linking agent (D) selected from the above.

  [6] A polymer (A), a compound (B) represented by the formula (b1), and a crosslinking agent (D) having a functional group (d) capable of reacting with the following functional group (b) of the compound (B). A resin composition containing:

［式（ｂ１）中、Ａｒは、単環芳香族環および縮合多環芳香族環から選ばれる芳香族環であり；Ｒ^B1は、エチレン性不飽和二重結合を有する基、カチオン反応性基を有する基、カルボキシル基、カルボン酸無水物基を有する基、または水酸基であり、ここでエチレン性不飽和二重結合、カチオン反応性基、カルボキシル基、カルボン酸無水物基および水酸基から選ばれる少なくとも１種を「官能基（ｂ）」と記載し；Ｒ^B2は、前記芳香族環に結合する基であり、直接結合または２価の基であり；Ｒ^B3は、前記芳香族環に結合する基であり、ハロゲン原子または炭素数１〜２０の炭化水素基であり；−ＯＨは、前記芳香族環に結合しており；ａは１以上の整数であり；ｂは０以上の整数であり；ｃは２以上の整数である。］

[In the formula (b1), Ar is an aromatic ring selected from a monocyclic aromatic ring and a condensed polycyclic aromatic ring; R ^B1 is a group having an ethylenically unsaturated double bond, a cation-reactive group. A group having a, a carboxyl group, a group having a carboxylic acid anhydride group, or a hydroxyl group, wherein at least an ethylenically unsaturated double bond, a cation reactive group, a carboxyl group, a carboxylic acid anhydride group and a hydroxyl group are selected. One is described as "functional group (b)"; R ^B2 is a group bonded to the aromatic ring, is a direct bond or a divalent group, and R ^B3 is bonded to the aromatic ring. A group, a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms; -OH is bonded to the aromatic ring; a is an integer of 1 or more; b is an integer of 0 or more. C is an integer of 2 or more. ]

  [7] The resin composition according to the above [6], further containing at least one photoreactive compound (C) selected from a photopolymerization initiator and a photocation generator.

  [8] The resin composition according to the above [7], wherein the photoreactive compound (C) is a photopolymerization initiator.

  [9] The functional group (d) contained in the cross-linking agent (D) is at least one selected from an ethylenically unsaturated double bond and a cation reactive group, and the functional group (b) contained in the compound (B). The resin composition according to the above [7] or [8], which is a group capable of reacting with ).

  [10] The any one of the above-mentioned [1] to [9], wherein at least two of —OH in the formula (b1) are respectively bonded to adjacent carbon atoms constituting the aromatic ring in Ar. Resin composition.

  [11] Step (1) of forming a coating film of the resin composition according to any one of [3] to [5] and [7] to [9] on a substrate, at least the coating film. A method for producing a resist pattern, which comprises a step (2) of exposing a part of the resist and a step (3) of developing the coating film after the exposure.

  [12] The method for producing a resist pattern according to the above [11], wherein the substrate has a molybdenum-containing metal member on the surface that comes into contact with the coating film.

  [13] A touch panel member in which a molybdenum-containing metal member is protected by a resist pattern formed from the resin composition according to any one of [3] to [5] and [7] to [9].

  According to the present invention, a resin composition and a photosensitive resin composition capable of forming a resin film having excellent adhesion to a metal material, particularly a metal material containing molybdenum, and a resist pattern using the photosensitive resin composition It is possible to provide a manufacturing method and a touch panel member in which the molybdenum-containing metal member is protected by the resist pattern.

Hereinafter, modes for carrying out the invention will be described, including preferred embodiments.
[Resin composition and photosensitive resin composition]
The resin composition of the present invention contains a polymer (A) and a compound (B) described below. When the resin composition further contains the photoreactive compound (C), the resin composition is also referred to as a "photosensitive resin composition". The resin composition of the present invention can form a resin film or a protective film having excellent adhesiveness to a metal material and a metal member thereof, particularly a metal material containing molybdenum and the metal member.

A first aspect of the resin composition of the present invention is a polymer having a compound (B) represented by the formula (b1) described below and a functional group (a) capable of reacting with the functional group (b) of the compound (B). And (A).
A second aspect of the resin composition of the present invention is a polymer (A), a compound (B) represented by the formula (b1) described later, and a functional group capable of reacting with the functional group (b) of the compound (B). And a cross-linking agent (D) having (d).
In the following description, when the first and second aspects are not particularly distinguished, they are simply referred to as the “resin composition of the present invention”, and the description of each component corresponds to both aspects unless otherwise specified.

[Polymer (A)]
The polymer (A) in the first aspect has a functional group (a) capable of reacting with the functional group (b) of the compound (B). The functional group (a) is, for example, at least one selected from a cation-reactive group (excluding an ethylenically unsaturated double bond), a carboxyl group, a carboxylic acid anhydride group, a hydroxyl group and an ethylenically unsaturated double bond. Is.

  The polymer (A) in the second embodiment is selected from a cation-reactive group (excluding an ethylenically unsaturated double bond), a carboxyl group, a carboxylic acid anhydride group, a hydroxyl group and an ethylenically unsaturated double bond. You may have at least 1 sort(s).

  Examples of the cation-reactive group include oxiranyl group, oxetanyl group, cyclic ether group such as oxolanyl group, thiylanyl group, cyclic thioether group such as thietanyl group, alkyl etherified amino group, isocyanate group, aldehyde group, and methylol group. , A cyclic acetal structure, a cyclic lactone structure, and a spiro orthoester structure. Of these, cyclic ether groups are preferred.

  Examples of the polymer (A) in the first embodiment include an unsaturated compound having a cation reactive group, an unsaturated compound having a carboxyl group or a carboxylic acid anhydride group, an unsaturated compound having a hydroxyl group, and an ethylenic unsaturated group. A copolymer of at least one unsaturated compound (a1) selected from unsaturated compounds having a saturated double bond and another unsaturated compound (a2) can be mentioned.

  Examples of the polymer (A) in the second aspect include polymers of other unsaturated compounds (a2), and specifically, a copolymer of the unsaturated compound (a1) and the other unsaturated compound (a2) Polymers may be mentioned.

  Examples of the unsaturated compound having a cation reactive group include epoxidized (cyclo)alkyl(meth)acrylate such as glycidyl(meth)acrylate, epoxidized cycloalkylalkyl(meth)acrylate, and α-alkylacrylic acid epoxidized ( Oxiranyl group-containing unsaturated compounds such as cyclo)alkyl ester and vinylbenzyl glycidyl ether; 3-((meth)acryloyloxyalkyl)oxetane, 3-((meth)acryloyloxyalkyl)-3-alkyloxetane, 3-(( Examples thereof include meth)acryloyloxyalkyl)-2-alkyloxetane, 3-((meth)acryloyloxyalkyl)-2-aryloxetane, and oxetanyl group-containing unsaturated compounds such as fluorinated compounds thereof.

  Examples of the unsaturated compound having a carboxyl group or a carboxylic acid anhydride group include (meth)acrylic acid, crotonic acid, 2-(meth)acryloyloxyethylsuccinic acid, 2-(meth)acryloyloxyethylhexahydrophthalic acid. Unsaturated dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid; maleic anhydride, citraconic acid, itaconic anhydride and the like dicarboxylic acid anhydrides Can be mentioned. Alternatively, the carboxyl group may be regenerated by polymerizing an unsaturated compound in which the carboxyl group is protected by a protecting group such as a trialkylsilyl group, and then deprotecting it.

  Examples of the unsaturated compound having a hydroxyl group include hydroxyalkyl (meth)acrylates such as 2-hydroxyethyl (meth)acrylate; (meth)acrylates having a hydroxyl group and an alicyclic structure such as hydroxycyclohexyl (meth)acrylate; dihydroxy. Dihydroxyalkyl (meth)acrylates such as ethyl (meth)acrylate; (poly)alkylene glycol mono(meth)acrylates; aromatic compounds having a hydroxyl group and an ethylenically unsaturated double bond such as hydroxystyrene. The hydroxyalkyl group, dihydroxyalkyl group and alkylene group in the (meth)acrylate have 2 to 12 carbon atoms, for example. Examples of the alicyclic structure include a cycloalkane ring, a norbornane ring, and an adamantane ring.

  Examples of the unsaturated compound having an ethylenically unsaturated double bond include unsaturated compounds having an allyl group such as allyl (meth)acrylate and allyl crotonic acid. The unsaturated compound is a compound which further has an ethylenically unsaturated double bond in addition to the unsaturated group for copolymerization.

  Examples of the other unsaturated compound (a2) include, for example, a cation-reactive group, a carboxyl group, a carboxylic acid anhydride group, and a hydroxyl group, and an ester portion having no ethylenically unsaturated double bond (meth)acryl. Examples of the acid ester include alkyl (meth)acrylates such as methyl (meth)acrylate; alicyclic (meth)acrylates such as cyclohexyl (meth)acrylate; aryl (meth)acrylates such as phenyl (meth)acrylate; benzyl. Examples thereof include aralkyl (meth)acrylates such as (meth)acrylates; alkoxy (poly)alkylene glycol (meth)acrylates; aryloxy (poly)alkylene glycol (meth)acrylates. In addition, N-substituted maleimides represented by N-(cyclo)alkylmaleimides such as N-cyclohexylmaleimide and N-arylmaleimides such as N-phenylmaleimide; cyano group-containing unsaturated compounds such as (meth)acrylonitrile; maleic acid Unsaturated dicarboxylic acid dialkyl esters such as dialkyl esters; aromatic compounds having an ethylenically unsaturated double bond such as styrene, α-methylstyrene, o, m or p-methylstyrene, o, m or p-methoxystyrene Can be mentioned.

  The copolymer has a structural unit derived from the unsaturated compound (a1) in a range of preferably 1 to 90 mol%, more preferably 10 to 80 mol%, and further preferably 20 to 70 mol%. The structural unit derived from the saturated compound (a2) is preferably contained in the range of 99 to 10 mol%, more preferably 90 to 20 mol%, still more preferably 80 to 30 mol%. Here, the total of the structural units derived from the unsaturated compounds (a1) and (a2) is 100 mol %, and their contents can be measured by NMR.

  The polymer (A) can be produced, for example, by polymerizing the above unsaturated compound in the presence of a radical polymerization initiator in a suitable organic solvent. Examples of the radical polymerization initiator include azo compounds such as 2,2′-azobisisobutyronitrile and organic peroxides such as benzoyl peroxide. The polymer (A) can be produced by the methods described in JP-A-2015-69141, JP-A-2015-143813, and JP-A-2008-20566.

  The polymer having an ethylenically unsaturated double bond can also be obtained by reacting a hydroxyl group in a polymer having a hydroxyl group with a (meth)acryloyl group-containing isocyanate compound.

The polymer (A) may be used alone or in combination of two or more.
The weight average molecular weight (Mw) of the polymer (A) is usually 3,000 to 100,000, preferably 5,000 to 50,000, and more preferably 8,000 to 30,000. In this case, it is preferable in terms of heat resistance, developability, residual film rate, and pattern shape of the obtained resin film. Mw is a value measured by gel permeation chromatography and converted into standard polystyrene.

[Compound (B)]
The compound (B) is represented by formula (b1).

式（ｂ１）中の各記号は以下のとおりである。

Each symbol in formula (b1) is as follows.

Ar is an aromatic ring selected from a monocyclic aromatic ring and a condensed polycyclic aromatic ring.
R ^B1 is a group having an ethylenically unsaturated double bond, a group having a cation reactive group, a carboxyl group, a group having a carboxylic acid anhydride group, or a hydroxyl group. At least one selected from the ethylenically unsaturated double bond, the cation reactive group, the carboxyl group, the carboxylic acid anhydride group and the hydroxyl group, which the compound (B) has, is also referred to as a “functional group (b)”. R ^B2 is a group bonded to the aromatic ring and is a direct bond or a divalent group. R ^B3 is a group bonded to the aromatic ring and is a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms, except a group having an ethylenically unsaturated double bond.

  -OH is bonded to the aromatic ring. From the viewpoint of adhesiveness between the resin film and the metal member, at least two —OH are preferably bonded to adjacent carbon atoms forming the aromatic ring.

a is an integer of 1 or more, b is an integer of 0 or more, and c is an integer of 2 or more.
The compound (B) is considered to react with the above-mentioned polymer (A) and/or the below-mentioned crosslinking agent (D) upon exposure or heating. That is, the functional group (b) of the compound (B) and the functional group (a) of the polymer (A) and/or the functional group (d) of the cross-linking agent (D) react with each other to form a covalent bond or between functional groups. It is considered to form an interaction (hereinafter also referred to as "covalent bond or the like").

  The compound (B) acts as an adhesion aid that enhances the adhesive force of the resin film formed from the resin composition of the present invention to the substrate and the metal member. Therefore, the resin film has a high adhesive force to a metal member included in the touch panel member, for example, a metal member containing molybdenum and/or aluminum. The reason for this is that in the compound (B), two or more hydroxyl groups bonded to the aromatic ring enhance the adhesiveness between the metal member and the resin film, and the functional group (b) of the compound (B) is the polymer (A). ) And a component such as a cross-linking agent (D).

  In the first embodiment, a combination capable of reacting the functional group (b) of the compound (B) with the functional group (a) of the polymer (A) to form a covalent bond or the like is used. In, a combination is used in which the functional group (b) of the compound (B) and the functional group (d) of the crosslinking agent (D) can react to form a covalent bond or the like.

  When the compound (B) has at least one functional group selected from a carboxyl group, a carboxylic acid anhydride group and a hydroxyl group, it has a cationic reactive group capable of reacting with the functional group to form a covalent bond or the like. It is preferable to use the combination (A) and/or the cross-linking agent (D) having a cation-reactive group (specifically, the cation-reactive compound (D2) described later).

  When the compound (B) has a cation-reactive group, it has at least one functional group selected from a carboxyl group, a carboxylic acid anhydride group and a hydroxyl group, which can react with the functional group to form a covalent bond or the like. It is preferable to use the combination (A).

  When the compound (B) has an ethylenically unsaturated double bond, a polymer (A) having an ethylenically unsaturated double bond and/or an ethylenic group capable of reacting with the functional group to form a covalent bond or the like. It is preferable to use a crosslinking agent (D) having an unsaturated double bond (specifically, an unsaturated compound (D1) described later).

  In Ar in the formula (b1), examples of the monocyclic aromatic ring include a benzene ring, and examples of the condensed polycyclic aromatic ring include a naphthalene ring, anthracene ring, and a phenanthrene ring. Among these, a benzene ring is preferable because a resin film having excellent adhesion to a metal material containing molybdenum can be formed.

Examples of the group having an ethylenically unsaturated double bond, e.g., vinyl group, 1-methylvinyl group, allyl group, -X-CO-CR = CH 2 (X is -O- or -NH-, R is hydrogen Atom, a halogen atom or an alkyl group having 1 to 4 carbon atoms).

  Examples of the cation reactive group include the groups described in the section of the polymer (A), particularly an oxiranyl group and an oxetanyl group. Examples of the group having a cation reactive group include an epoxidized alkyl group. , An epoxidized cycloalkyl group, a group in which two hydrogen atoms bonded to the same carbon atom in the alkyl group are substituted with one oxetane ring, and the number of carbon atoms of the alkyl group constituting these groups is, for example, 1 to 30. And the cycloalkyl group has, for example, 4 to 20 carbon atoms.

Examples of the divalent group for R ^B2 include an alkanediyl group having 1 to 10 carbon atoms, —O—, —S—, —C(O)—, —C(O)O—, and —C(O ) A group having at least one selected from NH- and -C(S)-, and at least one hydrogen atom of the alkanediyl group may be substituted with -OH, an alkoxy group or an aryloxy group. ..

In R ^B3 , examples of the halogen atom include fluorine, bromine, chlorine and the like, and examples of the hydrocarbon group having 1 to 20 carbon atoms include an alkyl group and an aryl group.
a is an integer of 1 or more, preferably 1 to 2, and more preferably 1. b is an integer of 0 or more, preferably 0 to 2, and more preferably 0 to 1. c is an integer of 2 or more, preferably 2 to 4, and more preferably 2. In addition, when R ^B1 is a hydroxyl group and R ^B2 is a direct bond (eg, in the case of pyrogallol), the hydroxyl group is not counted as c (in the case of pyrogallol, a=1 and c=2).
As the compound (B), the compounds represented by the formulas (b11) to (b16) are preferable.

上記式（ｂ１１）〜（ｂ１６）中、Ｒ^B21は、式（ｂ１）中のＲ^B2と同義である。Ｒ^B31は、水素原子、ハロゲン原子、炭素数１〜２０のアルキル基または炭素数６〜２０のアリール基である。Ｒ^B4は、水素原子、ハロゲン原子または炭素数１〜４のアルキル基である。ｎは０または１である。

In the formulas (b11) to (b16), R ^B21 has the same meaning as R ^B2 in the formula (b1). R ^B31 is a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms. R ^B4 is a hydrogen atom, a halogen atom or an alkyl group having 1 to 4 carbon atoms. n is 0 or 1.

  Examples of the compounds represented by the formulas (b11) to (b16) include 3,4-dihydroxybenzenecarboxylic acid, 3,4-dihydroxyphenylacetic acid, pyrogallol, hydroxyquinol, 2′,3′-epoxypropyl-3,4. -Dihydroxybenzene, 3,4-dihydroxyallylbenzene, 1,2-dihydroxy-3-(meth)acryloyloxybenzene and 1,2-dihydroxy-4-(meth)acryloyloxybenzene. In addition, the following compounds may be mentioned.

上記式中、Ｒａは水素原子、ハロゲン原子または炭素数１〜４のアルキル基であり、Ｒｂは水素原子、炭素数１〜６のアルキル基または炭素数６〜１０のアリール基である。

In the above formula, Ra is a hydrogen atom, a halogen atom or an alkyl group having 1 to 4 carbon atoms, and Rb is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 10 carbon atoms.

As the above compound, a commercially available product can be used, or the compound can be synthesized by the method described in International Publication No. 2012/131717, International Publication No. 2015/17562, and JP-A-62-39545.
The compound (B) may be used alone or in combination of two or more.

  The resin composition of the present invention preferably contains the compound (B) in an amount of 1 to 50 parts by mass, more preferably 3 to 30 parts by mass, and further preferably 5 parts by mass relative to 100 parts by mass of the polymer (A). 10 to 10 parts by mass. By setting the content of the compound (B) within the above range, it is possible to form a resin film having excellent adhesiveness to a metal material containing molybdenum.

[Photoreactive compound (C)]
Examples of the photoreactive compound (C) (hereinafter also referred to as “component (C)”) include a photopolymerization initiator and a photocation generator. The photopolymerization initiator is a component that generates active species capable of initiating the polymerization of ethylenically unsaturated double bonds by irradiation with light such as visible light, ultraviolet light, and deep ultraviolet light. The photocation generator is a compound that generates cations by a treatment including irradiation with light.

When the resin composition of the present invention contains the photoreactive compound (C), photosensitivity is imparted to the resin composition, and the photosensitive resin composition of the present invention is obtained, preferably a negative composition.
For example, a photopolymerization initiator, a compound (B) having an ethylenically unsaturated double bond, a polymer (A) having an ethylenically unsaturated double bond and/or an unsaturated compound (D1) described below are used. A photosensitive resin composition containing; a photosensitive resin composition containing a photopolymerization initiator and an unsaturated compound (D1) described later; selected from a photocation generator, a carboxyl group, a carboxylic acid anhydride group and a hydroxyl group. Examples of the photosensitive resin composition include a compound (B) having at least one of the above compounds and a polymer (A) having a cation reactive group and/or a cation reactive compound (D2) described below.

  In addition, the photoreactive compound (C) generates an active species capable of initiating polymerization of an ethylenically unsaturated double bond and a cation that promotes a crosslinking reaction of a cation-reactive group when irradiated with light, Functional group (b) of (B), functional group (a) of polymer (A), ethylenically unsaturated double bond of unsaturated compound (D1), cation reactive group of cation reactive compound (D2) It is presumed that it functions as a reaction accelerator with the above.

  Examples of the photopolymerization initiator include oxime ester compounds, acetophenone compounds, alkylphenone compounds, benzophenone compounds, biimidazole compounds, benzoin compounds, α-diketone compounds, acylphosphine oxide compounds, polynuclear quinone compounds, xanthone compounds, and triazine compounds. Can be mentioned. Specific examples thereof include the photopolymerization initiators described in JP-A-2015-69141, JP-A-2015-143813, and JP-A-2008-20566, and 2-methyl-1- (4-Methylthiophenyl)-2-morpholinopropan-1-one, 1,2-propanedione, 1-[4-[[4-(2-hydroxyethoxy)phenyl]thio]phenyl], 2-(O -Acetoxy oxime) and the like.

Examples of the photocation generator include oxime sulfonate compounds, onium salts, N-sulfonyloxyimide compounds, halogen-containing compounds, diazomethane compounds, sulfone compounds, sulfonic acid ester compounds, and carboxylic acid ester compounds. Specific examples thereof include the photocation generators described in JP-A-2015-194583, JP-A-2015-176124, and JP-A-2015-175923.
As the component (C), one type may be used alone, or two or more types may be used in combination.

  The photosensitive resin composition of the present invention preferably contains the component (C) in an amount of 1 to 30 parts by mass, more preferably 2 to 20 parts by mass, and still more preferably 100 parts by mass of the polymer (A). Is 3 to 15 parts by mass, particularly preferably 5 to 10 parts by mass. By setting the content of the component (C) in the above range, it is possible to increase the difference in solubility between the exposed portion and the unexposed portion in the developing solution and improve the patterning performance.

[Crosslinking agent (D)]
The cross-linking agent (D) (hereinafter, also referred to as “component (D)”) is cross-linked by, for example, a component polymerized by an active species generated from a photopolymerization initiator by light irradiation or a cation generated from a photocation generator by light irradiation It is a component that reacts. The resin composition of the first aspect preferably further contains a crosslinking agent (D), and the resin composition of the second aspect contains a crosslinking agent (D).

  The cross-linking agent (D) in the second aspect has a functional group (d) capable of reacting with the functional group (b) of the compound (B), and the functional group (d) is, for example, an ethylenically unsaturated diamine. At least one selected from a heavy bond and a cation reactive group is included.

  Examples of the cross-linking agent (D) in the first and second aspects include an unsaturated compound (D1) having at least one, for example, two or more ethylenically unsaturated double bonds in one molecule, and 1 A cation-reactive compound (D2) having at least one, for example, two or more cation-reactive groups in the molecule can be mentioned.

Examples of the cation-reactive group include the groups described in the section of polymer (A).
As the component (D), an unsaturated compound (D1) is preferable because it is possible to form a resin film having excellent adhesion to a metal material containing molybdenum, and (meth)acrylate is preferable as the unsaturated compound (D1). Examples of the (meth)acrylate include a polyfunctional (meth)acrylate having two or more (meth)acryloyl groups and a monofunctional (meth)acrylate having one (meth)acryloyl group.

  Examples of polyfunctional (meth)acrylates include poly(meth)acrylates of trihydric or higher polyhydric alcohols such as glycerin, trimethylolpropane, pentaerythritol, and dipentaerythritol. Specifically, trimethylolpropane Di(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolpropane alkylene oxide modified tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth) Examples thereof include acrylate and dipentaerythritol hexa(meth)acrylate. In addition, tricyclodecane dimethanol di(meth)acrylate, alkylene glycol di(meth)acrylate, polyalkylene glycol di(meth)acrylate, isocyanurate skeleton containing di or tri(meth)acrylate, bisphenol A skeleton containing di(meth) An acrylate is mentioned.

  Examples of monofunctional (meth)acrylates include alkyl (meth)acrylates such as methyl (meth)acrylate, hydroxyalkyl (meth)acrylates such as 2-hydroxyethyl (meth)acrylate, and alicyclic rings such as cyclohexyl (meth)acrylate. Examples include aromatic ring-containing (meth)acrylates such as formula group-containing (meth)acrylate and benzyl (meth)acrylate. Other examples include alkoxyalkyl (meth)acrylates, polyalkylene glycol monoalkyl ether (meth)acrylates, (meth)acrylamides and their alkyl-substituted products, and aminoalkyl (meth)acrylates.

  As the unsaturated compound (D1), other than that, for example, at least one ethylene in one molecule described in JP-A-2015-69141, JP-A-2015-143813, and JP-A-2008-20566. Examples thereof include compounds having a sex unsaturated double bond.

  From the viewpoint of curability of the resist pattern, the content ratio of the polyfunctional (meth)acrylate is usually 20% by mass or more, preferably 50% by mass, with respect to the total amount of the polyfunctional (meth)acrylate and the monofunctional (meth)acrylate. % Or more.

  As the cation-reactive compound (D2), a compound having two or more alkyl etherified amino groups, an oxirane ring-containing compound, an oxetane ring-containing compound, an isocyanate group-containing compound (including a blocked one), and an aldehyde. Examples thereof include a group-containing phenol compound and a methylol group-containing phenol compound, which are described in, for example, JP 2000-321416 A, JP 6-180501 A, JP 2006-178059 A and JP 2012-226297 A. Cation reactive compounds.

As the component (D), one type may be used alone, or two or more types may be used in combination.
When the component (D) is used, the resin composition of the present invention preferably contains the component (D) in an amount of 50 to 400 parts by mass, more preferably 80 to 400 parts by mass, relative to 100 parts by mass of the polymer (A). The amount is 300 parts by mass, more preferably 100 to 200 parts by mass.

  The component (D) does not include the polymer (A) having a cation reactive group and/or an ethylenically unsaturated double bond. Further, the component (D) does not include the compound (B) represented by the formula (b1).

[Additive]
The resin composition of the present invention may further contain various additives, if necessary. Examples of the additive include a polymerization inhibitor, a surfactant, a dispersant, a heat resistance improver, organic or inorganic particles, and a silane coupling agent.

  Examples of the polymerization inhibitor include hydroquinone compounds such as 2,5-di-tert-butylhydroquinone, and nitroso compounds such as N-nitrosophenylhydroxylamine and aluminum salts thereof. The polymerization inhibitor may be used alone or in combination of two or more. The content of the polymerization inhibitor is preferably 1 part by mass or less, and more preferably 0.01 to 0.5 part by mass, relative to 100 parts by mass of the polymer (A).

  Examples of the surfactant include anionic surfactants, cationic surfactants, and nonionic surfactants, preferably polyoxyethylene alkyl ether, polyoxyethylene propylene alkyl ether, polyoxyethylene alkylphenyl ether. , Polyoxyethylene alkylphenyl ether, and polyether-modified silicone. The surfactant may be used alone or in combination of two or more. The content of the surfactant is preferably 5 parts by mass or less, more preferably 0.001 to 1 part by mass based on 100 parts by mass of the polymer (A).

[solvent]
The solvent may be used, for example, to adjust the solid content concentration of the resin composition of the present invention to a desired range or to improve the coatability and the film-forming property when the resin composition is applied to a substrate. it can.

  Examples of the solvent include alcohols such as methanol, ethanol, isopropyl alcohol, butanol, and octanol; ethyl acetate, butyl acetate, ethyl lactate, γ-butyrolactone, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and 3-methoxypropion. Esters such as methyl acidate and ethyl 3-ethoxypropionate; ethers such as ethylene glycol monobutyl ether, propylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol ethyl methyl ether; dimethylformamide, N,N-dimethylacetamide, N-methyl- Examples thereof include amides such as 2-pyrrolidone; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, and cyclohexanone; aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene.

The solvent may be used alone or in combination of two or more.
In the resin composition of the present invention, the content of the solvent is usually 10 to 90% by mass, preferably 30 to 80% by mass, more preferably 40 to 70% by mass.

[Preparation of resin composition]
The resin composition of the present invention can be prepared by mixing the above components. Further, in order to remove foreign matter, the respective components may be uniformly mixed and then the obtained mixture may be filtered with a filter or the like.

  The resin composition of the present invention has excellent adhesiveness to a metal member of a touch panel, particularly a molybdenum-containing metal member, and thus can be suitably used for forming a protective film for the metal member.

[Method for manufacturing resist pattern]
The method for producing a resist pattern of the present invention comprises a step (1) of forming a coating film of the photosensitive resin composition of the present invention on a substrate, a step (2) of exposing at least a part of the coating film, and It has the process (3) of developing the coating film after exposure.

[Step (1)]
In the step (1), a coating film of the photosensitive resin composition of the present invention is formed on the substrate.
Examples of the substrate include a transparent substrate, and specifically, an inorganic substrate such as a glass substrate; a polyester film such as a polyethylene terephthalate film; a polyolefin film such as a polyethylene film; a polyether sulfone film, a polycarbonate film, a polyacrylic film. , A polyvinyl chloride film, a polyimide film, a ring-opened polymer film of a cyclic olefin, and a film made of a hydrogenated product thereof; and the like; a silicon substrate, a ceramics substrate, an aluminum substrate, and the like can also be used.

The thickness of the substrate is usually 0.01 to 3 mm.
The substrate has a metal member formed of a metal material such as ITO; molybdenum, aluminum, silver, and copper on the surface thereof, and more preferably has a molybdenum-containing metal member. For example, a metal member containing molybdenum (Mo) and aluminum (Al), particularly a metal member having a laminated structure of Mo/Al/Mo can be mentioned. Examples of the metal member include metal wiring and metal electrodes.

  From the viewpoint of the visibility of the touch panel, the metal member preferably has a mesh shape, and examples thereof include a rectangular grid and metal wiring having a regular polygonal network.

  The coating film may be formed by applying the photosensitive resin composition of the present invention onto a substrate, and a support film, and a coating film comprising the photosensitive resin composition of the present invention formed on the support film. You may form by transferring the said coating film on a board|substrate from the photosensitive film which has. Examples of the support film include films made of synthetic resins such as polyethylene terephthalate, polycarbonate, polyethylene, polypropylene and polyether sulfone.

  Examples of the method for applying the photosensitive resin composition include a dipping method, a spray method, a bar coating method, a roll coating method, a spin coating method, a curtain coating method, a gravure printing method, a silk screen method, and an inkjet method.

  When forming a coating film, heating is performed as necessary to remove the solvent. The heating temperature is, for example, 60 to 250° C., and the heating time is 1 to 60 minutes, although it varies depending on the composition of the photosensitive resin composition.

[Step (2)]
In step (2), at least a part of the coating film is exposed. The exposure is usually performed through a photomask having a predetermined pattern suitable for forming the protective film of the touch panel.

Visible rays, ultraviolet rays, and deep ultraviolet rays are used for the exposure. Among these, light having a wavelength in the range of 190 to 450 nm is preferable, and light containing ultraviolet rays of 365 nm is particularly preferable. Exposure amount, the light intensity at a wavelength of 365 nm, a value measured by luminometer, preferably 50~1,000mJ / cm ^2, more preferably 100 to 500 mJ / cm ^2.

[Step 3]
In step (3), the exposed coating film is developed. Thereby, for example, when the negative composition is used, the non-exposed portion is removed to obtain a desired resist pattern.

  The developer used for the development is preferably an alkali developer containing an aqueous solution of an alkaline compound. Examples of the alkaline compound include compounds described in paragraph [0240] of JP 2012-88459 A, such as sodium hydroxide and tetramethylammonium hydroxide. The concentration of the alkaline compound in the alkaline developer is usually 0.1 to 5% by mass.

  Examples of the developing method include a puddle method, a dipping method, a rocking dipping method, and a shower method. The developing time varies depending on the composition of the photosensitive resin composition, but is usually 10 to 180 seconds.

  Following the development treatment, for example, washing with running water is performed for 30 to 90 seconds, and then air drying is performed, whereby a desired resist pattern can be formed. After the development treatment, the resist pattern may be further cured by further exposure if necessary. Further, instead of the exposure after the development treatment or in combination with the exposure, for example, a heat treatment at 80 to 280° C. for 10 to 100 minutes may be performed.

  The film thickness of the formed resist pattern is preferably 0.1 to 20.0 μm, more preferably 0.5 to 10.0 μm, and further preferably 1.0 to 5.0 μm. The film thickness can be measured by, for example, a contact type film thickness meter.

  A resin film having no pattern using the resin composition of the present invention is formed into a coating film and a coating film in the same manner as described above except that the exposure in step (2) and the development treatment in step (3) are not performed. It can be manufactured by performing heat treatment or the like. Note that light irradiation may be performed to cure the resin film.

[Touch panel member]
The touch panel member of the present invention has a substrate, a metal member disposed on the surface of the substrate, and a protective film that covers at least a part of the metal member, and the protective film is the resin composition or the photosensitive material of the present invention. It is formed from a resin composition.

  The touch panel member of the present invention can be manufactured by forming a protective film made of a resist pattern covering at least a part of the metal member on a substrate having a metal member according to the method for manufacturing a resist pattern. ..

  The metal member is, for example, a pattern film formed of ITO; a metal material such as molybdenum, aluminum, silver, or copper, and more preferably a molybdenum-containing metal member. For example, a metal member containing molybdenum (Mo) and aluminum (Al), particularly a metal member having a laminated structure of Mo/Al/Mo can be mentioned. Examples of the metal member include metal wiring and metal electrodes.

The touch panel member of the present invention is, for example, a capacitive touch panel member.
The protective film is patterned in the operation area of the touch panel member so as to cover and protect the metal member. The thickness of the protective film is preferably 0.1 to 20.0 μm, more preferably 0.5 to 10.0 μm, and further preferably 1.0 to 5.0 μm.

The protective film has excellent light transmittance and excellent adhesiveness to a metal member, particularly a molybdenum-containing metal member. Further, the protective film can suppress deterioration such as corrosion of the metal member.
The touch panel member of the present invention is mounted on a display such as a liquid crystal display device and an organic EL device, and can be suitably used as an input device to the display. Examples of the electronic device including the display include a mobile phone, a personal digital assistant, and a car navigation system device.

  Hereinafter, the present invention will be described more specifically based on examples, but the present invention is not limited to these examples. In the following description of Examples and the like, "part" is used to mean "part by mass" unless otherwise specified.

  The weight average molecular weight (Mw) of the polymer uses a GPC column manufactured by Tosoh Corporation (2 G2000HXL, 1 G3000HXL, 1 G4000HXL), and is measured in terms of polystyrene, “HLC-8220-GPC” ( It was measured using Tosoh Corporation.

1. Production of photosensitive resin composition
[Examples 1 to 3 and Comparative Examples 1 to 2]
A photosensitive resin composition was produced by uniformly mixing the components shown in Table 2.
Details of each component used in Examples and Comparative Examples are as follows.
A1: having a structural unit with the symbol a, a structural unit with the symbol b, a structural unit with the symbol c, and a structural unit with the symbol d shown in the following formula (A1), and these structural units A copolymer having a weight average molecular weight of 10,000, wherein the content ratio of a/b/c/d=21 mol%/29 mol%/15 mol%/35 mol%.

Ｂ１：下記式（Ｂ１）に示す化合物
Ｂ２：下記式（Ｂ２）に示す化合物
Ｂ３：下記式（Ｂ３）に示す化合物

B1: compound represented by the following formula (B1) B2: compound represented by the following formula (B2) B3: compound represented by the following formula (B3)

ＢＲ１：３−グリシドキプロピルトリメトキシシラン
Ｃ１：２−メチル−１−（４−メチルチオフェニル）−２−モルフォリノプロパン−１−オン
Ｃ２：下記式（Ｃ２）に示す化合物

BR1:3-glycidoxypropyltrimethoxysilane C1:2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one C2: compound represented by the following formula (C2)

Ｄ１−１：ジペンタエリスリトールヘキサアクリレート
（商品名「ＫＡＹＡＲＡＤ ＤＰＨＡ」、日本化薬（株）製）
Ｅ１：アルミニウム，Ｎ−ニトロソフェニルヒドロキシルアミン
Ｅ２：２，５−ジ−ｔｅｒｔ−ブチルハイドロキノン
Ｅ３：ポリエーテル変性シリコーン（商品名「ＤＯＷ ＣＯＲＮＩＮＧ ＴＯＲＡＹ ８０１９ ＡＤＤＩＴＩＶＥ」、東レ・ダウコーニング社製）
Ｆ１：ジエチレングリコールエチルメチルエーテル
Ｆ２：シクロペンタノン
Ｆ３：Ｎ−メチル−２−ピロリドン

D1-1: Dipentaerythritol hexaacrylate
(Product name "KAYARAD DPHA", manufactured by Nippon Kayaku Co., Ltd.)
E1: Aluminum, N-nitrosophenylhydroxylamine E2: 2,5-di-tert-butylhydroquinone E3: Polyether-modified silicone (trade name “DOW CORNING TORAY 8019 ADDITIVE”, manufactured by Toray Dow Corning)
F1: diethylene glycol ethyl methyl ether F2: cyclopentanone F3: N-methyl-2-pyrrolidone

2. Adhesion Evaluation After coating each photosensitive resin composition on a molybdenum substrate by a spin coating method, it was heated on a hot plate at 90° C. for 2 minutes and then at 230° C. for 30 minutes to give a film thickness of 1.5 μm. An adhesiveness evaluation substrate having the resin film was prepared.
The adhesiveness was evaluated by measuring the peel strength (kN/m) of the adhesiveness evaluation substrate by the SAICAS method. The evaluation results are shown in Table 2. The measurement conditions of the SAICAS method are as follows.

3. Production of resist pattern After coating each photosensitive resin composition on a substrate having a copper sputtered film on a silicon plate by using a spin coater, heating on a hot plate at 90° C. for 2 minutes, A coating film was formed. Then, exposure (wavelength: 365 nm, irradiation amount: 500 mJ/cm ² ) was performed using a mask aligner device (manufactured by Suss, model “MA-200”) through the mask. The exposed coating film was brought into contact with a 2.38 mass% tetramethylammonium hydroxide aqueous solution for 45 seconds, washed with running water, and then blown with nitrogen. Then, it was heated at 230° C. for 30 minutes to manufacture a resist pattern having a thickness of 1.5 μm. In this way, it was confirmed that the resist pattern could be manufactured well in the examples.

Claims (5)

An unsaturated compound having a cation-reactive group (excluding an ethylenically unsaturated double bond), and at least one unsaturated compound (a1) selected from an unsaturated compound having a carboxyl group or a carboxylic acid anhydride group; , (Meth)acrylic acid ester having no cation reactive group, carboxyl group, carboxylic acid anhydride group and hydroxyl group and having no ethylenically unsaturated double bond in the ester portion, N-substituted maleimide, cyano group-containing Polymer (A) which is a copolymer with a saturated compound, an unsaturated dicarboxylic acid dialkyl ester, and at least one other unsaturated compound (a2) selected from aromatic compounds having an ethylenically unsaturated double bond When,
A compound (B) represented by formula (b1),
A resin composition containing a cross-linking agent (D) having an ethylenically unsaturated double bond capable of reacting with the following functional group (b) of the compound (B).

[In formula (b1),
Ar is a benzene ring;
R ^B1 is a group having an ethylenically unsaturated double bond, wherein the ethylenically unsaturated double bond is referred to as a “functional group (b)”, and the group having the ethylenically unsaturated double bond is (the X -O- or -NH-, R is a hydrogen atom, a halogen atom or an alkyl group having 1 to 4 carbon atoms) -X-CO-CR = CH 2 be;
R ^B2 is a group bonded to the benzene ring and is an alkanediyl group having 1 to 10 carbon atoms;
R ^B3 is a group bonded to the benzene ring and is a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms;
-OH is attached to the benzene ring;
a is an integer of 1 or more; b is an integer of 0 or more; c is an integer of 2 or more, and at least two of —OH are respectively bonded to adjacent carbon atoms constituting the benzene ring in Ar. ing. ]   The resin composition according to claim 1, further comprising a photopolymerization initiator.   A step (1) of forming a coating film of the resin composition according to claim 2 on a substrate, a step (2) of exposing at least a part of the coating film, and a step of developing the coating film after the exposure. A method of manufacturing a resist pattern having (3).   The method for producing a resist pattern according to claim 3, wherein the substrate has a molybdenum-containing metal member on a surface that comes into contact with the coating film.   A touch panel member in which a molybdenum-containing metal member is protected by the resist pattern formed from the resin composition according to claim 2.