Curable resin composition, insulating cured film and insulating cured film for touch panel produced by curabing said composition, and touch panel

Abstract

The present invention provides a curable resin composition comprising: a thermosetting alkali-soluble resin (A1) having an acid value of 55-100 mgKOH / g; a photocurable alkali-soluble resin (A2) having an acid value of 20-100 mgKOH / g; a (meth) acrylic monomer (B1) having two polymerizable functional groups and a ring structure included between the two polymerizable functional groups; and a silane compound (C) represented by formula (1) or (2). (In the formula, R1 to R3 may be the same or different, all or at least one of R1 to R3 is an alkoxy group having 1 to 5 carbon atoms, and the others are alkyl groups having 1 to 5 carbon atoms. And R4-R6 may be the same or different and each represents an alkoxy group having 1-5 carbon atoms or an alkyl group having 1-5 carbon atoms. A represents a substituted or unsubstituted linear or branched alkylene group having 2-18 carbon atoms, and may include a divalent or trivalent linking group. And B represents a substituted or unsubstituted linear or branched alkylene group having 2-15 carbon atoms, and may contain a divalent linking group. And X is O, NH, NH-CO-NH or S. And p is an integer of 0 or 1. And q represents an integer of 1-3. And r represents an integer of 1-3. And s represents an integer of 1-3. And t represents an integer of 1-3). # imgabs0 #

Description

Technical Field

[0001] The present invention relates to a curable resin composition and an insulating cured film formed by curing the composition, for example, a curable resin composition useful for insulating cured film applications (e.g., insulating film applications, protective film applications, flat film applications, etc.) used in touch panels, etc., an insulating cured film for touch panels formed by curing the composition, and a touch panel having the cured film. Background Art

[0002] In recent years, with the development of electronic devices becoming more functional, diversified, small and lightweight, transparent touch panels are installed on the front surfaces of display elements such as liquid crystals. The text, symbols, patterns, etc. displayed by the display elements are viewed and selected through the transparent touch panels, and the functions of the equipment are switched by operating the transparent touch panels.

[0003] Touch panel detection methods include resistive film method, capacitive method, ultrasonic method, optical method, etc. In recent years, resistive film method and capacitive method have become popular. For example, the resistive film method is composed of a double-sided structure of an upper electrode film and a lower electrode glass, and a switch is pressed by applying pressure from above the upper electrode film with a pen tip or the like to react. In addition, the capacitive method is composed of a protective glass and a sensor glass on the surface, and an electrostatic coupling is generated by touching the surface glass with a finger, resulting in a capacitance difference with the inner glass, and the touched part is inferred based on the difference.

[0004] Capacitive touch panels use glass with an ITO film as the substrate. In order to prevent misidentification of the touch position, an insulating film and a protective film are provided in the laminated structure. As such a protective film, a high-hardness inorganic SiO2, SiN x , a protective film formed by transparent resins, etc., and an organic protective film. In addition, when the touch panel is combined with a liquid crystal display device, it can be divided into an out-cell structure, an on-cell structure, and an in-cell structure according to its setting location. In recent years, the surface-embedded structure and the in-cell structure with excellent visibility are becoming the mainstream. In these surface-embedded structures and in-cell structures, the touch panel is installed in the liquid crystal panel. Furthermore, as the structure of the touch panel, a double-sided type in which an X electrode is arranged on one side of the insulating film and a Y electrode is arranged on the other side, and a single-sided type in which an X electrode and a Y electrode are formed on the same plane are known.

[0005] As a technology applicable to such a touch panel, for example, a technology related to a cured film using a specific alkali-soluble resin and a photoreactive monomer and having excellent chemical resistance, developability, and wrinkle resistance has been proposed (for example, see Patent Document 1).

[0006] Prior art literature

[0007] Patent Literature

[0008] Patent Document 1: International Publication No. WO2020 / 251004 Summary of the invention

[0009] As described above, curable resin compositions are often used to form insulating films used in touch panels, liquid crystal display devices, etc. For purposes such as conducting between electrodes, patterns such as through holes (so-called through holes) and grooves may be formed in such insulating films.

[0010] In order to prepare a curable resin composition having patterning accuracy capable of forming small through-holes and narrow grooves, a positive type is considered to be advantageous. However, when a positive type curable resin composition is used, there is a problem that the cured product is colored.

[0011] On the other hand, in order to avoid the coloring of the cured product, the use of a negative curable resin composition is also considered. However, it is sometimes not easy to require high patterning accuracy for existing negative curable compositions, and in addition, patterning accuracy and anti-(electro)migration are generally in a trade-off relationship. Therefore, it is strongly desired to develop a technology related to a negative curable resin composition with a specified patterning accuracy and anti-migration.

[0012] The present invention aims to solve the above-mentioned problems and provides a curable resin composition having excellent patterning accuracy and migration resistance, an insulating cured film obtained by curing the composition, an insulating cured film for a touch panel, and a touch panel having the cured film.

[0013] The present inventors have conducted intensive research to solve the above-mentioned problems. As a result, they have found that the above-mentioned problems can be solved by using a composition comprising a thermosetting alkali-soluble resin having a specific acid value, a photocurable alkali-soluble resin having a specific acid value, and a monomer having a specific structure, and further comprising a silane compound having a specific structure, thereby completing the present invention.

[0014] <1>

[0015] A curable resin composition comprising:

[0016] A thermosetting alkali-soluble resin (A1) having an acid value of 55 to 100 mgKOH / g,

[0017] A photocurable alkali-soluble resin (A2) having an acid value of 20 to 100 mgKOH / g,

[0018] a (meth)acrylic monomer (B1) having two polymerizable functional groups and a ring structure between the two polymerizable functional groups, and

[0019] A silane compound (C) represented by the following formula (1) or (2).

[0020]

[0021] (Where R 1 ~R 3 They may be the same or different, and all or at least one of them may be an alkoxy group having 1 to 5 carbon atoms, and the others may be an alkyl group having 1 to 5 carbon atoms. 4 ~R 6 They may be the same or different and may be alkoxy groups having 1 to 5 carbon atoms or alkyl groups having 1 to 5 carbon atoms. A is a substituted or unsubstituted straight or branched alkylene group having 2 to 18 carbon atoms, which may contain a divalent or trivalent linking group. B is a substituted or unsubstituted straight or branched alkylene group having 2 to 15 carbon atoms, which may contain a divalent linking group. X is O, NH, NH-CO-NH or S. p is an integer of 0 or 1. q is an integer of 1 to 3. r is an integer of 1 to 3. s is an integer of 1 to 3. t is an integer of 1 to 3)

[0022] <2>

[0023] The curable resin composition according to the above <1>, wherein the thermosetting alkali-soluble resin (A1) has an acid group and a cyclic ether group.

[0024] <3>

[0025] The curable resin composition according to the above <1> or <2>, wherein the thermosetting alkali-soluble resin (A1) contains at least the following units (a1-1) and (a1-2).

[0026]

[0027] (In formula (a1-1), R 1 represents a hydrogen atom or a methyl group, X 1 represents a single bond or a linear or cyclic aliphatic hydrocarbon group having 1 to 15 carbon atoms which may contain an oxygen atom. 1 represents a hydrogen atom or a methyl group, R 3 represents a linear or branched aliphatic hydrocarbon group having 3 to 15 carbon atoms and having a cyclic ether structure and optionally containing an oxygen atom)

[0028] <4>

[0029] The curable resin composition according to the above <3>, wherein the thermosetting alkali-soluble resin (A1) further includes the following unit (a1-3).

[0030]

[0031] (Where R 1 represents a hydrogen atom or a methyl group, R 4 represents at least one selected from a linear, branched or cyclic aliphatic hydrocarbon group having 1 to 20 carbon atoms, an aromatic group and a combination thereof which may contain an oxygen atom)

[0032] <5>

[0033] The curable resin composition according to any one of <1> to <4>, wherein at least one of the thermosetting alkali-soluble resin (A1) and the photocurable alkali-soluble resin (A2) has a cyclic group.

[0034] <6>

[0035] The curable resin composition according to any one of <1> to <5>, wherein a weight average molecular weight of at least one of the thermosetting alkali-soluble resin (A1) and the photocurable alkali-soluble resin (A2) is 30,000 or less.

[0036] <7>

[0037] The curable resin composition according to any one of <1> to <6>, wherein the photocurable alkali-soluble resin (A2) contains at least the following units (a2-1) and (a2-2).

[0038]

[0039] (In unit (a2-1), R 1 Each independently represents a hydrogen atom or a methyl group, R 5 represents a chain, branched or cyclic aliphatic hydrocarbon group having 2 to 15 carbon atoms which may contain a hetero atom. 1 represents a hydrogen atom or a methyl group, X 1 represents a single bond or a linear or cyclic aliphatic hydrocarbon group having 1 to 15 carbon atoms which may contain an oxygen atom)

[0040] <8>

[0041] The curable resin composition according to the above <7>, wherein the photocurable alkali-soluble resin (A2) further includes the following unit (a2-3).

[0042]

[0043] (Where R 1 represents a hydrogen atom or a methyl group, R 4 represents at least one selected from a linear, branched or cyclic aliphatic hydrocarbon group having 1 to 20 carbon atoms, an aromatic group, and a combination thereof which may contain an oxygen atom)

[0044] <9>

[0045] The curable resin composition according to any one of <1> to <9>, wherein the ring structure in the (meth)acrylic monomer (B1) comprises any one selected from an aliphatic hydrocarbon group having 6 to 26 carbon atoms which may contain an oxygen atom, an aromatic hydrocarbon group having 6 to 26 carbon atoms which may contain an oxygen atom, and a combination thereof.

[0046] <10>

[0047] The curable resin composition according to any one of the above <1> to <9>, wherein the mass ratio [A:B] of the total amount [A] of the above thermosetting alkali-soluble resin (A1) and the above photocurable alkali-soluble resin (A2) to the total amount [B] of the polyfunctional (meth)acrylic monomer (B) including the above (meth)acrylic monomer (B1) is 100:40 to 80.

[0048] <11>

[0049] The curable resin composition according to any one of <1> to <10>, which is used for forming an insulating film.

[0050] <12>

[0051] An insulating cured film obtained by curing the curable resin composition according to any one of <1> to <10> above.

[0052] <13>

[0053] An insulating cured film for a touch panel, obtained by curing the curable resin composition described in any one of <1> to <10> above.

[0054] <14>

[0055] A touch panel comprising the insulating cured film for a touch panel according to <13>.

[0056] According to the present invention, there can be provided a curable resin composition having excellent patterning accuracy and migration resistance, an insulating cured film obtained by curing the composition, an insulating cured film for a touch panel, and a touch panel having the cured film. BRIEF DESCRIPTION OF THE DRAWINGS

[0057] Figure 1 It is a plan view showing the structure of one mode of the touch panel according to the present embodiment.

[0058] Figure 2 yes Figure 1 AA cross-section diagram.

[0059] Figure 3 It is a schematic diagram showing the cross-sectional shape of a through hole. DETAILED DESCRIPTION

[0060] Hereinafter, a mode for carrying out the present invention (hereinafter referred to as "this embodiment") will be described in detail. However, the present invention is not limited thereto, and various modifications can be made without departing from the gist of the present invention.

[0061] 《Curable resin composition》

[0062] The curable resin composition of the present embodiment comprises: a thermosetting alkali-soluble resin (A1) having an acid value of 55 to 100 mgKOH / g, a photocurable alkali-soluble resin (A2) having an acid value of 20 to 100 mgKOH / g, a (meth)acrylic monomer (B1) having two polymerizable functional groups and a ring structure contained between the two polymerizable functional groups, and a silane compound (C) represented by the following formula (1) or (2).

[0063]

[0064] (Where R 1 ~R 3 They may be the same or different, and all or at least one of them may be an alkoxy group having 1 to 5 carbon atoms, and the others may be an alkyl group having 1 to 5 carbon atoms. 4 ~R 6 They may be the same or different and may be alkoxy groups having 1 to 5 carbon atoms or alkyl groups having 1 to 5 carbon atoms. A is a substituted or unsubstituted straight or branched alkylene group having 2 to 18 carbon atoms, which may contain a divalent or trivalent linking group. B is a substituted or unsubstituted straight or branched alkylene group having 2 to 15 carbon atoms, which may contain a divalent linking group. X is O, NH, NH-CO-NH or S. p is an integer of 0 or 1. q is an integer of 1 to 3. r is an integer of 1 to 3. s is an integer of 1 to 3. t is an integer of 1 to 3)

[0065] Although the curable resin composition of the present embodiment is negative, it has excellent patterning accuracy and migration resistance. That is, the present invention has excellent water resistance and developer resistance in the exposure part (cured part) during development. On the other hand, the non-exposed part (uncured part) is easily dissolved in the developer, so it is possible to achieve high patterning accuracy. The reason why the patterning accuracy and migration resistance of the curable resin composition of the present embodiment are excellent is still uncertain, but it is speculated that the silane compound (C) contained in the curable resin composition plays a role in taking into account both patterning accuracy and migration resistance. Although not limited by theory, it is believed that the NH part of the silane compound (C) is prevented from forming a conductive path in the cured part by capturing the metal ions dissolved from the wiring, so that the migration resistance is excellent. In addition, it is believed that the curable resin composition of the present embodiment is excellent in developability of the non-latent image part (non-exposed part) by including each constituent element, and the resistance to the developer in the latent image part (exposed part) is high, so it is possible to achieve high patterning accuracy. In the description of the present embodiment, migration refers to electromigration.

[0066] <Alkali-soluble resin (A)>

[0067] The curable resin composition of the present embodiment comprises a thermosetting alkali-soluble resin (A1) and a photocurable alkali-soluble resin (A2). The thermosetting alkali-soluble resin (A1) and the photocurable alkali-soluble resin (A2) are different compounds. For "alkali-soluble resin", the non-cured portion shows solubility in the developer, and the cured portion shows insolubility or poor solubility in the developer. In addition, from the viewpoint of the resistance of the cured product to water penetration (hereinafter referred to as water resistance), it is preferred that at least one of the thermosetting alkali-soluble resin (A1) and the above-mentioned photocurable alkali-soluble resin (A2) has a cyclic group.

[0068] Hereinafter, the thermosetting alkali-soluble resin (A1) and the photocurable alkali-soluble resin (A2) are sometimes referred to as "alkali-soluble resin (A1)" or "alkali-soluble resin (A2)", respectively. In addition, the alkali-soluble resins (A1) and (A2) are sometimes collectively referred to as "alkali-soluble resin (A)". The curable resin composition of this embodiment may contain a plurality of alkali-soluble resins (A1) and (A2).

[0069] (Thermosetting alkali-soluble resin (A1))

[0070] The alkali-soluble resin (A1) is a thermosetting alkali-soluble resin having an acid value of 55 to 100 mgKOH / g. The alkali-soluble resin (A1) is a resin having a thermoreactive group and being cured at 70°C or above. The thermoreactive group is not particularly limited, and from the perspective of low-temperature curability, for example, an acid group (e.g., a carboxyl group, an acid anhydride group, a sulfonic group, a phosphoric acid group), a cyclic ether group, a hydroxyl group, an amino group, a thiol group, an isocyanate group, a silanol group, etc. can be cited. The alkali-soluble resin (A1) preferably has an acid group and a cyclic ether group (e.g., an epoxy group, an oxetane group, etc.) as a thermoreactive group. The temperature at which the thermosetting alkali-soluble resin (A1) is cured varies depending on the type and number of the thermoreactive group. From the perspective of low-temperature curability and the developability of the unexposed portion (the solubility of the unexposed portion in the developer), it is preferably 70°C or above, more preferably 80°C to 230°C, and particularly preferably 90°C to 150°C.

[0071] The acid value of the alkali-soluble resin (A1) is 55 to 100 mgKOH / g, preferably 60 to 95 mgKOH / g, and more preferably 70 to 90 mgKOH / g. If the acid value of the alkali-soluble resin (A1) is within the range of 55 to 100 mgKOH / g, poor development can be suppressed, and the developer (e.g., tetramethylammonium hydroxide) has high resistance, which can suppress overdevelopment. In addition, if the acid value is less than 55 mgKOH / g, the developability may be reduced. As the acid value of the alkali-soluble resin, the theoretical solid content acid value can be used, which can be calculated as follows.

[0072] Theoretical solid content acid value (mgKOH / g) = [56.1 (molecular weight of potassium hydroxide) × (total amount of acid group-containing units in alkali-soluble resin (A1) [g]) × 1000] / [(total amount of solid content of alkali-soluble resin (A1) [g]) × (molecular weight of acid group-containing units)]

[0073] As the thermosetting alkali-soluble resin (A1), a resin containing at least the following units (a1-1) and (a1-2) can be used. The thermosetting alkali-soluble resin (A1) can be a resin containing two or more of the same structural units described below (for example, two units (a1-2)).

[0074]

[0075] (In unit (a1-1), R 1 represents a hydrogen atom or a methyl group, X 1 represents a single bond or a linear or cyclic aliphatic hydrocarbon group having 1 to 15 carbon atoms which may contain an oxygen atom. 1 represents a hydrogen atom or a methyl group, R 3represents a linear or branched aliphatic hydrocarbon group having 3 to 15 carbon atoms and having a cyclic ether structure and optionally containing an oxygen atom)

[0076] -Unit (a1-1)-

[0077] The unit (a1-1) is a unit derived from an unsaturated carboxylic acid.

[0078] In unit (a1-1), R 1 represents a hydrogen atom or a methyl group, and is preferably a methyl group from the viewpoint of water resistance of the obtained cured product.

[0079] In addition, X 1 represents a single bond, or a linear or cyclic aliphatic hydrocarbon group (divalent bonding group) having 1 to 15 carbon atoms which may contain an oxygen atom. From the viewpoint of water resistance, the carbon number of the aliphatic hydrocarbon group which may contain an oxygen atom is preferably 1 to 9. These aliphatic hydrocarbon groups may have an -O- structure in the structure (structure containing an oxygen atom: for example, an ether group (-O-), an ester group (-CO-O-), an anhydride group (-CO-O-CO-)). Examples of linear aliphatic hydrocarbon groups include alkylene groups having 1 to 15 carbon atoms, aliphatic hydrocarbon groups having 3 to 15 carbon atoms which may contain a plurality of ester groups and anhydride groups (-CO-O-CO-), and the like. In addition, examples of cyclic aliphatic hydrocarbon groups include cycloalkylene groups having 3 to 15 carbon atoms, a cycloalkylene group having 3 to 15 carbon atoms which may contain a plurality of ester groups and anhydride groups, and the like. In addition, X 1 It may be an aliphatic hydrocarbon group containing both a linear portion and a cyclic portion. 1 Examples include -CO-O-CH2-CH2-O-CO-CH2-CH2-, -CO-O-CH2-CH2-O-CO-cyclohexyl-, and the like.

[0080] As the unit (a1-1), for example, methacrylic acid (hereinafter sometimes referred to as "MAA"), acrylic acid, crotonic acid (trans), maleic acid (cis), fumaric acid (trans), citraconic acid (cis), mesaconic acid (trans), itaconic acid, maleic anhydride, citraconic anhydride, itaconic anhydride, hexahydrophthalic acid-2-methacryloyloxyethyl ester, etc. As a preferred structure of the unit (a1-1), units derived from the following compounds can be exemplified.

[0081]

[0082] -Unit (a1-2)-

[0083] The unit (a1-2) is a unit derived from an unsaturated carboxylic acid having a cyclic ether structure.

[0084] In the following unit (a1-2), R 1represents a hydrogen atom or a methyl group, R 3 It represents a linear or branched aliphatic hydrocarbon group having 3 to 15 carbon atoms which has a cyclic ether structure and may contain an oxygen atom.

[0085]

[0086] In unit (a1-2), R 1 represents a hydrogen atom or a methyl group, and a methyl group is preferred from the viewpoint of water resistance.

[0087] In addition, R 3 It represents a straight-chain or branched aliphatic hydrocarbon group having 3 to 15 carbon atoms and which may contain oxygen atoms and has a cyclic ether structure. Here, from the viewpoint of developability, the number of carbon atoms of the straight-chain or branched aliphatic hydrocarbon group having a cyclic ether structure is preferably 3 to 7. These aliphatic hydrocarbon groups may have an -O- structure (a structure containing an oxygen atom: for example, an ether group (-O-), an ester group (-CO-O-), an anhydride group (-CO-O-CO-)) in the structure. Examples of the straight-chain or branched aliphatic hydrocarbon group having a cyclic ether structure include a group having a cyclic ether structure bonded to the end of an alkylene group (for example, a methylene group). As a preferred structure of the unit (a1-2), units from the following compounds can be exemplified.

[0088]

[0089] -Unit (a1-3)-

[0090] As the thermosetting alkali-soluble resin (A1), a resin containing the following unit (a1-3) in addition to the above-mentioned units (a1-1) and (a1-2) can be used from the viewpoint of resistance to a developer. The unit (a1-3) is a unit derived from an unsaturated compound.

[0091]

[0092] (Where R 1 represents a hydrogen atom or a methyl group, R 4 represents at least one selected from a linear, branched or cyclic aliphatic hydrocarbon group having 1 to 20 carbon atoms, an aromatic group and a combination thereof which may contain an oxygen atom)

[0093] In unit (a1-3), R 1 represents a hydrogen atom or a methyl group, and a methyl group is preferred from the viewpoint of water resistance.

[0094] In addition, R 4It is a straight-chain, branched or cyclic aliphatic hydrocarbon group with 1 to 20 carbon atoms, an aromatic group, or a combination of the above aliphatic hydrocarbon and aromatic group. Here, from the viewpoint of resistance to developer and developability, the carbon number of the above aliphatic hydrocarbon group is preferably 1 to 10. These aliphatic hydrocarbon groups may have an -O- structure (a structure containing an oxygen atom: for example, an ether group (-O-), an ester group (-CO-O-), an acid anhydride group (-CO-O-CO-)) in the structure. As the above straight-chain, branched or cyclic aliphatic hydrocarbon group, a straight-chain, branched or cyclic alkyl group with 1 to 20 carbon atoms can be cited. From the aspect of resistance to developer, methyl, n-propyl, n-butyl, n-hexyl, cyclopentyl, cyclohexyl, isobornyl, tricyclodecanyl, and adamantyl are preferred. In addition, as the above aromatic group, phenyl, biphenyl, naphthyl, anthracenyl, etc. can be cited. From the aspect of transparency of the cured product, phenyl is preferred. In addition, as a combination of an aliphatic hydrocarbon group having 1 to 20 carbon atoms and an aromatic group, alkoxyphenyl, alkylphenyl, alkoxynaphthyl, alkylnaphthyl, alkoxyanthryl, alkylanthryl, etc. can be cited, and from the perspective of the transparency of the cured product, alkoxyphenyl and alkylphenyl are preferred. As a preferred structure of unit (a1-3), units from the following compounds can be exemplified.

[0095]

[0096] - Composition ratio -

[0097] From the viewpoint of resistance to developer and developability, the content (mol %) of units (a1-1), units (a1-2) and units (a1-3) in the alkali-soluble resin (A) is preferably (a1-1) / (a1-2) / (a1-3) = 10 to 50 / 10 to 70 / 0 to 70, more preferably 15 to 40 / 15 to 60 / 15 to 65, and particularly preferably 15 to 30 / 20 to 50 / 30 to 60.

[0098] -Other components-

[0099] The alkali-soluble resin (A1) may contain other structural units that do not belong to any of the above-mentioned units (a1-1) to (a1-3). Examples of other structural units include benzyl methacrylate, 1,3-bis(methacryloyloxy)-2-propanol, 2-methacryloyloxyethyl isocyanate, 2-hydroxyethyl methacrylate, and N-cyclohexylsuccinimide.

[0100] From the viewpoint of achieving both resistance to a developer and developability, the content (mol %) of other structural units in the alkali-soluble resin (A1) is preferably 0 to 35 mol %, more preferably 0 to 20 mol %.

[0101] (Molecular weight)

[0102] From the viewpoint of developability, the weight average molecular weight of the alkali-soluble resin (A1) is preferably 3000 to 30000, more preferably 4000 to 25000, and particularly preferably 5500 to 13000. The molecular weight of the alkali-soluble resin (A) can be measured by gel permeation chromatography (manufactured by Tosoh Corporation, model: HLC-8120, column: G-5000HXL and G-3000HXL connected, detector: RI, mobile phase: tetrahydrofuran).

[0103] (Glass transition temperature)

[0104] From the viewpoint of heat resistance, developability and low-temperature curability, the glass transition temperature of the alkali-soluble resin (A1) is preferably 0 to 300° C., more preferably 30 to 250° C., particularly preferably 50 to 200° C. The glass transition temperature can be measured by differential scanning calorimetry (DSC).

[0105] (Epoxy Equivalent Weight)

[0106] From the viewpoint of achieving both resistance to a developer and developability, the epoxy equivalent of the alkali-soluble resin (A1) is preferably 200 to 1000, more preferably 250 to 800, and particularly preferably 300 to 600. The epoxy equivalent can be determined, for example, in accordance with JIS K7236 (2001).

[0107] (Double bond equivalent)

[0108] From the viewpoint of reactivity, the double bond equivalent of the alkali-soluble resin (A1) is preferably 150 to 2000, more preferably 150 to 1500, and particularly preferably 200 to 1000. The double bond equivalent can be determined, for example, by "(mass per mol of polymer) / (number of ethylenically unsaturated groups per mol)".

[0109] (specific example)

[0110] Specific examples of the alkali-soluble resin (A1) include the following polymers.

[0111]

[0112] (Photocurable alkali-soluble resin (A2))

[0113] The alkali-soluble resin (A2) is a resin cured by free radicals from a photopolymerization initiator (C). The alkali-soluble resin (A2) preferably has an ethylenically unsaturated double bond as a functional group that reacts with free radicals. The ethylenically unsaturated double bond is not particularly limited, and from the perspective of the chemical resistance of the resulting cured product, for example, (meth) acrylic group, vinyl group, allyl group, preferably (meth) acrylic group.

[0114] As the photocurable alkali-soluble resin (A2), a resin containing at least the following units (a2-1) and (a2-2) can be used. The photocurable alkali-soluble resin (A2) can be a resin containing two or more of the same constituent units (for example, two units (a2-2)) described below.

[0115]

[0116] (In unit (a2-1), R 1 Each independently represents a hydrogen atom or a methyl group, R 5 represents a chain, branched or cyclic aliphatic hydrocarbon group having 2 to 15 carbon atoms which may contain a hetero atom. 1 represents a hydrogen atom or a methyl group, X 1 represents a single bond or a linear or cyclic aliphatic hydrocarbon group having 1 to 15 carbon atoms which may contain an oxygen atom)

[0117] -Unit (a2-1)-

[0118] The unit (a2-1) is a unit derived from an unsaturated compound having a (meth)acryloyl group.

[0119] In unit (a2-1), R 1 Each independently represents a hydrogen atom or a methyl group, and a methyl group is preferred from the viewpoint of water resistance.

[0120] In addition, R 5It represents a chain, branched or cyclic aliphatic hydrocarbon group (divalent bonding group) having 2 to 15 carbon atoms which may contain heteroatoms. From the viewpoint of the reactivity of the composition, the carbon number of the aliphatic hydrocarbon group which may contain heteroatoms is preferably 3 to 10. These aliphatic hydrocarbon groups may have an -O- structure (a structure containing an oxygen atom: for example, -OH (hydroxyl), ether group (-O-), ester group (-CO-O-), acid anhydride group (-CO-O-CO-)), a structure containing a sulfur atom such as an -S- structure, and a structure containing a nitrogen atom such as an -NH- structure. Examples of the straight-chain or branched aliphatic hydrocarbon group include an alkylene group having 2 to 15 carbon atoms, an aliphatic hydrocarbon group having 2 to 15 carbon atoms which may contain a plurality of ester groups and acid anhydride groups (-CO-O-CO-), and the like. In addition, examples of the cyclic aliphatic hydrocarbon group include a cycloalkylene group having 3 to 15 carbon atoms, a cycloalkylene group having 3 to 15 carbon atoms which may contain a plurality of ester groups and acid anhydride groups, and the like. In addition, R 5 It may be an aliphatic hydrocarbon group containing both a straight chain portion and a cyclic portion. 5 Examples include -CH2-CH(OH)-CH2-, -CH2-CH2-O-CO-NH-CH2-CH2-O-, -CO-O-CH2-CH(OH)-CH2-O-, -CO-O-CH2-CH2-O-CO-NH-CH2-CH2-O-, -CO-O-CH2-CH2-CH2-O-CO-NH-CH2-CH2-O-, -CO-O-CH2-CH2-CH2-CH2-O-CO-NH-CH2-CH2-O-, etc.

[0121] Preferred structures of the unit (a2-1) include units derived from the following compounds.

[0122]

[0123] -Unit (a2-2)-

[0124] The unit (a2-2) is a unit derived from an unsaturated carboxylic acid and has the same structure as the above-mentioned unit (a1-1).

[0125] In unit (a2-2), R 1 , X 1 and R in unit (a1-1) 1 , X 1 The meanings are the same, and the preferred specific examples are also the same.

[0126] -Unit (a2-3)-

[0127] From the viewpoint of resistance to a developer, as the photocurable alkali-soluble resin (A2), a resin containing the following unit (a2-3) in addition to the above-mentioned units (a2-1) and (a2-2) can be used.

[0128]

[0129] (Where R 1 represents a hydrogen atom or a methyl group, R 4 represents at least one selected from a linear, branched or cyclic aliphatic hydrocarbon group having 1 to 20 carbon atoms, an aromatic group and a combination thereof which may contain an oxygen atom)

[0130] The unit (a2-3) is a unit derived from an unsaturated compound and has the same structure as the above-mentioned unit (a1-3).

[0131] In unit (a2-3), R 1 , R 4 and R in unit (a1-1) 1 , R 4 The meanings are the same, and the preferred specific examples are also the same.

[0132] - Composition ratio -

[0133] From the viewpoint of achieving both resistance to the developer and developability, the content (molar %) of units (a2-1), units (a2-2) and units (a2-3) in the alkali-soluble resin (A) is preferably (a2-1) / (a2-2) / (a2-3) = 10 to 70 / 1 to 50 / 0 to 70, further preferably 15 to 60 / 5 to 40 / 0 to 60, and particularly preferably 20 to 50 / 10 to 30 / 0 to 50.

[0134] -Other components-

[0135] The alkali-soluble resin (A2) may contain other structural units that do not belong to any of the above-mentioned units (a2-1) to (a2-3). Examples of other structural units include benzyl methacrylate, 2-methacryloyloxyethyl isocyanate, 2-hydroxyethyl methacrylate, and N-cyclohexylsuccinimide.

[0136] From the viewpoint of achieving both resistance to a developer and developability, the content (mol %) of other structural units in the alkali-soluble resin (A2) is preferably 0 to 30 mol %, more preferably 0 to 15 mol %.

[0137] (Molecular weight)

[0138] From the viewpoint of developability, the weight average molecular weight of at least one of the alkali-soluble resin (A1) and the alkali-soluble resin (A2) is preferably 30,000 or less, preferably 500 to 30,000, more preferably 1,000 to 20,000, more preferably 2,000 to 15,000, particularly preferably 3,000 to 10,000.

[0139] The molecular weight of the alkali-soluble resin (A) can be measured by gel permeation chromatography (manufactured by Tosoh Corporation, model: HLC-8120, columns: G-5000HXL and G-3000HXL connected, detector: RI, mobile phase: tetrahydrofuran).

[0140] (Acid value)

[0141] From the viewpoint of achieving both resistance to developer and developability, the acid value of the alkali-soluble resin (A2) is 20 to 100 mgKOH / g, more preferably 25 to 90 mgKOH / g, further preferably 30 to 80 mgKOH / g, and particularly preferably 30 to 70 mgKOH / g. The acid value of the alkali-soluble resin may be a theoretical acid value.

[0142] (Glass transition temperature)

[0143] From the viewpoint of heat resistance and developability, the glass transition temperature of the alkali-soluble resin (A2) is preferably 0 to 300° C., particularly preferably 30 to 250° C. The glass transition temperature can be measured by a differential scanning calorimeter (DSC).

[0144] (Double bond equivalent)

[0145] From the viewpoint of reactivity and developability, the double bond equivalent of the alkali-soluble resin (A2) is preferably 150 to 2000, more preferably 150 to 1500, and particularly preferably 200 to 1000. The double bond equivalent can be determined in the same manner as for the alkali-soluble resin (A1).

[0146] (specific example)

[0147] Specific examples of the alkali-soluble resin (A2) include the following polymers.

[0148]

[0149] (content)

[0150] The content of the alkali-soluble resin (A) in the curable resin composition of the present embodiment (the total amount of the alkali-soluble resin (A1) and the alkali-soluble resin (A2)) is not particularly limited, and for example, from the viewpoint of developability, it is preferably 30 to 80% by mass, more preferably 40 to 70% by mass, and particularly preferably 45 to 65% by mass relative to the total solid content in the composition. In this specification, "total solid content" refers to all components in the resin composition excluding the solvent.

[0151] (Combination of Alkali-Soluble Resin (A1) and Alkali-Soluble Resin (A2))

[0152] The mass ratio of the alkali-soluble resin (A1) to the alkali-soluble resin (A2) in the curable resin composition of the present embodiment is not particularly limited. For example, from the viewpoint of curability, the mass ratio (A1): (A2) is preferably 100:5 to 100, more preferably 100:5 to 60%, and particularly preferably 100:10 to 50.

[0153] <Other polymers>

[0154] The curable resin composition of the present embodiment may contain other polymers in addition to the alkali-soluble resin (A). The content of other polymers in the curable resin composition of the present embodiment is not particularly limited, for example, from the viewpoint of obtaining the effect brought by including other polymers without significantly hindering the chemical resistance of the cured film, etc., relative to 100 parts by mass of the alkali-soluble resin (A), preferably 5 to 30 parts by mass, more preferably 10 to 20 parts by mass.

[0155] <Multifunctional (meth)acrylic monomer (B)>

[0156] The multifunctional (meth) acrylic monomer B is a compound having two or more polymerizable functional groups, and has at least one (meth) acrylic group. The multifunctional (meth) acrylic monomer B of the present embodiment includes the (meth) acrylic monomer (B1) and the (meth) acrylic monomer (B2) described later. In addition, the curable resin composition of the present embodiment includes the (meth) acrylic monomer (B1), and further includes the (meth) acrylic monomer (B2) as needed.

[0157] From the viewpoint of the developability when forming a pattern, the content of the multifunctional (meth) acrylic monomer (B) in the curable resin composition of the present embodiment is set so that the mass ratio [A:B] of the total amount [A] of the thermosetting alkali-soluble resin (A1) and the photocurable alkali-soluble resin (A2) to the total amount [B] of the multifunctional (meth) acrylic monomer (B) is 100:40 to 80. If the total amount [B] of the multifunctional (meth) acrylic monomer (B) is less than 40 parts by mass relative to 100 parts by mass of the total amount [A] of the thermosetting alkali-soluble resin (A1) and the photocurable alkali-soluble resin (A2), the developability when forming a pattern may be reduced.

[0158] If the total amount [B] exceeds 80 parts by weight relative to 100 parts by weight of the total amount [A], the migration resistance of the curable resin composition may be deteriorated. From the viewpoint of pattern processability and migration resistance, the mass ratio [A:B] is preferably 100:40 to 75, more preferably 100:45 to 70, and particularly preferably 100:45 to 60.

[0159] Although not particularly limited, the combination of the alkali-soluble resin (A1), the alkali-soluble resin (A2) and the multifunctional (meth)acrylic monomer (B) is not particularly limited, and from the viewpoint of balancing resistance to a developer and developability, for example, it can be A1:A2:B=100:5 to 40:35 to 110.

[0160] Furthermore, although not particularly limited, the mass ratio [B1:B2] of the (meth)acrylic monomer (B1) to the (meth)acrylic monomer (B2) in the polyfunctional (meth)acrylic monomer B is set to 100:0 to 100.

[0161] <(Meth)acrylic acid monomer (B1)>

[0162] The (meth)acrylic monomer (B1) is a compound having two polymerizable functional groups and a ring structure between the two polymerizable functional groups, and has at least one (meth)acrylic group. The curable resin composition of this embodiment can improve the processability of the pattern by using the (meth)acrylic monomer (B1).

[0163] Here, "ring structure" refers to a structure having at least one cyclic skeleton, and includes structures consisting only of a cyclic skeleton and structures consisting of a cyclic skeleton and a linear structure bonded to the cyclic skeleton. In addition, "ring structure contained between two polymerizable functional groups" means that two polymerizable functional groups are bonded via a ring structure, and the polymerizable functional group can be directly bonded to the cyclic skeleton or indirectly bonded to the cyclic skeleton. From the viewpoint of resistance to developer, the ring structure of the (meth)acrylic monomer (B1) can be any one selected from aliphatic hydrocarbon groups having 6 to 26 carbon atoms that can contain oxygen atoms, aromatic hydrocarbons having 6 to 26 carbon atoms that can contain oxygen atoms, and combinations thereof (for example, combinations of aliphatic hydrocarbons and aromatic hydrocarbons, and combinations of different aliphatic hydrocarbons, different aromatic hydrocarbon compounds, etc.). As specific examples of cyclic skeletons, for example, fluorene skeletons, cyclohexane skeletons, bisphenol A skeletons, dicyclopentane skeletons, and combinations thereof can be cited.

[0164] "Polymerizable functional group" is a (meth)acryloyl group itself, a group containing one (meth)acrylic acid group, or a functional group containing one polymerizable group other than a (meth)acrylic acid group. Examples of polymerizable functional groups other than a (meth)acrylic acid group include vinyl, allyl, (meth)acrylamide, and the like. Hereinafter, "a group containing a (meth)acrylic acid group" refers to a (meth)acrylic acid group itself or a group containing one (meth)acrylic acid group. In the (meth)acrylic acid-based monomer (B1), the number of polymerizable functional groups is 2. If the number of polymerizable functional groups exceeds 2, the processability of the pattern is sometimes reduced. In addition, the two polymerizable functional groups may be the same or different from each other.

[0165] As the (meth)acrylic monomer (B1), a compound represented by the following formula (b1) can be used.

[0166]

[0167] (Where R 11 and R 12 Each independently represents a hydrogen atom or a methyl group, Y 1 and Y 2 Each independently represents a single bond, or a linear or branched aliphatic hydrocarbon group having 1 to 26 carbon atoms which may contain an oxygen atom, and X 11 represents an aliphatic hydrocarbon group or aromatic group having 6 to 26 carbon atoms and a cyclic skeleton; W1 and W2 each independently represent O, N or S)

[0168] In formula (b1), R 11 and R 12 Each independently represents a hydrogen atom or a methyl group, and a hydrogen atom is preferred from the viewpoint that the composition exhibits good curability (hereinafter simply referred to as “curability”) during exposure.

[0169] Y 1 and Y 2 Each independently represents a single bond, or a linear or branched aliphatic hydrocarbon group (divalent bonding group) having 1 to 26 carbon atoms which may contain an oxygen atom. From the viewpoint of curability, the carbon number of the aliphatic hydrocarbon group is preferably 1 to 20, and more preferably 1 to 12. Examples of the linear or branched aliphatic hydrocarbon group include alkylene groups having 1 to 26 carbon atoms, such as methylene, ethylene, 1-methylethylene, 1-methylpropylene, 2-methylpropylene, and 1,1-dimethylethylene. In addition, Y containing an oxygen atom may be 1 and Y 2 For example, -O(C2H4O) m - (m is 1 to 13), etc. 1 and Y 2, for example, a methylene group is preferred.

[0170] X 11 represents an aliphatic hydrocarbon group or aromatic group (divalent bonding group) having 6 to 26 carbon atoms and a cyclic skeleton. 11 The number of carbon atoms in the moiety is preferably 6 to 26.

[0171] Examples of the aliphatic hydrocarbon having 6 to 26 carbon atoms and having the cyclic skeleton include a divalent bonding group consisting of a cyclohexane ring, a cyclodecane ring, a tricyclodecane ring, an adamantane ring, a norbornane ring or a decalin ring, and examples of the aromatic group include a divalent bonding group consisting of a benzene ring or a naphthalene ring. 11 , preferably containing at least one divalent bonding group selected from the above-mentioned fluorene skeleton, cyclohexane skeleton, bisphenol A skeleton, dicyclopentane skeleton and a combination thereof.

[0172] Although it does not specifically limit as a (meth)acrylic-type monomer (B1), The following compounds are mentioned.

[0173]

[0174] From the viewpoint of developability when forming through holes, the content of the (meth) acrylic monomer (B) in the curable resin composition of the present embodiment is set so that the mass ratio [A:B] of the total amount [A] of the thermosetting alkali-soluble resin (A1) and the photocurable alkali-soluble resin (A2) to the total amount [B] of the (meth) acrylic monomer (B) is 100:35 to 80. If the total amount [B] of the (meth) acrylic monomer (B) is less than 35 parts by mass relative to 100 parts by mass of the total amount [A] of the thermosetting alkali-soluble resin (A1) and the photocurable alkali-soluble resin (A2), the developability when forming through holes may be reduced. From the viewpoint of through hole processability, the mass ratio [A:B] is preferably 100:40 to 75, and more preferably 100:45 to 70.

[0175] In addition, although not particularly limited, from the viewpoint of balancing resistance to developer and developability, the combination of the alkali-soluble resin (A1), the alkali-soluble resin (A2) and the (meth)acrylic monomer (B) may be, for example, A1:A2:B=100:5-40:35-110, or 100:10-30:50-100.

[0176] In addition, the curable resin composition of the present embodiment may contain a photoreactive monomer other than the (meth) acrylic monomer (B). Other photoreactive monomers are not particularly limited, and for example, compounds having three or more ethylenically unsaturated groups in the molecule may be cited. Examples of such compounds include trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol hexaacrylate, and the like.

[0177] (Double bond equivalent)

[0178] From the viewpoint of reactivity and developability, the double bond equivalent of the (meth)acrylic monomer (B1) is preferably 120 to 1000, more preferably 120 to 800, and particularly preferably 120 to 600. The double bond equivalent can be calculated according to (molecular weight of (meth)acrylic monomer (B)) / (the number of ethylenically unsaturated groups in (meth)acrylic monomer (B)).

[0179] (LogP)

[0180] The (meth)acrylic monomer (B) preferably has a LogP of 1 to 8, more preferably 1.5 to 7, further preferably 2 to 6, particularly preferably 2.5 to 6, and most preferably 3 to 5, from the viewpoint of resistance to a developer and developability.

[0181] The LogP can be determined by using a reverse phase column (C18) and HPLC (high performance liquid chromatography) according to OECD GUIDELINES FOR THE TESTING CHEMICALS Partition Coefficient (n-octanol / water), High Performance Liquid Chromatography (HPLC) Method 117 (Adopted 13 April 2004). Benzyl alcohol, anisole, toluene, and butylbenzene are used as standard substances with known LogP.

[0182] Examples of the measurement conditions of LogP are as follows.

[0183] · Apparatus: 1200 Series HPLC manufactured by Agilent Technology

[0184] Column: DiKMA Inspire C18 5 μm 150×4.6 mm (particle size 5 μm, inner diameter 4.6 mm, length 150 mm)

[0185] Mobile phase: a mixture of acetonitrile and 0.5 wt% phosphoric acid aqueous solution {mixing ratio 55:45 (volume ratio)}

[0186] Oven temperature: 40℃

[0187] Flow rate: 1mL / min

[0188] UV detection wavelength: 210nm

[0189] <(Meth)acrylic acid monomer (B2)>

[0190] The (meth)acrylic monomer (B2) is a compound having three or more polymerizable functional groups, and has at least one (meth)acrylic group. The curable resin composition of the present embodiment may further include a (meth)acrylic monomer (B2) in addition to the (meth)acrylic monomer (B1).

[0191] The (meth)acrylic monomer (B2) is not particularly limited, and trimethylolpropane triacrylate, dipentaerythritol hexaacrylate (DPHA), pentaerythritol triacrylate (PET-3A), or tripentaerythritol octaacrylate can be used.

[0192] (Combination of (meth)acrylic acid-based monomer (B1) and (meth)acrylic acid-based monomer (B2))

[0193] The mass ratio of the (meth)acrylic monomer (B1) to the (meth)acrylic monomer (B2) in the curable resin composition of the present embodiment is not particularly limited. For example, from the viewpoint of reactivity, the mass ratio (B1): (B2) is preferably 100:0 to 50, more preferably 100:0 to 40%, and particularly preferably 100:0 to 30.

[0194] The combination of the (meth)acrylic monomer (B1) and the (meth)acrylic monomer (B2) is not particularly limited, and may be, for example, a combination of dimethyloltricyclodecane diacrylate and dipentaerythritol hexaacrylate (DPHA) from the viewpoint of water resistance and reactivity.

[0195] Moreover, the curable resin composition of this embodiment may contain the photoreactive monomer (especially a monofunctional (meth)acrylic-based monomer) other than a polyfunctional (meth)acrylic-based monomer (B).

[0196] <Silane compound (C)>

[0197] The silane compound (C) is a so-called silane coupling agent. The silane compound (C) is represented by the following formula (1) or (2).

[0198]

[0199] (Where R 1 ~R 3They may be the same or different, and all or at least one of them may be an alkoxy group having 1 to 5 carbon atoms, and the others may be an alkyl group having 1 to 5 carbon atoms. 4 ~R 6 They may be the same or different and may be alkoxy groups having 1 to 5 carbon atoms or alkyl groups having 1 to 5 carbon atoms. A is a substituted or unsubstituted straight or branched alkylene group having 2 to 18 carbon atoms, which may contain a divalent or trivalent linking group. B is a substituted or unsubstituted straight or branched alkylene group having 2 to 15 carbon atoms, which may contain a divalent linking group. X is O, NH, NH-CO-NH or S. p is an integer of 0 or 1. q is an integer of 1 to 3. r is an integer of 1 to 3. s is an integer of 1 to 3. t is an integer of 1 to 3)

[0200] The amount of the silane compound (C) in the curable resin composition of the present embodiment is not limited, but is preferably 1 to 40 parts by mass, and more preferably 5 to 30 parts by mass, relative to 100 parts by mass of the total amount of the alkali-soluble resin (A), from the viewpoint of achieving both patterning accuracy and anti-migration properties of the curable resin composition.

[0201] In the above formula (1) or (2), R 1 ~R 3 They may be the same or different, and all or at least one of them may be an alkoxy group having 1 to 5 carbon atoms, and the others may be an alkyl group having 1 to 5 carbon atoms.

[0202] Examples of the alkoxy group having 1 to 5 carbon atoms include methoxy, ethoxy, 1-propoxy, 2-propoxy, 1-butoxy, 2-methylpropoxy, 2-butoxy, 1,1-dimethylethoxy, 1-pentyloxy, 3-methylbutoxy, 2,2-dimethylpropoxy, and 1,1-dimethylpropoxy. Preferably, methoxy or ethoxy is used.

[0203] Examples of the alkyl group having 1 to 5 carbon atoms include methyl, ethyl, 1-propyl, 2-propyl, 1-butyl, 2-methylpropyl, 2-butyl, 1,1-dimethylethyl, 1-pentyl, 3-methylbutyl, 2,2-dimethylpropyl, and 1,1-dimethylpropyl, and preferably methyl and ethyl groups are mentioned.

[0204] A is a substituted or unsubstituted linear or branched alkylene group having 2 to 18 carbon atoms.

[0205] The number of carbon atoms of the linear or branched alkylene group is preferably 2 to 12, and more preferably 2 to 6. As a substituent of the linear or branched alkylene group having 2 to 18 carbon atoms, an ester group bonded to an alkyl group having 1 to 5 carbon atoms can be mentioned. A can contain at least one divalent or trivalent linking group. As a divalent or trivalent linking group, a linking group represented by the following formula [A1] can be mentioned. The substituted or unsubstituted linear or branched alkylene group having 2 to 18 carbon atoms can be obtained by containing a trivalent linking group, where q and r in formula (1) are integers greater than 1.

[0206]

[0207] [R 7 , R 8 are the same or different hydrogen atoms, alkyl groups having 1 to 5 carbon atoms, aryl groups having 6 to 12 carbon atoms, -CH=,

[0208]

[0209] (R 9 , R 10 is an alkyl group having 1 to 5 carbon atoms, m3 is an integer of 1 to 5),

[0210]

[0211] (m4 is an integer from 1 to 5),

[0212]

[0213] (R 11 is an alkyl group having 1 to 5 carbon atoms), or a monovalent or divalent group represented by a cycloalkane having 3 to 6 carbon atoms which may have a substituent. 7 or R 8 When any one of them is a divalent group, the other is a hydrogen atom or a monovalent group],

[0214]

[0215] A substituted or unsubstituted cycloalkane having 3 to 6 carbon atoms and having at least 2 bonding sites,

[0216]

[0217] In the above [A1], the alkyl group having 1 to 5 carbon atoms is the same as the alkyl group exemplified in the above general formula (1). In addition, examples of the aryl group having 6 to 12 carbon atoms include phenyl, benzyl, tolyl, etc. Examples of the cycloalkane having 3 to 6 carbon atoms include cyclopropane, cyclobutane, cyclopentane, and cyclohexane.

[0218] An isocyanate group or a silicon atom is bonded to A. A can be a compound having a plurality of isocyanate groups in the molecule or a compound containing a plurality of silicon atoms in the molecule by containing one or more trivalent linking groups [A1]. In addition, even when a trivalent linking group is contained, a group that does not participate in the reaction, such as a methyl group or a cyano group, is bonded to the end of one of the bonding groups to sometimes form a divalent linking group.

[0219] q is an integer of 1 to 3, and preferably 1. r is an integer of 1 to 3, and preferably 1.

[0220] R 4 ~R 6 The alkoxy group having 1 to 5 carbon atoms or the alkyl group having 1 to 5 carbon atoms may be the same or different. Examples of the alkoxy group having 1 to 5 carbon atoms or the alkyl group having 1 to 5 carbon atoms include the following: 1 ~R 3 The alkyl groups exemplified in are the same alkyl groups.

[0221] B is a substituted or unsubstituted linear or branched alkylene group having 2 to 15 carbon atoms.

[0222] The number of carbon atoms of the linear or branched alkylene group is preferably 2 to 10, more preferably 2 to 6. B may contain at least one divalent linking group. Examples of the divalent linking group include an ether bond (—O—), a carbonyl group (—C(═O)—, and a group represented by the following formula [B1].

[0223]

[0224] X is O, NH, NH-CO-NH, or S.

[0225] The X group or the silicon atom is bonded to B, or the X group is directly bonded to the silicon atom. When there are multiple X groups in the molecule, the second or more X groups are bonded to the above-mentioned [B1], or the substituent [B1] itself is an NH-CO-NH group. In addition, when there are multiple silicon atoms in the molecule, the second or more silicon atoms are bonded to the above-mentioned [B1], or are substituents of linear or branched alkylene groups.

[0226] p is an integer of 0 or 1. s is an integer of 1 to 3, and preferably 1. t is an integer of 1 to 3, and preferably 1.

[0227] The silane compound (C) contained in the curable resin composition of the present embodiment is preferably a silane compound represented by any one of the following formulae (3) to (6) from the viewpoint of achieving more excellent adhesion of the cured film to the substrate.

[0228]

[0229] (Where R 1 ~R 3 They may be the same or different, and all or at least one of them may be an alkoxy group having 1 to 5 carbon atoms, and the others may be an alkyl group having 1 to 5 carbon atoms. 4 ~R 6 may be the same or different and are 1 to 5 alkyl groups. m is an integer of 2 to 18)

[0230]

[0231] (Where R 1 ~R 3 They may be the same or different, and all or at least one of them may be an alkoxy group having 1 to 5 carbon atoms, and the others may be an alkyl group having 1 to 5 carbon atoms. 4 ~R 6 They may be the same or different and are alkoxy groups having 1 to 5 carbon atoms or alkyl groups having 1 to 5 carbon atoms. m is an integer of 2 to 18, and n is an integer of 2 to 15)

[0232]

[0233] (Where R 1 ~R 3 They may be the same or different, and all or at least one of them may be an alkoxy group having 1 to 5 carbon atoms, and the others may be an alkyl group having 1 to 5 carbon atoms. 4 ~R 6 They may be the same or different and are alkoxy groups having 1 to 5 carbon atoms or alkyl groups having 1 to 5 carbon atoms. m is an integer of 2 to 18, and n is an integer of 2 to 15)

[0234]

[0235] (Where R 1 ~R 3 They may be the same or different, and all or at least one of them may be an alkoxy group having 1 to 5 carbon atoms, and the others may be an alkyl group having 1 to 5 carbon atoms. 4 ~R 6 They may be the same or different and are alkoxy groups having 1 to 5 carbon atoms or alkyl groups having 1 to 5 carbon atoms. m is an integer of 2 to 18, and n is an integer of 2 to 15)

[0236] The silane compound (C) is not limited, but the following compounds can be mentioned.

[0237]

[0238] (Photopolymerization Initiator)

[0239] The curable resin composition of the present embodiment is a negative curable resin composition containing a photopolymerization initiator. The photopolymerization initiator is a compound that is activated by various active light rays, such as ultraviolet rays, to initiate polymerization. As the photopolymerization initiator, for example, free radical photopolymerization initiators, cationic photopolymerization initiators, and anionic photopolymerization initiators can be cited. The photopolymerization initiator is not particularly limited, and for example, a photopolymerization initiator that generates free radicals that polymerize ethylenically unsaturated groups by ultraviolet rays to visible rays can be appropriately used.

[0240] The photopolymerization initiator is not particularly limited, and examples thereof include acetophenones such as acetophenone, 2,2'-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, dichloroacetophenone, trichloroacetophenone, and p-tert-butylacetophenone; α-aminoketone photopolymerization initiators such as 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butane-1-one, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholino-4-yl-phenyl)-butane-1-one, and 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropane-1-one; 1-[4-(phenylthio)phenyl]octane-1,2-dione = 2-(O-benzoyl oxime), 1-[9-ethyl- 6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone 1-(O-acetyl oxime), 1-[9-ethyl-6-benzoyl-9.H.-carbazol-3-yl]-octane-1-one oxime-O-acetate, 1-[9-ethyl-6-(2-methylbenzoyl)-9.H.-carbazol-3-yl]-ethane-1-one oxime-O-benzoate, 1-[9-n-butyl-6-(2-ethylbenzoyl)-9.H.-carbazol-3-yl]-ethane-1-one oxime-O-benzoate, 1-[9-ethyl-6-(2-methyl-4-tetrahydrofuranylbenzoyl)-9.H.-carbazol-3-yl]ethanone-1-(O-acetyl oxime), 1-[9-ethyl-6-( Oxime ester photopolymerization initiators such as 1-[2-methyl-4-tetrahydropyranylbenzoyl)-9.H.-carbazole-3-yl]ethanone-1-(O-acetoxime), 1-[9-ethyl-6-(2-methyl-5-tetrahydrofuranylbenzoyl)-9.H.-carbazole-3-yl]ethanone-1-(O-acetoxime), 1-[9-ethyl-6-{2-methyl-4-(2,2-dimethyl-1,3-dioxolyl)methoxybenzoyl}-9.H.-carbazole-3-yl]ethanone-1-(O-acetoxime); benzophenones such as benzophenone, 2-chlorobenzophenone, and p,p'-bisdimethylaminobenzophenone; benzil, benzoin, benzoin methyl ether, benzoin isopropyl ether, benzoin isobutyl ether ethers such as benzoin ethers; sulfur compounds such as benzil dimethyl ketal, thioxanthone, 2-chlorothioxanthone, 2,4-diethylthioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone; anthraquinones such as 2-ethylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-diphenylanthraquinone; triazines such as 2,4-trichloromethyl-(4'-methoxyphenyl)-6-triazine, 2,4-trichloromethyl-(4'-methoxynaphthyl)-6-triazine, 2,4-trichloromethyl-(piperonyl)-6-triazine, 2,4-trichloromethyl-(4'-methoxyphenyl)-6-triazine; organic peroxides such as azobisisobutyronitrile, benzoyl peroxide, and isopropyl peroxide; 2-mercaptobenzimidazole, 2-mercaptobenzoic acid Thiol compounds such as oxazole and 2-mercaptobenzothiazole, etc. From the viewpoint of reactivity, as the photopolymerization initiator, an oxime ester-based photopolymerization initiator is preferred. These photopolymerization initiators may be used alone or in combination of two or more.

[0241] The content of the photopolymerization initiator in the curable resin composition of the present embodiment is not particularly limited. For example, from the viewpoint of photoreactivity and storage stability, when the total amount of the multifunctional (meth)acrylic monomer (B), the photoreactive monomer and the photocurable alkali-soluble resin (A) is 100 parts by mass, the content is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass, and particularly preferably 2 to 15 parts by mass.

[0242] <Method for preparing curable resin composition>

[0243] The curable resin composition of the present embodiment is a negative curable resin comprising an alkali-soluble resin (A), a (meth)acrylic monomer (B) and a silane compound (C), and can be prepared by adding a solvent, a polymerization inhibitor, a photopolymerization initiator and the like and stirring and mixing.

[0244] (Solvent)

[0245] In the present embodiment, the solvent can be appropriately selected from known solvents according to the intended purpose.

[0246] Examples of the solvent include cyclohexanone, cyclopentanone, diethylene glycol methyl ethyl ether, acetylacetone, methanol, ethanol, ethyl cellosolve, ethyl cellosolve acetate, methyl cellosolve, methyl cellosolve acetate, diglyme, cyclohexanone, ethylbenzene, xylene, isoamyl acetate, n-amyl acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate (PGMAC), propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, diethylene glycol, dimethoxybenzene ... Ethylene glycol monomethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether, diethylene glycol ethyl methyl ether (EDM), diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, triethylene glycol, triethylene glycol monomethyl ether, triethylene glycol monomethyl ether acetate, triethylene glycol monoethyl ether, triethylene glycol monoethyl ether acetate, liquid polyethylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether, dipropylene glycol monoethyl ether acetate, lactic acid ester, methyl methoxypropionate, ethyl ethoxypropionate, etc.

[0247] The above solvents may be used alone or in combination of two or more.

[0248] In addition, the content of the solvent in the curable resin composition of the present embodiment is not particularly limited. For example, from the viewpoint of storage stability and coating properties, it is preferred to use the solvent in a manner where the total solid content (the total mass of the components in the composition excluding the solvent) concentration is preferably 1 to 40 mass %, more preferably 5 to 40 mass %, and particularly preferably 10 to 30 mass %. By making the solid content ratio within the above range, the viscosity of the curable resin composition can be appropriately made, and the coating properties when applied to a substrate or the like to form a film are particularly improved.

[0249] (Inhibitor)

[0250] The curable resin composition of the present embodiment may contain a polymerization inhibitor from the viewpoint of inhibiting polymerization of the photocurable alkali-soluble resin (A2), the (meth)acrylic monomer (B), etc. As the polymerization inhibitor, a known ultraviolet absorber may be used.

[0251] Examples of the polymerization inhibitor include phenolic compounds such as 4-methoxyphenol, 2,2'-methylenebis(4-ethyl-6-tert-butylphenol), 2,6-di-tert-butyl-4-methylphenol, 2,6-di-tert-butyl-N,N-dimethylamino-p-cresol, 2,4-dimethyl-6-tert-butylphenol, 4-tert-butylcatechol, 4,4'-thio-bis(3-methyl-6-tert-butylphenol), and 4,4'-butylene-bis(3-methyl-6-tert-butylphenol); 4-hydroxy-2,2,6,6-tetramethylpiperidinyl-N-oxyl free radical, 4-acetylamino-2,2,6,6-tetramethylpiperidinyl-N-oxyl free radical, 4-benzoyloxy-2,2,6,6-tetramethylpiperidinyl-N-oxyl free radical, 4-oxo-2,2,6,6-tetramethylpiperidinyl-N-oxyl free radical, and 4-oxo-2,2,6,6-tetramethylpiperidinyl-N-oxyl free radical. N-oxyl radical compounds such as tetramethylpiperidine-N-oxyl and 2,2,6,6-tetramethylpiperidine-N-oxyl; quinone compounds such as p-methoxyphenol (MEHQ), hydroquinone, 2,5-di-tert-butylhydroquinone, 2,6-di-tert-butylhydroquinone, and benzoquinone; cuprous chloride; dialkyldithiocarbamate copper such as dimethyldithiocarbamate; amino compounds such as phenothiazine, N,N'-diphenyl-p-phenylenediamine, phenyl-β-naphthylamine, N,N'-di-β-naphthyl-p-phenylenediamine, and N-phenyl-N'-isopropyl-p-phenylenediamine; hydroxylamine compounds such as 1,4-dihydroxy-2,2,6,6-tetramethylpiperidine, 1-hydroxy-2,2,6,6-tetramethylpiperidine, and 4-hydroxy-2,2,6,6-tetramethylpiperidine. As the polymerization inhibitor, for example, the above-mentioned p-methoxyphenol can be appropriately used. As the polymerization inhibitor, these may be used alone or in combination of two or more.

[0252] The amount of the polymerization inhibitor in the curable resin composition of the present embodiment is not particularly limited, but is preferably 0.1 to 0.6% by mass, more preferably 0.1 to 0.4% by mass, relative to the total solid content (the total mass of the components other than the solvent in the composition), from the viewpoint of processability of patterns such as through holes and grooves.

[0253] In addition, the curable resin composition of the present embodiment may also contain various additives such as inorganic fine particles, adhesion promoting additives, surfactants, storage stabilizers, leveling agents, light stabilizers, antioxidants, etc. as needed. Examples of these additives include, for example, additives described in Japanese Patent Application Laid-Open No. 2012-215833.

[0254] 《Insulating Cured Film》

[0255] The application of the curable resin composition of the present embodiment is not particularly limited, and can be used for the purpose of forming an insulating film, for example, it can be used as an insulating cured film, especially an insulating cured film for a touch panel. The insulating cured film for a touch panel can be formed by the following operation: using various imparting methods such as spin coating such as spin coating, cast coating such as die coating, coating based on roll coating, coating based on roll transfer method, etc. to form a coating film on a substrate such as a glass substrate, ITO, a metal film, an organic film, etc., and curing the coating film.

[0256] Specifically, the cured film of the present embodiment can be formed by coating the curable resin composition on a substrate such as a glass substrate and irradiating light to cure it. In addition, the cured film of the present embodiment can be patterned by irradiating light through a mask, developing, and then performing a heat treatment as needed.

[0257] The insulating cured film can be used for any application such as an insulating film application, a protective film application, a flat film application, etc. The insulating cured film using the curable resin composition of this embodiment can be particularly suitably used as a touch panel protective film or a touch panel insulating film.

[0258] The insulating cured film of the present embodiment can be used not only as a so-called permanent film maintained in a device such as a touch panel, but also as a resist film used when patterning an ITO film on a glass substrate.

[0259] (pattern)

[0260] For purposes such as energization between electrodes, the cured film used in the insulating cured film of the touch panel can be provided with a pattern such as a through hole or a groove of a desired size. As described above, although the curable resin composition of the present embodiment is a negative composition, the processability of the pattern is excellent, and a pattern having a cross-sectional shape of the hole or the groove that is fully open to the side of the hole or the bottom of the groove and the hole or the groove is observed as an inverted trapezoidal shape from the exposure direction can be formed. Therefore, it can be suitable for use as a cured film-forming composition (hereinafter, also referred to as a "cured film-forming composition with a pattern") having a through hole or a groove.

[0261] The method for producing a cured film having a pattern formed thereon (hereinafter also referred to as a "cured film with a pattern") using the curable resin composition of the present embodiment is not particularly limited, and a known method for forming a pattern and a method for producing a cured film can be appropriately selected. As an example of a method for producing a cured film with a pattern using the curable resin composition of the present embodiment, there can be mentioned a method including the following steps: a step of applying the curable resin composition of the present embodiment to a substrate to form a coating film (coating film forming step), a step of exposing the coating film through a mask for forming a pattern such as a through hole or a groove (exposure step), a step of removing the non-exposed portion of the coating film after exposure with a developer (development step), and a step of heating the coating film from which the non-exposed portion has been removed (for example, 90 to 230° C., 10 to 60 minutes) (post-baking step). Between the coating film forming step and the exposure step, a step of heating the coating film (for example, 80 to 100° C., 60 to 180 seconds) (pre-baking step) can be implemented.

[0262] The non-exposure part (non-cured part) of the curable resin composition of the present embodiment is excellent in developability, and the developer resistance of the exposure part (cured part) is high. Therefore, it is possible to suppress overdevelopment, and it is possible to form a desired fine pattern. In addition, since a thermosetting resin (alkali-soluble resin (A1)) is also included in addition to a photocurable resin (alkali-soluble resin (A2)), the wall surface of the pattern will not collapse in the post-baking process and the taper angle of the hole or groove cross-sectional shape can be maintained. In this way, if the curable resin composition of the present embodiment is used, even if it is a pattern with a small pore size (for example, an pore size of less than 5 μm in diameter), it is possible to form a pattern that is fully open to the side of the pattern and the cross-sectional shape of the pattern is observed as an inverted trapezoidal pattern from the exposure direction.

[0263] The thickness of the patterned cured film can be appropriately set depending on the purpose, and for example, from the viewpoint of migration resistance and developability, it can be 0.2 μm to 20 μm, and further can be 0.5 μm to 10 μm.

[0264] The pore size of the through hole formed in the patterned cured film can be appropriately set according to the purpose, for example, from the viewpoint of reactivity and developability, it can be 30 μm to 200 μm, and further can be 40 μm to 100 μm. Figure 3 As shown in FIG. 1 , the “aperture diameter” of a through hole formed in a patterned cured film can be defined as the aperture diameter at a height equivalent to 10% of the height from the bottom surface of the through hole ( Figure 3 10% bottom CD in the 10 ”).

[0265] The width of the grooves of the patterned cured film can be appropriately set depending on the purpose, and for example, from the viewpoint of reactivity and developability, may be 30 μm to 1000 μm, or further may be 50 μm to 500 μm.

[0266] Touch Panel

[0267] As described above, the curable resin composition of the present embodiment and the insulating cured film using the same can be suitably used as an insulating film for touch panels. Hereinafter, the insulating cured film of the present embodiment and the insulating film for touch panels may be simply collectively referred to as “the cured film of the present embodiment”.

[0268] The touch panel of the present embodiment may be any one of a resistive film type, a capacitive type, an ultrasonic type, and an optical type, and is preferably a capacitive type touch panel.

[0269] Capacitive touch panels, for example, use glass with an ITO film as a substrate, and in order to prevent misidentification of the contact position, an insulating film and a protective film are provided in the laminated structure (for example, between electrodes). When the touch panel of this embodiment is a capacitive touch panel, the touch panel of this embodiment can use the cured film of this embodiment, for example, as an insulating film, a protective film, or both in the laminated structure.

[0270] In addition, the touch panel can be divided into a double-sided structure in which an X electrode is arranged on one side of the insulating film and a Y electrode is arranged on the other side, and a single-sided structure in which the X electrode and the Y electrode are formed on the same plane. The touch panel of this embodiment can be either a double-sided structure or a single-sided structure, and a touch panel of a single-sided structure is particularly preferred.

[0271] In the single-sided touch panel structure, the X electrode is electrically separated from the Y electrode. At this time, according to the pattern of the electrode, for example, it can be divided into an island pattern, a through-hole pattern, etc. For example, in the case of an island pattern, in addition, in the single-sided touch panel structure, the separated electrodes are electrically connected to each other by a component such as a jumper. In addition, the electrode jumper uses a transparent electrode such as an ITO film, but in the case where the separated Y electrodes are combined with each other in the jumper, for example, in order to maintain insulation from the X electrode, an insulating layer is provided at the bottom of the jumper. In addition, usually, an insulating film (protective film) is uniformly formed on each electrode arranged on the single-sided type.

[0272] Therefore, when the touch panel of this embodiment has a single-sided touch panel structure, the touch panel of this embodiment can use the cured film of this embodiment for example as an insulating film formed on an electrode, an insulating layer formed under a jumper portion, or both.

[0273] Furthermore, when the touch panel is installed in a liquid crystal display device, it can be divided into an external embedded structure, a surface embedded structure, and an embedded structure according to its installation location. In the surface embedded structure and the embedded structure, the touch panel is installed in the liquid crystal panel, and in the external embedded structure, the touch panel is installed on the outside of the liquid crystal panel. In the surface embedded structure, the touch panel is arranged between the polarizer on the viewing direction side and the liquid crystal laminate (a laminate composed of a pair of substrate glasses and a liquid crystal layer interposed therebetween). In addition, in the embedded structure, the liquid crystal layer of the liquid crystal laminate has a touch panel function. The touch panel of this embodiment can be applied in any structure, but is preferably used in, for example, a surface embedded structure.

[0274] Hereinafter, one aspect of the touch panel according to the present embodiment will be described using drawings. Figure 1 FIG. 1 is a top view showing a configuration of a touch panel according to the present embodiment. Figure 1 As shown, when the touch panel of the present embodiment is a single-sided touch panel, ITO (indium tin oxide) electrodes ( X1 to X3 , Y1 to Y3 ) are formed on the glass substrate 10 .

[0275] The material of the glass substrate 10 is not particularly limited, and for example, a glass plate of soda-lime glass, low-alkali borosilicate glass, alkali-free aluminoborosilicate glass, etc. can be used. In addition, a plastic plate or plastic film made of polyethylene terephthalate (PET), triacetylcellulose (TAC), polymethyl methacrylate (PMMA), polycarbonate (PC), etc. can be used instead of the glass substrate.

[0276] ITO electrodes (X1 to X3, Y1 to Y3) are transparent electrodes. In the present embodiment, ITO is used as the material of the transparent electrode, but as long as it can be disposed on the surface of the substrate, there is no particular limitation. In addition to ITO, for example, inorganic conductive materials such as ZnO (zinc oxide), organic conductive materials such as PEDOT / PSS (polyethylene dioxythiophene / polystyrene sulfonic acid), polyaniline, and polypyrrole may also be used. Only one of these materials may be used, or two or more of them may be used in combination.

[0277] It should be noted that although Figure 1 and 2 Although the description is omitted in the figure, in each electrode and jumper portion X12, a metal thin film having a function as a metal wiring can be used as its lower layer or in place of the transparent electrode. The metal thin film can be made of metal materials such as Mo (molybdenum), Al (aluminum), Ag (silver), and Pd (palladium), and preferably one or more of Mo and Al are used.

[0278] like Figure 1 As shown, ITO electrodes X1 to X3 are Figure 1 The ITO electrodes X1 to X3 are arranged in the direction of the arrow P in FIG. 1 , and are separated from the adjacent electrodes, but are electrically connected to the adjacent electrodes in the direction of P via the jumper portion X12. The jumper portion X12 can be formed of the same material as the transparent electrode, such as ITO. In addition, at the lower part of the jumper portion X12 in the thickness direction, there is a Figure 2 The insulating film 14 is shown. Furthermore, in order to electrically connect the electrodes adjacent to each other in the P direction, through holes 20 are provided at both ends of each jumper portion X12.

[0279] In addition, ITO electrodes Y1 to Y3 are Figure 1 The electrodes are arranged in the direction of the arrow Q in FIG. The ITO electrodes Y1 to Y3 are continuously coupled to the electrodes adjacent in the Q direction via the connecting portions formed by the ITO film and are electrically connected in the Q direction. It should be noted that the ITO electrodes Y1 to Y3 are usually continuously formed as one with each connecting portion when the electrodes are formed.

[0280] Hereinafter, the electrode group electrically connected in the P direction is referred to as "X electrode", and the electrode group electrically connected in the Q direction is referred to as "Y electrode". Figure 1 As shown, in a single-sided touch panel, the X electrodes are arranged along the P direction, and the Y electrodes are arranged along the Q direction.

[0281] Next use Figure 2 The cross-sectional structure of the touch panel according to the present embodiment will be described. Figure 2 yes Figure 1 AA cross-section diagram. Figure 2As shown in FIG. 1 , an insulating film 14 and a connecting portion Y12 of the ITO electrodes Y1 and Y2 are interposed between the ITO electrodes X2 and X3. The ITO electrodes X2 and X3 are electrically connected by the jumper portion X12 as described above. In addition, a portion of the insulating film 14 extends between the jumper portion X12 and the connecting portion Y12 at the lower portion in the thickness direction to maintain the insulation between the jumper portion X12 and the connecting portion Y12. In addition, an insulating protective layer 16 is provided on the upper side of the insulating film 14 and the jumper portion X12 in the thickness direction.

[0282] In this embodiment, the cured film of this embodiment is used for at least one of the insulating film 14 and the insulating protective layer 16. However, the other may be formed using a known material conventionally used for the insulating film or the protective film, but it is preferred that both the insulating film 14 and the insulating protective layer 16 are the cured films of this embodiment.

[0283] In the above-mentioned touch panel, the method for forming the cured film of the present embodiment is not particularly limited. For example, a coating film can be formed on a lower layer (for example, a glass substrate 10 and an ITO electrode for an insulating film 14, or an ITO electrode for an insulating protective layer 16, etc.) by a coating method such as spraying, spin coating, slit die coating, roller coating, or rod coating. At this time, the dry film thickness of the coating film is not particularly limited. For example, in the case of an insulating protective layer 16, it is preferably 0.5 to 20 μm, and more preferably 1.0 to 10 μm. Similarly, in the case of an insulating film 14, the dry film thickness is preferably 0.2 to 10 μm, and more preferably 0.5 to 5 μm. In addition, as required, the coating film can be exposed by a mask having a prescribed pattern set in contact or non-contact with the coating film. The type of light during exposure is not particularly limited, and visible light, ultraviolet light, far infrared light, electron beam, X-ray, etc. can be cited, among which ultraviolet light is preferred. The illuminance of the light is not particularly limited, but is preferably 5 to 150 mW / cm at 365 nm. 2 , particularly preferably 5 to 35 mW / cm 2 .

[0284] Thereafter, the non-cured portion is removed by immersing in an aqueous alkaline developer such as sodium carbonate, sodium hydroxide, potassium hydroxide, or tetramethylammonium hydroxide (TMAH) as required, or spraying the developer by spraying, etc., to form a desired pattern. Furthermore, in order to promote the polymerization of the photosensitive composition and cure it, heating (post-baking) can be performed as required. It should be noted that when forming the cured film, the above-mentioned method for forming the through hole can be applied.

[0285] Furthermore, for example, when forming the jumper portion X12, first, patterned X electrodes and Y electrodes may be formed on the glass substrate 10, and then a curable resin composition may be applied to the surface of the glass substrate 10 and the X electrodes, and the curable resin composition may be exposed and developed using a mask capable of forming the insulating film 14 and the through hole 20. Next, a material (such as ITO) that will become the jumper portion X12 is deposited on the insulating film 14 and the through hole 20 by PVD or the like to form a conductive layer. Thereafter, only the portion where the jumper portion X12 is to be formed (such as Figure 2 A protective layer is provided on the surface of the conductive layer of the insulating film 14 on the connection portion Y12, and an etching process is performed, thereby forming a jumper portion X12 on the insulating film 14 on the connection portion Y12.

[0286] Example

[0287] Hereinafter, the present invention will be described in more detail using Examples and Comparative Examples. The present invention is not limited to the following Examples in any way.

[0288] [Examples and Comparative Examples]

[0289] The components were mixed according to the formulation shown in the following table to prepare a curable resin composition. The mixing was performed at room temperature while shielding ultraviolet rays so as not to initiate a polymerization reaction.

[0290] [Table 1]

[0291]

[0292] ※In the table, "OXE01" means Irgacure OXE01 (BASF JAPAN Co., Ltd.).

[0293] In addition, the numerical value about each component in a table|surface shows mass % with respect to the whole composition (it does not include a solvent).

[0294] The components in the above table used were those shown in the table below.

[0295] [Table 2]

[0296]

[0297] [Table 3]

[0298]

[0299] [Table 4]

[0300]

[0301] "evaluate"

[0302] The curable compositions of the Examples and Comparative Examples obtained above were subjected to various evaluations. The results are shown in the following table.

[0303] (Formation of through-hole)

[0304] The obtained curable resin composition was applied on a substrate having an ITO film by spin coating and pre-baked on a hot plate at 90°C for 120 seconds to form a coating film. Next, a rectangular contact hole pattern (hole pitch 200 μm / size 50 μm×50 μm) for negative film was used and the reaction mixture was heated at 150 mJ / cm 2 Irradiate with light from an ultra-high pressure mercury lamp (illuminance at 365 nm: 20 mW / cm 2 ). Next, the substrate was developed using 2.38% tetramethylammonium hydroxide (TMAH) for 30 seconds and heated at 120° C. for 30 minutes, thereby preparing a substrate with a cured film having a film thickness of 2.0 μm.

[0305] The cross section of the obtained cured film-attached substrate was observed with a laser microscope (manufactured by LASERTEC, product name: OPTELICS HYBRID), and each evaluation was performed based on the following criteria.

[0306] 〔Opening of through hole〕

[0307] A: The through hole penetrates to the substrate.

[0308] C: The membrane was confirmed at the bottom of the well, but no opening was observed.

[0309] 〔Migration Evaluation〕

[0310] A substrate with a cured film was prepared by the same method as the above-mentioned substrate with a cured film except that a substrate with copper wiring patterned into a comb shape was used and no through-holes were provided. The resistance value of the obtained substrate with a cured film after heating for 300 hours under the conditions of 85°C and 85%RH was observed using an insulation degradation characteristic evaluation tester (manufactured by Kusumoto Chemicals Co., Ltd., product name SIR13), and each evaluation was performed according to the following criteria.

[0311] A: 1.0E+10(1.0×10 10 )Ω or more

[0312] B: 5.0E+9(5.0×10 9 )Ω or more

[0313] C: less than 5.0E+9 (5.0×10 9 )Ω

[0314] According to the obtained results, it was confirmed that in Comparative Example 1 in which the thermosetting alkali-soluble resin (A1) of the present embodiment was not used, and in Comparative Example 3 in which the (meth)acrylic monomer (B2) was used instead of the (meth)acrylic monomer (B1), the migration resistance was high, but on the other hand, the through-holes were not penetrated. In addition, it was confirmed that in Comparative Example 2 in which the silane compound (C) was not used, the through-holes were penetrated, but on the other hand, the migration resistance was low.

[0315] On the other hand, the through-holes of the examples using the curable composition of the present embodiment were penetrated, and high migration resistance was confirmed. Therefore, it can be seen that the curable composition of the examples has both high patterning accuracy and high migration resistance.

[0316] Explanation of symbols

[0317] 10: Glass substrate, X12: Jumper, Y12: Connector, 14: Insulating film, 16: Insulating protective layer, X1-X3, Y1-Y4: ITO electrodes, X34: Connector, K1, K5: ITO film / insulating film interface, K2: ITO film / protective film interface, K3, K4: Glass substrate / ITO film interface

[0318] The disclosed contents of Japanese Patent Application No. 2022-106885 filed on July 1, 2022 are incorporated into this specification by reference in their entirety.

[0319] In addition, all documents, patent applications, and technical standards described in the specification are incorporated herein by reference to the same extent as if each document, patent application, and technical standard was specifically and individually described as being incorporated by reference.

Claims

1. A curable resin composition comprising: Thermosetting alkali-soluble resin A1 having an acid value of 55 to 100 mgKOH / g, A photocurable alkali-soluble resin A2 having an acid value of 20 to 100 mgKOH / g, a (meth)acrylic monomer B1 having two polymerizable functional groups and a ring structure between the two polymerizable functional groups, and A silane compound C represented by the following formula (1) or (2); In the formula, R 1 ~R 3 may be the same or different, all or at least one of which is an alkoxy group having 1 to 5 carbon atoms, and the others are alkyl groups having 1 to 5 carbon atoms, R 4 ~R 6 may be the same or different, and are alkoxy groups having 1 to 5 carbon atoms or alkyl groups having 1 to 5 carbon atoms, A is a substituted or unsubstituted straight-chain or branched alkylene group having 2 to 18 carbon atoms, and may contain a divalent or trivalent linking group, B is a substituted or unsubstituted straight-chain or branched alkylene group having 2 to 15 carbon atoms, and may contain a divalent linking group, X is O, NH, NH-CO-NH or S, p is an integer of 0 or 1, q is an integer of 1 to 3, r is an integer of 1 to 3, s is an integer of 1 to 3, and t is an integer of 1 to 3.

2. The curable resin composition according to claim 1, wherein The thermosetting alkali-soluble resin A1 has an acid group and a cyclic ether group.

3. The curable resin composition according to claim 1, wherein The thermosetting alkali-soluble resin A1 contains at least the following units (a1-1) and (a1-2), In formula (a1-1), R 1 represents a hydrogen atom or a methyl group, X 1 represents a single bond, or a linear or cyclic aliphatic hydrocarbon group having 1 to 15 carbon atoms which may contain an oxygen atom. In the formula (a1-2), R 1 represents a hydrogen atom or a methyl group, R 3 It represents a linear or branched aliphatic hydrocarbon group having 3 to 15 carbon atoms which has a cyclic ether structure and may contain an oxygen atom.

4. The curable resin composition according to claim 3, wherein The thermosetting alkali-soluble resin A1 further comprises the following unit (a1-3), In the formula, R 1 represents a hydrogen atom or a methyl group, R 4 It represents at least one selected from a linear, branched or cyclic aliphatic hydrocarbon group having 1 to 20 carbon atoms which may contain an oxygen atom, an aromatic group, and a combination thereof.

5. The curable resin composition according to claim 1, wherein At least one of the thermosetting alkali-soluble resin A1 and the photocurable alkali-soluble resin A2 has a cyclic group.

6. The curable resin composition according to claim 1, wherein The weight average molecular weight of at least one of the thermosetting alkali-soluble resin A1 and the photocurable alkali-soluble resin A2 is 30,000 or less.

7. The curable resin composition according to claim 1, wherein The photocurable alkali-soluble resin A2 contains at least the following units (a2-1) and (a2-2), In unit (a2-1), R 1 Each independently represents a hydrogen atom or a methyl group, R 5 represents a chain, branched or cyclic aliphatic hydrocarbon group having 2 to 15 carbon atoms which may contain a hetero atom. In the unit (a2-2), R 1 represents a hydrogen atom or a methyl group, X 1 It represents a single bond or a linear or cyclic aliphatic hydrocarbon group having 1 to 15 carbon atoms which may contain an oxygen atom.

8. The curable resin composition according to claim 7, wherein The photocurable alkali-soluble resin A2 further comprises the following unit (a2-3), In the formula, R 1 represents a hydrogen atom or a methyl group, R 4 It represents at least one selected from a linear, branched or cyclic aliphatic hydrocarbon group having 1 to 20 carbon atoms which may contain an oxygen atom, an aromatic group, and a combination thereof.

9. The curable resin composition according to claim 1, wherein The ring structure in the (meth)acrylic monomer B1 includes any one selected from an aliphatic hydrocarbon group having 6 to 26 carbon atoms which may contain an oxygen atom, an aromatic hydrocarbon group having 6 to 26 carbon atoms which may contain an oxygen atom, and a combination thereof.

10. The curable resin composition according to claim 1, wherein The mass ratio A:B of the total amount A of the thermosetting alkali-soluble resin A1 and the photocurable alkali-soluble resin A2 to the total amount B of the multifunctional (meth)acrylic monomer B including the (meth)acrylic monomer B1 is 100:40-80. 11 . The curable resin composition according to claim 1 , which is used for forming an insulating film. 12 . An insulating cured film obtained by curing the curable resin composition according to claim 1 . 13 . An insulating cured film for a touch panel, which is obtained by curing the curable resin composition according to claim 1 . 14 . A touch panel comprising the insulating cured film for a touch panel according to claim 13 .

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