Photosensitive resin composition, transfer film, cured film, laminate, and method for producing touch panel

Abstract

The present invention provides a photosensitive resin composition having a low moisture permeability and excellent bending resistance of the obtained cured film, and a method for producing a transfer film, a cured film, a laminate, and a touch panel using the photosensitive resin composition. The photosensitive resin composition contains a binder polymer having an I / O value of 0.5 or more and 0.7 or less, an ethylenically unsaturated compound, and a photopolymerization initiator, wherein the ethylenically unsaturated compound includes a compound A represented by the following formula (1). In formula (1), Q 1 and Q 2 Each independently represents a (meth)acryloyloxy group, R 1 represents a divalent linking group having a chain structure. 2 ‑R 1 ‑Q 1 Formula (1)

Description

Technical Field

[0001] The present invention relates to a photosensitive resin composition, a transfer film, a cured film, a laminate and a method for producing a touch panel. Background Art

[0002] In recent years, touch input devices have been installed on the surfaces of liquid crystal displays (LCDs) and other electronic devices such as mobile phones, car navigation systems, personal computers, ticket vending machines, and bank terminals. In these electronic devices, by referring to a pointing image displayed on the image display area of ​​the LCD device and touching the area where the pointing image is displayed with a finger or a stylus, information corresponding to the pointing image can be input.

[0003] Input devices such as the above (hereinafter also referred to as "touch panels") include resistive film and electrostatic capacitance types. Electrostatic capacitance input devices have the advantage of requiring only a light-transmitting conductive film formed on a single substrate. Examples of such electrostatic capacitance input devices include devices that extend electrode patterns in intersecting directions and detect changes in capacitance between electrodes when a finger or the like touches the input position.

[0004] In capacitive input devices, a transparent resin layer is provided on the side opposite to the surface where input is performed with a finger, etc., to protect the electrode pattern and the routing wiring (e.g., metal wiring such as copper wire) contained within the frame. A photosensitive resin composition is used to form this transparent resin layer.

[0005] Examples of the photosensitive resin composition include compositions described in Patent Documents 1 to 3.

[0006] Patent Document 1 describes a touch panel electrode protective film-forming composition characterized by containing a compound represented by Formula 1 as component A, a binder polymer as component B, and a photopolymerization initiator as component C.

[0007] Q 2 -R 1 -Q 1 (1)

[0008] In formula (1), Q 1 and Q 2 Each independently represents a (meth)acryloyloxy group or a (meth)acryloyloxyalkyl group, R 1 represents a divalent hydrocarbon group.

[0009] Patent Document 2 describes a photosensitive resin composition for an insulating film, characterized in that it comprises (A) an alkali-soluble resin, (B) a photocurable monomer, (C) a photopolymerization initiator, and (D) a solvent, wherein the alkali-soluble resin (A) contains a resin (a) having repeating units derived from (meth)acrylic acid, the content of the aromatic group-containing repeating units in the resin (a) is 40 mol% or less, and the photocurable monomer (B) contains a compound having two or three (meth)acryloyloxy groups linked by a divalent aliphatic group that can be interrupted by an oxygen atom.

[0010] Patent document 3 describes a photocurable composition for molding, which is characterized in that it contains a polymer compound (A), a reactive diluent (B), and a photopolymerization initiator (C), wherein the polymer compound (A) contains a structural unit composed of a compound of the following formula (1) and / or a structural unit composed of a compound of the following formula (2) as a structural unit, the total weight of the compound of the above formula (1) and / or the compound of the above formula (2) is 60% by weight or more of the total weight of the polymer compound (A), and the reactive diluent (B) contains the compound of the above formula (1) and / or the compound of the above formula (2).

[0011] [Chemical Formula 1]

[0012]

[0013] [Chemical Formula 2]

[0014]

[0015] Previous technical literature

[0016] Patent Literature

[0017] Patent Document 1: Japanese Patent Application Laid-Open No. 2016-51470

[0018] Patent Document 2: Japanese Patent Application Laid-Open No. 2017-173525

[0019] Patent Document 3: International Publication No. 2014 / 148148 Summary of the Invention

[0020] Technical issues to be solved by the invention

[0021] An object of one embodiment of the present invention is to provide a photosensitive resin composition having low moisture permeability and excellent flex resistance in the resulting cured film.

[0022] Furthermore, another embodiment of the present invention aims to provide a method for producing a transfer film, a cured film, a laminate, and a touch panel using the photosensitive resin composition.

[0023] Means for solving technical problems

[0024] Means for solving the above-mentioned problems include the following aspects.

[0025] <1> A photosensitive resin composition comprising a binder polymer P having an I / O value of 0.5 or more and 0.7 or less, an ethylenically unsaturated compound, and a photopolymerization initiator, wherein the ethylenically unsaturated compound includes a compound A represented by the following formula (1).

[0026] Q 2 -R 1 -Q 1 Formula (1)

[0027] In formula (1), Q 1 and Q 2 Each independently represents a (meth)acryloyloxy group, R 1 It represents a divalent linking group having a chain structure.

[0028] <2> The photosensitive resin composition according to <1>, wherein

[0029] The binder polymer P has a structural unit represented by the following formula (S).

[0030] [Chemical Formula 3]

[0031]

[0032] <3> The photosensitive resin composition according to <1> or <2>, wherein

[0033] The binder polymer P has a structural unit represented by the following formula (Cy).

[0034] [Chemical Formula 4]

[0035]

[0036] In formula (Cy), R M represents a hydrogen atom or a methyl group, R Cy It represents a monovalent group having an aliphatic hydrocarbon ring structure.

[0037] <4> The photosensitive resin composition according to any one of <1> to <3>, wherein

[0038] The binder polymer P has a structural unit represented by the following formula (S) and a structural unit represented by the following formula (Cy).

[0039] The molar amount nS of the structural unit represented by the following formula (S) and the molar amount nCy of the structural unit represented by the following formula (Cy) in the binder polymer P satisfy the relationship represented by the following formula (SCy).

[0040] 0.2≤nS / (nS+nCy)≤0.8 Formula (SCy)

[0041] [Chemical Formula 5]

[0042]

[0043] In formula (Cy), R M represents a hydrogen atom or a methyl group, R Cy It represents a monovalent group having an aliphatic hydrocarbon ring structure.

[0044] <5> The photosensitive resin composition according to <3> or <4>, wherein the aliphatic hydrocarbon ring structure is a tetrahydrodicyclopentadiene ring structure.

[0045] <6> The photosensitive resin composition according to any one of <1> to <5>, wherein the content of the compound A is M A The content M of the above-mentioned binder polymer P P The mass ratio M A / M P It is 0.10~0.30.

[0046] <7> The photosensitive resin composition according to any one of <1> to <6>, wherein the R 1 is an alkylene group, an alkyleneoxyalkylene group or a polyalkyleneoxyalkylene group.

[0047] <8> The photosensitive resin composition according to any one of <1> to <7>, wherein the R 1 It is a straight-chain alkylene group having 6 to 18 carbon atoms.

[0048] <9> The photosensitive resin composition according to any one of <1> to <8>, which is a photosensitive resin composition for forming a protective film in a touch panel.

[0049] <10> A transfer film comprising: a temporary support; and a photosensitive layer composed of the photosensitive resin composition according to any one of <1> to <9> or formed by drying the photosensitive resin composition.

[0050] <11> A cured film obtained by curing the photosensitive resin composition according to any one of <1> to <9>.

[0051] <12> A laminate comprising a substrate and a cured film formed by curing the photosensitive resin composition according to any one of <1> to <9>.

[0052] <13> A method for manufacturing a touch panel, comprising the following steps:

[0053] A touch panel substrate having a surface on which at least one of touch panel electrodes and touch panel wiring is arranged is prepared; a photosensitive layer composed of a photosensitive resin composition described in any one of <1> to <9> or a photosensitive layer obtained by drying the photosensitive resin composition is formed on the surface of the touch panel substrate on which at least one of the touch panel electrodes and touch panel wiring is arranged is formed; the photosensitive layer formed on the touch panel substrate is subjected to pattern exposure; and the pattern-exposed photosensitive layer is developed to obtain a protective film that protects at least a portion of at least one of the touch panel electrodes and touch panel wiring.

[0054] Effects of the Invention

[0055] According to one embodiment of the present invention, a photosensitive resin composition can be provided in which the obtained cured film has low moisture permeability and excellent flex resistance.

[0056] Furthermore, according to another embodiment of the present invention, there can be provided a method for producing a transfer film, a cured film, a laminate, and a touch panel using the photosensitive resin composition. BRIEF DESCRIPTION OF THE DRAWINGS

[0057] Figure 1 This is a schematic cross-sectional view showing an example of the transfer film according to the present invention.

[0058] Figure 2 This is a schematic cross-sectional view showing a first specific example of a touch panel to which a photosensitive layer including the photosensitive resin composition according to the present invention is applied.

[0059] Figure 3 This is a schematic cross-sectional view showing a second specific example of a touch panel to which a photosensitive layer including the photosensitive resin composition according to the present invention is applied.

[0060] Figure 4 It is a schematic cross-sectional view showing the state of a sample for bending resistance evaluation in the bending resistance evaluation. DETAILED DESCRIPTION

[0061] The following describes the present invention in detail. Although the following description of the components may be based on representative embodiments of the present invention, the present invention is not limited to such embodiments.

[0062] In addition, in the present invention, "to" indicating a numerical range is used to mean that the numerical values ​​described before and after it are included as the lower limit and the upper limit.

[0063] In the numerical ranges described in this specification, the upper limit or lower limit of one numerical range may be replaced by the upper limit or lower limit of another numerical range described in another stage. In addition, in the numerical ranges described in this specification, the upper limit or lower limit of the numerical range may be replaced by the value shown in the Examples.

[0064] Furthermore, in the notation of groups (atomic groups) in the present invention, the notation not indicating "substituted" or "unsubstituted" includes both groups (atomic groups) having no substituent and groups (atomic groups) having substituents. For example, "alkyl" includes not only alkyl groups having no substituent (unsubstituted alkyl groups) but also alkyl groups having substituents (substituted alkyl groups).

[0065] In the present invention, "mass %" and "weight %" have the same meaning, and "parts by mass" and "parts by weight" have the same meaning.

[0066] Furthermore, in the present invention, a combination of two or more preferred embodiments is a more preferred embodiment.

[0067] In the present invention, when a plurality of substances corresponding to each component are present in the composition, the amount of each component in the composition represents the total amount of the plurality of substances present in the composition unless otherwise specified.

[0068] In the present invention, the term "process" includes not only independent processes but also processes that cannot be clearly distinguished from other processes as long as the intended purpose of the process can be achieved.

[0069] In the present invention, “(meth)acrylic acid” is a concept encompassing both acrylic acid and methacrylic acid, “(meth)acrylate” is a concept encompassing both acrylate and methacrylate, and “(meth)acryloyl” is a concept encompassing both acryloyl and methacryloyl.

[0070] Unless otherwise specified, the weight average molecular weight (Mw) and number average molecular weight (Mn) in the present invention are molecular weights calculated using THF (tetrahydrofuran) as a solvent, a differential refractometer, and polystyrene as a standard substance in a gel permeation chromatography (GPC) analyzer using TSKgel GMHxL, TSKgel G4000HxL, or TSKgel G2000HxL (all trade names, manufactured by TOSOH CORPORATION) columns.

[0071] In the present invention, unless otherwise specified, the molecular weight of a compound having a molecular weight distribution is a weight average molecular weight.

[0072] In the present invention, unless otherwise specified, the ratio of the structural units of the polymer is a molar ratio.

[0073] In the present invention, unless otherwise specified, the refractive index is a value measured at a wavelength of 550 nm at 25° C. using an ellipsometer.

[0074] Hereinafter, the present invention will be described in detail.

[0075] (Photosensitive resin composition)

[0076] The photosensitive resin composition of the present invention contains a binder polymer P having an I / O value of 0.5 to 0.7, an ethylenically unsaturated compound, and a photopolymerization initiator. The ethylenically unsaturated compound includes a compound A represented by the following formula (1).

[0077] Q 2 -R 1 -Q 1 Formula (1)

[0078] In formula (1), Q 1 and Q 2 Each independently represents a (meth)acryloyloxy group, R 1 It represents a divalent linking group having a chain structure.

[0079] The photosensitive resin composition of the present invention is preferably used as a photosensitive resin composition for touch panels, more preferably as a photosensitive composition for forming a protective film in touch panels, and particularly preferably as a photosensitive composition for forming an electrode protective film in touch panels, because the resulting cured film has low moisture permeability and excellent flex resistance.

[0080] As a result of intensive research, the present inventors have found that by adopting the above-mentioned structure, a photosensitive resin composition can be provided in which the obtained cured film has low moisture permeability and excellent flex resistance.

[0081] The mechanism of action of the excellent effects described above is not yet clear, but is presumed to be as follows.

[0082] That is, it is speculated that by including the binder polymer P having an I / O value of 0.5 or more and 0.7 or less and the compound represented by the above formula (1), in the cured film formed by curing the photosensitive resin composition, the meshes in the three-dimensional cross-linked structure become larger, and the flexibility is excellent, so that the obtained cured film has excellent bending resistance. Moreover, by using a relatively hydrophobic binder polymer having an I / O value in the above range, as described above, even if the meshes in the three-dimensional cross-linked structure are large, the permeability of water can be suppressed, and the moisture permeability of the obtained cured film can be reduced.

[0083] <Compound A>

[0084] The photosensitive resin composition according to the present invention contains an ethylenically unsaturated compound. The ethylenically unsaturated compound includes a compound A represented by the following formula (1) (also simply referred to as "compound A").

[0085] Q 2 -R 1 -Q 1 Formula (1)

[0086] In formula (1), Q 1 and Q 2 Each independently represents a (meth)acryloyloxy group, R 1 It represents a divalent linking group having a chain structure.

[0087] From the viewpoint of ease of synthesis, Q in formula (1) 1 and Q 2 The same groups are preferred.

[0088] Furthermore, from the viewpoint of reactivity, Q in formula (1) 1 and Q 2 An acryloyloxy group is preferred.

[0089] From the viewpoint of the bending resistance of the obtained cured film, R in formula (1) 1 Preferably, alkylene, alkyleneoxyalkylene (-L 1 -OL 1 -), or polyalkyleneoxyalkylene (-(L 1 -O) p -L 1-), more preferably a hydrocarbon group or polyalkyleneoxyalkylene group having 2 to 20 carbon atoms, further preferably an alkylene group having 4 to 20 carbon atoms, and particularly preferably a linear alkylene group having 6 to 18 carbon atoms. The hydrocarbon group may have a chain structure at least in part, and may be, for example, linear, branched, cyclic, or any combination thereof. From the viewpoint of the flex resistance of the resulting cured film, an alkylene group or a group combining two or more alkylene groups and one or more arylene groups is preferred, an alkylene group is more preferred, and a linear alkylene group is particularly preferred.

[0090] In addition, the above L 1 Each independently represents an alkylene group, preferably a vinyl group, a propylene group, or a butylene group, more preferably a vinyl group or a 1,2-propylene group. p represents an integer of 2 or greater, preferably an integer of 2 to 10.

[0091] Furthermore, from the viewpoint of moisture permeability and flexural resistance of the obtained cured film, the linking Q in compound A is 1 and Q 2 The number of atoms in the shortest connecting chain between them is preferably 3 to 50, more preferably 4 to 40, further preferably 6 to 20, and particularly preferably 8 to 12.

[0092] In the present invention, "Connect Q 1 and Q 2 The number of atoms in the shortest link between the two atoms is the number of atoms in the shortest link between the two atoms. 1 R 1 The atoms in Q are connected to the atoms in 2 R 1 The shortest atomic number of the atoms in the .

[0093] Specific examples of compound A include 1,3-butanediol di(meth)acrylate, tetramethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,7-heptanediol di(meth)acrylate, 1,8-octanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, 1,4-cyclohexanediol di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, di(meth)acrylate of hydrogenated bisphenol A, di(meth)acrylate of hydrogenated bisphenol F, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, poly(ethylene glycol / propylene glycol) di(meth)acrylate, and polybutylene glycol di(meth)acrylate. These ester monomers may also be used as a mixture.

[0094] From the viewpoint of the flex resistance of the obtained cured film, among the above compounds, at least one compound selected from the group consisting of 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, and neopentyl glycol di(meth)acrylate is preferred. At least one compound selected from the group consisting of 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, and 1,10-decanediol di(meth)acrylate is more preferred. At least one compound selected from the group consisting of 1,9-nonanediol di(meth)acrylate and 1,10-decanediol di(meth)acrylate is particularly preferred.

[0095] Compound A may be used alone or in combination of two or more.

[0096] From the viewpoint of moisture permeability and flex resistance of the obtained cured film, the content of compound A is preferably 10% by mass to 90% by mass, more preferably 15% by mass to 70% by mass, further preferably 20% by mass to 50% by mass, and particularly preferably 25% by mass to 35% by mass, relative to the total mass of the ethylenically unsaturated compounds in the photosensitive resin composition.

[0097] In addition, the ethylenically unsaturated compound in the present invention refers to a compound having a (weight average) molecular weight of 10,000 or less and having an ethylenically unsaturated group.

[0098] From the viewpoint of moisture permeability and flex resistance of the obtained cured film, the content of compound A is preferably 1% by mass to 30% by mass, more preferably 3% by mass to 25% by mass, further preferably 5% by mass to 20% by mass, and particularly preferably 6% by mass to 14.5% by mass, relative to the total solid content in the photosensitive resin composition.

[0099] In addition, the total solid content in the photosensitive resin composition in the present invention means the amount of volatile components excluding the solvent and the like.

[0100] <Binder polymer P>

[0101] The photosensitive resin composition according to the present invention contains a binder polymer P (hereinafter also referred to as “binder polymer P”) having an I / O value of 0.5 or more and 0.7 or less.

[0102] From the viewpoint of the moisture permeability of the obtained cured film and the adhesiveness of the obtained uncured film, the I / O value of the binder polymer P is preferably 0.50 to 0.67, more preferably 0.50 to 0.65, and particularly preferably 0.52 to 0.64.

[0103] The I / O value is a value that represents the polarity of various organic compounds, referred to as the (inorganicity value) / (organicity value), in terms of organic concepts. It is one of the functional group assignment methods used to set parameters for each functional group. Specifically, the I / O value is described in detail in Organic Concept Diagram (written by Yoshio Koda, Sankyo Publishing (1984)); Kumamoto Pharmaceutical Bulletin, Vol. 1, pp. 1-16 (1954); Chemical Field, Vol. 11, No. 10, pp. 719-725 (1957); Fragrance Journal, No. 34, pp. 97-111 (1979); and Fragrance Journal, No. 50, pp. 79-82 (1981).

[0104] The concept of the I / O value is to divide the properties of a compound into organic groups exhibiting covalent bonding and inorganic groups exhibiting ionic bonding, and to express them by positioning all organic compounds on rectangular coordinates designated as the organic axis and the inorganic axis.

[0105] The above-mentioned inorganic value is a numerical value that quantifies the influence of various substituents and bonds on the boiling point of an organic compound, using the hydroxyl group as the reference. Specifically, if the distance between the boiling point curve of a straight-chain alcohol and the boiling point curve of a straight-chain alkane is approximately 100°C, then the influence of one hydroxyl group is set to 100. Based on this value, the influence of various substituents and bonds on the boiling point is quantified to obtain the inorganic value of the substituents in the organic compound. For example, the inorganic value of the -COOH group is 150, and the inorganic value of a double bond is 2. Therefore, the inorganic value of a particular organic compound refers to the sum of the inorganic values ​​of the various substituents and bonds in the compound.

[0106] The organicity value is determined based on the influence of the carbon atom representing the methylene group within the molecule on the boiling point. For example, the average boiling point increase caused by the addition of a single carbon atom to a linear saturated hydrocarbon with 5 to 10 carbon atoms is 20°C. Based on this, the organicity value of one carbon atom is set to 20. Based on this value, the influence of various substituents and bonds on the boiling point is quantified as the organicity value. For example, the organicity value of the nitro group (-NO2) is 70.

[0107] The closer the I / O value is to 0, the more non-polar the organic compound is (hydrophobicity and strong organicity), and the larger the I / O value is, the more polar the organic compound is (hydrophilicity and strong inorganicity).

[0108] In the present invention, when calculating the I / O value of the binder polymer, the I value and the O value in each structural unit of the binder polymer are calculated and the value is calculated by the following formula.

[0109] The various values ​​in the adhesive polymer are set as follows: that is, the I value of structural unit a: IMa, the O value of structural unit a: OMa, the content of structural unit a relative to the entire adhesive polymer: αmol%, the I value of structural unit b: IMb, the O value of structural unit b: OMb, the content of structural unit b relative to the entire adhesive polymer: βmol%, the I value of structural unit c: IMc, the O value of structural unit c: OMc, the content of structural unit c relative to the entire adhesive polymer: γmol%, and the I / O value of the adhesive polymer is calculated by the following formula.

[0110] I / O of the binder polymer = (IMaxα+IMbxβ+IMcxγ+...) / (OMaxα+OMbxβ+OMcxγ+...)

[0111] The binder polymer is preferably an alkali-soluble resin.

[0112] For example, from the viewpoint of developability, the binder polymer is preferably a binder polymer having an acid value of 60 mgKOH / g or more, and more preferably an alkali-soluble resin having an acid value of 60 mgKOH / g or more.

[0113] In the present invention, "alkali-soluble" means that the solubility in a 1% by mass aqueous solution of sodium carbonate at 22°C is 0.1% by mass or more.

[0114] Furthermore, for example, from the viewpoint of easily forming a strong film by thermal cross-linking with the cross-linking component by heating, the binder polymer is further preferably a resin having a carboxyl group (so-called carboxyl-containing resin) having an acid value of 60 mgKOH / g or more, and is particularly preferably an acrylic resin having a carboxyl group (so-called carboxyl-containing acrylic resin) having an acid value of 60 mgKOH / g or more.

[0115] In the present invention, acrylic resin refers to a resin having a structural unit derived from a (meth)acrylic compound, and the content of the structural unit is preferably 30% by mass or more, more preferably 50% by mass or more, based on the total mass of the resin.

[0116] From the viewpoints of the moisture permeability and flex resistance of the obtained cured film and the adhesiveness of the obtained uncured film, the binder polymer P is preferably an acrylic resin or a styrene-acrylic acid copolymer, and more preferably a styrene-acrylic acid copolymer.

[0117] In the present invention, the styrene-acrylic acid copolymer refers to a resin having structural units derived from a styrene compound and structural units derived from a (meth)acrylic acid compound. The total content of the structural units derived from the styrene compound and the structural units derived from the (meth)acrylic acid compound is preferably 30% by mass or more, more preferably 50% by mass or more, relative to the total mass of the copolymer.

[0118] Furthermore, the content of the structural unit derived from the styrene compound is preferably 1% by mass or more, more preferably 5% by mass or more, and particularly preferably 5% by mass or more and 80% by mass or less, relative to the total mass of the copolymer.

[0119] The content of the structural unit derived from the (meth)acrylic acid compound is preferably 5% by mass or more, more preferably 10% by mass or more, and particularly preferably 20% by mass or more and 95% by mass or less, based on the total mass of the copolymer.

[0120] Examples of the (meth)acrylic compound include (meth)acrylate compounds, (meth)acrylic acid, (meth)acrylamide compounds, and (meth)acrylonitrile. Among these, at least one compound selected from the group consisting of (meth)acrylate compounds and (meth)acrylic acid is also preferred.

[0121] -Structural unit having an aromatic ring-

[0122] From the viewpoint of the moisture permeability and strength of the obtained cured film, the binder polymer P preferably contains a structural unit having an aromatic ring.

[0123] Examples of the monomer that forms the structural unit having an aromatic ring include styrene, tert-butoxystyrene, methylstyrene, α-methylstyrene, and benzyl (meth)acrylate.

[0124] Among them, styrene compounds are preferred, and styrene is particularly preferred.

[0125] From the viewpoint of the moisture permeability and strength of the obtained cured film, the binder polymer P more preferably has a structural unit represented by the following formula (S) (structural unit derived from styrene).

[0126] [Chemical Formula 6]

[0127]

[0128] From the viewpoint of moisture permeability and strength of the obtained cured film, when the binder polymer P contains a structural unit having an aromatic ring, the content of the structural unit having an aromatic ring is preferably 5% by mass to 90% by mass, more preferably 10% by mass to 70% by mass, and particularly preferably 20% by mass to 50% by mass relative to the total mass of the binder polymer P.

[0129] Furthermore, from the viewpoint of moisture permeability and strength of the obtained cured film, the content of the structural unit having an aromatic ring in the binder polymer P is preferably 5 mol% to 70 mol%, more preferably 10 mol% to 60 mol%, and particularly preferably 20 mol% to 50 mol%, relative to the total amount of the binder polymer P.

[0130] Furthermore, from the viewpoint of moisture permeability and strength of the obtained cured film, the content of the structural unit represented by the above formula (S) in the binder polymer P is preferably 5 mol% to 70 mol%, more preferably 10 mol% to 60 mol%, and particularly preferably 20 mol% to 50 mol%, relative to the total amount of the binder polymer P.

[0131] In the present invention, when the content of a "structural unit" is specified by molar ratio, the "structural unit" has the same meaning as the "monomer unit." Furthermore, in the present invention, the "monomer unit" may be modified after polymerization, such as by a polymer reaction. This also applies hereinafter.

[0132] -Structural unit having an aliphatic hydrocarbon ring-

[0133] From the viewpoint of the strength of the obtained cured film and the adhesiveness of the obtained uncured film, the binder polymer P preferably contains a structural unit having an aliphatic hydrocarbon ring.

[0134] Examples of the aliphatic hydrocarbon ring in the structural unit having an aliphatic hydrocarbon ring include a tricyclodecane ring, a cyclohexane ring, a cyclopentane ring, a norbornane ring, and an isophorone ring.

[0135] Among these, from the viewpoint of the strength of the obtained cured film and the adhesiveness of the obtained uncured film, a ring formed by condensing two or more aliphatic hydrocarbon rings is preferred, and a tetrahydrodicyclopentadiene ring (tricyclo[5.2.1.0 2,6 ]decane ring).

[0136] Examples of the monomer that forms the structural unit having an aliphatic hydrocarbon ring include dicyclopentanyl (meth)acrylate, cyclohexyl (meth)acrylate, and isobornyl (meth)acrylate.

[0137] From the viewpoint of the strength of the obtained cured film and the adhesiveness of the obtained uncured film, the binder polymer P more preferably has a structural unit represented by the following formula (Cy), and particularly preferably has a structural unit represented by the above formula (S) and a structural unit represented by the following formula (Cy).

[0138] [Chemical Formula 7]

[0139]

[0140] In formula (Cy), R M represents a hydrogen atom or a methyl group, R Cy It represents a monovalent group having an aliphatic hydrocarbon ring structure.

[0141] R in formula (Cy) M Preferred is methyl.

[0142] From the viewpoint of the strength of the obtained cured film and the adhesiveness of the obtained uncured film, R in the formula (Cy) Cy It is preferably a monovalent group having an aliphatic hydrocarbon ring structure having 5 to 20 carbon atoms, more preferably a monovalent group having an aliphatic hydrocarbon ring structure having 6 to 16 carbon atoms, and particularly preferably a monovalent group having an aliphatic hydrocarbon ring structure having 8 to 14 carbon atoms.

[0143] From the viewpoint of the strength of the obtained cured film and the adhesiveness of the obtained uncured film, R in formula (Cy) Cy The aliphatic hydrocarbon ring structure in is preferably a cyclopentane ring structure, a cyclohexane ring structure, a tetrahydrodicyclopentadiene ring structure, a norbornane ring, or an isophorone ring, more preferably a cyclohexane ring structure or a tetrahydrodicyclopentadiene ring structure, and particularly preferably a tetrahydrodicyclopentadiene ring structure.

[0144] Furthermore, from the viewpoint of the strength of the obtained cured film and the adhesiveness of the obtained uncured film, R in the formula (Cy) Cy The aliphatic hydrocarbon ring structure in is preferably a ring structure in which two or more aliphatic hydrocarbon rings are condensed, and more preferably a ring structure in which two or more and four or less aliphatic hydrocarbon rings are condensed.

[0145] Furthermore, from the viewpoint of the strength of the obtained cured film and the adhesiveness of the obtained uncured film, R in the formula (Cy) is preferably Cy Preferred is a group in which the oxygen atom of -C(=O)O- in formula (Cy) is directly bonded to the aliphatic hydrocarbon ring structure, that is, an aliphatic hydrocarbon ring group, more preferably a cyclohexyl group or a dicyclopentyl group, and particularly preferably a dicyclopentyl group.

[0146] The binder polymer P may have a single type of structural unit having an aliphatic hydrocarbon ring, or may have two or more types.

[0147] From the viewpoint of moisture permeability and strength of the obtained cured film, when the binder polymer P contains a structural unit having an aliphatic hydrocarbon ring, the content of the structural unit having an aliphatic hydrocarbon ring is preferably 5% by mass to 90% by mass, more preferably 10% by mass to 80% by mass, and particularly preferably 20% by mass to 70% by mass, relative to the total mass of the binder polymer P.

[0148] Furthermore, from the viewpoint of moisture permeability and strength of the obtained cured film, the content of the structural unit having an aliphatic hydrocarbon ring in the binder polymer P is preferably 5 mol% to 70 mol%, more preferably 10 mol% to 60 mol%, and particularly preferably 20 mol% to 50 mol%, relative to the total amount of the binder polymer P.

[0149] Furthermore, from the viewpoint of moisture permeability and strength of the obtained cured film, the content of the structural unit represented by the above formula (Cy) in the binder polymer P is preferably 5 mol% to 70 mol%, more preferably 10 mol% to 60 mol%, and particularly preferably 20 mol% to 50 mol%, relative to the total amount of the binder polymer P.

[0150] From the viewpoint of moisture permeability, flex resistance, and strength of the obtained cured film, when the binder polymer P contains structural units having an aromatic ring and structural units having an aliphatic hydrocarbon ring, the total content of the structural units having an aromatic ring and the structural units having an aliphatic hydrocarbon ring is preferably 10% by mass to 90% by mass, more preferably 20% by mass to 80% by mass, and particularly preferably 40% by mass to 75% by mass, relative to the total mass of the binder polymer P.

[0151] Furthermore, from the viewpoint of moisture permeability and strength of the obtained cured film, the total content of the structural units having an aromatic ring and the structural units having an aliphatic hydrocarbon ring in the binder polymer is preferably 10 mol% to 80 mol%, more preferably 20 mol% to 70 mol%, and particularly preferably 40 mol% to 60 mol%, relative to the total amount of the binder polymer.

[0152] Furthermore, from the viewpoint of moisture permeability, flexural resistance, and strength of the obtained cured film, the total content of the structural unit represented by the above formula (S) and the structural unit represented by the above formula (Cy) in the binder polymer P is preferably 10 mol% to 80 mol%, more preferably 20 mol% to 70 mol%, and particularly preferably 40 mol% to 60 mol%, relative to the total amount of the binder polymer P.

[0153] Furthermore, from the viewpoint of moisture permeability, flexural resistance, and strength of the obtained cured film, the molar amount nS of the structural unit represented by the above formula (S) and the molar amount nCy of the structural unit represented by the above formula (Cy) in the binder polymer P preferably satisfy the relationship represented by the following formula (SCy), more preferably satisfy the following formula (SCy-1), and particularly preferably satisfy the following formula (SCy-2).

[0154] 0.2≤nS / (nS+nCy)≤0.8 Formula (SCy)

[0155] 0.30≤nS / (nS+nCy)≤0.75 formula (SCy-1)

[0156] 0.40≤nS / (nS+nCy)≤0.70 formula (SCy-2)

[0157] -Structural unit having an acid group-

[0158] From the viewpoint of the strength and developability of the obtained cured film, the binder polymer P preferably contains a structural unit having an acid group.

[0159] Examples of the acid group include a carboxyl group, a sulfonic acid group, a phosphonic acid group, and a phosphoric acid group, and a carboxyl group is preferred.

[0160] As the structural unit having the acid group, preferably, a structural unit derived from (meth)acrylic acid as shown below is mentioned, and more preferably, a structural unit derived from methacrylic acid is mentioned.

[0161] [Chemical Formula 8]

[0162]

[0163] The binder polymer P may have a single type of structural unit having an acid group, or may have two or more types.

[0164] From the viewpoint of the strength and developability of the obtained cured film, when the binder polymer P contains a structural unit having an acid group, the content of the structural unit having an acid group is preferably 5% by mass to 50% by mass, more preferably 5% by mass to 40% by mass, and particularly preferably 10% by mass to 30% by mass relative to the total mass of the binder polymer P.

[0165] Furthermore, from the viewpoint of the strength and developability of the obtained cured film, the content of the structural unit having an acid group in the binder polymer P is preferably 5 mol% to 70 mol%, more preferably 10 mol% to 50 mol%, and particularly preferably 20 mol% to 40 mol%, relative to the total amount of the binder polymer P.

[0166] Furthermore, from the viewpoint of the strength and developability of the obtained cured film, the content of the structural units derived from (meth)acrylic acid in the binder polymer P is preferably 5 mol% to 70 mol%, more preferably 10 mol% to 50 mol%, and particularly preferably 20 mol% to 40 mol%, relative to the total amount of the binder polymer P.

[0167] -Constituent unit having a reactive group-

[0168] From the viewpoint of the strength of the obtained cured film and the adhesiveness of the obtained uncured film, the binder polymer P preferably has a reactive group, and more preferably contains a structural unit having a reactive group.

[0169] The reactive group is preferably a radical polymerizable group, more preferably an ethylenically unsaturated group. When the binder polymer P has an ethylenically unsaturated group, the binder polymer P preferably contains a structural unit having an ethylenically unsaturated group in a side chain.

[0170] In the present invention, the “main chain” refers to the relatively longest bond chain in the molecules of the polymer compound constituting the resin, and the “side chain” refers to an atomic group branched from the main chain.

[0171] The ethylenically unsaturated group is preferably a (meth)acrylic group, and more preferably a (meth)acryloyloxy group.

[0172] Examples of the structural unit having a reactive group include the following structural units, but the present invention is not limited to these.

[0173] [Chemical Formula 9]

[0174]

[0175] The binder polymer P may have a single type of structural unit having a reactive group, or may have two or more types.

[0176] From the viewpoint of the strength of the obtained cured film and the adhesiveness of the obtained uncured film, when the binder polymer P contains a structural unit having a reactive group, the content of the structural unit having a reactive group is preferably 5% by mass to 70% by mass, more preferably 10% by mass to 50% by mass, and particularly preferably 20% by mass to 40% by mass, relative to the total mass of the binder polymer.

[0177] Furthermore, from the viewpoint of the strength of the obtained cured film and the adhesiveness of the obtained uncured film, the content of the structural unit having a reactive group in the binder polymer P is preferably 5 mol% to 70 mol%, more preferably 10 mol% to 60 mol%, and particularly preferably 20 mol% to 50 mol%, relative to the total amount of the binder polymer P.

[0178] Examples of methods for introducing reactive groups into the binder polymer P include reacting epoxy compounds, blocked isocyanate compounds, isocyanate compounds, vinyl sulfone compounds, aldehyde compounds, methylol compounds, carboxylic anhydride, and the like with hydroxyl groups, carboxyl groups, primary amino groups, secondary amino groups, acetoacetyl groups, sulfonic acids, and the like.

[0179] A preferred example of a method for introducing reactive groups into the binder polymer P is to synthesize a polymer having carboxyl groups by polymerization, and then react glycidyl (meth)acrylate with a portion of the carboxyl groups of the resulting polymer by polymer reaction to introduce (meth)acryloyloxy groups into the polymer. This method can produce a binder polymer having (meth)acryloyloxy groups on its side chains.

[0180] The polymerization reaction is preferably carried out at a temperature of 70°C to 100°C, more preferably at a temperature of 80°C to 90°C. The polymerization initiator used in the polymerization reaction is preferably an azo initiator, and more preferably V-601 (trade name) or V-65 (trade name) manufactured by FUJIFILM Wako Pure Chemical Corporation. The polymer reaction is preferably carried out at a temperature of 80°C to 110°C. In the polymer reaction, a catalyst such as an ammonium salt is preferably used.

[0181] Preferred examples of the binder polymer P include the following polymers: The content ratio (a to d) and weight average molecular weight Mw of each structural unit shown below can be appropriately changed depending on the intended purpose.

[0182] [Chemical Formula 10]

[0183]

[0184] [Chemical Formula 11]

[0185]

[0186] From the viewpoint of the strength of the obtained cured film and the adhesiveness of the obtained uncured film, the weight average molecular weight (Mw) of the binder polymer P is preferably 5,000 or more, more preferably 10,000 or more, further preferably 10,000 to 50,000, and particularly preferably 20,000 to 30,000.

[0187] The acid value of the binder polymer P is preferably 10 mgKOH / g to 200 mgKOH / g, more preferably 60 mgKOH / g to 200 mgKOH / g, further preferably 60 mgKOH / g to 150 mgKOH / g, and particularly preferably 60 mgKOH / g to 110 mgKOH / g.

[0188] The acid value of the binder polymer is a value measured according to the method described in JIS K0070:1992.

[0189] The photosensitive resin composition according to the present invention may contain only one type of binder polymer P, or may contain two or more types of binder polymers P.

[0190] For example, from the viewpoint of the strength of the cured film and the handleability in the transfer film, the content of the binder polymer P is preferably 10% by mass to 90% by mass, more preferably 20% by mass to 80% by mass, and even more preferably 30% by mass to 70% by mass relative to the total solid content of the photosensitive resin composition.

[0191] From the viewpoint of the moisture permeability and flexural resistance of the obtained cured film and the adhesiveness of the obtained uncured film, the content of the compound A in the photosensitive resin composition of the present invention is M A and the content M of the above-mentioned binder polymer P P The mass ratio M A / M P It is preferably 0.05 to 0.50, more preferably 0.08 to 0.40, further preferably 0.10 to 0.30, and particularly preferably 0.12 to 0.25.

[0192] <Other binder polymers>

[0193] The photosensitive resin composition according to the present invention may contain other binder polymers in addition to the binder polymer P.

[0194] The other binder polymer is preferably an alkali-soluble resin.

[0195] Furthermore, from the viewpoint of developability, the other binder polymer is preferably a binder polymer having an acid value of 60 mgKOH / g or higher, and more preferably an alkali-soluble resin having an acid value of 60 mgKOH / g or higher.

[0196] Furthermore, for example, from the viewpoint of easily forming a strong film by thermal cross-linking with the cross-linking component by heating, other binder polymers are further preferably resins having a carboxyl group (so-called carboxyl-containing resins) with an acid value of 60 mgKOH / g or more, and particularly preferably acrylic resins having a carboxyl group (so-called carboxyl-containing acrylic resins) with an acid value of 60 mgKOH / g or more.

[0197] When the binder polymer is a resin having carboxyl groups, for example, thermal crosslinking by adding blocked isocyanate can increase the three-dimensional crosslinking density. Furthermore, if the carboxyl groups of the resin having carboxyl groups are dehydrated and hydrophobized, the moist heat resistance can be improved.

[0198] The carboxyl group-containing acrylic resin having an acid value of 60 mgKOH / g or more is not particularly limited as long as the above-mentioned acid value conditions are satisfied, and can be appropriately selected from known acrylic resins for use.

[0199] For example, carboxyl-containing acrylic resins having an acid value of 60 mgKOH / g or higher among polymers described in paragraph 0025 of JP-A-2011-95716 and carboxyl-containing acrylic resins having an acid value of 60 mgKOH / g or higher among polymers described in paragraphs 0033 to 0052 of JP-A-2010-237589 can be preferably used.

[0200] The photosensitive resin composition of the present invention may also contain a polymer containing a structural unit having a carboxylic acid anhydride structure (hereinafter also referred to as "polymer B") as another binder polymer. The inclusion of the specific polymer B in the photosensitive resin composition can improve developability and strength after curing.

[0201] The carboxylic acid anhydride structure may be either a chain carboxylic acid anhydride structure or a cyclic carboxylic acid anhydride structure, and is preferably a cyclic carboxylic acid anhydride structure.

[0202] The ring of the cyclic carboxylic acid anhydride structure is preferably a 5- to 7-membered ring, more preferably a 5-membered ring or a 6-membered ring, and particularly preferably a 5-membered ring.

[0203] The structural unit having a carboxylic acid anhydride structure is preferably a structural unit containing in the main chain a divalent group obtained by removing two hydrogen atoms from a compound represented by the following formula P-1, or a structural unit in which a monovalent group obtained by removing one hydrogen atom from a compound represented by the following formula P-1 is bonded to the main chain directly or via a divalent linking group.

[0204] [Chemical Formula 12]

[0205]

[0206] In formula P-1, R A1a represents a substituent, n 1a R A1a Can be the same or different, Z 1a represents a divalent group forming a ring containing -C(=O)-OC(=O)-, n 1a Indicates an integer greater than 0.

[0207] As RA1a Examples of the substituent represented by include an alkyl group.

[0208] As Z 1a , preferably an alkylene group having 2 to 4 carbon atoms, more preferably an alkylene group having 2 or 3 carbon atoms, and particularly preferably an alkylene group having 2 carbon atoms.

[0209] n 1a Indicates an integer greater than 0. 1a In the case of an alkylene group having 2 to 4 carbon atoms, n 1a It is preferably an integer of 0 to 4, more preferably an integer of 0 to 2, and particularly preferably 0.

[0210] In n 1a When representing an integer greater than 2, multiple R A1a Can be the same or different. A1a They may bond to each other to form a ring, but preferably do not bond to each other to form a ring.

[0211] The structural unit having a carboxylic acid anhydride structure is preferably a structural unit derived from an unsaturated carboxylic acid anhydride, more preferably a structural unit derived from an unsaturated cyclic carboxylic acid anhydride, further preferably a structural unit derived from an unsaturated aliphatic cyclic carboxylic acid anhydride, particularly preferably a structural unit derived from maleic anhydride or itaconic anhydride, and most preferably a structural unit derived from maleic anhydride.

[0212] Specific examples of the structural unit having a carboxylic acid anhydride structure are given below, but the structural unit having a carboxylic acid anhydride structure is not limited to these specific examples. In the following structural unit, Rx represents a hydrogen atom, a methyl group, a CH2OH group or a CF3 group, and Me represents a methyl group.

[0213] [Chemical Formula 13]

[0214]

[0215] [Chemical Formula 14]

[0216]

[0217] The structural unit having a carboxylic acid anhydride structure in the polymer B may be of a single type or of two or more types.

[0218] The total content of the structural units having a carboxylic acid anhydride structure is preferably 0 to 60 mol %, more preferably 5 to 40 mol %, and particularly preferably 10 to 35 mol %, based on the total amount of polymer B.

[0219] The photosensitive resin composition of the present invention may contain only one type of polymer B, or may contain two or more types of polymers B.

[0220] From the viewpoints of photocurability, developability, and the strength of the obtained cured film, when the photosensitive resin composition of the present invention contains polymer B, the content of polymer B is preferably 0.1% by mass to 30% by mass, more preferably 0.2% by mass to 20% by mass, further preferably 0.5% by mass to 20% by mass, and particularly preferably 1% by mass to 20% by mass, relative to the total solid content of the photosensitive resin composition.

[0221] From the viewpoint of the strength of the obtained cured film and the adhesiveness of the obtained uncured film, the weight average molecular weight (Mw) of the other binder polymer P is preferably 5,000 or more, more preferably 10,000 or more, further preferably 10,000 to 50,000, and particularly preferably 20,000 to 30,000.

[0222] The acid value of the other binder polymer is preferably 10 mgKOH / g to 200 mgKOH / g, more preferably 60 mgKOH / g to 200 mgKOH / g, further preferably 60 mgKOH / g to 150 mgKOH / g, and particularly preferably 60 mgKOH / g to 110 mgKOH / g.

[0223] The photosensitive resin composition according to the present invention may contain only one type of other binder polymer, or may contain two or more types of other binder polymers.

[0224] From the viewpoint of the moisture permeability of the obtained cured film and the adhesiveness of the obtained uncured film, the content of the binder polymer P in the photosensitive resin composition of the present invention is preferably 50% by mass or more, more preferably 80% by mass or more, further preferably 90% by mass or more, and particularly preferably 95% by mass or more, relative to the total mass of the binder polymer.

[0225] The content of other binder polymers in the photosensitive resin composition of the present invention is preferably equal to or less than the content of the binder polymer P, and more preferably less than the content of the binder polymer P, from the viewpoint of the moisture permeability of the obtained cured film and the adhesiveness of the obtained uncured film.

[0226] Furthermore, from the viewpoint of the moisture permeability of the obtained cured film and the adhesiveness of the obtained uncured film, the content of the other binder polymer in the photosensitive resin composition of the present invention is preferably 50% by mass or less, more preferably 20% by mass or less, further preferably 10% by mass or less, and particularly preferably 5% by mass or less, relative to the total mass of the binder polymer.

[0227] From the perspective of patterning properties and reliability, the content of residual monomers in each structural unit in the binder polymer P and other binder polymers is preferably 5,000 ppm by mass or less, more preferably 2,000 ppm by mass or less, and even more preferably 500 ppm by mass or less, relative to the total mass of the binder polymer having that structural unit. The lower limit is not particularly limited, but is preferably 1 ppm by mass or more, and more preferably 10 ppm by mass or more.

[0228] From the perspective of patterning properties and reliability, the residual monomer content of each structural unit of the binder polymer is preferably 3,000 ppm by mass or less, more preferably 600 ppm by mass or less, and even more preferably 100 ppm by mass or less, relative to the total mass of the photosensitive layer described below. While the lower limit is not particularly limited, it is preferably 0.1 ppm by mass or more, and more preferably 1 ppm by mass or more.

[0229] The residual monomer content of monomers when synthesizing a binder polymer by polymer reaction is also preferably within the above range. For example, when synthesizing a binder polymer by reacting glycidyl acrylate with a carboxylic acid side chain, the glycidyl acrylate content is preferably within the above range.

[0230] <Other ethylenically unsaturated compounds>

[0231] The photosensitive resin composition according to the present invention preferably contains an ethylenically unsaturated compound other than the compound A (other ethylenically unsaturated compound) as the ethylenically unsaturated compound.

[0232] In the photosensitive resin composition of the present invention, the ethylenically unsaturated compound contributes to photosensitivity (ie, photocurability) and the strength of the cured film.

[0233] Furthermore, the ethylenically unsaturated compound in the present invention is a compound other than the above-mentioned binder polymer, and preferably has a molecular weight of less than 5,000.

[0234] As other ethylenically unsaturated compounds, it is preferred to contain a bifunctional or higher functional ethylenically unsaturated compound.

[0235] In the present invention, the "bifunctional or higher-functional ethylenically unsaturated compound" means a compound having two or more ethylenically unsaturated groups in one molecule.

[0236] As the ethylenically unsaturated group in the other ethylenically unsaturated compounds, a (meth)acryloyl group is preferred.

[0237] As other ethylenically unsaturated compounds, (meth)acrylate compounds are preferred.

[0238] As other ethylenically unsaturated compounds, for example, from the viewpoint of the strength of the cured film after curing, it is particularly preferred to contain a bifunctional ethylenically unsaturated compound (preferably a bifunctional (meth)acrylate compound) and a trifunctional or higher functional ethylenically unsaturated compound (preferably a trifunctional or higher functional (meth)acrylate compound).

[0239] The bifunctional ethylenically unsaturated compound is not particularly limited and can be appropriately selected from known compounds.

[0240] Examples of the bifunctional ethylenically unsaturated compound include tricyclodecane dimethanol di(meth)acrylate, tricyclodecane dimethanol diacrylate, 1,9-nonanediol di(meth)acrylate, and 1,6-hexanediol di(meth)acrylate.

[0241] Examples of commercially available bifunctional ethylenically unsaturated compounds include tricyclodecanedimethanol diacrylate (trade name: NK ESTETR A-DCP, manufactured by SHIN-NAKAMURA CHEMICAL CO., LTD.), tricyclodecanedimethanol diacrylate (trade name: NK ESTETR DCP, manufactured by SHIN-NAKAMURA CHEMICAL CO., LTD.), 1,9-nonanediol diacrylate (trade name: NK ESTETR A-NOD-N, manufactured by SHIN-NAKAMURA CHEMICAL CO., LTD.), and 1,6-hexanediol diacrylate (trade name: NK ESTETR A-HD-N, manufactured by SHIN-NAKAMURA CHEMICAL CO., LTD.).

[0242] The trifunctional or higher functional ethylenically unsaturated compound is not particularly limited and can be appropriately selected from known compounds.

[0243] Examples of trifunctional or higher-functional ethylenically unsaturated compounds include dipentaerythritol (tri / tetra / penta / hexa) (meth)acrylate, pentaerythritol (tri / tetra) (meth)acrylate, trimethylolpropane tri(meth)acrylate, di-trimethylolpropane tetra(meth)acrylate, isocyanuric acid (meth)acrylate, and (meth)acrylate compounds having a glycerol tri(meth)acrylate skeleton.

[0244] Here, “(tri / tetra / penta / hexa) (meth)acrylate” is a concept including tri(meth)acrylate, tetra(meth)acrylate, penta(meth)acrylate, and hexa(meth)acrylate, and “(tri / tetra) (meth)acrylate” is a concept including tri(meth)acrylate and tetra(meth)acrylate.

[0245] Other ethylenically unsaturated compounds include caprolactone-modified (meth)acrylate compounds (e.g., KAYARAD (registered trademark) DPCA-20 manufactured by Nippon Kayaku Co., Ltd. and A-9300-1CL manufactured by Shin Nakamura Chemical Co., Ltd.), alkylene oxide-modified (e.g., KAYARAD (registered trademark) RP-1040 manufactured by Nippon Kayaku Co., Ltd. and ATM-35E and A-9300 manufactured by Shin Nakamura Chemical Co., Ltd. and EBECRYL (registered trademark) 135 manufactured by Daicel-All Nex Ltd.), and ethoxylated glyceryl triacrylate (e.g., NK ESTETR A-GLY-9E manufactured by Shin Nakamura Chemical Co., Ltd.).

[0246] As other ethylenically unsaturated compounds, urethane (meth)acrylate compounds [preferably trifunctional or higher-functional urethane (meth)acrylate compounds] may also be mentioned.

[0247] Examples of trifunctional or higher functional urethane (meth)acrylate compounds include 8UX-015A (manufactured by Taisei Fine Chemical Co., Ltd.), NK ESTETR UA-32P (manufactured by Shin Nakamura Chemical Co., Ltd.), and NK ESTETR UA-1100H (manufactured by Shin Nakamura Chemical Co., Ltd.).

[0248] As other ethylenically unsaturated compounds, from the viewpoint of improving developability, an ethylenically unsaturated compound having an acid group is preferably contained.

[0249] Examples of the acid group include a phosphoric acid group, a sulfonic acid group, and a carboxyl group.

[0250] Among them, the acid group is preferably a carboxyl group.

[0251] Examples of the ethylenically unsaturated compound having an acid group include trifunctional to tetrafunctional ethylenically unsaturated compounds having an acid group [formed by introducing a carboxyl group into the skeleton of pentaerythritol tri- and tetraacrylate (PETA) (acid value: 80 mgKOH / g to 120 mgKOH / g)], and pentafunctional to hexafunctional ethylenically unsaturated compounds having an acid group [formed by introducing a carboxyl group into the skeleton of dipentaerythritol penta- and hexaacrylate (DPHA) (acid value: 25 mgKOH / g to 70 mgKOH / g)].

[0252] These trifunctional or higher-functional ethylenically unsaturated compounds having an acid group may be used together with a bifunctional ethylenically unsaturated compound having an acid group, as needed.

[0253] As the ethylenically unsaturated compound having an acid group, at least one selected from the group consisting of bifunctional or higher-functional ethylenically unsaturated compounds having a carboxyl group and carboxylic anhydrides thereof is preferred.

[0254] When the ethylenically unsaturated compound having an acid group is at least one selected from the group consisting of bifunctional or higher-functional ethylenically unsaturated compounds having a carboxyl group and carboxylic anhydrides thereof, the developability and the film strength are further improved.

[0255] The bifunctional or higher functional ethylenically unsaturated compound having a carboxyl group is not particularly limited and can be appropriately selected from known compounds.

[0256] Preferred examples of bifunctional or higher-functional ethylenically unsaturated compounds having a carboxyl group include ARONIX (registered trademark) TO-2349 (manufactured by Toagosei Co., Ltd.), ARONIX (registered trademark) M-520 (manufactured by Toagosei Co., Ltd.), and ARONIX (registered trademark) M-510 (manufactured by Toagosei Co., Ltd.).

[0257] As the ethylenically unsaturated compound having an acid group, the polymerizable compounds having an acid group described in paragraphs 0025 to 0030 of JP-A-2004-239942 can be preferably used, and the contents described in this publication can be incorporated into the present invention.

[0258] The photosensitive resin composition of the present invention may contain one type of ethylenically unsaturated compound having an acid group, or may contain two or more types of ethylenically unsaturated compounds having an acid group.

[0259] From the viewpoint of developability and the adhesiveness of the resulting uncured film, the content of the ethylenically unsaturated compound having an acid group is preferably 0.1% by mass to 30% by mass, more preferably 0.5% by mass to 20% by mass, further preferably 1% by mass to 10% by mass, and particularly preferably 1% by mass to 5% by mass, relative to the total solid content of the photosensitive resin composition.

[0260] Furthermore, from the viewpoints of the moisture permeability and flex resistance of the obtained cured film and the adhesiveness of the obtained uncured film, the other ethylenically unsaturated compound preferably includes a bifunctional ethylenically unsaturated compound having an aliphatic hydrocarbon ring structure, more preferably includes a bifunctional ethylenically unsaturated compound having a ring structure consisting of two or more condensed aliphatic hydrocarbon rings, and particularly preferably includes tricyclodecane dimethanol di(meth)acrylate.

[0261] From the viewpoints of the moisture permeability and flex resistance of the resulting cured film and the adhesiveness of the resulting uncured film, the aliphatic hydrocarbon ring structure is preferably a cyclopentane ring structure, a cyclohexane ring structure, a tricyclodecane ring structure, a norbornane ring, or an isophorone ring, more preferably a cyclohexane ring structure or a tricyclodecane ring structure, and particularly preferably a tricyclodecane ring structure.

[0262] Furthermore, from the viewpoints of the moisture permeability and flex resistance of the obtained cured film and the adhesiveness of the obtained uncured film, the photosensitive resin composition of the present invention preferably contains a bifunctional ethylenically unsaturated compound having an aliphatic hydrocarbon ring structure and a binder polymer containing a structural unit having an aliphatic hydrocarbon ring.

[0263] The photosensitive resin composition according to the present invention may contain one type of bifunctional ethylenically unsaturated compound having an aliphatic hydrocarbon ring structure, or may contain two or more types.

[0264] From the viewpoints of moisture permeability and flex resistance of the resulting cured film and the adhesiveness of the resulting uncured film, the content of the bifunctional ethylenically unsaturated compound having an aliphatic hydrocarbon ring structure relative to the total solids content of the photosensitive resin composition is preferably 1% by mass to 50% by mass, more preferably 5% by mass to 40% by mass, further preferably 10% by mass to 30% by mass, and particularly preferably 15% by mass to 25% by mass.

[0265] The molecular weight of the other ethylenically unsaturated compound is preferably 200 to 3,000, more preferably 250 to 2,600, further preferably 280 to 2,200, and particularly preferably 300 to 2,200.

[0266] Among the ethylenically unsaturated compounds contained in the photosensitive resin composition of the present invention, the ratio of the content of ethylenically unsaturated compounds having a molecular weight of 300 or less relative to the content of all ethylenically unsaturated compounds contained in the photosensitive resin composition is preferably 30% by mass or less, more preferably 25% by mass or less, and even more preferably 20% by mass or less.

[0267] The photosensitive resin composition of the present invention may contain only one other ethylenically unsaturated compound, or may contain two or more other ethylenically unsaturated compounds.

[0268] The content of the ethylenically unsaturated compound containing compound A in the photosensitive resin composition of the present invention is preferably 1% by mass to 70% by mass, more preferably 10% by mass to 70% by mass, further preferably 20% by mass to 60% by mass, and particularly preferably 20% by mass to 50% by mass, relative to the total solid content of the photosensitive resin composition.

[0269] When the photosensitive resin composition of the present invention contains a bifunctional ethylenically unsaturated compound and a trifunctional or higher-functional ethylenically unsaturated compound as other ethylenically unsaturated compounds, the content of compound A and bifunctional ethylenically unsaturated compounds other than compound A is preferably 10% by mass to 90% by mass, more preferably 20% by mass to 85% by mass, and even more preferably 30% by mass to 80% by mass, relative to the total content of all ethylenically unsaturated compounds contained in the photosensitive resin composition.

[0270] The photosensitive resin composition according to the present invention may further contain a monofunctional ethylenically unsaturated compound.

[0271] The content of the difunctional or higher functional ethylenically unsaturated compound in the ethylenically unsaturated compound containing compound A is preferably 60% to 100% by mass, more preferably 80% to 100% by mass, and particularly preferably 90% to 100% by mass, relative to the total content of all ethylenically unsaturated compounds contained in the photosensitive resin composition.

[0272] <Photopolymerization initiator>

[0273] The photosensitive resin composition according to the present invention contains a photopolymerization initiator.

[0274] The photopolymerization initiator is not particularly limited, and a known photopolymerization initiator can be used.

[0275] Examples of the photopolymerization initiator include a photopolymerization initiator having an oxime ester structure (hereinafter also referred to as an "oxime-based photopolymerization initiator"), a photopolymerization initiator having an α-aminoalkylphenone structure (hereinafter also referred to as an "α-aminoalkylphenone-based photopolymerization initiator"), a photopolymerization initiator having an α-hydroxyalkylphenone structure (hereinafter also referred to as an "α-hydroxyalkylphenone-based polymerization initiator"), a photopolymerization initiator having an acylphosphine oxide structure (hereinafter also referred to as an "acylphosphine oxide-based photopolymerization initiator"), and a photopolymerization initiator having an N-phenylglycine structure (hereinafter also referred to as an "N-phenylglycine-based photopolymerization initiator"), etc.

[0276] The photopolymerization initiator preferably includes at least one selected from the group consisting of oxime-based photopolymerization initiators, α-aminoalkylphenone-based photopolymerization initiators, α-hydroxyalkylphenone-based photopolymerization initiators, and N-phenylglycine-based photopolymerization initiators, and more preferably includes at least one selected from the group consisting of oxime-based photopolymerization initiators, α-aminoalkylphenone-based photopolymerization initiators, and N-phenylglycine-based photopolymerization initiators.

[0277] Furthermore, as the photopolymerization initiator, for example, the polymerization initiators described in paragraphs 0031 to 0042 of JP-A-2011-95716 and paragraphs 0064 to 0081 of JP-A-2015-014783 may also be used.

[0278] Examples of commercially available photopolymerization initiators include 1-[4-(phenylthio)phenyl]-1,2-octanedione-2-(o-benzoyloxime) [trade name: IRGACURE (registered trademark) OXE-01, manufactured by BASF], 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone-1-(o-acetyloxime) [trade name: IRGACURE (registered trademark) OXE-02, manufactured by BASF], and [8-[5-(2,4,6-trimethylphenyl)-11-(2-ethylphenyl)-11-(2-ethylphenyl)-11-(2-ethylphenyl)-11-(2-ethylphenyl)-11-(2-ethylphenyl)-11-(2-ethylphenyl)-11-(2-ethylphenyl)-11-(2-ethylphenyl)-11-(2-ethylphenyl)-11-(2-ethylphenyl)-11-(2-ethylphenyl)-11-(2-ethylphenyl)-11-(2-ethylphenyl)-11-(2-ethylphenyl)-11-(2-methylbenzoyl ...methylbenzoyl)-11-(2-methylbenzoyl)-11-(2-ethylphenyl)-11-(2-ethylphenyl)-11-(2-ethylphenyl)-11-(2 [hexyl)-11H-benzo[a]carbazole][2-(2,2,3,3-tetrafluoropropoxy)phenyl]methanone-(o-acetoxime) [Trade name: IRGACURE (registered trademark) OXE-03, manufactured by BASF], 1-[4-[4-(2-benzofuranylcarbonyl)phenyl]thio]phenyl]-4-methylpentanone-1-(o-acetoxime) [Trade name: IRGACURE (registered trademark) OXE-04, manufactured by BASF], 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[ 4-(4-morpholino)phenyl]-1-butanone [trade name: IRGACURE (registered trademark) 379EG, manufactured by BASF], 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one [trade name: IRGACURE (registered trademark) 907, manufactured by BASF], 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionyl)benzyl]phenyl}-2-methylpropan-1-one [trade name: IRGACURE (registered trademark) 127, manufactured by BASF], 2 Benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone-1-one [trade name: IRGACURE (registered trademark) 369, manufactured by BASF], 2-hydroxy-2-methyl-1-phenylpropan-1-one [trade name: IRGACURE (registered trademark) 1173, manufactured by BASF], 1-hydroxycyclohexylphenyl ketone [trade name: IRGACURE (registered trademark) 184, manufactured by BASF], 2,2-dimethoxy-1,2-phenylethane-1-one [trade name: IRGACURE 651, manufactured by BASF], and oxime ester-based products [trade name: Lunar (registered trademark) 6, manufactured by DKSH Management Ltd.], etc.

[0279] The photosensitive resin composition according to the present invention may contain only one type of photopolymerization initiator, or may contain two or more types of photopolymerization initiators.

[0280] The content of the photopolymerization initiator in the photosensitive resin composition of the present invention is not particularly limited, but is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and even more preferably 1.0% by mass or more, based on the total solid content of the photosensitive resin composition.

[0281] Furthermore, the content of the photopolymerization initiator in the photosensitive resin composition of the present invention is preferably 10% by mass or less, more preferably 5% by mass or less, relative to the total solid content of the photosensitive resin composition.

[0282] <Heterocyclic compounds>

[0283] The photosensitive resin composition of the present invention preferably further contains a heterocyclic compound. The heterocyclic compound contributes to improving the adhesion to a substrate (especially a copper substrate) and the corrosion resistance of metals (especially copper).

[0284] The heterocyclic ring of the heterocyclic compound may be either a monocyclic ring or a polycyclic ring.

[0285] Examples of the heteroatom possessed by the heterocyclic compound include a nitrogen atom, an oxygen atom, a sulfur atom, etc. The heterocyclic compound preferably has at least one atom selected from the group consisting of a nitrogen atom, an oxygen atom, and a sulfur atom, and more preferably has a nitrogen atom.

[0286] As the heterocyclic compound, for example, preferably a triazole compound, a benzotriazole compound, a tetrazole compound, a thiadiazole compound, a triazine compound, a rhodanine compound, a thiazole compound, a benzothiazole compound, a benzimidazole compound, a benzoxazole compound or a pyrimidine compound can be mentioned. Among the above, the heterocyclic compound is preferably at least one compound selected from the group consisting of a triazole compound, a benzotriazole compound, a tetrazole compound, a thiadiazole compound, a triazine compound, a rhodanine compound, a thiazole compound, a benzimidazole compound and a benzoxazole compound, and more preferably at least one compound selected from the group consisting of a triazole compound, a benzotriazole compound, a tetrazole compound, a thiadiazole compound, a thiazole compound, a benzothiazole compound, a benzimidazole compound and a benzoxazole compound.

[0287] Preferred specific examples of the heterocyclic compound are shown below. As the triazole compound and the benzotriazole compound, the following compounds can be exemplified.

[0288] [Chemical Formula 15]

[0289]

[0290] Examples of the tetrazole compound include the following compounds.

[0291] [Chemical Formula 16]

[0292]

[0293] Examples of the thiadiazole compound include the following compounds.

[0294] [Chemical Formula 17]

[0295]

[0296] Examples of the triazine compound include the following compounds.

[0297] [Chemical Formula 18]

[0298]

[0299] Examples of the rhodanine compound include the following compounds.

[0300] [Chemical Formula 19]

[0301]

[0302] Examples of the thiazole compound include the following compounds.

[0303] [Chemical Formula 20]

[0304]

[0305] Examples of the benzothiazole compound include the following compounds.

[0306] [Chemical Formula 21]

[0307]

[0308] Examples of the benzimidazole compound include the following compounds.

[0309] [Chemical Formula 22]

[0310]

[0311] Examples of the benzoxazole compound include the following compounds.

[0312] [Chemical Formula 23]

[0313]

[0314] The photosensitive resin composition of the present invention may contain only one heterocyclic compound, or may contain two or more heterocyclic compounds.

[0315] When the photosensitive resin composition of the present invention contains a heterocyclic compound, the content of the heterocyclic compound is preferably 0.01% to 20% by mass, more preferably 0.1% to 10% by mass, further preferably 0.3% to 8% by mass, and particularly preferably 0.5% to 5% by mass relative to the total solid content of the photosensitive resin composition. When the content of the heterocyclic compound is within the above range, the adhesion to the substrate (especially a copper substrate) and the corrosion resistance of the metal (especially copper) can be improved.

[0316] <Aliphatic thiol compounds>

[0317] The photosensitive resin composition according to the present invention preferably contains an aliphatic thiol compound.

[0318] When the photosensitive resin composition of the present invention contains an aliphatic thiol compound, the aliphatic thiol compound undergoes an ene-thiol reaction, thereby suppressing the curing shrinkage of the formed film and alleviating stress. As a result, the adhesion of the formed cured film to the substrate (particularly, the adhesion after exposure) tends to be improved.

[0319] Generally, when a photosensitive resin composition contains an aliphatic thiol compound, metals (particularly copper) are more susceptible to corrosion. In contrast, the photosensitive resin composition of the present invention has the advantage of being able to form a cured film with excellent corrosion resistance against metals (particularly copper), even when containing an aliphatic thiol compound.

[0320] As the aliphatic thiol compound, a monofunctional aliphatic thiol compound or a polyfunctional aliphatic thiol compound (ie, an aliphatic thiol compound having two or more functional groups) can be preferably used.

[0321] Among them, the aliphatic thiol compound preferably contains a polyfunctional aliphatic thiol compound, and more preferably a polyfunctional aliphatic thiol compound, from the viewpoint of adhesion of the formed cured film to the substrate (particularly adhesion after exposure).

[0322] In the present invention, the "polyfunctional aliphatic thiol compound" refers to an aliphatic compound having two or more thiol groups (also referred to as "mercapto groups") in the molecule.

[0323] The polyfunctional aliphatic thiol compound is preferably a low molecular weight compound having a molecular weight of not less than 100. Specifically, the molecular weight of the polyfunctional aliphatic thiol compound is more preferably 100 to 1,500, and even more preferably 150 to 1,000.

[0324] For example, from the viewpoint of adhesion of the formed cured film to the substrate, the number of functional groups of the polyfunctional aliphatic thiol compound is preferably difunctional to decafunctional, more preferably difunctional to octafunctional, and even more preferably difunctional to hexafunctional.

[0325] Examples of the polyfunctional aliphatic thiol compound include trimethylolpropane tris(3-mercaptobutyrate), 1,4-bis(3-mercaptobutyryloxy)butane, pentaerythritol tetrakis(3-mercaptobutyrate), 1,3,5-tris(3-mercaptobutyryloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, trimethylolethane tris(3-mercaptobutyrate), tris[(3-mercaptopropionyloxy)ethyl]isocyanate. Urate, trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptopropionate), tetraethylene glycol bis(3-mercaptopropionate), dipentaerythritol hexa(3-mercaptopropionate), ethylene glycol bisthiopropionate, 1,2-ethanedithiol, 1,3-propanedithiol, 1,6-hexamethylenedithiol, 2,2'-(ethylenedithio)diethanethiol, meso-2,3-dimercaptosuccinic acid, bis(mercaptoethyl) ether, etc.

[0326] Among them, the polyfunctional aliphatic thiol compound is preferably at least one selected from the group consisting of trimethylolpropane tris(3-mercaptobutyrate), 1,4-bis(3-mercaptobutyryloxy)butane, and 1,3,5-tris(3-mercaptobutyryloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione.

[0327] Examples of the monofunctional aliphatic thiol compound include 1-octanethiol, 1-dodecylthiol, β-mercaptopropionic acid, methyl-3-mercaptopropionate, 2-ethylhexyl-3-mercaptopropionate, n-octyl-3-mercaptopropionate, methoxybutyl-3-mercaptopropionate, and stearyl-3-mercaptopropionate.

[0328] The photosensitive resin composition of the present invention may contain only one type of aliphatic thiol compound, or may contain two or more types of aliphatic thiol compounds.

[0329] When the photosensitive resin composition of the present invention contains an aliphatic thiol compound, the content of the aliphatic thiol compound is preferably 5% by mass or more, more preferably 5% by mass to 50% by mass, further preferably 5% by mass to 30% by mass, and particularly preferably 8% by mass to 20% by mass, relative to the total solid content of the photosensitive resin composition.

[0330] When the content of the aliphatic thiol compound is 5% by mass or more relative to the total solid content of the photosensitive resin composition, a cured film having better adhesion (especially adhesion after exposure) to a substrate (especially a copper substrate) tends to be formed.

[0331] Thermally cross-linkable compounds

[0332] From the viewpoint of the strength of the obtained cured film and the adhesiveness of the obtained uncured film, the photosensitive resin composition according to the present invention preferably contains a thermally crosslinkable compound.

[0333] Examples of the heat-crosslinkable compound include epoxy compounds, oxetane compounds, methylol compounds, blocked isocyanate compounds, etc. Among them, blocked isocyanate compounds are preferred from the viewpoint of the strength of the obtained cured film and the adhesiveness of the obtained uncured film.

[0334] The blocked isocyanate compound reacts with a hydroxyl group and a carboxyl group. Therefore, for example, when at least one of the binder polymer and the radically polymerizable compound having an ethylenically unsaturated group has at least one of a hydroxyl group and a carboxyl group, the hydrophilicity of the formed film tends to decrease, and the function as a protective film tends to increase.

[0335] The blocked isocyanate compound refers to a "compound having a structure in which the isocyanate group of isocyanate is protected (so-called masked) by a blocking agent."

[0336] The dissociation temperature of the blocked isocyanate compound is not particularly limited, but is preferably 100°C to 160°C, more preferably 130°C to 150°C.

[0337] The dissociation temperature of the blocked isocyanate in the present invention means "the temperature of an endothermic peak accompanying the deprotection reaction of the blocked isocyanate when measured by DSC (Differential Scanning Calorimetry) analysis using a differential scanning calorimeter."

[0338] As the differential scanning calorimeter, for example, a differential scanning calorimeter (model: DSC6200) manufactured by Seiko Instruments Inc. can be preferably used. However, the differential scanning calorimeter is not limited to this.

[0339] Examples of end-capping agents having a dissociation temperature of 100°C to 160°C include active methylene compounds [malonic acid diesters (such as dimethyl malonate, diethyl malonate, di-n-butyl malonate, and di-2-ethylhexyl malonate)], oxime compounds (formaldehyde oxime, acetaldehyde oxime, acetone oxime, methyl ethyl ketone oxime, cyclohexanone oxime, and other compounds having a structure represented by -C(=N-OH)- in the molecule).

[0340] Among them, as the blocking agent having a dissociation temperature of 100° C. to 160° C., for example, at least one selected from oxime compounds is preferred from the viewpoint of storage stability.

[0341] For example, from the viewpoint of improving the brittleness of the film and enhancing the adhesion to the transfer target, the blocked isocyanate compound preferably has an isocyanurate structure.

[0342] The blocked isocyanate compound having an isocyanurate structure is obtained by, for example, isocyanurating hexamethylene diisocyanate and then protecting it.

[0343] Among blocked isocyanate compounds having an isocyanurate structure, compounds having an oxime structure using an oxime compound as a blocking agent are preferred from the viewpoints of making the dissociation temperature fall within a preferred range and reducing development residue more easily than compounds not having an oxime structure.

[0344] For example, from the viewpoint of the strength of the cured film, the blocked isocyanate compound preferably has a polymerizable group, and more preferably has a radical polymerizable group.

[0345] The polymerizable group is not particularly limited, and a known polymerizable group can be used.

[0346] Examples of the polymerizable group include ethylenically unsaturated groups such as a (meth)acryloyloxy group, a (meth)acrylamide group, and a styryl group, and groups having an epoxy group such as a glycidyl group.

[0347] Among these, as the polymerizable group, from the viewpoints of the surface shape, development speed, and reactivity of the obtained cured film, an ethylenically unsaturated group is preferred, a (meth)acryloyloxy group is more preferred, and an acryloyloxy group is particularly preferred.

[0348] As the blocked isocyanate compound, a commercially available product can be used.

[0349] Examples of commercially available blocked isocyanate compounds include Karenz (registered trademark) AOI-BM, Karenz (registered trademark) MOI-BM, and Karenz (registered trademark) MOI-BP (all manufactured by SHOWA DENKO KK), and blocked Duranate series products (for example, Duranate (registered trademark) TPA-B80E, manufactured by Asahi Kasei Corporation).

[0350] The photosensitive resin composition according to the present invention may contain only one type of thermally crosslinkable compound, or may contain two or more types of thermally crosslinkable compounds.

[0351] When the photosensitive resin composition of the present invention contains a thermally crosslinkable compound, the content of the thermally crosslinkable compound is preferably 1 to 50% by mass, more preferably 5 to 30% by mass, based on the total solid content of the photosensitive resin composition.

[0352] Surfactants

[0353] The photosensitive resin composition according to the present invention may contain a surfactant.

[0354] The surfactant is not particularly limited, and a known surfactant can be used.

[0355] Examples of the surfactant include those described in paragraph 0017 of Japanese Patent No. 4502784 and paragraphs 0060 to 0071 of Japanese Patent Application Laid-Open No. 2009-237362.

[0356] As the surfactant, a fluorine-based surfactant is preferable.

[0357] Examples of commercially available particles of fluorine-based surfactants include MEGAFACE (registered trademark) F551A (manufactured by DIC Corporation).

[0358] The photosensitive resin composition of the present invention may contain only one surfactant or two or more surfactants.

[0359] When the photosensitive resin composition of the present invention contains a surfactant, the content of the surfactant is preferably 0.01 to 3 mass %, more preferably 0.05 to 1 mass %, and even more preferably 0.1 to 0.8 mass %, relative to the total solid content of the photosensitive resin composition.

[0360] <Hydrogen-donating compounds>

[0361] The photosensitive resin composition according to the present invention preferably contains a hydrogen-donating compound.

[0362] In the photosensitive resin composition of the present invention, the hydrogen-donating compound has the functions of further increasing the sensitivity of the photopolymerization initiator to activating light and suppressing the polymerization inhibition of the polymerizable compound by oxygen.

[0363] Examples of the hydrogen-donating compound include amines, for example, compounds described in "Journal of Polymer Society" by MR Sander et al., Vol. 10, p. 3173 (1972), Japanese Patent Publication No. 44-20189, Japanese Patent Application Laid-Open No. 51-82102, Japanese Patent Application Laid-Open No. 52-134692, Japanese Patent Application Laid-Open No. 59-138205, Japanese Patent Application Laid-Open No. 60-84305, Japanese Patent Application Laid-Open No. 62-18537, Japanese Patent Application Laid-Open No. 64-33104, Research Disclosure No. 33825, and the like.

[0364] Specific examples of the hydrogen-donating compound include triethanolamine, ethyl p-dimethylaminobenzoate, p-formyldimethylaniline, and p-methylthiodimethylaniline.

[0365] In addition, examples of hydrogen-donating compounds include amino acid compounds (N-phenylglycine, etc.), organometallic compounds described in Japanese Patent Publication No. 48-42965 (tributyltin acetate, etc.), hydrogen donors described in Japanese Patent Publication No. 55-34414, and sulfur compounds (trithiane, etc.) described in Japanese Patent Application Laid-Open No. 6-308727.

[0366] The photosensitive resin composition according to the present invention may contain only one type of hydrogen-donating compound, or may contain two or more types of hydrogen-donating compounds.

[0367] When the photosensitive resin composition of the present invention contains a hydrogen donating compound, the content of the hydrogen donating compound is preferably 0.01% by mass to 10% by mass, more preferably 0.03% by mass to 5% by mass, and even more preferably 0.05% by mass to 3% by mass relative to the total solid content of the photosensitive resin composition, for example, from the viewpoint of improving the curing rate by balancing the polymerization growth rate and chain transfer.

[0368] Solvents

[0369] The photosensitive resin composition according to the present invention preferably contains a solvent.

[0370] When the photosensitive resin composition according to the present invention contains a solvent, it tends to be easy to form a photosensitive layer by coating.

[0371] As the solvent, any commonly used solvent can be used without particular limitation.

[0372] As the solvent, an organic solvent is preferred.

[0373] Examples of the organic solvent include methyl ethyl ketone, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate (also known as 1-methoxy-2-propyl acetate), diethylene glycol ethyl methyl ether, cyclohexanone, methyl isobutyl ketone, ethyl lactate, methyl lactate, caprolactam, n-propanol, and 2-propanol.

[0374] As the solvent, a mixed solvent of methyl ethyl ketone and propylene glycol monomethyl ether acetate or a mixed solvent of diethylene glycol ethyl methyl ether and propylene glycol monomethyl ether acetate is preferred.

[0375] As the solvent, Solvent described in paragraphs 0054 and 0055 of US Patent Application Publication No. 2005 / 282073 can also be used, and the contents of this specification are incorporated into the present invention.

[0376] Furthermore, as the solvent, an organic solvent (high boiling point solvent) having a boiling point of 180° C. to 250° C. can be used as needed.

[0377] When the photosensitive resin composition according to the present invention contains a solvent, it may contain only one type of solvent or two or more types of solvents.

[0378] When the photosensitive resin composition of the present invention contains a solvent, the solid content of the photosensitive resin composition of the present invention is preferably 5% by mass to 80% by mass, more preferably 5% by mass to 40% by mass, and particularly preferably 5% by mass to 30% by mass, relative to the total solid content of the photosensitive resin composition.

[0379] When the photosensitive resin composition of the present invention contains a solvent, the viscosity of the photosensitive resin composition at 25° C. is preferably 1 to 50 mPa·s, more preferably 2 to 40 mPa·s, and even more preferably 3 to 30 mPa·s, from the viewpoint of coating properties.

[0380] The viscosity is measured using a viscometer. As the viscometer, for example, a viscometer manufactured by TOKI SANGYO CO., LTD. (trade name: VISCOMETER TV-22) can be preferably used. However, the viscometer is not limited to this.

[0381] When the photosensitive resin composition of the present invention contains a solvent, for example, from the viewpoint of coating properties, the surface tension of the photosensitive resin composition at 25° C. is preferably 5 mN / m to 100 mN / m, more preferably 10 mN / m to 80 mN / m, and even more preferably 15 mN / m to 40 mN / m.

[0382] The surface tension is measured using a surface tensiometer. As the surface tensiometer, for example, a surface tensiometer (trade name: Automatic Surface Tensiometer CBVP-Z) manufactured by Kyowa Interface Science Co., Ltd. can be preferably used. However, the surface tensiometer is not limited to this.

[0383] <Other ingredients>

[0384] The photosensitive resin composition according to the present invention may contain components other than the components already described (so-called other components).

[0385] Examples of other components include particles (for example, metal oxide particles) and colorants.

[0386] Furthermore, examples of other components include the thermal polymerization inhibitors described in paragraph 0018 of Japanese Patent No. 4502784 and other additives described in paragraphs 0058 to 0071 of Japanese Patent Application Laid-Open No. 2000-310706.

[0387] -particle-

[0388] The photosensitive resin composition according to the present invention may contain particles (for example, metal oxide particles; the same shall apply hereinafter) for the purpose of adjusting the refractive index, light transmittance, and the like.

[0389] The metal in the metal oxide particles also includes semimetals such as B, Si, Ge, As, Sb, and Te.

[0390] For example, from the viewpoint of transparency of the cured film, the average primary particle size of the particles is preferably 1 nm to 200 nm, more preferably 3 nm to 80 nm.

[0391] The average primary particle size of the particles is calculated by measuring the particle sizes of 200 random particles using an electron microscope and taking the arithmetic average of the measurement results. In addition, when the shape of the particles is not spherical, the longest side is used as the particle size.

[0392] When the photosensitive resin composition of the present invention contains particles, it may contain only one type of particles having different metal types, sizes, etc., or may contain two or more types of particles having different metal types, sizes, etc.

[0393] The photosensitive resin composition of the present invention preferably contains no particles, or the content of particles is greater than 0% by mass and less than 35% by mass relative to the total solid content of the photosensitive resin composition. More preferably, the composition contains no particles, or the content of particles is greater than 0% by mass and less than 10% by mass relative to the total solid content of the photosensitive resin composition. Further preferably, the composition contains no particles, or the content of particles is greater than 0% by mass and less than 5% by mass relative to the total solid content of the photosensitive resin composition. Further preferably, the composition contains no particles, or the content of particles is greater than 0% by mass and less than 1% by mass relative to the total solid content of the photosensitive resin composition. Particularly preferably, the composition contains no particles.

[0394] -Colorant-

[0395] The photosensitive resin composition according to the present invention may contain a trace amount of a colorant (a pigment, a dye, etc.), but preferably contains substantially no colorant, for example, from the viewpoint of transparency.

[0396] When the photosensitive resin composition according to the present invention contains a colorant, the content of the colorant is preferably less than 1% by mass, more preferably less than 0.1% by mass, relative to the total solid content of the photosensitive resin composition.

[0397] <Application>

[0398] The photosensitive resin composition of the present invention is not particularly limited in its use. However, since the resulting cured film has low moisture permeability and excellent flex resistance, it is preferably used as a photosensitive resin composition for touch panels, more preferably as a photosensitive composition for forming a protective film in touch panels, and particularly preferably as a photosensitive composition for forming an electrode protective film in touch panels.

[0399] (cured film)

[0400] The cured film of the present invention is a film formed by curing the photosensitive resin composition of the present invention. Furthermore, when the photosensitive resin composition of the present invention contains a solvent, the cured film of the present invention is a cured film formed by curing the solid content of the photosensitive resin composition of the present invention.

[0401] Furthermore, when the photosensitive resin composition of the present invention contains a solvent, it is preferred that the photosensitive resin composition of the present invention is applied to a substrate in a film form, at least a portion of the solvent is removed by a known method such as heat drying, air drying, or reduced pressure drying, and then cured to form a cured film.

[0402] Furthermore, the cured film may have a desired pattern shape.

[0403] The cured film of the present invention can be preferably used as an interlayer insulating film (so-called insulating film) or an overcoat film (so-called protective film). Furthermore, the cured film of the present invention has excellent film properties and is therefore preferably used in organic EL display devices, liquid crystal display devices, and the like.

[0404] Furthermore, the cured film according to the present invention can be preferably used as a protective film for a touch panel, and can be particularly preferably used as an electrode protective film for a touch panel.

[0405] The thickness of the cured film according to the present invention is not particularly limited, but is preferably 1 μm to 20 μm, more preferably 2 μm to 15 μm, and even more preferably 3 μm to 12 μm.

[0406] (Transfer film)

[0407] The transfer film of the present invention comprises a temporary support and a photosensitive layer containing at least the solid content of the photosensitive resin composition of the present invention, preferably a photosensitive layer composed of the photosensitive resin composition of the present invention or obtained by drying the photosensitive resin composition.

[0408] Temporary support

[0409] The transfer film according to the present invention includes a temporary support.

[0410] The temporary support is preferably a film, more preferably a resin film. As the temporary support, a film that is flexible and does not significantly deform, shrink, or stretch under pressure or under pressure and heating can be used.

[0411] Examples of such films include polyethylene terephthalate films (for example, biaxially stretched polyethylene terephthalate films), triacetyl cellulose films, polystyrene films, polyimide films, and polycarbonate films.

[0412] Among them, a biaxially stretched polyethylene terephthalate film is particularly preferred as the temporary support.

[0413] Furthermore, it is preferable that the film used as a temporary support body has no deformation such as wrinkles or scratches.

[0414] From the viewpoint of enabling pattern exposure via the temporary support, the temporary support preferably has high transparency, and the transmittance at 365 nm is preferably 60% or more, more preferably 70% or more.

[0415] From the viewpoint of pattern formation during pattern exposure via a temporary support and transparency of the temporary support, the smaller the haze of the temporary support, the better. Specifically, the haze value of the temporary support is preferably 2% or less, more preferably 0.5% or less, and particularly preferably 0.1% or less.

[0416] From the viewpoint of pattern formation during pattern exposure via a temporary support and the transparency of the temporary support, the smaller the number of microparticles, foreign matter, and defects contained in the temporary support, the better. The number of microparticles, foreign matter, or defects with a diameter of 1 μm or more is preferably 50 / 10 mm. 2 Less than 10 pieces / 10mm, more preferably 10 pieces / 10mm 2 Below, more preferably 3 / 10mm 2 Below, particularly preferably 0 / 10mm 2 .

[0417] Furthermore, from the perspective of enhancing operability, a layer containing fine particles (lubricant layer) may be provided on the surface of the temporary support. The lubricant layer may be provided on one surface of the temporary support or on both surfaces. The diameter of the particles contained in the lubricant layer may be set to 0.05 μm to 0.8 μm. Furthermore, the film thickness of the lubricant layer may be set to 0.05 μm to 1.0 μm.

[0418] The thickness of the temporary support is not particularly limited, but is preferably 5 μm to 200 μm, more preferably 10 μm to 150 μm, and even more preferably 10 μm to 50 μm from the viewpoint of ease of handling and versatility.

[0419] Examples of the temporary support include a biaxially stretched polyethylene terephthalate film having a film thickness of 16 μm, a biaxially stretched polyethylene terephthalate film having a film thickness of 12 μm, and a biaxially stretched polyethylene terephthalate film having a film thickness of 9 μm.

[0420] Preferred forms of temporary supports are described, for example, in paragraphs 0017 to 0018 of Japanese Patent Application Publication No. 2014-85643, paragraphs 0019 to 0026 of Japanese Patent Application Publication No. 2016-27363, paragraphs 0041 to 0057 of WO 2012 / 081680A1, and paragraphs 0029 to 0040 of WO 2018 / 179370A1. The contents of these publications may be incorporated into this specification.

[0421] Preferred commercially available products of the temporary support include Lumirror (registered trademark) 16QS40 (16KS40), Lumirror (registered trademark) 16FB40 (all manufactured by Toray Industries, Inc.), COSMOSHINE (registered trademark) A4100, COSMOSHINE (registered trademark) A4300, and COSMOSHINE (registered trademark) A8300 (all manufactured by TOYOBO CO., LTD.).

[0422] <Photosensitive layer>

[0423] The transfer film according to the present invention has a photosensitive layer containing at least the solid content of the photosensitive resin composition according to the present invention, and preferably has a photosensitive layer composed of the photosensitive resin composition according to the present invention or formed by drying the photosensitive resin composition.

[0424] When the photosensitive resin composition according to the present invention contains a solvent, it is preferred to remove at least a portion of the solvent by a known method to form a photosensitive layer.

[0425] The solvent does not need to be completely removed. For example, the content of the solvent in the photosensitive layer is preferably 5% by mass or less, more preferably 1% by mass or less, and particularly preferably 0.5% by mass or less, relative to the total mass of the photosensitive layer.

[0426] The thickness of the photosensitive layer is not particularly limited, but is preferably 20 nm or less, more preferably 15 nm or less, and even more preferably 12 nm or less.

[0427] When the thickness of the photosensitive layer is 20 μm or less, there are advantages in reducing the overall thickness of the transfer film, improving the transmittance of the photosensitive layer or the obtained cured film, and suppressing yellowing of the photosensitive layer or the obtained cured film.

[0428] From the viewpoint of production applicability, for example, the thickness of the photosensitive layer is preferably 1 μm or more, more preferably 2 μm or more, and particularly preferably 3 μm or more.

[0429] The thickness of the photosensitive layer was calculated as an average value of the thickness at five arbitrary locations measured by cross-sectional observation using a scanning electron microscope (SEM).

[0430] The refractive index of the photosensitive layer is not particularly limited, but is preferably 1.47 to 1.56, more preferably 1.50 to 1.53, further preferably 1.50 to 1.52, and particularly preferably 1.51 to 1.52.

[0431] The method for forming the photosensitive layer is not particularly limited, and a known method can be used.

[0432] As an example of a method for forming a photosensitive layer, there is mentioned a method of forming a photosensitive layer by applying a photosensitive resin composition containing a solvent onto a temporary support and drying the composition as needed.

[0433] As the coating method, a known method can be used.

[0434] Examples of the coating method include printing, spraying, roll coating, rod coating, curtain coating, spin coating, and die coating (ie, slit coating).

[0435] Among them, the die coating method is preferable as the coating method.

[0436] As the drying method, known methods such as natural drying, heat drying, and reduced-pressure drying can be used, and these methods can be used alone or in combination.

[0437] In the present invention, "drying" means removing at least a portion of the solvent contained in the composition.

[0438] <Second resin layer>

[0439] The transfer film according to the present invention may further include a second resin layer on the side opposite to the side where the temporary support is present when viewed from the photosensitive layer.

[0440] As the second resin layer, a refractive index adjusting layer is preferably used.

[0441] The second resin layer is preferably arranged adjacent to the photosensitive layer.

[0442] From the viewpoint of suppressing wiring visibility, the refractive index of the second resin layer is preferably higher than the refractive index of the photosensitive layer.

[0443] The refractive index of the second resin layer is preferably 1.50 or greater, more preferably 1.55 or greater, further preferably 1.60 or greater, and particularly preferably 1.70 or greater.

[0444] The upper limit of the refractive index of the second resin layer is not particularly limited, but is preferably 2.10 or less, more preferably 1.85 or less, further preferably 1.78 or less, and particularly preferably 1.74 or less.

[0445] The second resin layer may be photocurable (ie, photosensitivity), thermosetting, or both. However, from the perspective of forming a cured film with excellent strength, the second resin layer is preferably photocurable.

[0446] The second resin layer preferably has alkali solubility (for example, solubility in a weak alkaline aqueous solution).

[0447] The thickness of the second resin layer is not particularly limited.

[0448] The thickness of the second resin layer is preferably 50 nm to 500 nm, more preferably 55 nm to 110 nm, and even more preferably 60 nm to 100 nm.

[0449] The thickness of the second resin layer was calculated as an average value of five arbitrary positions measured by cross-sectional observation using a scanning electron microscope (SEM).

[0450] The method for controlling the refractive index of the second resin layer is not particularly limited. Examples thereof include a method of using a resin having a predetermined refractive index alone, a method of using a resin and metal oxide particles or metal particles, and a method of using a composite of a metal salt and a resin.

[0451] The type of the metal oxide particles is not particularly limited, and known metal oxide particles can be used.

[0452] Specifically, the metal oxide particles are preferably at least one selected from the group consisting of zirconium oxide particles (ZrO 2 particles), Nb 2 O 5 particles, titanium oxide particles (TiO 2 particles), and silicon dioxide particles (SiO 2 particles).

[0453] Among these, the metal oxide particles are more preferably at least one selected from the group consisting of zirconium oxide particles and titanium oxide particles, for example, from the viewpoint of easily adjusting the refractive index of the second resin layer to 1.6 or more.

[0454] When the second resin layer contains metal oxide particles, the second resin layer may contain only one type of metal oxide particles, or may contain two or more types of metal oxide particles.

[0455] From the perspective of improving the concealment of concealed objects such as electrode patterns and effectively improving the visibility of the concealed objects, the content of the metal oxide particles is preferably 1% by mass to 95% by mass, more preferably 20% by mass to 90% by mass, and further preferably 40% by mass to 85% by mass, relative to the total mass of the second resin layer.

[0456] When titanium oxide is used as the metal oxide particles, the content of titanium oxide is preferably 1 to 95% by mass, more preferably 20 to 90%, and even more preferably 40 to 85% by mass, based on the total mass of the second resin layer.

[0457] Furthermore, the second resin layer preferably contains a binder polymer and an ethylenically unsaturated compound.

[0458] Regarding the components of the second resin layer, reference can be made to the components of the curable second resin layer described in paragraphs 0019 to 0040 and 0144 to 0150 of JP-A-2014-108541, the components of the transparent layer described in paragraphs 0024 to 0035 and 0110 to 0112 of JP-A-2014-10814, and the components of the composition having an ammonium salt described in paragraphs 0034 to 0056 of WO 2016 / 009980.

[0459] As the binder polymer contained in the second resin layer, the same binder polymer as that contained in the photosensitive layer can be used, and the preferred range is also the same.

[0460] As the ethylenically unsaturated compound contained in the second resin layer, the same ethylenically unsaturated compound as the radically polymerizable compound having an ethylenically unsaturated compound contained in the photosensitive layer can be used, and the preferred range is also the same.

[0461] Furthermore, from the viewpoint of suppressing oxidation of metal in contact with the second resin layer, the second resin layer preferably contains at least one metal antioxidant.

[0462] Preferred examples of the metal antioxidant include compounds having an aromatic ring containing a nitrogen atom in the molecule.

[0463] Examples of the metal antioxidant particles include imidazole, benzimidazole, tetrazole, mercaptothiadiazole, and benzotriazole.

[0464] The second resin layer may contain other components in addition to the above-mentioned components.

[0465] Examples of other components that may be contained in the second resin layer include the same components as those contained in the photosensitive layer described above.

[0466] The second resin layer preferably contains a surfactant as another component.

[0467] There is no particular limitation on the method for forming the second resin layer.

[0468] An example of a method for forming the second resin layer is a method of applying the above-described second resin layer-forming composition containing an aqueous solvent onto the photosensitive layer formed on the temporary support and drying the composition as needed.

[0469] Specific examples of the coating and drying methods in the method for forming the second resin layer are the same as the specific examples of the coating and drying methods in the method for forming the photosensitive layer.

[0470] <Protective film>

[0471] The transfer film according to the present invention may further include a protective film on the side opposite to the temporary support when viewed from the photosensitive layer.

[0472] When the transfer film according to the present invention has a second resin layer on the side opposite to the temporary support when viewed from the photosensitive layer, it preferably has a protective film on the side opposite to the temporary support when viewed from the second resin layer.

[0473] The protective film is preferably the outermost layer on the side opposite to the temporary support in the transfer film according to the present invention.

[0474] Examples of the protective film include polyethylene terephthalate films, polypropylene films, polystyrene films, and polycarbonate films.

[0475] As the protective film, for example, the films described in paragraphs 0083 to 0087 and 0093 of Japanese Patent Application Laid-Open No. 2006-259138 can be used.

[0476] The protective film can be obtained as, for example, ALPHAN (registered trademark) FG-201 and ALPHAN (registered trademark) E-201F manufactured by Oji F-Tex Co., Ltd., Cerapeel (registered trademark) 25WZ manufactured by TORAY ADVANCED FILM CO., LTD., or Lumirror (registered trademark) 16QS62 (16KS40) manufactured by TORAY INDUSTRIES, INC.

[0477] The number of fisheyes with a diameter of 80 μm or more contained in the protective film is preferably 5 / m 2 Fisheyes are formed when foreign matter, undissolved matter, oxidative degradation products, etc. of the material are mixed into the film when the material is melted and then produced through kneading, extrusion, biaxial stretching, and cast coating methods.

[0478] The number of particles with a diameter of 3 μm or more contained in the protective film is preferably 30 particles / mm 2 Below, more preferably 10 / mm 2 Below, more preferably 5 / mm 2 Thereby, it is possible to suppress defects caused by the transfer of the unevenness caused by the particles contained in the protective film to the photosensitive resin layer.

[0479] The arithmetic mean roughness Ra of the protective film surface is preferably 0.01 μm or greater, more preferably 0.02 μm or greater, and even more preferably 0.03 μm or greater. This improves the windability of the transfer film when it is long. Furthermore, to prevent defects during transfer, the Ra is preferably less than 0.50 μm, more preferably 0.40 μm or less, and even more preferably 0.30 μm or less.

[0480] <Thermoplastic resin layer>

[0481] The transfer film according to the present invention may further include a thermoplastic resin layer between the temporary support and the photosensitive layer.

[0482] If the transfer film also has a thermoplastic resin layer, when the transfer film is transferred to a substrate to form a laminate, bubbles caused by lamination are less likely to occur. When the laminate is used in an image display device, image unevenness is less likely to occur, and excellent display characteristics can be obtained.

[0483] The thermoplastic resin layer is preferably alkali-soluble.

[0484] The thermoplastic resin layer functions as a buffer material that absorbs the unevenness of the substrate surface during transfer.

[0485] The unevenness on the substrate surface also includes formed images, electrodes, wiring, etc.

[0486] The thermoplastic resin layer preferably has a property of being deformable according to the concavities and convexities.

[0487] The thermoplastic resin layer preferably contains an organic polymer described in Japanese Patent Application Laid-Open No. 5-72724, and more preferably contains an organic polymer having a softening point of about 80° C. or lower according to the Vicat method (specifically, the polymer softening point measurement method according to ASTM D1235).

[0488] The thickness of the thermoplastic resin layer is, for example, preferably 3 μm to 30 μm, more preferably 4 μm to 25 μm, and even more preferably 5 μm to 20 μm.

[0489] When the thickness of the thermoplastic resin layer is 3 μm or more, the ability to follow the irregularities on the substrate surface is further improved, and thus the irregularities on the substrate surface can be absorbed more effectively.

[0490] If the thickness of the thermoplastic resin layer is 30 μm or less, the manufacturing adaptability is further improved. Therefore, for example, the load of drying (so-called drying for removing the solvent) when the thermoplastic resin layer is coated on the temporary support is further reduced, and the development time of the thermoplastic resin layer after transfer is further shortened.

[0491] The thickness of the thermoplastic resin layer was calculated as the average value of the thickness at five arbitrary locations measured by cross-sectional observation using a scanning electron microscope (SEM).

[0492] The thermoplastic resin layer can be formed by applying a thermoplastic resin layer-forming composition containing a solvent and a thermoplastic organic polymer onto a temporary support and drying the composition as needed.

[0493] Specific examples of the coating and drying methods in the method for forming the thermoplastic resin layer are the same as the specific examples of the coating and drying methods in the method for forming the photosensitive layer.

[0494] The solvent is not particularly limited as long as it dissolves the polymer component forming the thermoplastic resin layer.

[0495] Examples of the solvent include organic solvents (for example, methyl ethyl ketone, cyclohexanone, propylene glycol monomethyl ether acetate, n-propanol, and 2-propanol).

[0496] The viscosity of the thermoplastic resin layer measured at 100° C. is preferably 1,000 Pa·s to 10,000 Pa·s. Furthermore, the viscosity of the thermoplastic resin layer measured at 100° C. is preferably lower than the viscosity of the photosensitive layer measured at 100° C.

[0497] <Middle layer>

[0498] The transfer film according to the present invention may further include an intermediate layer between the temporary support and the photosensitive layer.

[0499] When the transfer film according to the present invention has a thermoplastic resin layer, the intermediate layer is preferably disposed between the thermoplastic resin layer and the photosensitive layer.

[0500] Examples of the component contained in the intermediate layer include at least one polymer selected from the group consisting of polyvinyl alcohol, polyvinyl pyrrolidone, and cellulose.

[0501] Furthermore, as the intermediate layer, an intermediate layer described as a “separation layer” in Japanese Patent Application Laid-Open No. 5-72724 can also be used.

[0502] When manufacturing a transfer film having a thermoplastic resin layer, an intermediate layer, and a photosensitive layer in this order on a temporary support, the intermediate layer can be formed, for example, by applying a solvent that does not dissolve the thermoplastic resin layer and an intermediate layer-forming composition containing the above-mentioned polymer as a component of the intermediate layer and drying it as needed.

[0503] Specifically, first, a thermoplastic resin layer-forming composition is applied to a temporary support and dried as needed to form a thermoplastic resin layer. Next, an intermediate layer-forming composition is applied to the formed thermoplastic resin layer and dried as needed to form an intermediate layer. Next, a photosensitive resin composition containing an organic solvent (so-called photosensitive layer-forming composition) is applied to the formed intermediate layer and dried to form a photosensitive layer. In addition, the organic solvent contained in the photosensitive layer-forming composition is preferably an organic solvent that does not dissolve the intermediate layer.

[0504] Specific examples of the coating and drying methods in the method for forming the intermediate layer are the same as the specific examples of the coating and drying methods in the method for forming the photosensitive layer.

[0505] -Impurities-

[0506] In the transfer film according to the present invention, from the viewpoint of improving reliability and pattern formability, the content of impurities in the photosensitive layer and the second resin layer is preferably low.

[0507] Specific examples of impurities include sodium, potassium, magnesium, calcium, iron, manganese, copper, aluminum, titanium, chromium, cobalt, nickel, zinc, tin, and ions thereof, as well as halide ions (chloride ions, bromide ions, iodide ions, etc.). Among them, sodium ions, potassium ions, and chloride ions are not easily mixed in as impurities, and therefore, the following contents are particularly preferred.

[0508] The impurity content in each layer is preferably 1,000 ppm or less, more preferably 200 ppm or less, and particularly preferably 40 ppm or less, based on mass. While the lower limit is not particularly limited, it can be set to 10 ppb or more, and can be set to 100 ppb or more, based on mass, from the perspective of practical reducibility and measurement limits.

[0509] Methods for reducing impurities to the above range include selecting materials for each layer that do not contain impurities, preventing impurities from entering during layer formation, and removing them by cleaning. These methods can keep the impurity content within the above range.

[0510] Impurities can be quantified by known methods such as ICP (Inductively Coupled Plasma) emission spectrometry, atomic absorption spectrometry, and ion chromatography.

[0511] Furthermore, the content of compounds such as benzene, formaldehyde, trichloroethylene, 1,3-butadiene, carbon tetrachloride, chloroform, N,N-dimethylformamide, N,N-dimethylacetamide, and hexane in each layer is preferably low. The content of these compounds in the photosensitive layer is preferably 1,000 ppm by mass or less, more preferably 200 ppm by mass or less, and particularly preferably 40 ppm by mass or less. While the lower limit is not particularly limited, it can be set to 10 ppb by mass or greater, and can be set to 100 ppb by mass or greater, based on practical reducibility and measurement limits.

[0512] The content of compound impurities can be suppressed by the same method as the above-mentioned metal impurities and can be quantified by known measurement methods.

[0513] -Specific example of transfer film-

[0514] Figure 1 FIG is a schematic cross-sectional view of a transfer film 10 as a specific example of the transfer film according to the present invention. Figure 1As shown, the transfer film 10 has a laminated structure of protective film 16 / second resin layer 20A / photosensitive layer 18A / temporary support 12 (i.e., a laminated structure in which temporary support 12, photosensitive layer 18A, second resin layer 20A, and protective film 16 are arranged in this order).

[0515] However, the transfer film of the present invention is not limited to the transfer film 10. For example, the second resin layer 20A and the protective film 16 may be omitted. Furthermore, at least one of the thermoplastic resin layer and the intermediate layer described above may be provided between the temporary support 12 and the photosensitive layer 18A.

[0516] The second resin layer 20A is a layer disposed on the side opposite to the side where the temporary support 12 is present when viewed from the photosensitive layer 18A, and has a refractive index of 1.50 or more at a wavelength of 550 nm.

[0517] The transfer film 10 is a negative-type material (so-called negative-type film).

[0518] The method for producing the transfer film 10 is not particularly limited.

[0519] The method for producing the transfer film 10 includes, for example, the steps of forming the photosensitive layer 18A on the temporary support 12 , forming the second resin layer 20A on the photosensitive layer 18A, and forming the protective film 16 on the second resin layer 20A in this order.

[0520] The method for manufacturing the transfer film 10 may include a step of volatilizing ammonia as described in paragraph 0056 of International Publication No. 2016 / 009980 between the step of forming the second resin layer 20A and the step of forming the protective film 16 .

[0521] The photosensitive layer and the second resin layer are preferably neutral colors. Specifically, total reflection (incident angle 8°, light source: D-65 (2° field of view)) in CIE1976 (L * , a * , b * ) color space, the pattern’s L * The value is preferably 10 to 90, and the pattern a * The value is preferably -1.0 to 1.0, and the b * The value is preferably -1.0 to 1.0.

[0522] (Laminated body and capacitive input device)

[0523] The laminated body according to the present invention includes a substrate and a cured film formed by curing the photosensitive resin composition according to the present invention.

[0524] The laminated body according to the present invention may have the cured film according to the present invention, but is preferably a laminated body in which a substrate, an electrode, and the cured film according to the present invention are laminated in this order.

[0525] The cured film can be formed into a desired pattern shape.

[0526] The capacitive input device according to the present invention includes the cured film according to the present invention or the laminated body according to the present invention.

[0527] The substrate is preferably a substrate including electrodes of an electrostatic capacitance input device.

[0528] The electrodes are preferably electrodes of a capacitive input device.

[0529] The electrodes of the capacitive input device may be transparent electrode patterns or may be routing wirings.

[0530] In the laminate, the electrodes of the capacitive input device are preferably electrode patterns, and more preferably transparent electrode patterns.

[0531] The laminated body of the present invention and the cured film formed by curing the photosensitive resin composition of the present invention are preferably neutral in color. Specifically, total reflection (incident angle 8°, light source: D-65 (2° field of view)) in CIE1976 (L * , a * , b * *) In color space, the L of the pattern * The value is preferably 10 to 90, and the pattern a * The value is preferably -1.0 to 1.0, and the b * The value is preferably -1.0 to 1.0.

[0532] The laminate according to the present invention comprises a substrate, a transparent electrode pattern, a second resin layer disposed adjacent to the transparent electrode pattern, and a photosensitive layer disposed adjacent to the second resin layer. The refractive index of the second resin layer is preferably higher than that of the photosensitive layer.

[0533] The refractive index of the second resin layer is preferably 1.6 or higher.

[0534] When the laminate is configured as described above, the concealability of the transparent electrode pattern becomes good.

[0535] As the substrate, a glass substrate or a resin substrate is preferable.

[0536] Furthermore, the substrate is preferably a transparent substrate, more preferably a transparent resin substrate.

[0537] The refractive index of the substrate is preferably 1.50 to 1.52.

[0538] As the glass substrate, for example, tempered glass such as Gorilla Glass (registered trademark) from Corning Incorporated can be used.

[0539] As the resin substrate, it is preferred to use at least one of a resin substrate without optical distortion and a resin substrate with high transparency. Examples include substrates formed from resins such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polycarbonate (PC), triacetyl cellulose (TAC), polyimide (PI), polybenzoxazole (PBO), and cycloolefin polymer (COP).

[0540] As the material of the transparent substrate, the materials described in Japanese Patent Application Laid-Open Nos. 2010-86684, 2010-152809, and 2010-257492 are preferable.

[0541] As the electrostatic capacitance input device, a touch panel can be preferably used.

[0542] As an example of the touch panel electrode, a transparent electrode pattern disposed at least in the image display area of ​​the touch panel can be mentioned. The touch panel electrode can extend from the image display area to the frame of the touch panel.

[0543] Examples of the touch panel wiring include routing wiring (so-called lead-out wiring) disposed in the frame of the touch panel.

[0544] As a form of the touch panel substrate and the touch panel, a form in which a part of the routing wiring is laminated on a portion of the transparent electrode pattern extending to the frame portion of the touch panel is preferably used to electrically connect the transparent electrode pattern and the routing wiring.

[0545] As a material for the transparent electrode pattern, a metal oxide film such as ITO (indium tin oxide) or IZO (indium zinc oxide), or a metal mesh or a metal fine wire such as a silver nanowire is preferable.

[0546] Examples of the metal thin wires include thin wires of silver, copper, and the like, among which silver conductive materials such as silver mesh and silver nanowires are preferred.

[0547] The material of the routing wiring is preferably metal.

[0548] Examples of metals used as the material for the routing wiring include gold, silver, copper, molybdenum, aluminum, titanium, chromium, zinc, and manganese, as well as alloys containing two or more of these metal elements. Preferably, the material for the routing wiring is copper, molybdenum, aluminum, or titanium, and particularly preferably copper.

[0549] The touch panel electrode protective film formed using the transfer film of the present invention is provided to protect electrodes (ie, at least one of touch panel electrodes and touch panel wiring) directly or through another layer to cover the electrodes.

[0550] The preferred range of the thickness of the touch panel electrode protective film is the same as the preferred range of the thickness of the photosensitive layer described above.

[0551] The electrode protection film (preferably an electrode protection film for a touch panel) may have an opening.

[0552] The opening can be formed by dissolving the non-exposed portion of the photosensitive layer with a developer.

[0553] The touch panel may further include a first refractive index adjustment layer between the electrode and the touch panel electrode protection layer (for example, refer to a first specific example of a touch panel described later).

[0554] Preferred embodiments of the first refractive index adjusting layer are the same as those of the second resin layer that may be included in the transfer film. However, when the second resin layer is curable, the first refractive index adjusting layer is a cured layer. As for preferred embodiments of the first refractive index adjusting layer, it goes without saying that preferred embodiments of the second resin layer, such as photocurable, thermosetting, and alkali-soluble, do not apply.

[0555] The first refractive index adjusting layer may be formed by applying and drying the first refractive index adjusting layer-forming composition, or may be formed by transferring the refractive index adjusting layer from a transfer film having the refractive index adjusting layer.

[0556] A touch panel including a first refractive index adjusting layer is preferably formed by using a transfer film according to the present invention having a second resin layer and transferring the photosensitive layer and the second resin layer from the transfer film. In this case, the photosensitive layer of the transfer film forms the touch panel electrode protective layer, and the second resin layer of the transfer film forms the first refractive index adjusting layer.

[0557] Furthermore, the touch panel or the touch panel substrate may include a second refractive index adjustment layer between the substrate and the electrodes or the like (for example, refer to the first specific example of the touch panel described later).

[0558] Preferred aspects of the second refractive index adjusting layer are the same as preferred aspects of the second resin layer that the transfer film may have.

[0559] The touch panel including the first refractive index adjusting layer (more preferably, including the first and second refractive index adjusting layers) has the advantage of making electrodes and the like less visible (so-called pattern visibility is suppressed).

[0560] Regarding the structure of the touch panel, reference may be made to the structures of electrostatic capacitance input devices described in Japanese Patent Application Laid-Open Nos. 2014-10814 and 2014-108541.

[0561] -First Specific Example of Touch Panel-

[0562] Figure 2 FIG is a schematic cross-sectional view of a touch panel 30 as a first specific example of the touch panel according to the present invention. Figure 2 It is a schematic cross-sectional view of the image display area of ​​the touch panel 30 .

[0563] like Figure 2 As shown, the touch panel 30 has a structure in which a substrate 32 , a second refractive index adjusting layer 36 , a transparent electrode pattern 34 as a touch panel electrode, a first refractive index adjusting layer 20 , and a touch panel electrode protective film 18 are arranged in this order.

[0564] In touch panel 30, touch panel electrode protection film 18 and first refractive index adjustment layer 20 cover the entire transparent electrode pattern 34. However, the touch panel of the present invention is not limited to this embodiment. It is sufficient that touch panel electrode protection film 18 and first refractive index adjustment layer 20 cover at least a portion of transparent electrode pattern 34.

[0565] The second refractive index adjusting layer 36 and the first refractive index adjusting layer 20 preferably cover the first region 40 where the transparent electrode pattern 34 exists and the second region 42 where the transparent electrode pattern 34 does not exist, directly or through other layers. In this manner, the transparent electrode pattern 34 becomes less visible.

[0566] The second refractive index adjusting layer 36 and the first refractive index adjusting layer 20 preferably directly cover the first region 40 and the second region 42 rather than covering the first region 40 and the second region 42 via another layer.

[0567] Examples of “other layers” include insulating layers and electrode patterns other than the transparent electrode pattern 34 .

[0568] The first refractive index adjusting layer 20 is stacked over both the first region 40 and the second region 42. The first refractive index adjusting layer 20 is adjacent to the second refractive index adjusting layer 36 and is also adjacent to the transparent electrode pattern 34.

[0569] When the shape of the end portion of the transparent electrode pattern 34 in contact with the second refractive index adjusting layer 36 is as follows Figure 2 In the case of the tapered shape shown, it is preferable to laminate the first refractive index adjusting layer 20 along the tapered shape (ie, with the same slope as the tapered angle).

[0570] As the transparent electrode pattern 34 , an ITO transparent electrode pattern is preferable.

[0571] The transparent electrode pattern 34 can be formed by, for example, the following method.

[0572] An electrode thin film (e.g., an ITO film) is formed on the substrate 32 having the second refractive index adjusting layer 36 formed thereon by sputtering. An etching protection layer is then formed on the formed electrode thin film by coating an etching photosensitive resist or by transferring the etching photosensitive film. The formed etching protection layer is then patterned into the desired shape through exposure and development. The portions of the electrode thin film not covered by the patterned etching protection film are then removed by etching, leaving the electrode thin film patterned into the desired shape (i.e., the transparent electrode pattern 34). The patterned etching protection layer is then removed using a stripping solution.

[0573] The first refractive index adjusting layer 20 and the touch panel electrode protection film 18 are formed, for example, as follows on a substrate 32 (ie, a touch panel substrate) on which the second refractive index adjusting layer 36 and the transparent electrode pattern 34 are sequentially provided.

[0574] First, prepare Figure 1 The transfer film 10 shown (ie, the transfer film 10 having a laminated structure of protective film 16 / second resin layer 20A / photosensitive layer 18A / temporary support 12 ).

[0575] Next, the protective film 16 is removed from the transfer film 10 .

[0576] Next, the transfer film 10, from which the protective film 16 has been removed, is laminated onto a substrate 32 (i.e., a touch panel substrate) on which a second refractive index adjusting layer 36 and a transparent electrode pattern 34 are sequentially provided. Lamination is performed so that the second resin layer 20A of the transfer film 10, from which the protective film 16 has been removed, contacts the transparent electrode pattern 34. This lamination results in a laminate having a laminate structure of temporary support 12 / photosensitive layer 18A / second resin layer 20A / transparent electrode pattern 34 / second refractive index adjusting layer 36 / substrate 32.

[0577] Next, the temporary support 12 is removed from the stacked body.

[0578] Next, the laminated body with the temporary support 12 removed is subjected to pattern exposure to cure the photosensitive layer 18A and the second resin layer 20A in a patterned manner. The patterned curing of the photosensitive layer 18A and the second resin layer 20A can be performed individually by separate pattern exposures, but is preferably performed simultaneously by a single pattern exposure.

[0579] Next, the unexposed portions (i.e., uncured portions) of the photosensitive layer 18A and the second resin layer 20A are removed by development, thereby obtaining the touch panel electrode protection film 18 (pattern shape not shown), which is a patterned cured product of the photosensitive layer 18A, and the first refractive index adjustment layer 20 (pattern shape not shown), which is a patterned cured product of the second resin layer 20A. The development of the pattern-exposed photosensitive layer 18A and the second resin layer 20A can be performed separately, but is preferably performed simultaneously in a single development process.

[0580] Preferred methods of lamination, pattern exposure, and development will be described later.

[0581] -Second Specific Example of Touch Panel-

[0582] Figure 3 It is a schematic cross-sectional view of a touch panel 90 as a second specific example of the touch panel according to the present invention.

[0583] like Figure 3 As shown, the touch panel 90 includes an image display area 74 and an image non-display area 75 (ie, a frame portion).

[0584] Furthermore, the touch panel 90 includes touch panel electrodes on both surfaces of the substrate 32. Specifically, the touch panel 90 includes a first transparent electrode pattern 70 on one surface of the substrate 32 and a second transparent electrode pattern 72 on the other surface.

[0585] In the touch panel 90, the first transparent electrode pattern 70 and the second transparent electrode pattern 72 are each connected to a routing wiring 56. The routing wiring 56 is, for example, a copper wiring.

[0586] In the touch panel 90 , a touch panel electrode protection film 18 is formed on one surface of the substrate 32 so as to cover the first transparent electrode pattern 70 and the bypass wiring 56 , and a touch panel electrode protection film 18 is formed on the other surface of the substrate 32 so as to cover the second transparent electrode pattern 72 and the bypass wiring 56 .

[0587] The first refractive index adjustment layer and the second refractive index adjustment layer in the first specific example may be formed on one surface and the other surface of the substrate 32 , respectively.

[0588] (Method for Manufacturing Touch Panel)

[0589] The method for manufacturing the touch panel according to the present invention is not particularly limited, but the following method is preferred.

[0590] The method for manufacturing a touch panel according to the present invention preferably includes the following steps:

[0591] Preparing a touch panel substrate having a structure in which electrodes and the like (i.e., at least one of touch panel electrodes and touch panel wiring) are arranged on the substrate (hereinafter also referred to as a "preparation step");

[0592] forming a photosensitive layer comprising the photosensitive resin composition of the present invention on a surface of a touch panel substrate on which electrodes and the like are disposed (hereinafter also referred to as a "photosensitive layer forming step");

[0593] Performing pattern exposure on the photosensitive layer formed on the touch panel substrate (hereinafter also referred to as "pattern exposure step"); and

[0594] The pattern-exposed photosensitive layer is developed to obtain a touch panel electrode protective film that protects at least a portion of the electrode and the like (hereinafter also referred to as a "development step").

[0595] According to the preferred method for manufacturing a touch panel according to the present invention, it is possible to manufacture a touch panel including a cured film having excellent adhesion to a substrate and excellent corrosion resistance to metals.

[0596] Hereinafter, each step in a preferred method for manufacturing a touch panel according to the present invention will be described.

[0597] <Preparation process>

[0598] The preparation step is a step for convenience, and is a step of preparing a touch panel substrate having a structure in which electrodes and the like (ie, at least one of touch panel electrodes and touch panel wirings) are arranged on the substrate.

[0599] The preparation step may be a step of simply preparing a touch panel substrate manufactured in advance, or may be a step of manufacturing the touch panel substrate.

[0600] Preferred embodiments of the touch panel substrate are as described above.

[0601] <Photosensitive layer forming step>

[0602] The photosensitive layer forming step is a step of forming a photosensitive layer made of the photosensitive resin composition according to the present invention on the surface of the touch panel substrate on which electrodes and the like are arranged.

[0603] Hereinafter, an embodiment of forming a photosensitive layer containing the photosensitive resin composition according to the present invention using the transfer film according to the present invention in the photosensitive layer forming step will be described.

[0604] In this method, the transfer film of the present invention is laminated on the surface of a touch panel substrate where electrodes and the like are arranged, and the photosensitive layer of the transfer film of the present invention is transferred to the surface to form a photosensitive layer on the surface.

[0605] Lamination (so-called transfer of the photosensitive layer) can be performed using a well-known laminator such as a vacuum laminator and an automatic cutting laminator.

[0606] As lamination conditions, general conditions can be applied.

[0607] The lamination temperature is preferably 80°C to 150°C, more preferably 90°C to 150°C, and even more preferably 100°C to 150°C.

[0608] When a laminator equipped with a rubber roller is used, the laminating temperature refers to the temperature of the rubber roller.

[0609] The substrate temperature during lamination is not particularly limited.

[0610] The substrate temperature during lamination is preferably 10°C to 150°C, more preferably 20°C to 150°C, and even more preferably 30°C to 150°C.

[0611] When a resin substrate is used as the substrate, the substrate temperature during lamination is preferably 10°C to 80°C, more preferably 20°C to 60°C, and even more preferably 30°C to 50°C.

[0612] Furthermore, the linear pressure during lamination is preferably 0.5 N / cm to 20 N / cm, more preferably 1 N / cm to 10 N / cm, and even more preferably 1 N / cm to 5 N / cm.

[0613] Furthermore, the conveying speed during lamination (lamination speed) is preferably 0.5 m / min to 5 m / min, and more preferably 1.5 m / min to 3 m / min.

[0614] When using a transfer film having a laminated structure of protective film / photosensitive layer / intermediate layer / thermoplastic resin layer / temporary support, the protective film is first peeled off from the transfer film to expose the photosensitive layer. Next, the transfer film and touch panel substrate are bonded together so that the exposed photosensitive layer contacts the surface of the touch panel substrate on which the electrodes, etc., are disposed. Subsequently, heating and pressure are applied. This operation transfers the photosensitive layer of the transfer film to the surface of the touch panel substrate on which the electrodes, etc., are disposed, forming a laminate having a laminated structure of temporary support / thermoplastic resin layer / intermediate layer / photosensitive layer / electrodes, etc. / substrate. In this laminated structure, the "electrodes, etc. / substrate" portion represents the touch panel substrate.

[0615] Then, the temporary support is peeled off from the laminate as needed. However, the pattern exposure described later can also be performed with the temporary support left.

[0616] As an example of a method of transferring a photosensitive layer of a transfer film onto a touch panel substrate and performing pattern exposure and development, reference can also be made to the description in paragraphs 0035 to 0051 of Japanese Patent Application Laid-Open No. 2006-23696.

[0617] Pattern Exposure Process

[0618] The pattern exposure step is a step of performing pattern exposure on the photosensitive layer formed on the touch panel substrate.

[0619] “Pattern exposure” means exposure in a pattern-like manner, that is, exposure in which exposed areas and non-exposed areas exist.

[0620] In the photosensitive layer on the touch panel substrate, the exposed portion during the pattern exposure is cured, and finally forms a cured film.

[0621] On the other hand, in the photosensitive layer on the touch panel substrate, the non-exposed areas during pattern exposure are not cured and are dissolved and removed by the developer in the subsequent development step. The non-exposed areas can form openings in the cured film after the development step.

[0622] The pattern exposure may be exposure through a mask or digital exposure using a laser or the like.

[0623] As a light source for pattern exposure, any light having a wavelength range capable of curing the photosensitive layer (for example, 365 nm or 405 nm) can be appropriately selected and used.

[0624] Examples of the light source include various lasers, light emitting diodes (LEDs), ultrahigh-pressure mercury lamps, high-pressure mercury lamps, and metal halide lamps.

[0625] The exposure dose is preferably 5 mJ / cm 2 ~200mJ / cm 2 , more preferably 10 mJ / cm 2 ~200mJ / cm 2 .

[0626] When a photosensitive layer is formed on a substrate using a transfer film, pattern exposure may be performed after peeling off the temporary support, or pattern exposure may be performed before peeling off the temporary support and then peeling off the temporary support.

[0627] Furthermore, in the exposure step, the photosensitive layer may be subjected to a heat treatment (so-called PEB (Post Exposure Bake)) after pattern exposure and before development.

[0628] <Development Process>

[0629] The development step is a step of developing the pattern-exposed photosensitive layer (ie, dissolving the non-exposed portion in the pattern-exposed layer in a developer) to obtain a touch panel electrode protection film that protects at least a portion of the electrode and the like.

[0630] The developer used for development is not particularly limited, and a known developer such as the developer described in Japanese Patent Application Laid-Open No. 5-72724 can be used.

[0631] As the developer, an alkaline aqueous solution is preferably used.

[0632] Examples of the alkaline compound that may be contained in the alkaline aqueous solution include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, and choline (2-hydroxyethyltrimethylammonium hydroxide).

[0633] The pH of the alkaline aqueous solution at 25°C is preferably 8 to 13, more preferably 9 to 12, and particularly preferably 10 to 12.

[0634] The content of the basic compound in the basic aqueous solution is preferably 0.1% by mass to 5% by mass, more preferably 0.1% by mass to 3% by mass, relative to the total mass of the basic aqueous solution.

[0635] The developer may contain an organic solvent that is miscible with water.

[0636] Examples of the organic solvent include methanol, ethanol, 2-propanol, 1-propanol, butanol, diacetone alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-butyl ether, benzyl alcohol, acetone, methyl ethyl ketone, cyclohexanone, ε-caprolactone, γ-butyrolactone, dimethylformamide, dimethylacetamide, hexamethylphosphoramide, ethyl lactate, methyl lactate, ε-caprolactam, and N-methylpyrrolidone.

[0637] The concentration of the organic solvent is preferably 0.1% by mass to 30% by mass.

[0638] The developer may contain a known surfactant.

[0639] The concentration of the surfactant is preferably 0.01% by mass to 10% by mass.

[0640] The liquid temperature of the developer is preferably 20°C to 40°C.

[0641] Examples of the development method include spin immersion development, shower development, shower and spin development, and immersion development.

[0642] When shower development is performed, a developing solution is sprayed in a shower shape on the photosensitive layer after pattern exposure to remove the non-exposed portion of the photosensitive layer.

[0643] When using a transfer film having a photosensitive layer and at least one of a thermoplastic resin layer and an intermediate layer, after transferring these layers onto a substrate and before developing the photosensitive layer, at least one of the thermoplastic resin layer and the intermediate layer (or both if present) can be removed in advance by spraying an alkaline liquid with low solubility on the photosensitive layer.

[0644] Furthermore, after development, it is preferable to remove development residues by spraying a cleaning agent or the like with a shower and wiping with a brush or the like.

[0645] The liquid temperature of the developer is preferably 20°C to 40°C.

[0646] The development step may include a step of performing the development described above and a step of performing a heat treatment (hereinafter also referred to as "post-baking") on the cured film obtained by the development described above.

[0647] When the substrate is a resin substrate, the temperature of the post-bake is preferably 100°C to 160°C, more preferably 130°C to 160°C.

[0648] This post-baking can also adjust the resistance value of the transparent electrode pattern.

[0649] When the photosensitive layer contains a carboxyl group-containing (meth)acrylic resin, at least a portion of the carboxyl group-containing (meth)acrylic resin can be converted to carboxylic anhydride by post-baking. This conversion results in excellent developability and cured film strength.

[0650] The development process may include a step of performing the development described above and a step of exposing the cured film obtained by the development described above (hereinafter also referred to as "post-exposure").

[0651] When the development process includes two steps of a post-exposure step and a post-baking step, it is preferable to perform the post-baking after the post-exposure step.

[0652] Regarding pattern exposure, development, and the like, for example, reference can also be made to the description in paragraphs 0035 to 0051 of Japanese Patent Application Laid-Open No. 2006-23696.

[0653] The method for manufacturing a touch panel according to the present invention may include steps other than the steps already described (so-called other steps).

[0654] Examples of other steps include known steps (for example, a cleaning step) that may be included in a normal photolithography step.

[0655] Example

[0656] Hereinafter, the present invention will be described in more detail with reference to examples.

[0657] The materials, usage amounts, ratios, treatment contents, and treatment procedures shown in the following examples can be appropriately modified without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below.

[0658] <Synthesis of polymer P-1>

[0659] A three-necked flask was charged with 244.2 parts by mass of propylene glycol monomethyl ether (MFG, manufactured by FUJIFILM Wako Pure Chemical Corporation) and maintained at 90°C under nitrogen. A mixed solution of 118.7 parts by mass of dicyclopentyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.), 94.7 parts by mass of methacrylic acid (MAA, manufactured by FUJIFILM Wako Pure Chemical Corporation), 90.9 parts by mass of styrene (manufactured by FUJIFILM Wako Pure Chemical Corporation), 188.5 parts by mass of MFG, 0.0610 parts by mass of p-methoxyphenol (manufactured by FUJIFILM Wako Pure Chemical Corporation), and 16.7 parts by mass of V-601 (dimethyl 2,2'-azobis(2-methylpropionate), manufactured by FUJIFILM Wako Pure Chemical Corporation) was added dropwise over 3 hours.

[0660] After the dropwise addition, the mixture was stirred at 90°C for 1 hour, and a mixture of V-601 (2.1 parts by mass) and MFG (5.2 parts by mass) was added. After stirring for 1 hour, a mixture of V-601 (2.1 parts by mass) and MFG (5.2 parts by mass) was further added. After stirring for 1 hour, a mixture of V-601 (2.1 parts by mass) and MFG (5.2 parts by mass) was further added. After stirring for 3 hours, 2.9 parts by mass of MFG and 166.9 parts by mass of propylene glycol monomethyl ether acetate (PGMEA, manufactured by Daicel Corporation) were added, and the mixture was stirred until homogeneous.

[0661] To the reaction solution, 1.5 parts by mass of tetramethylammonium bromide (TEAB, manufactured by Tokyo Chemical Industry Co., Ltd.) and 0.7 parts by mass of p-methoxyphenol were added as additional catalysts, and the temperature was raised to 100°C. Furthermore, 61.9 parts by mass of glycidyl methacrylate (GMA, manufactured by Fujifilm Wako Pure Chemical Corporation) was added, and the mixture was stirred at 100°C for 9 hours to obtain a MFG / PGMEA mixed solution of polymer P-1. The weight-average molecular weight of P-1, as measured by GPC, was 20,000 (polystyrene equivalent), and the solids concentration was 36.3% by mass.

[0662] <Synthesis of polymers P-2 to P-8 and PC-1>

[0663] Each of the synthesized products was synthesized by the same method as that for the polymer P-1, except that the types and amounts of the monomers were changed.

[0664] (Example 1)

[0665] <Production of photosensitive transfer material (transfer film)>

[0666] <<Formation of Photosensitive Layer>>

[0667] A photosensitive layer is formed by applying a coating liquid having the following formula 101 onto a polyethylene terephthalate film having a thickness of 16 μm (temporary support, 16QS62 (manufactured by TORAY INDUSTRIES, INC.)) using a slit nozzle to adjust the thickness after drying to 4.5 μm, and drying the film using a hot air convection dryer having a temperature gradient of 75°C to 120°C to remove the solvent.

[0668] -Photosensitive layer coating liquid: Prescription 101 (Organic solvent-based resin composition (photosensitive resin composition))-

[0669] Compound A

[0670] A-HD-N (M-1, 1,6-hexanediol diacrylate, manufactured by SHIN-NAKAMURA CHEMICAL CO., LTD.): 9.52 parts

[0671] Other ethylenically unsaturated compounds

[0672] A-DCP (MO-1, tricyclodecane dimethanol diacrylate, manufactured by Shin Nakamura Chemical Co., Ltd.): 19.03 parts

[0673] ARONIX TO-2349 (MO-2, a polyfunctional ethylenically unsaturated compound having a carboxylic acid group, manufactured by TOAGOS EI CO., LTD.): 3.17 parts

[0674] Adhesive polymers

[0675] P-1 (resin shown below, structural unit derived from styrene (St) / structural unit derived from dicyclopentyl methacrylate (DCPMA) / structural unit derived from methacrylic acid (MAA) / structural unit obtained by adding glycidyl methacrylate to structural unit derived from methacrylic acid (GMA-MAA) = 33.5 / 21.9 / 27.0 / 17.7 (mol %), I / O value 0.608, nS / (nS+nCy) = 0.55, Mw = 20,000): 52.87 parts (solid content)

[0676] Photopolymerization initiator

[0677] 1-[9-Ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone-1-(o-acetyl oxime) (C-1, Irgacure OXE-02, manufactured by BASF): 0.36 parts

[0678] 2-Methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one (C-2, Irgacure 907, manufactured by BASF): 0.73 parts

[0679] Thermally cross-linkable compounds

[0680] Currants AOI-BM (D-1, 2-(O-[1'-methylaminopropylidene]carboxyamino)ethyl acrylate, manufactured by Showa Denko KK): 12.50 parts

[0681] Other additives

[0682] Rust inhibitor (AD-1, 1,2,4-triazole, manufactured by Tokyo Chemical Industry Co., Ltd.): 0.20 parts

[0683] Hydrogen-donating compound (AD-3, N-phenylglycine, manufactured by JUNSEI CHEMICAL CO., LTD.): 0.10 part

[0684] Styrene / maleic anhydride = 4:1 (molar ratio) copolymer (AD-4, SMA EF-40, anhydride weight 1.94 mmol / g, weight average molecular weight 10,500, manufactured by Cray Valley): 1.20 parts

[0685] Surfactant (AD-5, fluorine-based surfactant, MEGAFACE F551A, manufactured by DIC Corporation): 0.32 parts

[0686] • Organic solvent: A 1:1 (mass ratio) mixed solvent of 1-methoxy-2-propyl acetate and methyl ethyl ketone was added so that the solid content concentration of the photosensitive layer-forming coating liquid became 29 mass %.

[0687] [Chemical Formula 24]

[0688]

[0689] <<Formation of the Second Resin Layer>>

[0690] Next, a second resin layer coating solution comprising the following formula 201 was applied onto the photosensitive layer using a slit nozzle to a thickness of 70 nm after drying. The solution was then dried using a hot air convection dryer with a temperature gradient of 40°C to 95°C to remove the solvent, thereby forming a second resin layer in direct contact with the photosensitive layer. The refractive index of the second resin layer at a wavelength of 550 nm at 25°C was 1.68.

[0691] Here, the formulation 201 was prepared using a resin having an acid group and an aqueous ammonia solution. The resin having an acid group was neutralized with the aqueous ammonia solution to prepare an aqueous resin composition containing an ammonium salt of the resin having an acid group, that is, a coating liquid for the second resin layer.

[0692] -Coating liquid for the second resin layer: Prescription 201 (water-based resin composition)-

[0693] Acrylic resin (ZB-015M, manufactured by Fuji Fine Chemical Co., Ltd., methacrylic acid / allyl methacrylate copolymer resin, weight average molecular weight 25,000, component ratio (molar ratio) = 20 / 80, solid content 5.00%, ammonia solution): 4.92 parts

[0694] · Polyfunctional ethylenically unsaturated compound having a carboxylic acid group (ARONIX TO-2349, manufactured by TOAGOSEI CO., LTD.): 0.04 parts

[0695] ZrO2 (NanoUse OZ-S30M, solid content 30.5%, methanol 69.5%, refractive index 2.2, average particle size: about 12 nm, manufactured by Nissan Chemical Corporation): 4.34 parts

[0696] Rust inhibitor (benzotriazole derivative, BT-LX, manufactured by JOHOKU CHEMICAL CO., LTD.): 0.03 parts

[0697] Surfactant (fluorinated surfactant, MEGAFACE F444, manufactured by DIC Corporation): 0.01 part

[0698] Distilled water: 24.83 parts

[0699] Methanol: 65.83 parts

[0700] <<Protective film formation>>

[0701] A polyethylene terephthalate film (protective film, 16QS62 (manufactured by TORAY INDUSTRIES, INC.)) with a thickness of 16 μm was pressed onto the second resin layer of a laminate obtained as described above, in which a photosensitive layer and a second resin layer arranged in direct contact with the photosensitive layer are sequentially provided on a temporary support, thereby producing the photosensitive transfer material of Example 1.

[0702] Evaluation Method

[0703] The obtained photosensitive transfer material was used to perform evaluation as follows.

[0704] <<Evaluation of bending resistance>>

[0705] -Preparation of samples for bending resistance evaluation-

[0706] After peeling off the protective film, the resulting photosensitive transfer material was laminated onto both sides of a polyethylene terephthalate film (COSMOSHINE A4300, 50 μm thick) manufactured by TOYOBO CO., LTD., which had been heat-treated at 145°C for 30 minutes. This formed a laminate A having a laminate structure of temporary support / photosensitive layer / second resin layer / COSMOSHINE A4300 (50 μm thick) / second resin layer / photosensitive layer / temporary support. Lamination conditions were a pressure roller temperature of 100°C, a linear pressure of 3 N / cm, and a conveyor speed of 4 m / min.

[0707] Then, a proximity exposure machine equipped with an ultra-high pressure mercury lamp (manufactured by Hitachi High-Tech Electronics Engineering Co., Ltd.) was used to expose the film at an exposure dose of 120 mJ / cm2 via a temporary support. 2 After peeling off the temporary supports on both sides, the two surfaces were exposed to light at an exposure dose of 375 mJ / cm 2The photosensitive layer was cured by performing double-side exposure (i-line) and post-baking at 145° C. for 30 minutes to form a cured film.

[0708] In this manner, a sample for evaluation of bending resistance consisting of a cured film having a thickness of 4 μm / COSMOSHINE A4300 (thickness of 50 μm) / a cured film having a thickness of 4 μm was obtained.

[0709] -Evaluation of bending resistance-

[0710] Using the samples for evaluation of bending resistance, bending resistance was evaluated in the following manner.

[0711] Figure 4 It is a schematic cross-sectional view showing the form of a sample for bending resistance evaluation in the bending resistance evaluation.

[0712] The bending resistance evaluation sample obtained above was cut into a rectangle of 5 cm × 12 cm. Figure 4 As shown, a 100 g weight 104 was added to one side of the short side of the cut sample 102 for evaluation of bending resistance, and the weight was increased so that the sample was kept in contact with a metal rod 106 having a diameter of d mm at an angle of 90° ( Figure 4 Then, the sample 102 for evaluation of bending resistance is bent so as to surround the metal rod 106 until the sample 102 for evaluation of bending resistance is bent at 180° ( Figure 4 The bending resistance evaluation sample 102A after bending was reciprocated 10 times to return to the original position (reciprocating direction D), and the presence or absence of cracks on the surface of the sample was visually confirmed.

[0713] The above operation was performed while changing the diameter d of the metal rod 106 to determine the minimum d at which no cracks occurred. In the following evaluation criteria, A represents the best bending resistance and E represents the worst. Any of A, B, and C is preferred, with A being particularly preferred.

[0714] A: The minimum d without cracks is less than 2mm

[0715] B: The minimum d without cracks is greater than 2mm and less than 3mm

[0716] C: The minimum d without cracks is greater than 3mm and less than 4mm

[0717] D: The minimum d without cracks is greater than 4mm and less than 5mm

[0718] E: The minimum d without cracks is greater than 5mm

[0719] <<Evaluation of Water Vapor Permeability (WVTR, Moisture Permeability)>>

[0720] -Preparation of Samples for Moisture Permeability Measurement-

[0721] After peeling off the protective film, the resulting transfer film was laminated onto a PTFE (tetrafluoroethylene resin) membrane filter FP-100-100 manufactured by Sumitomo Electric Industries, Ltd., thereby forming a laminate A having a laminate structure of temporary support / photosensitive layer / second resin layer / membrane filter. Lamination conditions were a membrane filter temperature of 40°C, a pressure roller temperature of 100°C, a linear pressure of 3 N / cm, and a conveyor speed of 4 m / min.

[0722] Furthermore, the temporary support is peeled off from the stack A, and the transfer film with the protective film peeled off is further laminated 4 times on the photosensitive layer in the same manner as above, forming a stack B having a stacking structure of temporary support / (photosensitive layer / second resin layer) × 5 layers / membrane filter.

[0723] The photosensitive layer of the obtained laminate B was exposed to light at an exposure dose of 120 mJ / cm2 via a temporary support using a proximity exposure machine equipped with an ultra-high pressure mercury lamp (manufactured by Hitachi High-Tech Electronics Engineering Co., Ltd.). 2 After peeling off the temporary support, the exposure was further carried out at an exposure dose of 375 mJ / cm 2 The photosensitive layer was exposed to light (i-line) and post-baked at 145° C. for 30 minutes to form a cured film.

[0724] As described above, a sample for measuring moisture permeability having a laminated structure of a cured film / membrane filter with a total film thickness of 20 μm was obtained.

[0725] -Measurement of Water Vapor Permeability (WVTR)-

[0726] Using a sample for water vapor permeability measurement, water vapor permeability measurement was performed by the cup method with reference to JIS-Z-0208 (1976).

[0727] First, a circular sample with a diameter of 70 mm was cut out from the sample for measuring moisture permeability. Next, 20 g of dried calcium chloride was placed in a measuring cup, and the measuring cup was covered with the circular sample to prepare a measuring cup with a lid.

[0728] The measuring cup with a lid was placed in a constant temperature and humidity chamber at 65°C and 90% RH for 24 hours. The water vapor permeability (WVTR) of the circular sample (unit: g / (m 2 ·sky)).

[0729] The above measurement was performed three times, and the average WVTR value of the three measurements was calculated. Based on the average WVTR value, the water vapor permeability (WVTR) was evaluated according to the following evaluation criteria. In the following evaluation criteria, any of A, B, and C is preferred, A or B is more preferred, and A is particularly preferred.

[0730] In the above measurement, the WVTR of the circular test specimen having the laminated structure of the cured membrane / membrane filter was measured as described above. However, the WVTR of the membrane filter is significantly higher than that of the cured membrane, so the above measurement essentially measured the WVTR of the cured membrane itself.

[0731] -Evaluation criteria for water vapor permeability (WVTR)-

[0732] A: The average value of WVTR is less than 220g / (m 2 ·sky)

[0733] B: The average WVTR is 220g / (m 2 ·day) and less than 240g / (m 2 ·sky)

[0734] C: The average WVTR is 240g / (m 2 ·day) and less than 260g / (m 2 ·sky)

[0735] D: The average value of WVTR is 260g / (m 2 ·day) and less than 280g / (m 2 ·sky)

[0736] E: The average value of WVTR is 280g / (m 2 · days) or more

[0737] <<Evaluation of Adhesion Property of Uncured Film (Transfer Position Misalignment Suppression Property)>>

[0738] The obtained transfer film was cut into a rectangle of 5 cm x 18 cm. A PFA (polytetrafluoroethylene) film having a thickness of 500 μm was cut into a rectangle of 10 cm x 15 cm and fixed on a horizontal surface. The PFA film and the transfer film were overlapped so that the PFA film and the surface of the photosensitive layer formed on the cut transfer film were in contact with each other, and a 70 g weight in the shape of a rectangular parallelepiped with a bottom of 4 cm x 6 cm was added thereto. Using a SHIMPO force gauge stand, the overlapped transfer films were stretched at a constant speed in a horizontal direction parallel to the long side of the transfer films, and the friction force (unit: N) under the load of the weight was measured.

[0739] The value obtained by dividing the frictional force by 70 (hereinafter also referred to as “viscosity index value”) is used as an index of viscosity.

[0740] In the following evaluation criteria, any one of A, B, and C is preferred, A or B is more preferred, and A is particularly preferred.

[0741] -Evaluation criteria for adhesion of uncured films-

[0742] A: The viscosity index value is less than 3.

[0743] B: The viscosity index value is 3 or more and less than 6.

[0744] C: The viscosity index value is 6 or more and less than 10.

[0745] D: The viscosity index value is 10 or more and less than 12.

[0746] E: The viscosity index value is 12 or more.

[0747] (Examples 2 to 43 and Comparative Examples 1 to 5)

[0748] A photosensitive resin composition and a photosensitive transfer material were each produced in the same manner as in Example 1, except that the types and contents (solid content) of the components other than the solvent were changed as described in Tables 1 to 3.

[0749] In Examples 17, 18, and 19, the coating was performed so that the thickness after drying was adjusted to 3.5 μm, 6.0 μm, and 8.0 μm, respectively.

[0750] Then, each evaluation was performed in the same manner as in Example 1 using the obtained photosensitive transfer material.

[0751] The evaluation results are summarized in Tables 1 to 3.

[0752]

[0753]

[0754] [Table 3]

[0755]

[0756] In addition, regarding P-1 to P-8 in Tables 1 to 3, the I / O value is within the range of 0.5 to 0.7, and they are polymers corresponding to the binder polymer P.

[0757] The abbreviations described in Tables 1 to 3 other than those described above are as follows.

[0758] M-2: 1,9-nonanediol diacrylate (A-NOD-N, manufactured by SHIN-NAKAMURA CHEMICAL CO., LTD.)

[0759] M-3: 1,10-Decanediol diacrylate (A-DOD-N, manufactured by SHIN-NAKAMURA CHEMICAL CO., LTD.)

[0760] M-4: the following compound (A-PTMG-65, manufactured by SHIN-NAKAMURA CHEMICAL CO., LTD.)

[0761] [Chemical Formula 25]

[0762]

[0763] M-5: Neopentyl glycol dimethacrylate (NPG, manufactured by Shin-Nakamura Chemical Co., Ltd.)

[0764] M-6: tripropylene glycol diacrylate, the following compound (APG-200, manufactured by Shin-Nakamura Chemical Co., Ltd.)

[0765] [Chemical Formula 26]

[0766]

[0767] M-7: Polyethylene glycol (n=4) diacrylate (A-200, manufactured by Shin-Nakamura Chemical Co., Ltd.)

[0768] M-8: 1,10-Decanediol dimethacrylate (DOD-N, manufactured by Shin-Nakamura Chemical Co., Ltd.)

[0769] MO-3: Urethane acrylate 8UX-015A (manufactured by Taisei Fine Chemical Co., Ltd.)

[0770] MO-4: Dipentaerythritol hexaacrylate (A-DPH, manufactured by Shin-Nakamura Chemical Co., Ltd.)

[0771] MO-5: Pentaerythritol tetraacrylate (A-TMMT, manufactured by Shin-Nakamura Chemical Co., Ltd.)

[0772] P-2: Resin shown below, structural unit derived from styrene (St) / structural unit derived from dicyclopentyl methacrylate (DCPMA) / structural unit derived from methacrylic acid (MAA) / structural unit obtained by adding glycidyl methacrylate to structural unit derived from methacrylic acid (GMA-MAA) = 29.4 / 23.3 / 25.8 / 21.5 (mol %), I / O value 0.633, nS / (nS+nCy) = 0.56, Mw = 19,000

[0773] [Chemical Formula 27]

[0774]

[0775] P-3: Resin shown below, St / DCPMA / MAA / GMA-MAA=8.3 / 47.1 / 27.0 / 17.7 (mol%), I / O value=0.623, nS / (nS+nCy)=0.15, Mw=20,000

[0776] [Chemical Formula 28]

[0777]

[0778] P-4: Resin shown below, St / DCPMA / MAA / GMA-MAA = 12.2 / 43.2 / 27.0 / 17.7 (mol%), I / O value = 0.621, nS / (nS+nCy) = 0.22, Mw = 20,000)

[0779] [Chemical Formula 29]

[0780]

[0781] P-5: Resin shown below, St / DCPMA / MAA / GMA-MAA = 47.1 / 8.3 / 27.0 / 17.7 (mol%), I / O value = 0.598, nS / (nS+nCy) = 0.85, Mw = 20,000)

[0782] [Chemical formula 30]

[0783]

[0784] P-6: Resin shown below, St / DCPMA / MAA / GMA-MAA = 43.2 / 12.2 / 27.0 / 17.7 (mol%), I / O value = 0.598, nS / (nS+nCy) = 0.78, Mw = 20,000)

[0785] [Chemical Formula 31]

[0786]

[0787] P-7: Resin shown below, St / structural unit derived from cyclohexyl methacrylate (CHMA) / MAA / GMA-MAA=29.4 / 23.3 / 25.8 / 21.5 (mol%), I / O value=0.663, nS / (nS+nCy)=0.56, Mw=23,000)

[0788] [Chemical Formula 32]

[0789]

[0790] P-8: Resin shown below, St / DCPMA / MAA / GMA-MAA = 42.4 / 15.7 / 21.3 / 20.6 (mol%), I / O value = 0.537, nS / (nS+nCy) = 0.73, Mw = 20,000)

[0791] [Chemical Formula 33]

[0792]

[0793] PC-1: The resin shown below (the ratio of each structural unit is a molar ratio), I / O value = 0.745, Mw = 35,000

[0794] [Chemical Formula 34]

[0795]

[0796] C-3: 2-(Dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone (IRGACURE 379EG, manufactured by BASF)

[0797] D-2: Duranate TPA-B80E (blocked isocyanate compound, manufactured by Asahi Kasei Chemicals Corporation)

[0798] D-3: Karenz MOI-BM (photopolymerizable blocked isocyanate compound, manufactured by Showa Denko KK)

[0799] AD-2: Benzimidazole (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0800] (Examples 44 to 86)

[0801] In Examples 1 to 43, transfer films were prepared and evaluated in the same manner as in Examples 1 to 43, except that the second resin layer was not formed. All the evaluation results were the same as in Examples 1 to 43.

[0802] (Examples 87 to 90)

[0803] In Example 8, except for Figure 4 Except for changing the temporary support and the protective film, a transfer film and a laminate were produced in the same manner as in Example 8, and evaluated in the same manner as in Example 8. The same evaluation results as in Example 8 were obtained.

[0804] [Table 4]

[0805]

[0806] The results shown in Tables 1 to 3 indicate that the photosensitive resin compositions of Examples 1 to 43 according to the present invention provide cured films having lower moisture permeability and superior flex resistance than the photosensitive resin compositions of Comparative Examples 1 to 5.

[0807] Furthermore, it was found that the photosensitive resin compositions of Examples 1 to 43 of the curable compositions according to the present invention were excellent in the adhesiveness of the obtained uncured films.

[0808] (Examples 101 to 190)

[0809] <Production of Transparent Laminate>

[0810] A substrate was prepared in which a second refractive index adjusting layer, an ITO transparent electrode pattern, and copper routing wiring were formed on a cycloolefin transparent film.

[0811] Using the transfer films of each example, with the protective film removed, a second refractive index adjusting layer, an ITO transparent electrode pattern, and copper routing wiring were laminated onto the areas covered by the transfer film. Lamination was performed using a vacuum laminator manufactured by MCK Co., Ltd. under the following conditions: a cycloolefin transparent film temperature of 40°C, a rubber roller temperature of 100°C, a linear pressure of 3 N / cm, and a conveyor speed of 2 m / min.

[0812] Then, a proximity exposure machine equipped with an ultra-high pressure mercury lamp (manufactured by Hitachi High-Tech Electronics Engineering Co., Ltd.) was used to bring the surface of an exposure mask (a quartz exposure mask having a pattern for forming an overcoat) into close contact with a temporary support, and an exposure dose of 100 mJ / cm was applied through the temporary support. 2 (i-ray) pattern exposure was performed.

[0813] After the temporary support was peeled off, a development treatment was performed in a 1% sodium carbonate aqueous solution at 33° C. for 45 seconds.

[0814] Afterward, ultrapure water was sprayed from an ultrahigh-pressure cleaning nozzle onto the developed transparent film substrate to remove any residue. Air was then blown in to remove moisture from the transparent film substrate, followed by post-baking at 145°C for 30 minutes. This resulted in a transparent laminate consisting of a second refractive index adjusting layer, an ITO transparent electrode pattern, copper routing wiring, a second refractive index adjusting layer, and a cured film, layered sequentially on the transparent film substrate.

[0815] A touch panel was fabricated using the produced transparent laminate according to a known method, and the produced touch panel was bonded to a liquid crystal display element produced by the method described in paragraphs 0097 to 0119 of Japanese Patent Application Laid-Open No. 2009-47936 to produce a liquid crystal display device including the touch panel.

[0816] It was confirmed that the liquid crystal display device including the touch panel had excellent display characteristics and operated without any problems.

[0817] Explanation of symbols

[0818] 10-transfer film, 12-temporary support, 16-protective film, 18-photosensitive layer (electrode protective film for touch panel), 20, 20A-second resin layer (first refractive index adjustment layer), 30-touch panel, 32-substrate, 34-transparent electrode pattern, 36-second refractive index adjustment layer, 40-first region where the transparent electrode pattern exists, 42-transparent electrode, second region where the pattern does not exist, 56-circuit wiring, 70-first transparent electrode pattern, 72-second transparent electrode pattern, 74-image display region, 75-image non-display region, 90-touch panel, 102-sample for evaluating bending resistance, 102A: sample for evaluating bending resistance in a state bent 180°, 104: weight, 106: metal rod, D: reciprocating direction, d: diameter of the metal rod 106.

Claims

1. A photosensitive resin composition comprising a binder polymer P having an I / O value of 0.598 or more and 0.7 or less, an ethylenically unsaturated compound, and a photopolymerization initiator. The ethylenically unsaturated compound includes a compound A represented by the following formula (1): Q 2 -R 1 -Q 1 Formula (1) In formula (1), Q 1 and Q 2 Each independently represents a (meth)acryloyloxy group, R 1 represents a divalent linking group having a chain structure, The binder polymer P has a structural unit represented by the following formula (S) and a structural unit represented by the following formula (Cy), The molar amount nS of the structural unit represented by the following formula (S) and the molar amount nCy of the structural unit represented by the following formula (Cy) in the binder polymer P satisfy the relationship represented by the following formula (Scy-1): 0.30≤nS / (nS+nCy)≤0.75 Formula (SCy-1) In formula (Cy), R M represents a hydrogen atom or a methyl group, R Cy It represents a monovalent group having an aliphatic hydrocarbon ring structure.

2. The photosensitive resin composition according to claim 1, wherein The total content of the structural unit represented by the formula (S) and the structural unit represented by the formula (Cy) is 40 mol % or more and 70 mol % or less relative to the total amount of the binder polymer P. The binder polymer P further contains a structural unit having a reactive group, The content of the structural unit having a reactive group is 10 mol % or more and 50 mol % or less relative to the total amount of the binder polymer P.

3. The photosensitive resin composition according to claim 2, wherein The photosensitive resin composition does not contain a colorant, or the content of the colorant is less than 1% by mass relative to the total solid content of the photosensitive resin composition.

4. The photosensitive resin composition according to claim 1, wherein The aliphatic hydrocarbon ring structure is a tetrahydrodicyclopentadiene ring structure.

5. The photosensitive resin composition according to any one of claims 1 to 4, wherein The content of compound A M A The content M of the binder polymer P P The mass ratio M A / M P It is 0.10~0.

30.

6. The photosensitive resin composition according to any one of claims 1 to 4, wherein The R 1 is an alkylene group, an alkyleneoxyalkylene group or a polyalkyleneoxyalkylene group.

7. The photosensitive resin composition according to any one of claims 1 to 4, wherein The R 1 It is a straight-chain alkylene group having 6 to 18 carbon atoms.

8. The photosensitive resin composition according to any one of claims 1 to 4, wherein The R 1 For-L 1 -OL 1 -or- (L 1 -O) p -L 1 - represents a group, said L 1 Each independently represents an ethylene group, a propylene group or a butylene group, and p represents an integer of 2 or greater. 9 . The photosensitive resin composition according to claim 1 , which is a photosensitive resin composition for forming a protective film in a touch panel.

10. A transfer film comprising: temporary supports; and A photosensitive layer composed of the photosensitive resin composition according to any one of claims 1 to 4 or formed by drying the photosensitive resin composition. 11 . A cured film formed by curing the photosensitive resin composition according to claim 1 . 12 . A laminate comprising a substrate and a cured film formed by curing the photosensitive resin composition according to claim 1 .

13. A method for manufacturing a touch panel, comprising the following steps: preparing a touch panel substrate having a surface on which at least one of touch panel electrodes and touch panel wiring is arranged; forming a photosensitive layer comprising the photosensitive resin composition according to any one of claims 1 to 4 or a photosensitive layer obtained by drying the photosensitive resin composition on the surface of the touch panel substrate on which at least one of the touch panel electrodes and the touch panel wiring is arranged; performing pattern exposure on the photosensitive layer formed on the touch panel substrate; as well as The pattern-exposed photosensitive layer is developed to obtain a protective film that protects at least a portion of at least one of the touch panel electrodes and the touch panel wiring.

Images